CN114713226B - Preparation method and application of slow-release micro-nano zero-valent iron material - Google Patents
Preparation method and application of slow-release micro-nano zero-valent iron material Download PDFInfo
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- CN114713226B CN114713226B CN202210215772.1A CN202210215772A CN114713226B CN 114713226 B CN114713226 B CN 114713226B CN 202210215772 A CN202210215772 A CN 202210215772A CN 114713226 B CN114713226 B CN 114713226B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000004021 humic acid Substances 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 24
- 239000002028 Biomass Substances 0.000 claims abstract description 21
- 239000012452 mother liquor Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000010413 mother solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 241000195493 Cryptophyta Species 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000010806 kitchen waste Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 210000003608 fece Anatomy 0.000 claims description 2
- 244000144972 livestock Species 0.000 claims description 2
- 239000010871 livestock manure Substances 0.000 claims description 2
- 244000144977 poultry Species 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 14
- 238000005815 base catalysis Methods 0.000 abstract description 3
- 239000011258 core-shell material Substances 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 125000005385 peroxodisulfate group Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
- B01J23/745—Iron
-
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Compounds Of Iron (AREA)
Abstract
The application discloses a preparation method of a slow-release micro-nano zero-valent iron material, which adopts natural biomass as a raw material, firstly obtains humic acid mother liquor with high concentration and good quality through high-temperature pretreatment-hydrothermal base catalysis, then simultaneously realizes the removal of an oxide layer on the surface of zero-valent iron and the self-assembly of humic acid into a shell through acid regulation and control, prepares the slow-release micro-nano zero-valent iron material with a core-shell structure, realizes the assumption that the surface of micro-nano zero-valent iron is coated with a carbon layer in situ, and improves the oxidation resistance, the reactivity and the slow-release property of the micro-nano zero-valent iron material.
Description
Technical Field
The application relates to the field of functional composite materials, in particular to a preparation method and application of a slow-release micro-nano zero-valent iron material.
Background
Zero-valent iron is a metal with active chemical properties, has the characteristics of stronger reducing capability, good electrochemical property, coordination chemical property, environmental friendliness and the like, and can directly reduce or indirectly catalyze, oxidize and degrade pollutants, so that the toxicity of the zero-valent iron is reduced, the characteristics of environmental friendliness, low price, strong catalytic effect, wide application range and the like are shown, and the zero-valent iron has application examples in industrial water treatment or groundwater remediation. The micro-nano zero-valent iron has better activation effect due to the larger specific surface area, so that the oxidation reaction efficiency is higher. However, the surface of the micro-nano zero-valent iron is easy to passivate, a layer of compact oxide film is formed, electron transfer between the zero-valent iron and oxidant and pollutant is hindered, and the catalytic activity is reduced.
The carbon-based material has the physical and chemical properties of large specific surface area, rich oxygen-containing groups on the surface, strong acid and alkali resistance, certain conductivity and the like, has the characteristics of wide sources, low price, environmental friendliness and the like, can remarkably improve the catalytic activity, the dispersibility and the electron utilization rate of the micro-nano zero-valent iron, and has been widely studied and applied at present. However, the carbon-based micro-nano zero-valent iron material is mainly composed of carbon, and the zero-valent iron content is low and is generally less than 50%, so that the catalytic potential of the composite material is greatly limited. And the carbonaceous component is coated on the surface of the micro-nano zero-valent iron by physical or chemical means, so that the direct contact between the inner core zero-valent iron and the outside air is isolated, and passivation of the zero-valent iron caused by surface oxidation can be avoided. In addition, the inner core zero-valent iron and the carbon layer coated by the outer layer form a micro battery, and electrons in the inner core zero-valent iron continuously transport and activate the oxidant through the conductive carbon layer to generate active oxygen species so as to degrade pollutants. The carbon coating means has great application potential in the catalytic degradation of pollutants by micro-nano zero-valent iron.
At present, the carbon-coated micro-nano zero-valent iron is mainly prepared by a liquid phase reduction method, wherein ferric salt and an organic solution are mixed in the preparation process, iron ions and organic components are combined through the effects of adsorption, complexation, chelation and the like, then the iron ions in the composite are reduced into zero-valent iron by adding a reducing agent, and finally the organic components are carbonized and coated on the surface of the zero-valent iron through the means of pyrolysis, calcination and the like, so that the carbon-coated micro-nano zero-valent iron material is prepared. The humic acid structure contains a large number of hydroxyl groups, carboxyl groups, aldehyde groups and carbonyl groups, can be tightly combined with iron ions through complexation, chelation and other actions, and has the potential of preparing the slow-release micro-nano zero-valent iron material. However, the direct use of biomass as a raw material for preparing humic acid through hydrothermal method has low conversion rate, low yield of humic acid, unstable product and poor quality, and is unfavorable for preparing carbon-coated iron material. How to green prepare a slow-release micro-nano zero-valent iron with high iron content, wide raw material sources and low price is a current research hot spot.
Disclosure of Invention
The application aims to provide a slow-release type micro-nano zero-valent iron material with a core-shell structure, which is prepared by taking natural biomass as a raw material, firstly obtaining humic acid mother liquor with high concentration and good quality through high-temperature pretreatment-hydrothermal base catalysis, then simultaneously removing an oxide layer on the surface of micro-nano zero-valent iron and self-assembling humic acid into a shell through acid regulation and control, and has high catalytic activity and strong slow release property so as to overcome the defects in the prior art.
In order to solve the technical problems, the technical scheme of the application is as follows:
the preparation method of the slow-release micro-nano zero-valent iron material comprises the following steps:
s1 biomass high-temperature pretreatment
Grinding natural biomass raw materials into powder, heating to 250-400 ℃ at a speed of 1-10 ℃/min in a pyrolysis furnace under the protection of nitrogen, maintaining for 0.3-5h, naturally cooling, and grinding to obtain pretreated raw materials;
s2 pretreatment raw material hydrothermal alkali catalysis preparation of humic acid
Weighing pretreatment raw materials, uniformly mixing the pretreatment raw materials with a strong alkali solution, transferring the mixture into a reaction kettle, carrying out hydrothermal reaction at a certain temperature, naturally cooling, centrifuging the reaction solution to remove residues, regulating the pH value with a strong acid solution under stirring conditions, continuously stirring for a certain time, and carrying out suction filtration to obtain humic acid solid after humic acid in the reaction solution is completely precipitated; dissolving humic acid solid in a strong alkali solution to obtain humic acid mother solution;
preparation of slow-release micro-nano zero-valent iron by regulating and controlling S3 acid
Measuring a certain amount of humic acid mother liquor, adding deionized water into a container to adjust the total volume of the solution, slowly adding micro-nano zero-valent iron powder into the solution under the stirring condition, continuously stirring for a certain time, then slowly adding strong acid solution into a reaction system at a uniform speed, continuously stirring uniformly, centrifuging to remove supernatant, washing with deionized water for three times, centrifuging, and drying to obtain the slow-release micro-nano zero-valent iron material.
Preferably, as a preferred embodiment, the biomass raw material in S1 is one or more selected from agriculture and forestry waste, kitchen waste, marine algae waste, and livestock and poultry feces.
Preferably, as a preferred embodiment, the pyrolysis furnace comprises an atmosphere furnace and a tube furnace, and the process is to heat up to 250-400 ℃ at a speed of 1-10 ℃/min under the protection of nitrogen and maintain for 0.3-5h, and the heating rate, the equilibrium temperature and the pyrolysis time are properly adjusted according to different biomass raw materials so as to ensure the sufficient pyrolysis of biomass.
Preferably, as a preferred embodiment, the mass ratio of the pretreatment raw material to the strong alkali solution is 0.1-2g, 25-75g, the strong alkali solution is one or more of sodium hydroxide, potassium hydroxide and ammonia water, and the strong alkali is used in the hydrothermal concentration of 0.1-2M.
Preferably, as a preferred embodiment, the temperature of the hydrothermal reaction is 180-220 ℃ and the hydrothermal time is 5-20h.
Preferably, in the step S2, the alkali is used in the concentration of 0.01-0.05M in the dissolution of humic acid, and the alkali is used in an amount of 1-50g.
Preferably, in the step S2, the strong acid is selected from one or more of hydrochloric acid, sulfuric acid and nitric acid, and the strong acid is used at a concentration of 0.1-5M, and the pH is adjusted to be less than 2.
Preferably, in the step S3, the amount of the humic acid mother solution is 1-10mL, and the total volume of the reaction solution is 40-80mL.
Preferably, in the step S3, the stirring is mechanical stirring, and the stirring speed is 300-800rpm.
Preferably, as a preferred embodiment, in the step S3, the micro-nano zero-valent iron used in the step S3 has a particle size ranging from 50 nm to 10000nm and an addition amount ranging from 1g to 10g; the strong acid is one or more of hydrochloric acid, sulfuric acid and nitric acid, the concentration range is 0.1-5M, and the addition amount is 0.1-10mL.
Preferably, in step S3, the drying mode is one or more of drying, sun drying and freeze drying.
The application also aims at providing an application of the slow-release micro-nano zero-valent iron material, which comprises the following steps:
the slow-release micro-nano zero-valent iron prepared by the method is placed in a glass bottle with a cover, phenol solution is added, and then oxidant is added to initiate reaction.
Preferably, as a preferred embodiment, the application amount of the slow release micro-nano zero-valent iron material is 10-50mg, the total volume of the reaction solution is 15-40mL, and the concentration of the phenol solution is 100-300mg/L.
Preferably, as a preferred embodiment, the oxidizing agent is selected from one or more of peroxodisulfate, peroxomonosulfate and hydrogen peroxide, and the concentration of the oxidizing agent is 1 to 10mM.
Preferably, as a preferred embodiment, the capped glass bottle is placed in a shaking table at a rotation speed of 150rpm, 0.5ml of the reaction solution is taken at a fixed reaction time point, and mixed with 0.5ml of methanol solution through a 0.22 μm filter membrane to terminate the reaction, and the mixed solution is diluted 10 times and then is put on a machine for testing, so that the phenol removal rate is calculated.
It should be noted that, the key to regulating the yield of humic acid is that the pyrolysis temperature of the early raw material and the hydrothermal base catalysis of the later stage are both too high or too low, and too high or too low concentration of the base are both unfavorable for improving the yield of humic acid.
In the process of acid regulation, the ratio of humic acid to zero-valent iron, the addition amount and the addition speed of the acid directly influence the film thickness and the catalytic activity of the carbon-coated iron material.
Compared with the prior art, the application has the beneficial effects that:
(1) The method realizes the conversion of common natural biomass into the slow-release micro-nano zero-valent iron carbon film, has simple step operation, short time consumption, low cost and strong broad spectrum, and biomass involved in production and life, including agriculture and forestry waste, kitchen waste, marine algae waste, livestock manure and the like, can be used as raw materials to prepare high-quality slow-release micro-nano zero-valent iron materials through the process; the process is a comprehensive new technology for realizing the resource utilization of wastes, has high raw material conversion rate and can realize the full utilization of raw materials in the preparation process.
(2) According to the application, by combining high-temperature pretreatment and hydrothermal alkali catalysis, organic components which are difficult to be subjected to hydrothermal decomposition, such as cellulose and the like, in the original natural biomass are converted into carbide which is easy to be subjected to hydrothermal decomposition, so that the technical problems of low yield, poor product quality and the like of the humic acid prepared by using biomass raw materials in a hydrothermal manner are solved, the waste of biomass raw materials in the preparation process is reduced, and the prepared high-quality humic acid provides a guarantee for the self-assembly of humic acid into a shell in the subsequent acid regulation and control process.
(3) The acid regulation and control process realizes the simultaneous removal of the iron oxide layer on the micro-nano zero-valent surface and the carbon film coating by simply controlling the acid addition parameters, basically does not generate byproducts in the process, realizes the 100 percent conversion of humic acid and micro-nano zero-valent iron to slow-release micro-nano zero-valent iron, maintains the particle size and the morphology of the original iron powder, simultaneously stores the Fe0 content of the original iron powder to the greatest extent, and has the advantages of simple preparation process, high raw material conversion rate, good structural performance of the prepared material and the like.
(4) The application realizes the resource utilization of waste biomass and the self-assembly of humic acid into a shell, is suitable for the coating of zero-valent iron (including nanometer and micrometer) with different particle sizes, and the prepared carbon-coated iron material has controllable film thickness, high catalytic activity, high electron utilization rate and obvious slow release effect, and can be applied to the organic pollution of soil and groundwater by high-grade oxidation as a slow release type high-efficiency catalyst.
Drawings
FIG. 1 is an SEM image of a slow release micro-nano zero-valent iron material;
FIG. 2 shows the catalytic degradation effect of the slow-release micro-nano zero-valent iron material prepared with different acid addition amounts on phenol (example 1);
FIG. 3 shows the catalytic degradation effect of the slow-release micro-nano zero-valent iron material prepared by different humic acid addition amounts on phenol (example 2);
fig. 4 is a comparison of catalytic degradation effects of the original nano zero-valent iron and the slow release nano zero-valent iron material on phenol.
Detailed Description
The contents of the present application can be more easily understood by referring to the following detailed description of preferred embodiments of the present application and examples included. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In case of conflict, the present specification, definitions, will control. The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed.
Approximating language, in the specification and claims, may be applied to modify an amount that would not limit the application to the specific amount, but would include an acceptable portion that would be close to the amount without resulting in a change in the basic function involved. Accordingly, the modification of a numerical value with "about", "about" or the like means that the present application is not limited to the precise numerical value. In some examples, the approximating language may correspond to the precision of an instrument for measuring the value. In the description and claims of the application, the range limitations may be combined and/or interchanged, if not otherwise specified, including all the sub-ranges subsumed therein.
Furthermore, the indefinite articles "a" and "an" preceding an element or component of the application are not limited to the requirements of the number of elements or components (i.e. the number of occurrences). Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component also includes the plural reference unless the amount is obvious to the singular reference.
1. Examples
1. Example 1:
a preparation method of a slow-release micro-nano zero-valent iron material comprises the following steps:
s1 biomass high-temperature pretreatment
Grinding the rice straw biomass raw material into powder, heating to 300 ℃ at a speed of 5 ℃/min in a pyrolysis furnace under the protection of nitrogen, maintaining for 1h, naturally cooling, and grinding to obtain a pretreated raw material;
s2 pretreatment raw material hydrothermal alkali catalysis preparation of humic acid
1g of pretreatment raw material is weighed and evenly mixed with 50g of NaOH solution with the concentration of 1M, the mixture is transferred into a 100ml of reaction kettle, hydrothermal treatment is carried out for 12 hours at the temperature of 200 ℃, residues are removed by centrifuging the reaction solution after natural cooling, the pH value of the reaction solution is regulated to be less than 2 by using 2M of strong acid solution under the stirring condition, the stirring is continued for 30min, humic acid in the reaction solution is completely precipitated, the humic acid solid is obtained by suction filtration, and the obtained humic acid solid is dissolved in 20g of NaOH solution with the concentration of 0.025M, so as to obtain humic acid mother liquor;
s3, preparing slow-release micro-nano zero-valent iron by using different acid addition amounts
Weighing 2.5ml of humic acid mother liquor in a beaker, adding deionized water to adjust the total volume of the solution to 60ml, slowly adding 5g of micro-nano zero-valent iron powder into the solution under the condition of mechanical stirring at 600rpm, continuously stirring for 5min, then slowly adding 0.75/1.5/3/6/9ml of hydrochloric acid solution with the concentration of 2M into a reaction system at a constant speed, continuously stirring for 1h, centrifuging to remove supernatant, washing with deionized water for 3 times, centrifuging, and drying to obtain a slow-release micro-nano zero-valent iron material;
2. example 2
A preparation method of a slow-release micro-nano zero-valent iron material comprises the following steps:
s1 biomass high-temperature pretreatment
Grinding the rice straw biomass raw material into powder, heating to 300 ℃ at a speed of 5 ℃/min in a pyrolysis furnace under the protection of nitrogen, maintaining for 1h, naturally cooling, and grinding to obtain a pretreated raw material;
s2 pretreatment raw material hydrothermal alkali catalysis preparation of humic acid
1g of pretreatment raw material is weighed and evenly mixed with 50g of NaOH solution with the concentration of 1M, the mixture is transferred into a 100ml of reaction kettle, hydrothermal treatment is carried out for 12 hours at the temperature of 200 ℃, residues are removed by centrifuging the reaction solution after natural cooling, the pH value of the reaction solution is regulated to be less than 2 by using 2M of strong acid solution under the stirring condition, the stirring is continued for 30min, humic acid in the reaction solution is completely precipitated, the humic acid solid is obtained by suction filtration, and the obtained humic acid solid is dissolved in 20g of NaOH solution with the concentration of 0.025M, so as to obtain humic acid mother liquor;
s3, preparing different slow-release micro-nano zero-valent irons by fixing humic acid and hydrochloric acid in proportion
Weighing 1, 2.5, 5 or 7.5ml of humic acid mother solution in a beaker, adding deionized water to adjust the total volume of the solution to 60ml, slowly adding 5g of micro-nano zero-valent iron powder into the solution under the mechanical stirring condition of 600rpm, continuously stirring for 5min, then slowly adding hydrochloric acid solution with the concentration of 2M into the corresponding reaction system at uniform speed until the pH value of the system is reduced to 2, continuously stirring for 1h, centrifuging to remove supernatant, washing with deionized water for 3 times, centrifuging, and drying to obtain the carbon-coated iron material.
2. Different embodiments catalytic applications
30mg of the slow-release nano zero-valent iron material prepared in the embodiment is placed in a glass bottle with a cover, phenol solution is added, then persulfate is added to initiate reaction, the total volume of the final reaction solution is controlled to be 40ml, wherein the phenol concentration is 120mg/L, the PDS concentration is 5mM, the glass bottle with the cover is placed in a shaking table with the rotating speed of 150rpm, 0.5ml of the reaction solution is taken at a fixed reaction time point, the reaction is stopped by mixing with 0.5ml of methanol solution through a 0.22 mu m filter membrane, the mixed solution is diluted by 10 times, and then the machine test is carried out, so that the phenol removal rate is calculated.
3. Performance testing
In the preparation process, the humic acid mother solution is added with 2.5ml, the slow-release micro-nano zero-valent iron prepared under the condition that the hydrochloric acid addition amount is 1.5ml is subjected to projection electron microscope characterization, and the result is shown in figure 1. And detecting the effect of the slow-release micro-nano zero-valent iron in catalyzing the persulfate to degrade the phenol to obtain a phenol degradation kinetic curve, wherein the result is shown in figures 2-4.
As can be seen from fig. 1 and 2, the catalytic activity and the slow release performance of the slow release micro-nano zero-valent iron prepared by changing the addition amount of humic acid and hydrochloric acid are controlled, and the performance of degrading phenol by activating peroxodisulfate and the slow release effect of the material can be obviously improved by controlling the ratio of humic acid to hydrochloric acid and the addition amount to a certain range; as can be seen from fig. 3, in the process of degrading phenol by activating the peroxodisulfate, the slow release micro-nano zero-valent iron shows excellent catalytic effect compared with the original micro-nano zero-valent iron; as can be seen from fig. 4, the slow release micro-nano zero-valent iron is composed of a core-shell structure, a thin layer carbon film is wrapped on the shell, and the inner core is an fe° component, so that the structure is more beneficial to the promotion of the catalytic activity, slow release property and electron utilization rate of the micro-nano zero-valent iron.
It will be evident to those skilled in the art that the application is not limited to the details of the foregoing illustrative embodiments, and that the present application may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (6)
1. The preparation method of the slow-release micro-nano zero-valent iron material is characterized by comprising the following steps of:
s1 biomass high-temperature pretreatment
Grinding natural biomass raw materials into powder, heating to 250-400 ℃ at a speed of 1-10 ℃/min in a pyrolysis furnace under the protection of nitrogen, maintaining 0.3-5h, naturally cooling, and grinding to obtain pretreated raw materials;
s2 pretreatment raw material hydrothermal alkali catalysis preparation of humic acid
Weighing pretreatment raw materials, uniformly mixing the pretreatment raw materials with a strong alkali solution, transferring the mixture into a reaction kettle, carrying out hydrothermal reaction at a certain temperature, naturally cooling, centrifuging the reaction solution to remove residues, regulating the pH value with a strong acid solution under stirring conditions, continuously stirring for a certain time, and carrying out suction filtration to obtain humic acid solid after humic acid in the reaction solution is completely precipitated; dissolving humic acid solid in a strong alkali solution to obtain humic acid mother solution;
preparation of slow-release micro-nano zero-valent iron by regulating and controlling S3 acid
Measuring a certain amount of humic acid mother liquor, adding deionized water to regulate the total volume of the solution, slowly adding micro-nano zero-valent iron powder into the solution under the stirring condition, continuously stirring for a certain time, then slowly adding strong acid solution into a reaction system at a uniform speed, continuously stirring uniformly, centrifuging to remove supernatant, washing with deionized water for three times, centrifuging, and drying to obtain the slow-release nano zero-valent iron material;
in the step S3, the particle size range of the micro-nano zero-valent iron is 50-10000nm, and the addition amount is 1-10g; the strong acid is one or more of hydrochloric acid, sulfuric acid and nitric acid, the concentration range is 0.1-5M, and the addition amount is 0.1-10 mL:
the natural biomass raw material is one or more selected from agriculture and forestry waste, kitchen waste, marine algae waste and livestock and poultry manure;
the pyrolysis furnace comprises an atmosphere furnace and a tubular furnace;
the mass ratio of the pretreatment raw material to the strong alkali solution is 0.1-2g:25-75g, the strong alkali solution is one or more of sodium hydroxide, potassium hydroxide and ammonia water, and the use concentration of the strong alkali in the hydrothermal process is 0.1-2M.
2. The method for preparing a slow release micro-nano zero-valent iron material according to claim 1, wherein the temperature of the hydrothermal reaction is 180-220 ℃ and the hydrothermal time is 5-20h.
3. The method for preparing a slow release micro-nano zero-valent iron material according to claim 1, wherein in the step S2, the use concentration of strong base in humic acid dissolution is 0.01-0.05M, and the use amount of strong base is 1-50g.
4. The method for preparing a slow release type micro-nano zero-valent iron material according to claim 1, wherein in the step S2, strong acid is selected from one or more of hydrochloric acid, sulfuric acid and nitric acid, the use concentration of the strong acid is 0.1-5M, and the pH value is adjusted to be below 2.
5. A slow release micro-nano zero-valent iron material prepared by the preparation method according to any one of claims 1-4.
6. The use of a slow release micro-nano zero-valent iron material according to claim 5, comprising the steps of:
placing the slow release micro-nano zero-valent iron prepared by the preparation method of any one of claims 1-4 into a glass bottle with a cover, adding a phenol solution, and then adding an oxidant to initiate a reaction.
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| CN104628792A (en) * | 2013-11-11 | 2015-05-20 | 中国科学院烟台海岸带研究所 | Method for preparing humic acid by using wheat straws |
| CN110894084A (en) * | 2019-12-06 | 2020-03-20 | 中国科学技术大学 | Nano zero-valent iron load material, preparation method thereof and purification method of hexavalent chromium in sewage |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628792A (en) * | 2013-11-11 | 2015-05-20 | 中国科学院烟台海岸带研究所 | Method for preparing humic acid by using wheat straws |
| CN110894084A (en) * | 2019-12-06 | 2020-03-20 | 中国科学技术大学 | Nano zero-valent iron load material, preparation method thereof and purification method of hexavalent chromium in sewage |
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