CN111111619A - Efficient adsorbent for treating volatile organic compounds in coal chemical production process - Google Patents
Efficient adsorbent for treating volatile organic compounds in coal chemical production process Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/11—Clays
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/202—Polymeric adsorbents
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- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
Abstract
The invention provides a high-efficiency adsorbent for treating volatile organic compounds in the coal chemical production process, which relates to the field of adsorbents, and the preparation method comprises the following steps: preparing modified black wattle bark powder; adding OP-10 into a zinc nitrate solution, stirring and mixing uniformly, then adding ethanol and expanded graphite, heating to 40-45 ℃, stirring and mixing for 20-30min, then dropwise adding a sodium hydroxide solution, continuously stirring and reacting for 1-5h after dropwise adding, performing suction filtration, washing and drying a filter cake, calcining for 1-3h under the protection of nitrogen, and cooling to room temperature to obtain ZnO/expanded graphite; preparing an aminated chitosan solution; the method comprises the steps of mixing and stirring modified black wattle bark powder, ZnO/expanded graphite, bentonite and aminated chitosan solution for 1-3 hours to obtain a mixture, distilling the mixture under reduced pressure to remove the solvent, and drying the obtained solid in an oven at 110 ℃ for 10-20 hours.
Description
Technical Field
The invention relates to the field of adsorbents, and particularly relates to a high-efficiency adsorbent for treating volatile organic compounds in a coal chemical production process.
Background
Coal chemical refers to the process of converting coal into gas, liquid and solid fuels and chemicals by chemical processing using coal as a raw material. Mainly comprises coal gasification, liquefaction, dry distillation, tar processing, calcium carbide acetylene chemical industry and the like. Coal chemical processing. The chemical structure of organic matter in coal is a macromolecular structure with aromatic condensed rings as core units, bridge bonds for mutual connection and various functional groups, and can convert coal into various fuels and chemical products through thermal processing and catalytic processing.
Besides the main carbon, coal also contains small amount of hydrogen, nitrogen, sulfur, oxygen and other elements and inorganic mineral substances. The coal chemical industry is a process of using coal as a raw material, converting the coal into gas, liquid and solid products or semi-products through chemical processing, and then further processing the products into chemical and energy products. The coal chemical industry mainly comprises coal gasification, liquefaction, dry distillation, tar processing, calcium carbide acetylene chemical industry and the like. The emission states and compositions of volatile organic compounds generated by different processing technologies in the coal chemical industry are also different.
These volatile organic compounds include several major classes of non-methane hydrocarbons, oxygen-containing organic compounds, halogenated hydrocarbons, nitrogen-containing organic compounds, sulfur-containing organic compounds, etc., and these volatile organic compounds participate in the formation of ozone and secondary aerosols in the atmospheric environment, which have important contributions to regional atmospheric ozone pollution, PM2.5 pollution. Most VOCs have uncomfortable special odor and have toxicity, irritation, teratogenicity and carcinogenicity, particularly benzene, toluene, formaldehyde and the like can cause great harm to human health, and the VOCs are important precursors for causing urban haze and photochemical smog.
At present, the coal chemical industry generally directly burns or adsorbs volatile organic compounds, air pollution caused by direct combustion is large, so the coal chemical industry is not suitable for the volatile organic compounds at present, an adsorbent for the volatile organic compounds mainly takes high-efficiency activated carbon and activated carbon fibers, the activated carbon fibers have the advantages of large specific surface area, high adsorption and desorption speeds and the like, the activated carbon fibers are easy to prepare into paper and felt forms, the generated gas resistance is small, but the price is high, the technology is monopolized by foreign enterprises, the conventional activated carbon has huge specific surface area and pore volume, the adsorption performance to gas is excellent, but the adsorption selectivity is poor, and the adsorption and desorption requirements of various organic gases cannot be met.
Chinese patent CN104801283A discloses a preparation method of a composite adsorbent for purifying VOCs in air, belonging to the field of treatment of VOCs in the atmosphere. The method comprises the following specific steps: step one, mixing and uniformly mixing raw materials: (1) uniformly mixing activated alumina, activated carbon and iron ore powder to prepare a mixture A; (2) evenly mixing the pellet sieve material, the biomass material, the magnesium laterite-nickel ore and the kaolin to prepare a mixture B; (3) uniformly mixing the mixture A and the mixture B to prepare an adsorbent uniformly-mixed material; step two: granulating, namely adding the uniformly mixed adsorbent material into a cylindrical mixer, and uniformly mixing to prepare adsorbent particles; step three: and (3) heating, namely placing the adsorbent particles into an oven for heating, and preparing the adsorbent after heating. The adsorbent provided by the invention has higher porosity and specific surface area, and can be fully contacted with VOCs, so that the adsorption efficiency of the adsorbent is improved, and the high-efficiency and low-cost emission reduction of the VOCs is realized.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a high-efficiency adsorbent for treating volatile organic compounds in the coal chemical production process.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
a high-efficiency adsorbent for treating volatile organic compounds in the coal chemical production process is prepared by the following steps:
(1) drying the black wattle bark in an oven at 70-90 ℃ for 15-20h, crushing into powder, adding the powder into a reaction kettle with a condenser, adding distilled water and formaldehyde, stirring uniformly, adding hydrochloric acid dropwise, heating for reaction for 2-5h after dropwise adding, performing suction filtration, washing a filter cake to be neutral, and drying to obtain modified black wattle bark powder;
(2) crushing natural crystalline flake graphite, adding the crushed natural crystalline flake graphite into a reaction kettle, slowly adding concentrated sulfuric acid, continuously stirring in the adding process until the natural crystalline flake graphite is uniformly mixed, adding potassium permanganate powder for multiple times, stirring at room temperature for 30-50min, heating to 50-60 ℃, reacting for 4-8h, carrying out suction filtration, washing a filter cake to be neutral, drying at 80-100 ℃ for 5-10h, and transferring the filter cake to a muffle furnace for roasting for 20-30s to obtain expanded graphite;
(3) adding OP-10 into a zinc nitrate solution, stirring and mixing uniformly, adding ethanol and the expanded graphite, heating to 40-45 ℃, stirring and mixing for 20-30min, then dropwise adding a sodium hydroxide solution, continuously stirring and reacting for 1-5h after dropwise adding, performing suction filtration, washing a filter cake to be neutral, drying for 10-15h at 60-80 ℃, transferring to a carbon tube furnace, heating to 600-;
(4) uniformly mixing a chitosan ethanol solution with a certain mass concentration and an ethylenediamine aqueous solution, heating to 40-45 ℃, reacting for 4-6h, dropwise adding a formaldehyde aqueous solution, and then continuously reacting for 30-50min to obtain an aminated chitosan solution;
(5) mixing and stirring the modified black wattle bark powder, ZnO/expanded graphite, bentonite and an aminated chitosan solution for 1-3h to obtain a mixture, distilling the mixture under reduced pressure to remove the solvent, and drying the obtained solid in an oven at the temperature of 110 ℃ for 10-20 h.
Further, the molar concentration of the hydrochloric acid in the step (1) is 0.3-0.8 mol/L.
Further, the reaction temperature in the step (1) is 40-70 ℃.
Further, the mass ratio of the natural crystalline flake graphite to the potassium permanganate powder in the step (2) is 100: 1-5.
Further, the calcination temperature in the step (2) is 900-.
Further, the molar concentration of the zinc nitrate solution in the step (3) is 0.1-1 mol/L.
Further, the molar concentration of the sodium hydroxide solution in the step (3) is 0.5-2 mol/L.
Further, the temperature rising speed of the medium carbon tube furnace in the step (3) is 5-20 ℃/min.
Further, in the step (4), the mass concentration of the chitosan ethanol solution is 2-6%, and the molar concentration of the ethylenediamine aqueous solution is 0.05-0.1 mol/L.
Further, in the step (5), the weight ratio of the modified black wattle bark powder, ZnO/expanded graphite and bentonite is 5-10: 4-8: 1.
(III) advantageous effects
The invention provides a high-efficiency adsorbent for treating volatile organic compounds in the coal chemical production process, which has the following beneficial effects:
cellulose, lignin and other components in the black wattle bark have organic matter adsorption capacity, natural black wattle bark is modified in the invention, the adsorption capacity of the natural black wattle bark on organic matters is further enhanced, currently, bark adsorbents are mostly used for chelating and adsorbing metal ions, but no report is found on the adsorption of volatile organic matters, the expanded graphite belongs to a hexagonal crystal system, is similar to worms in shape, contains a large number of net-shaped microporous structures in the expanded graphite, has the advantages of adsorption, corrosion resistance and high temperature resistance, has strong adsorption capacity on the volatile organic matters generated in the coal chemical production process, and hardly reduces the secondary adsorption capacity after desorption, the invention utilizes the expanded graphite to load nano ZnO, utilizes the nano ZnO to change alcohol, aldehyde and acid on the volatile organic matters adsorbed by the expanded graphite, thereby degrading the volatile organic matters, the aminated chitosan reduces the acid solubility and alkali solubility of the chitosan, improves the adsorption performance to different volatile organic compounds, compounds the modified black wattle bark powder, ZnO/expanded graphite, bentonite and aminated chitosan, has excellent adsorption effect to various volatile organic compounds generated in the production process of coal chemical industry, and can well meet the adsorption requirement of various volatile organic compounds through the synergistic effect among the modified black wattle bark powder, ZnO/expanded graphite, bentonite and aminated chitosan which are known through comparison experiments
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of the efficient adsorbent for treating volatile organic compounds in the coal chemical production process comprises the following steps:
drying black wattle bark in an oven at 80 ℃ for 18h, crushing the dried black wattle bark into powder, adding the powder into a reaction kettle with a condenser, adding distilled water and formaldehyde, stirring uniformly, dropwise adding hydrochloric acid with the molar concentration of 0.6mol/L, heating to 70 ℃ after dropwise adding, reacting for 4h, performing suction filtration, washing a filter cake to be neutral, drying to obtain modified black wattle bark powder, crushing natural scale graphite, adding the crushed natural scale graphite into the reaction kettle, slowly adding concentrated sulfuric acid, continuously stirring in the adding process until the mixture is uniform, adding potassium permanganate powder for multiple times, wherein the mass ratio of the natural scale graphite to the potassium permanganate powder is 100: 1, stirring at room temperature for 40min after adding, heating to 50 ℃ for reaction for 8h, then carrying out suction filtration, washing a filter cake to be neutral, drying at 100 ℃ for 8h, then transferring to a muffle furnace, roasting at 900 ℃ for 20s to obtain expanded graphite, adding OP-10 into a zinc nitrate solution with the molar concentration of 0.2mol/L, stirring and mixing uniformly, then adding ethanol and the expanded graphite, heating to 45 ℃, stirring and mixing for 20min, then dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L, stirring and reacting for 1h after dropwise adding, carrying out suction filtration, washing a filter cake to be neutral, drying at 60 ℃ for 12h, transferring to a carbon tube furnace, heating to 650 ℃ at the speed of 10 ℃/min under the protection of nitrogen, calcining for 2h, cooling to room temperature to obtain ZnO/expanded graphite, mixing a chitosan ethanol solution with the mass concentration of 5% and an ethylenediamine aqueous solution with the molar concentration of 0.1mol/L uniformly, heating to 45 ℃ for reaction for 5h, dropwise adding a formaldehyde water solution, and continuing to react for 30min after dropwise adding to obtain an aminated chitosan solution, wherein the weight ratio of (8: 5: 1, adding the mixture of the modified black wattle bark powder, ZnO/expanded graphite and bentonite into an aminated chitosan solution, mixing and stirring for 1h to obtain a mixture, distilling the mixture under reduced pressure to remove the solvent, and drying the obtained solid in an oven at 100 ℃ for 12 h.
Example 2:
a preparation method of the efficient adsorbent for treating volatile organic compounds in the coal chemical production process comprises the following steps:
drying black wattle bark in an oven at 70 ℃ for 15 hours, crushing the dried black wattle bark into powder, adding the powder into a reaction kettle with a condenser, adding distilled water and formaldehyde, stirring uniformly, dropwise adding hydrochloric acid with the molar concentration of 0.8mol/L, heating to 60 ℃ after dropwise adding, reacting for 5 hours, performing suction filtration, washing a filter cake to be neutral, drying to obtain modified black wattle bark powder, crushing natural scale graphite, adding the crushed natural scale graphite into the reaction kettle, slowly adding concentrated sulfuric acid, continuously stirring in the adding process until the mixture is uniform, adding potassium permanganate powder for multiple times, wherein the mass ratio of the natural scale graphite to the potassium permanganate powder is 100: 3, stirring at room temperature for 50min after adding, heating to 50 ℃ for reaction for 6h, then carrying out suction filtration, washing a filter cake to be neutral, drying at 80 ℃ for 10h, then transferring to a muffle furnace, roasting at 1000 ℃ for 20s to obtain expanded graphite, adding OP-10 into a zinc nitrate solution with the molar concentration of 0.5mol/L, stirring and mixing uniformly, adding ethanol and the expanded graphite, heating to 45 ℃, stirring and mixing for 20min, then dropwise adding a sodium hydroxide solution with the molar concentration of 0.5mol/L, stirring and reacting for 1h after dripping, carrying out suction filtration, washing a filter cake to be neutral, drying at 60 ℃ for 15h, transferring to a carbon tube furnace, heating to 600 ℃ at the speed of 10 ℃/min under the protection of nitrogen, calcining for 3h, cooling to room temperature to obtain ZnO/expanded graphite, mixing a chitosan ethanol solution with the mass concentration of 5% and an ethylenediamine aqueous solution with the molar concentration of 0.05mol/L uniformly, heating to 40 ℃ for reaction for 5h, dropwise adding a formaldehyde water solution, and continuing to react for 40min after dropwise adding to obtain an aminated chitosan solution, wherein the weight ratio of (1): 6: 1, adding the mixture of the modified black wattle bark powder, ZnO/expanded graphite and bentonite into an aminated chitosan solution, mixing and stirring for 1h to obtain a mixture, distilling the mixture under reduced pressure to remove the solvent, and drying the obtained solid in an oven at 110 ℃ for 10 h.
Example 3:
a preparation method of the efficient adsorbent for treating volatile organic compounds in the coal chemical production process comprises the following steps:
drying black wattle bark in an oven at 90 ℃ for 20 hours, crushing the dried black wattle bark into powder, adding the powder into a reaction kettle with a condenser, adding distilled water and formaldehyde, stirring uniformly, dropwise adding hydrochloric acid with the molar concentration of 0.3mol/L, heating to 60 ℃ after dropwise adding, reacting for 2 hours, performing suction filtration, washing a filter cake to be neutral, drying to obtain modified black wattle bark powder, crushing natural scale graphite, adding the crushed natural scale graphite into the reaction kettle, slowly adding concentrated sulfuric acid, continuously stirring in the adding process until the mixture is uniform, adding potassium permanganate powder for multiple times, wherein the mass ratio of the natural scale graphite to the potassium permanganate powder is 50: 1, stirring at room temperature for 50min after adding, heating to 60 ℃, reacting for 6h, then carrying out suction filtration, washing a filter cake to be neutral, drying at 100 ℃ for 5h, then transferring to a muffle furnace, roasting at 1000 ℃ for 30s to obtain expanded graphite, adding OP-10 into a zinc nitrate solution with the molar concentration of 0.1mol/L, stirring and mixing uniformly, then adding ethanol and the expanded graphite, heating to 40 ℃, stirring and mixing for 20min, then dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L, stirring and reacting for 4h after dripping, carrying out suction filtration, washing a filter cake to be neutral, drying at 70 ℃ for 12h, transferring to a carbon tube furnace, heating to 650 ℃ at the speed of 15 ℃/min under the protection of nitrogen, calcining for 2h, cooling to room temperature to obtain ZnO/expanded graphite, mixing a chitosan ethanol solution with the mass concentration of 4% and an ethylenediamine aqueous solution with the molar concentration of 0.1mol/L uniformly, heating to 45 ℃ for reaction for 5h, dropwise adding a formaldehyde water solution, and continuing to react for 35min after dropwise adding to obtain an aminated chitosan solution, wherein the weight ratio of (8: 5: 1, adding the mixture of the modified black wattle bark powder, ZnO/expanded graphite and bentonite into an aminated chitosan solution, mixing and stirring for 1h to obtain a mixture, distilling the mixture under reduced pressure to remove the solvent, and drying the obtained solid in an oven at 100 ℃ for 18 h.
Example 4:
a preparation method of the efficient adsorbent for treating volatile organic compounds in the coal chemical production process comprises the following steps:
drying black wattle bark in an oven at 70 ℃ for 15 hours, crushing the dried black wattle bark into powder, adding the powder into a reaction kettle with a condenser, adding distilled water and formaldehyde, stirring uniformly, dropwise adding hydrochloric acid with the molar concentration of 0.5mol/L, heating to 60 ℃ after dropwise adding, reacting for 2 hours, performing suction filtration, washing a filter cake to be neutral, drying to obtain modified black wattle bark powder, crushing natural scale graphite, adding the crushed natural scale graphite into the reaction kettle, slowly adding concentrated sulfuric acid, continuously stirring in the adding process until the mixture is uniform, adding potassium permanganate powder for multiple times, wherein the mass ratio of the natural scale graphite to the potassium permanganate powder is 100: 1, stirring at room temperature for 30min after adding, heating to 50 for reaction for 5h, then carrying out suction filtration, washing a filter cake to be neutral, drying at 100 ℃ for 5h, then transferring to a muffle furnace, roasting at 950 ℃ for 30s to obtain expanded graphite, adding OP-10 into a zinc nitrate solution with the molar concentration of 0.1mol/L, stirring and mixing uniformly, adding ethanol and the expanded graphite, heating to 40 ℃, stirring and mixing for 30min, then dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L, stirring and reacting for 3h after dripping, carrying out suction filtration, washing the filter cake to be neutral, drying at 60 ℃ for 10h, transferring to a carbon tube furnace, heating to 600 ℃ at the speed of 10 ℃/min under the protection of nitrogen, calcining for 1h, cooling to room temperature to obtain ZnO/expanded graphite, mixing a chitosan ethanol solution with the mass concentration of 4% and an ethylenediamine aqueous solution with the molar concentration of 0.1mol/L uniformly, heating to 45 ℃ for reaction for 5h, dropwise adding a formaldehyde water solution, and continuing to react for 50min after dropwise adding to obtain an aminated chitosan solution, wherein the weight ratio of (1): 5: 1, adding the mixture of the modified black wattle bark powder, ZnO/expanded graphite and bentonite into an aminated chitosan solution, mixing and stirring for 1h to obtain a mixture, distilling the mixture under reduced pressure to remove the solvent, and drying the obtained solid in an oven at 110 ℃ for 15 h.
Example 5:
a preparation method of the efficient adsorbent for treating volatile organic compounds in the coal chemical production process comprises the following steps:
drying black wattle bark in an oven at 90 ℃ for 20 hours, crushing the dried black wattle bark into powder, adding the powder into a reaction kettle with a condenser, adding distilled water and formaldehyde, stirring uniformly, dropwise adding hydrochloric acid with the molar concentration of 0.5mol/L, heating to 50 ℃ after dropwise adding, reacting for 5 hours, performing suction filtration, washing a filter cake to be neutral, drying to obtain modified black wattle bark powder, crushing natural scale graphite, adding the crushed natural scale graphite into the reaction kettle, slowly adding concentrated sulfuric acid, continuously stirring in the adding process until the mixture is uniform, adding potassium permanganate powder for multiple times, wherein the mass ratio of the natural scale graphite to the potassium permanganate powder is 20: 1, stirring at room temperature for 50min after adding, heating to 50 ℃ for reaction for 6h, then carrying out suction filtration, washing a filter cake to be neutral, drying at 80 ℃ for 10h, then transferring to a muffle furnace, roasting at 950 ℃ for 30s to obtain expanded graphite, adding OP-10 into a zinc nitrate solution with the molar concentration of 0.1mol/L, stirring and mixing uniformly, then adding ethanol and the expanded graphite, heating to 45 ℃, stirring and mixing for 20min, then dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L, stirring and reacting for 2h after dropwise adding, carrying out suction filtration, washing a filter cake to be neutral, drying at 80 ℃ for 12h, transferring to a carbon tube furnace, heating to 600 ℃ at the speed of 5 ℃/min under the protection of nitrogen, calcining for 2h, cooling to room temperature to obtain ZnO/expanded graphite, mixing a chitosan ethanol solution with the mass concentration of 2% and an ethylenediamine aqueous solution with the molar concentration of 0.05mol/L uniformly, heating to 40 ℃ for reaction for 6h, dropwise adding a formaldehyde water solution, and continuing the reaction for 30min after the dropwise adding is finished to obtain an aminated chitosan solution, wherein the weight ratio of (1): 5: 1, adding the mixture of the modified black wattle bark powder, ZnO/expanded graphite and bentonite into an aminated chitosan solution, mixing and stirring for 1h to obtain a mixture, distilling the mixture under reduced pressure to remove the solvent, and drying the obtained solid in an oven at 100 ℃ for 10 h.
Example 6:
a preparation method of the efficient adsorbent for treating volatile organic compounds in the coal chemical production process comprises the following steps:
drying black wattle bark in an oven at 70 ℃ for 15 hours, crushing the dried black wattle bark into powder, adding the powder into a reaction kettle with a condenser, adding distilled water and formaldehyde, stirring uniformly, dropwise adding hydrochloric acid with the molar concentration of 0.3mol/L, heating to 40 ℃ after dropwise adding, reacting for 2 hours, performing suction filtration, washing a filter cake to be neutral, drying to obtain modified black wattle bark powder, crushing natural scale graphite, adding the crushed natural scale graphite into the reaction kettle, slowly adding concentrated sulfuric acid, continuously stirring in the adding process until the mixture is uniform, adding potassium permanganate powder for multiple times, wherein the mass ratio of the natural scale graphite to the potassium permanganate powder is 100: 1, stirring at room temperature for 30min after adding, heating to 50 ℃ for reaction for 4h, then carrying out suction filtration, washing a filter cake to be neutral, drying at 80 ℃ for 5h, then transferring to a muffle furnace, roasting at 900 ℃ for 20s to obtain expanded graphite, adding OP-10 into a zinc nitrate solution with the molar concentration of 0.1mol/L, stirring and mixing uniformly, adding ethanol and the expanded graphite, heating to 40 ℃, stirring and mixing for 20min, then dropwise adding a sodium hydroxide solution with the molar concentration of 0.5mol/L, stirring and reacting for 1h after dropwise adding, carrying out suction filtration, washing a filter cake to be neutral, drying at 60 ℃ for 10h, transferring to a carbon tube furnace, heating to 600 ℃ at the speed of 5 ℃/min under the protection of nitrogen, calcining for 1h, cooling to room temperature to obtain ZnO/expanded graphite, mixing a chitosan ethanol solution with the mass concentration of 2% and an ethylenediamine aqueous solution with the molar concentration of 0.05mol/L uniformly, heating to 40 ℃ for reaction for 4h, dropwise adding a formaldehyde water solution, and continuing the reaction for 30min after the dropwise adding is finished to obtain an aminated chitosan solution, wherein the weight ratio of (1): 4: 1, adding the mixture of the modified black wattle bark powder, ZnO/expanded graphite and bentonite into an aminated chitosan solution, mixing and stirring for 1h to obtain a mixture, distilling the mixture under reduced pressure to remove the solvent, and drying the obtained solid in an oven at 100 ℃ for 10 h.
Example 7:
a preparation method of the efficient adsorbent for treating volatile organic compounds in the coal chemical production process comprises the following steps:
drying black wattle bark in an oven at 90 ℃ for 20 hours, crushing the dried black wattle bark into powder, adding the powder into a reaction kettle with a condenser, adding distilled water and formaldehyde, stirring uniformly, dropwise adding hydrochloric acid with the molar concentration of 0.8mol/L, heating to 70 ℃ after dropwise adding, reacting for 5 hours, performing suction filtration, washing a filter cake to be neutral, drying to obtain modified black wattle bark powder, crushing natural scale graphite, adding the crushed natural scale graphite into the reaction kettle, slowly adding concentrated sulfuric acid, continuously stirring in the adding process until the mixture is uniform, adding potassium permanganate powder for multiple times, wherein the mass ratio of the natural scale graphite to the potassium permanganate powder is 25: 1, stirring at room temperature for 50min after adding, heating to 60 ℃, reacting for 8h, then carrying out suction filtration, washing a filter cake to be neutral, drying at 100 ℃ for 10h, then transferring to a muffle furnace, roasting at 1000 ℃ for 30s to obtain expanded graphite, adding OP-10 into a zinc nitrate solution with the molar concentration of 1mol/L, stirring and mixing uniformly, then adding ethanol and the expanded graphite, heating to 45 ℃, stirring and mixing for 30min, then dropwise adding a sodium hydroxide solution with the molar concentration of 2mol/L, stirring and reacting for 5h after dripping, carrying out suction filtration, washing the filter cake to be neutral, drying at 80 ℃ for 15h, transferring to a carbon tube furnace, heating to 650 ℃ at the speed of 20 ℃/min under the protection of nitrogen, calcining for 3h, cooling to room temperature to obtain ZnO/expanded graphite, mixing a chitosan ethanol solution with the mass concentration of 6% and an ethylenediamine aqueous solution with the molar concentration of 0.1mol/L uniformly, heating to 45 ℃ for reaction for 6h, dropwise adding a formaldehyde water solution, and continuing to react for 50min after dropwise adding to obtain an aminated chitosan solution, wherein the weight ratio of (1): 8: 1, adding the mixture of the modified black wattle bark powder, ZnO/expanded graphite and bentonite into an aminated chitosan solution, mixing and stirring for 3 hours to obtain a mixture, distilling the mixture under reduced pressure to remove the solvent, and drying the obtained solid in an oven at 110 ℃ for 20 hours.
Example 8:
a preparation method of the efficient adsorbent for treating volatile organic compounds in the coal chemical production process comprises the following steps:
drying black wattle bark in an oven at 80 ℃ for 15 hours, crushing the dried black wattle bark into powder, adding the powder into a reaction kettle with a condenser, adding distilled water and formaldehyde, stirring uniformly, dropwise adding hydrochloric acid with the molar concentration of 0.4mol/L, heating to 50 ℃ after dropwise adding, reacting for 2 hours, performing suction filtration, washing a filter cake to be neutral, drying to obtain modified black wattle bark powder, crushing natural scale graphite, adding the crushed natural scale graphite into the reaction kettle, slowly adding concentrated sulfuric acid, continuously stirring in the adding process until the mixture is uniform, adding potassium permanganate powder for multiple times, wherein the mass ratio of the natural scale graphite to the potassium permanganate powder is 100: 1, stirring at room temperature for 50min after adding, heating to 50 ℃ for reaction for 6h, then carrying out suction filtration, washing a filter cake to be neutral, drying at 100 ℃ for 10h, then transferring to a muffle furnace for roasting at 900 ℃ for 25s to obtain expanded graphite, adding OP-10 into a zinc nitrate solution with the molar concentration of 0.1mol/L, stirring and mixing uniformly, then adding ethanol and the expanded graphite, heating to 40 ℃, stirring and mixing for 20min, then dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L, stirring and reacting for 1h after dropwise adding, carrying out suction filtration, washing a filter cake to be neutral, drying at 60 ℃ for 12h, transferring to a carbon tube furnace for heating to 600 ℃ under the protection of nitrogen at the speed of 10 ℃/min, calcining for 2h, cooling to room temperature to obtain ZnO/expanded graphite, mixing a chitosan ethanol solution with the mass concentration of 3% and an ethylenediamine aqueous solution with the molar concentration of 0.05mol/L uniformly, heating to 40 ℃ for reaction for 5h, dropwise adding a formaldehyde water solution, and continuing to react for 40min after dropwise adding to obtain an aminated chitosan solution, wherein the weight ratio of (1): 6: 1, adding the mixture of the modified black wattle bark powder, ZnO/expanded graphite and bentonite into an aminated chitosan solution, mixing and stirring for 3 hours to obtain a mixture, distilling the mixture under reduced pressure to remove the solvent, and drying the obtained solid in an oven at 110 ℃ for 15 hours.
Comparative example 1:
a preparation method of the efficient adsorbent for treating volatile organic compounds in the coal chemical production process comprises the following steps:
adding the natural crystalline flake graphite after smashing into reation kettle again with concentrated sulfuric acid slowly add, add the in-process and constantly stir until after the misce bene, add potassium permanganate powder in a lot of again, the mass ratio of natural crystalline flake graphite and potassium permanganate powder is 100: 1, stirring at room temperature for 40min after adding, heating to 50 ℃ for reaction for 8h, then carrying out suction filtration, washing a filter cake to be neutral, drying at 100 ℃ for 8h, then transferring to a muffle furnace, roasting at 900 ℃ for 20s to obtain expanded graphite, adding OP-10 into a zinc nitrate solution with the molar concentration of 0.2mol/L, stirring and mixing uniformly, then adding ethanol and the expanded graphite, heating to 45 ℃, stirring and mixing for 20min, then dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L, stirring and reacting for 1h after dropwise adding, carrying out suction filtration, washing a filter cake to be neutral, drying at 60 ℃ for 12h, transferring to a carbon tube furnace, heating to 650 ℃ at the speed of 10 ℃/min under the protection of nitrogen, calcining for 2h, cooling to room temperature to obtain ZnO/expanded graphite, mixing a chitosan ethanol solution with the mass concentration of 5% and an ethylenediamine aqueous solution with the molar concentration of 0.1mol/L uniformly, heating to 45 ℃ for reaction for 5h, dropwise adding a formaldehyde water solution, and continuing to react for 30min after dropwise adding to obtain an aminated chitosan solution, wherein the weight ratio of (1): 1, adding the mixed ZnO/expanded graphite and bentonite into an aminated chitosan solution, mixing and stirring for 1h to obtain a mixture, distilling the mixture under reduced pressure to remove the solvent, and drying the obtained solid in an oven at 100 ℃ for 12 h.
Comparative example 2:
a preparation method of the efficient adsorbent for treating volatile organic compounds in the coal chemical production process comprises the following steps:
drying black wattle bark in an oven at 80 ℃ for 18h, crushing the dried black wattle bark into powder, adding the powder into a reaction kettle with a condenser, adding distilled water and formaldehyde, stirring uniformly, dropwise adding hydrochloric acid with the molar concentration of 0.6mol/L, heating to 70 ℃ after dropwise adding, reacting for 4h, performing suction filtration, washing a filter cake to be neutral, drying to obtain modified black wattle bark powder, uniformly mixing a chitosan ethanol solution with the mass concentration of 5% and an ethylenediamine aqueous solution with the molar concentration of 0.1mol/L, heating to 45 ℃, reacting for 5h, dropwise adding a formaldehyde aqueous solution, continuously reacting for 30min after dropwise adding to obtain an aminated chitosan solution, and mixing the following components in a weight ratio of 8: 1, adding the mixture of the modified black wattle bark powder and the bentonite into the aminated chitosan solution, mixing and stirring for 1h to obtain a mixture, distilling the mixture under reduced pressure to remove the solvent, and drying the obtained solid in an oven at 100 ℃ for 12 h.
Comparative example 3:
a preparation method of the efficient adsorbent for treating volatile organic compounds in the coal chemical production process comprises the following steps:
drying black wattle bark in an oven at 80 ℃ for 18h, crushing the dried black wattle bark into powder, adding the powder into a reaction kettle with a condenser, adding distilled water and formaldehyde, stirring uniformly, dropwise adding hydrochloric acid with the molar concentration of 0.6mol/L, heating to 70 ℃ after dropwise adding, reacting for 4h, performing suction filtration, washing a filter cake to be neutral, drying to obtain modified black wattle bark powder, crushing natural scale graphite, adding the crushed natural scale graphite into the reaction kettle, slowly adding concentrated sulfuric acid, continuously stirring in the adding process until the mixture is uniform, adding potassium permanganate powder for multiple times, wherein the mass ratio of the natural scale graphite to the potassium permanganate powder is 100: 1, stirring at room temperature for 40min after adding, heating to 50 ℃ for reaction for 8h, then carrying out suction filtration, washing a filter cake to be neutral, drying at 100 ℃ for 8h, then transferring to a muffle furnace, roasting at 900 ℃ for 20s to obtain expanded graphite, adding OP-10 into a zinc nitrate solution with the molar concentration of 0.2mol/L, stirring and mixing uniformly, adding ethanol and the expanded graphite, heating to 45 ℃, stirring and mixing for 20min, dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L, stirring and reacting for 1h after dripping is finished, carrying out suction filtration, washing the filter cake to be neutral, drying at 60 ℃ for 12h, transferring to a carbon tube furnace, heating to 650 ℃ at the speed of 10 ℃/min under the protection of nitrogen, calcining for 2h, cooling to room temperature to obtain ZnO/expanded graphite, and carrying out vacuum filtration on the basis of weight ratio of 8: 5: 1, uniformly mixing the modified black wattle bark powder, ZnO/expanded graphite and bentonite, and drying in an oven at 100 ℃ for 12 hours.
And (3) testing the adsorption performance:
inventive example 1 and comparative example 1-3 the prepared high-efficiency adsorbent is respectively filled into the glass tubes, the filling height is 50mm, different volatile organic compounds are respectively used for carrying out adsorption performance test, and the concentration W of the volatile organic compounds at the inlet of the glass tubes is respectively measured1And the concentration W of volatile organic compounds at the outlet2The adsorption rate η was calculated, and the results are shown in Table 1 below.
η＝[(W1-W2)/W1]×100％
Table 1:
| volatile organic compounds | Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Benzene and its derivatives | 86.2％ | 80.3％ | 64.6％ | 66.5％ |
| Toluene | 89.1％ | 81.8％ | 82.4％ | 77.9％ |
| Hydrogen sulfide | 95.2％ | 83.3％ | 71.2％ | 74.4％ |
| Sulfur dioxide | 92.4％ | 83.6％ | 85.4％ | 81.2％ |
| Methane | 82.1％ | 80.6％ | 77.2％ | 74.1％ |
| Ethyl acetate | 95.3％ | 82.1％ | 88.6％ | 84.6％ |
| Ammonia gas | 97.6％ | 81.5％ | 82.0％ | 85.3％ |
| Chlorine gas | 90.5％ | 77.6％ | 74.2％ | 81.8％ |
| Hydrogen chloride | 87.8％ | 75.2％ | 70.4％ | 69.6％ |
| Nitric oxide | 95.7％ | 84.9％ | 76.4％ | 78.1％ |
From the above table 1, the high-efficiency adsorbent of the present invention has an excellent adsorption effect on various volatile organic compounds generated in the coal chemical production process, and a comparison experiment shows that the synergistic effect of the modified black wattle bark powder, the ZnO/expanded graphite, the bentonite and the aminated chitosan is outstanding, and the adsorption requirement of the various volatile organic compounds can be well satisfied.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The efficient adsorbent for treating volatile organic compounds in the coal chemical production process is characterized in that the preparation method comprises the following steps:
(1) drying the black wattle bark in an oven at 70-90 ℃ for 15-20h, crushing into powder, adding the powder into a reaction kettle with a condenser, adding distilled water and formaldehyde, stirring uniformly, adding hydrochloric acid dropwise, heating for reaction for 2-5h after dropwise adding, performing suction filtration, washing a filter cake to be neutral, and drying to obtain modified black wattle bark powder;
(2) crushing natural crystalline flake graphite, adding the crushed natural crystalline flake graphite into a reaction kettle, slowly adding concentrated sulfuric acid, continuously stirring in the adding process until the natural crystalline flake graphite is uniformly mixed, adding potassium permanganate powder for multiple times, stirring at room temperature for 30-50min, heating to 50-60 ℃, reacting for 4-8h, carrying out suction filtration, washing a filter cake to be neutral, drying at 80-100 ℃ for 5-10h, and transferring the filter cake to a muffle furnace for roasting for 20-30s to obtain expanded graphite;
(3) adding OP-10 into a zinc nitrate solution, stirring and mixing uniformly, adding ethanol and the expanded graphite, heating to 40-45 ℃, stirring and mixing for 20-30min, then dropwise adding a sodium hydroxide solution, continuously stirring and reacting for 1-5h after dropwise adding, performing suction filtration, washing a filter cake to be neutral, drying for 10-15h at 60-80 ℃, transferring to a carbon tube furnace, heating to 600-;
(4) uniformly mixing a chitosan ethanol solution with a certain mass concentration and an ethylenediamine aqueous solution, heating to 40-45 ℃, reacting for 4-6h, dropwise adding a formaldehyde aqueous solution, and then continuously reacting for 30-50min to obtain an aminated chitosan solution;
(5) mixing and stirring the modified black wattle bark powder, ZnO/expanded graphite, bentonite and an aminated chitosan solution for 1-3h to obtain a mixture, distilling the mixture under reduced pressure to remove the solvent, and drying the obtained solid in an oven at the temperature of 110 ℃ for 10-20 h.
2. The efficient adsorbent for treating volatile organic compounds in the coal chemical production process according to claim 1, wherein the molar concentration of the hydrochloric acid in the step (1) is 0.3-0.8 mol/L.
3. The efficient adsorbent for treating volatile organic compounds in the coal chemical production process as claimed in claim 1, wherein the reaction temperature in step (1) is 40-70 ℃.
4. The efficient adsorbent for treating volatile organic compounds in the coal chemical production process as claimed in claim 1, wherein the mass ratio of the natural crystalline flake graphite to the potassium permanganate powder in step (2) is 100: 1-5.
5. The efficient adsorbent for treating volatile organic compounds in the coal chemical production process as claimed in claim 1, wherein the calcination temperature in step (2) is 900-1000 ℃.
6. The efficient adsorbent for treating volatile organic compounds in the coal chemical production process according to claim 1, wherein the molar concentration of the zinc nitrate solution in the step (3) is 0.1-1 mol/L.
7. The efficient adsorbent for treating volatile organic compounds in the coal chemical production process according to claim 1, wherein the molar concentration of the sodium hydroxide solution in the step (3) is 0.5-2 mol/L.
8. The efficient adsorbent for treating volatile organic compounds in the coal chemical production process according to claim 1, wherein the temperature rise speed of the carbon tube furnace in the step (3) is 5-20 ℃/min.
9. The efficient adsorbent for treating volatile organic compounds in the coal chemical production process as claimed in claim 1, wherein the mass concentration of the chitosan ethanol solution in the step (4) is 2-6%, and the molar concentration of the ethylenediamine aqueous solution is 0.05-0.1 mol/L.
10. The efficient adsorbent for treating volatile organic compounds in the coal chemical production process as claimed in claim 1, wherein the weight ratio of the modified black wattle bark powder, ZnO/expanded graphite and bentonite in step (5) is 5-10: 4-8: 1.
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