CN106311125B - A kind of application of manganese oxide/alumina composite material in terms of polyvinyl alcohol processing - Google Patents
A kind of application of manganese oxide/alumina composite material in terms of polyvinyl alcohol processing Download PDFInfo
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- CN106311125B CN106311125B CN201610964133.XA CN201610964133A CN106311125B CN 106311125 B CN106311125 B CN 106311125B CN 201610964133 A CN201610964133 A CN 201610964133A CN 106311125 B CN106311125 B CN 106311125B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- 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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/38—Polymers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The present invention relates to a kind of application of manganese oxide/alumina composite material in terms of polyvinyl alcohol processing, belong to offal treatment and environmental protection technical field.It uses dipping calcination method to prepare MnxOy/γ‑Al2O3Composite material, and the absorption for polyvinyl alcohol and catalytic degradation processing.Mn prepared by the present inventionxOy/γ‑Al2O3Composite material can be realized simultaneously absorption and the catalytic degradation of polyvinyl alcohol, can be used for the processing of solid polyethylene alcohol and polyvinyl alcohol waste water the like waste, used MnxOy/γ‑Al2O3Composite material can be realized by washing, filtering and drying calcining to be regenerated, regenerated MnxOy/γ‑Al2O3Composites have many advantages, such as simple high adsorption, high catalytic property, reusable, method, simple operation, at low cost, efficient.
Description
Technical field
The present invention relates to a kind of application of manganese oxide/alumina composite material in terms of polyvinyl alcohol processing, belong to discarded
Object processing and environmental protection technical field.
Background technology
Polyvinyl alcohol (PVA) is a kind of to be widely used in the fields such as textile garment, printing and dyeing, papermaking, chemical industry, building
Artificial synthesized high molecular material.Reagent and additive in polymerization, fabric containing polyvinyl alcohol and paper making pulp, building coating, coating, adhesive
Generated waste water has certain viscosity to equal materials in the production and use process, and COD value is higher, and water is big, organic pollution
Complicated component, it is unprocessed be discharged into nature after, problem of environmental pollution will be caused.
Manganese oxide is stronger one kind of catalytic capability in all metal oxides present in nature, they can conduct
The electron acceptor of many redox reactions.γ-Al2O3With good mechanical performance and thermal stability, under the high temperature conditions
Almost without loss, and there is very high absorption property, is commonly used to do the carrier of organic catalyst.With γ-Al2O3For carrier,
Manganese oxide/alumina composite material that load manganese series oxides obtain in the above, meso-hole structure make it have larger ratio
Surface area, excellent absorption property and preferable catalytic action, while there is higher surface-active and thermal stability, not only may be used
Using as the residues of banned pesticides in good adsorbent collaboration microwave method removal agricultural chemicals waste water, such as glyphosate waste water can also be applied
The CO and NO in mercury removal, vehicle exhaust in flue coal combustion exhaustxRemoving and O3 catalytic oxidation gas pollutant
Etc..The present invention select manganese oxide/alumina composite material as containing polyvinyl alcohol waste water absorption and catalyst, can solve
It is insufficient present in certainly existing polyvinyl alcohol Waste Disposal Technology.
Invention content
It is insufficient present in existing polyvinyl alcohol Waste Disposal Technology the purpose of the present invention is overcoming, a kind of oxidation is provided
Application of the manganese/alumina composite material in terms of polyvinyl alcohol processing can not only synchronize the adsorption treatment for realizing polyvinyl alcohol
And catalytic degradation processing, and with the features such as renewable, at low cost, efficient, easy to operate.
According to technical solution provided by the invention, a kind of manganese oxide/alumina composite material is in terms of polyvinyl alcohol processing
Application, pass through MnxOy/γ-Al2O3Composite material carries out adsorption treatment to polyvinyl alcohol water solution or catalytic degradation is handled.
Adsorption treatment is as follows：The polyvinyl alcohol water solution for preparing 10~70g/L of 1L mass concentrations, uses quality
A concentration of 0.15~0.30% dilute hydrochloric acid adjusts solution ph to 3~4.5, and 1~10g manganese oxide/alumina composite material is added
MnxOy/γ-Al2O3, it is sufficiently stirred under the conditions of 25~80 DEG C 2~6 hours；Polyvinyl alcohol water solution is dense before and after absorption
Degree is chosen supernatant and is tested using Finley methods.
Absorption and catalytic degradation polyvinyl alcohol water solution are as follows：Prepare the poly- of 10~70g/L of 1L mass concentrations
Vinyl alcohol aqueous solution is that 0.15~0.30% dilute hydrochloric acid adjusts solution ph to 3~4.5 with mass concentration, 1~10g oxygen is added
Change manganese/alumina composite material MnxOy/γ-Al2O3And 10~30% hydrogen peroxide of 50~300mL, in 25~80 DEG C of conditions
Under be sufficiently stirred 2~6 hours, while realizing absorption and the catalytic degradation of polyvinyl alcohol；Polyvinyl alcohol water solution before and after the processing
Concentration is chosen supernatant and is tested using Finley methods.
The manganese oxide/alumina composite material preparation method is as follows：Mn is prepared using dip-calcination methodxOy/γ-
Al2O3Composite material；In the MnSO that 1L mass concentrations are 7.5g/L41~5g γ-Al are added in solution2O3Powder is sufficiently stirred 12
~24 hours, solid particle is obtained by filtration, through being dried in vacuo 2~4 hours under the conditions of 90~110 DEG C, 0.08~0.09MPa, obtains
To dry blocks of solid, after fully grinding, 300~650 DEG C are warming up to the heating rate of 10~20 DEG C/min, calcining 1~5
Hour, natural cooling obtains manganese oxide/alumina composite material MnxOy/γ-Al2O3Powder.
The MnxOy/γ-Al2O3Composite material can be used for the aqueous solution of adsorption treatment polyvinyl alcohol, to polyethylene
Alcohol adsorption rate reaches as high as 13.6%；And used MnxOy/γ-Al2O3It is dry that composite material can pass through washing-filtering-
The step of dry-calcining, realizes regeneration, through 5 regenerated MnxOy/γ-Al2O3Composite material is still reachable to polyvinyl alcohol adsorption rate
To 13.1%.
The MnxOy/γ-Al2O3Composite material, can be used for simultaneously adsorb and catalytic degradation polyvinyl alcohol it is water-soluble
Liquid reaches as high as 99.0% to the total handling rate of polyvinyl alcohol；And used MnxOy/γ-Al2O3Composite material can pass through
The step of washing-filtering-drying-calcining, realizes regeneration, through 5 regenerated MnxOy/γ-Al2O3Composite material is to polyvinyl alcohol
Total handling rate still can reach 98.8%.
Beneficial effects of the present invention：Mn prepared by the present inventionxOy/γ-Al2O3Composite material can be realized simultaneously polyethylene
The absorption of alcohol and catalytic degradation can be used for the processing of solid polyethylene alcohol and polyvinyl alcohol waste water the like waste, have repeatable
Using, method simple, simple operation, it is at low cost, efficient the advantages that.
Specific implementation mode
With reference to test example and specific implementation mode, the present invention is described in further detail.But this should not be understood
It is only limitted to embodiment below for the range of the above-mentioned theme of the present invention, it is all that this is belonged to based on the technology that the content of present invention is realized
The range of invention.
The absorption of 1 polyvinyl alcohol water solution of embodiment
(1)MnxOy/γ-Al2O3The preparation of composite material：The present invention prepares Mn using dip-calcination methodxOy/γ-Al2O3
Composite material, in the MnSO that 1L mass concentrations are 7.5g/L44g γ-Al are added in solution2O3Powder is sufficiently stirred 24 hours, mistake
Filter obtains solid particle, is dried in vacuo 2 hours through 110 DEG C, 0.08MPa, obtains dry blocks of solid, after fully grinding, with
The heating rate of 10 DEG C/min is warming up to 450 DEG C, calcines 2 hours, natural cooling obtains MnxOy/γ-Al2O3Composite wood feed powder
End.
(2)MnxOy/γ-Al2O3Composite material adsorption treatment polyvinyl alcohol water solution：Prepare 1L mass concentrations 10g/L's
Polyvinyl alcohol water solution adjusts solution ph to 3 with dilute hydrochloric acid, 1g Mn/ γ-Al is added2O3Composite material, under the conditions of 80 DEG C
It is sufficiently stirred 6 hours, takes the supernatant of the front and back polyvinyl alcohol water solution of absorption respectively, it is front and back poly- using the test absorption of Finley methods
Ethylene determining alcohol, is calculated adsorption rate.
Using the present embodiment absorption and catalytic degradation polyvinyl alcohol water solution, adsorption rate is up to 13.4%.
The absorption of 2 polyvinyl alcohol water solution of embodiment and catalytic degradation
Gained Mn is prepared using embodiment 1xOy/γ-Al2O3Composite material.
MnxOy/γ-Al2O3Composite material catalytic degradation polyvinyl alcohol water solution：Prepare the poly- second of 1L mass concentrations 10g/L
Enol aqueous solution adjusts solution ph to 3 with dilute hydrochloric acid, 1g Mn/ γ-Al is added2O3The hydrogen peroxide of composite material and 120mL,
It is sufficiently stirred under the conditions of 80 DEG C 4 hours, takes the supernatant of polyvinyl alcohol water solution before and after the processing respectively, surveyed using Finley methods
Polyvinyl alcohol concentration before and after the processing is tried, total handling rate is calculated.
The total handling rate of the present embodiment is up to 99.0%.
Used MnxOy/γ-Al2O3Composite material can be realized by the step of washing-filtering-drying-calcining
Regeneration, through 5 regenerated MnxOy/γ-Al2O3Composite material still can reach 98.6% to the total handling rate of polyvinyl alcohol.
The absorption of 3 polyvinyl alcohol water solution of embodiment
Gained Mn is prepared using embodiment 1xOy/γ-Al2O3Composite material.
MnxOy/γ-Al2O3Composite material adsorption treatment polyvinyl alcohol water solution：Prepare the poly- second of 1L mass concentrations 50g/L
Enol aqueous solution adjusts solution ph to 3 with dilute hydrochloric acid, 2g Mn/ γ-Al is added2O3Composite material, under the conditions of 60 DEG C fully
Stirring 6 hours takes the supernatant of the front and back polyvinyl alcohol water solution of absorption respectively, using the front and back polyethylene of Finley methods test absorption
Adsorption rate is calculated in determining alcohol.
Using the present embodiment absorption and catalytic degradation polyvinyl alcohol water solution, adsorption rate is up to 12.9%.
The absorption of 4 polyvinyl alcohol water solution of embodiment and catalytic degradation
Gained Mn is prepared using embodiment 1xOy/γ-Al2O3Composite material.
MnxOy/γ-Al2O3Composite material catalytic degradation polyvinyl alcohol water solution：Prepare the poly- second of 1L mass concentrations 50g/L
Enol aqueous solution adjusts solution ph to 3 with dilute hydrochloric acid, 2g Mn/ γ-Al is added2O3The hydrogen peroxide of composite material and 100mL,
It is sufficiently stirred under the conditions of 60 DEG C 6 hours, takes the supernatant of polyvinyl alcohol water solution before and after the processing respectively, surveyed using Finley methods
Polyvinyl alcohol concentration before and after the processing is tried, total handling rate is calculated.
Total handling rate of the present embodiment is up to 97.6.
Used MnxOy/γ-Al2O3Composite material can be realized by the step of washing-filtering-drying-calcining
Regeneration, through 5 regenerated MnxOy/γ-Al2O3Composite material still can reach 97.3% to the total handling rate of polyvinyl alcohol.
Claims (1)
1. a kind of application of manganese oxide/alumina composite material in terms of polyvinyl alcohol processing, it is characterized in that：Pass through MnxOy/γ-
Al2O3Composite material carries out adsorption treatment to polyvinyl alcohol water solution or catalytic degradation is handled；
Adsorption treatment is as follows：The polyvinyl alcohol water solution for preparing 10 ~ 70g/L of 1L mass concentrations, uses mass concentration
Solution ph is adjusted to 3 ~ 4.5 for 0.15 ~ 0.30% dilute hydrochloric acid, and 1 ~ 10g manganese oxide/alumina composite material Mn is addedxOy/γ-
Al2O3, it is sufficiently stirred under the conditions of 25 ~ 80 DEG C 2 ~ 6 hours；The concentration of the front and back polyvinyl alcohol water solution of absorption chooses supernatant
Liquid is tested using Finley methods；
Absorption and catalytic degradation polyvinyl alcohol water solution are as follows：Prepare the polyvinyl alcohol of 10 ~ 70g/L of 1L mass concentrations
Aqueous solution is that 0.15 ~ 0.30% dilute hydrochloric acid adjusts solution ph to 3 ~ 4.5 with mass concentration, 1 ~ 10g manganese oxide/oxidation is added
Aluminium composite material MnxOy/γ-Al2O3And 10 ~ 30% hydrogen peroxide of 50 ~ 300mL, it is sufficiently stirred 2 ~ 6 under the conditions of 25 ~ 80 DEG C
Hour, while realizing absorption and the catalytic degradation of polyvinyl alcohol；The concentration of polyvinyl alcohol water solution chooses supernatant before and after the processing
It is tested using Finley methods；
The manganese oxide/alumina composite material preparation method is as follows：Mn is prepared using dip-calcination methodxOy/ γ-Al2O3It is multiple
Condensation material；In the MnSO that 1L mass concentrations are 7.5g/L41 ~ 5g γ-Al are added in solution2O3It is small to be sufficiently stirred 12 ~ 24 for powder
When, solid particle is obtained by filtration, through being dried in vacuo 2 ~ 4 hours under the conditions of 90 ~ 110 DEG C, 0.08 ~ 0.09 MPa, obtains drying
Blocks of solid, after fully grinding, be warming up to 300 ~ 650 DEG C with the heating rate of 10 ~ 20 DEG C/min, calcine 1 ~ 5 hour, it is natural
It is cooling, obtain manganese oxide/alumina composite material MnxOy / γ-Al2O3Powder.
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| CN201610964133.XA CN106311125B (en) | 2016-11-04 | 2016-11-04 | A kind of application of manganese oxide/alumina composite material in terms of polyvinyl alcohol processing |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102233259A (en) * | 2010-05-04 | 2011-11-09 | 北京林业大学 | Adsorbent for removing heavy metal from water and preparation method of adsorbent |
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| CN1812835A (en) * | 2003-04-29 | 2006-08-02 | 约翰逊马西有限公司 | Manganese ozone decomposition catalysts and process for its preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102233259A (en) * | 2010-05-04 | 2011-11-09 | 北京林业大学 | Adsorbent for removing heavy metal from water and preparation method of adsorbent |
Non-Patent Citations (3)
| Title |
|---|
| Elemental mercury oxidation from flue gas by microwave catalytic oxidation over Mn/g-Al2O3;Z.S Wei et al.;《Journal of Industrial and Engineering Chemistry》;20141013;第24卷;第315-321页 * |
| 催化氧化法处理聚乙烯醇废水;刘宝生等;《广东化工》;20101231;第37卷(第12期);第101-102,115页 * |
| 聚乙烯醇在Al2O3、SiO2颗粒上的吸附及对Zeta电位的影响;韦园红 等;《华东理工大学学报》;20010228;第27卷(第1期);第99-102页 * |
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