CN102008939A - Method for preparing aluminum-manganese composite oxide modified molecular sieve - Google Patents
Method for preparing aluminum-manganese composite oxide modified molecular sieve Download PDFInfo
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- CN102008939A CN102008939A CN 201010543259 CN201010543259A CN102008939A CN 102008939 A CN102008939 A CN 102008939A CN 201010543259 CN201010543259 CN 201010543259 CN 201010543259 A CN201010543259 A CN 201010543259A CN 102008939 A CN102008939 A CN 102008939A
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Abstract
The invention discloses a method for preparing an aluminum-manganese composite oxide modified molecular sieve, which comprises the following steps of: preparing the mixed solution of aluminum salt and manganese salt, slowly adding a proper amount of oxidant solution with uniform stirring into the mixed solution of aluminum salt and manganese salt, continuing to perform stirring for a while to ensure full reaction, adding a proper amount of alkali liquor adjusting solution to adjust the pH value of the solution to be 6 to 8, adding a proper amount of molecular sieve into the solution, completely oscillating the solution, standing and aging the solution for a while, taking the molecular sieve out, and washing with water and drying the molecular sieve to obtain the aluminum-manganese composite oxide modified molecular sieve.
Description
Technical field
The present invention relates to a kind of be used for removing aluminium manganese composite oxide modified molecular screen preparation of adsorbent method water arsenic contamination thing, that have high-specific surface area and good absorption property and the using method in water treatment applications.The invention belongs to field of water processing technology.
Background technology
Arsenic element is subjected to common concern because of it has severe toxicity with strong carcinogenicity at the occurring in nature ubiquity.Inorganic arsenic comprises trivalent arsenic As (III) and pentavalent arsenic As (V), and the harm of As (III) far is better than As (V), and toxicity can reach more than 60 times of the latter.The long-term drinking arsenic-containing water will increase the danger of suffering from carcinoma of urinary bladder, lung cancer, kidney and cutaneum carcinoma, The World Health Organization (WHO) also is decided to be 10 μ g/L with the new standard of the As in the drinking water, and the arsenic of therefore how removing and controlling in the drinking water is to study focus at present both at home and abroad.
Compare with other dearsenicating method such as Coagulation Method, ion-exchange and film processing etc., absorption method is used widely in handling the lower water treatment system of arsenic concentration because of it has advantage such as easy, economic, renewable.But it is in the arsenic-removing adsorption agent commonly used at present,, only As (V) is had the good adsorption ability usually, but relatively poor to the removal ability of As (III) as activated alumina, active carbon.Not only increase processing cost and operation easier and add pre-oxidation, also may produce the accessory substance that health is had potential hazard.On the other hand, according to the report of nearest domestic and foreign literature, material with low cost is less to the adsorption capacity of arsenic usually, as carrying iron sand, native iron manganese ore etc.; Often cost is too high and have material than high-adsorption-capacity, as titanium dioxide.This has also limited and has removed applying of arsenic adsorbent material.Therefore, research and development are with low cost and be to study both at home and abroad at present and the focus and the difficult point problem of technological development to the novel absorption material that As (III) and As (V) all have a good removal effect.
Aluminum oxide has good removal ability to As (V), but is difficult to remove As (III).Manganese dioxide has good oxidation susceptibility to As (III), but lower to the adsorption capacity of As (V).
Molecular sieve is a kind of alumino-silicate compound with cubic lattice, mainly connects the skeleton structure of main city spaciousness by sial by oxo bridge, and uniform duct, a lot of apertures and marshalling, hole that internal surface area is very big are arranged in structure.Molecular sieve has low fluid resistance, high adsorption rate, and adsorption capacity is big, and selectivity is strong, the mechanical strength advantages of higher, but simple molecular sieve does not have high selectivity to arsenic.
Therefore, how effectively the chemical characteristic of aluminum oxide and manganese dioxide is combined, and utilize the architectural characteristic of molecular sieve to remove As (III)/As (V) synchronously, become a problem that requires study.At present, bibliographical information and patent disclosure are not seen in research and the application of using aluminium manganese composite oxide modified molecular screen to remove arsenic in the water.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of adsorbent-aluminium manganese composite oxide modified molecular screen of arsenic removal pollutant, and the using method of this adsorbent in water treatment.In the sorbing material that the present invention relates to, the molecular sieve with loose structure is the load matrix, and aluminium manganese composite metal oxide is the main part for adsorbing then.The sorbing material that the present invention relates to all has the good absorption usefulness of wide spectrum to As (III) and As (V).
Technical scheme of the present invention:
A kind of preparation method of aluminium manganese composite oxide modified molecular screen, the mixed solution of preparation aluminium salt and manganese salt, under even stirring condition, in aluminium salt and manganese mixed salt solution, slowly add an amount of oxidizing agent solution, continue to stir 15min-2h, add appropriate alkaline liquor regulator solution pH value afterwards and be 6-8 to guarantee abundant reaction, adding an amount of molecule then is sieved in the solution, vibration earlier fully, still aging again 2-24h takes out molecular sieve at last and prepares and get through washing and dry run.
The preparation method of described aluminium manganese composite oxide modified molecular screen, described aluminum salt solution comprises a kind of in aluminum sulfate, aluminium chloride, polyaluminium sulfate, aluminium polychloride, the alum or it is arbitrarily than mixture; Described manganese salt is selected from a kind of in manganese chloride, manganese sulfate, the manganese nitrate or it is arbitrarily than mixture.
The preparation method of described aluminium manganese composite oxide modified molecular screen, it is 1: 1 to 18: 1 that described aluminium salt and manganese salt satisfy aluminium manganese mol ratio, the reaction time behind the adding oxidant is 15min to 2h.
The preparation method of described aluminium manganese composite oxide modified molecular screen, used alkali lye is the mixture of a kind of or its any ratio in NaOH, potassium hydroxide, sodium carbonate, the potash.
The preparation method of described aluminium manganese composite oxide modified molecular screen, described oxidizing agent solution is a permanganate, the mol ratio of oxidant and described manganese salt is 2: 3.
The preparation method of described aluminium manganese composite oxide modified molecular screen, described oxidizing agent solution is a kind of in hypochlorite, hydrogen peroxide, the liquid chlorine etc., the mol ratio of oxidizing agent solution and manganese salt is 1: 1.
The preparation method of described aluminium manganese composite oxide modified molecular screen, described load matrix is selected from the molecular sieve of particle size range 0.2mm-2mm, and its kind is one or more any combination in 3A type, 4A type, 5A type, 13X type and the HY type.
The preparation method of described aluminium manganese composite oxide modified molecular screen, after molecular sieve added mixed liquor, duration of oscillation was 0.5-12h, and the temperature of described aging step is that room temperature, digestion time are 2-24 hour.
The preparation method of described aluminium manganese composite oxide modified molecular screen, described drying steps is under 50-75 ℃ of condition dry 6-24 hour, is warming up to afterwards 90-180 ℃ of dry 3-12 hour again.
Characteristics of the present invention:
Aluminium manganese composite oxide modified molecular screen adsorbent preparation process is simple, with low cost.
Aluminium manganese composite oxide modified molecular screen adsorbent can all show good removal effect to trivalent arsenic As (III) and pentavalent arsenic As pollutants such as (V).
Prepared aluminium manganese composite oxide modified molecular screen adsorbent has that adsorption rate is fast, capacity is big, has excellent purification of water quality usefulness.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
The preparation of embodiment 1 aluminium manganese composite oxide/adsorbent of molecular sieve: the aluminium chloride of configuration 200ml 0.25mol/L and the manganese chloride mixed solution of 0.15mol/L.Stirring condition adds the 200ml0.1mol/L liquor potassic permanganate down in aluminium manganese mixed salt solution fast, continues to stir 15min, and using sodium hydroxide solution (0.01M-5M) regulator solution pH afterwards is 6-8; The 3A type molecular sieve that with the 200g particle diameter is 0.2mm-0.5mm then joins in the mixed liquor, vibrates 30 minutes, leaves standstill then, room temperature ageing 2 hours.Through ageing, skim supernatant, add a small amount of sig water or pickle again and be neutralized to neutrality, add the 200ml deionized water then, stir, washed 10 minutes, carry out Separation of Solid and Liquid with filter method, solid absorbent continues to add deionized water washing 3-4 time, isolate adsorbent after, be placed in the baking oven and dried by the fire 24 hours down in 50 ℃, be warming up to 90 ℃ and kept 12 hours, promptly get aluminium manganese composite oxide/adsorbent of molecular sieve sample 1.
The preparation of embodiment 2 aluminium manganese composite oxide/adsorbent of molecular sieve: the aluminum sulfate of configuration 200ml 0.25mol/L and the manganese sulfate mixed solution of 0.15mol/L.Stirring condition adds the 200ml0.1mol/L liquor potassic permanganate down in aluminium manganese mixed salt solution fast, continues to stir 30min, and using potassium hydroxide solution (0.01M-5M) regulator solution pH afterwards is 6-8; The 5A type molecular sieve that with the 200g particle diameter is 0.5mm-0.8mm then joins in the mixed liquor, and vibration 1h leaves standstill, room temperature ageing 6 hours then.Through ageing, skim supernatant, add a small amount of sig water or pickle again and be neutralized to neutrality, add the 200ml deionized water then, stir, washed 10 minutes, carry out Separation of Solid and Liquid with filter method, solid absorbent continues to add deionized water washing 3-4 time, isolate adsorbent after, be placed in the baking oven and dried by the fire 18 hours down in 55 ℃, be warming up to 100 ℃ and kept 10 hours, promptly get aluminium manganese composite oxide/adsorbent of molecular sieve sample 2.
The preparation of embodiment 3 aluminium manganese composite oxide/adsorbent of molecular sieve: the alum of configuration 200ml 0.45mol/L and the manganese nitrate mixed solution of 0.15mol/L.Under quick stirring condition, in aluminium manganese mixed salt solution, add an amount of hydrogenperoxide steam generator, the mol ratio that makes oxidant and manganese salt is 1: 1, continuation stirring 1h, and be 6-8 with sodium carbonate liquor (0.01M-5M) regulator solution concentration; The 13X type molecular sieve that with the 200g particle diameter is 0.8mm-1.0mm then joins in the mixed liquor, and vibration 3h leaves standstill, room temperature ageing 10 hours then.Through ageing, skim supernatant, add a small amount of sig water again and be neutralized to neutrality, add the 200ml deionized water then, stir, washed 10 minutes, carry out Separation of Solid and Liquid with filter method, solid absorbent continues to add deionized water washing 3-4 time, isolate adsorbent after, be placed in the baking oven and dried by the fire 12 hours down in 60 ℃, be warming up to 110 ℃ and kept 8 hours, promptly get aluminium manganese composite oxide/adsorbent of molecular sieve sample 3.
The preparation of embodiment 4 aluminium manganese composite oxide/adsorbent of molecular sieve: polyaluminium sulfate and the manganese sulfate mixed solution of configuration 200ml, the mol ratio that makes aluminium manganese is 6: 1.Under quick stirring condition, in aluminium manganese mixed salt solution, add an amount of liquor natrii hypochloritis, the mol ratio that makes oxidant and manganese salt is 1: 1, continuation stirring 1.5h, and be 6-8 with solution of potassium carbonate (0.01M-5M) regulator solution concentration; The 5A type molecular sieve that with the 200g particle diameter is 1.0mm-1.5mm then joins in the mixed liquor, and vibration 6h leaves standstill, room temperature ageing 16 hours then.Through ageing, skim supernatant, add a small amount of sig water again and be neutralized to neutrality, add the 200ml deionized water then, stir, washed 10 minutes, carry out Separation of Solid and Liquid with filter method, solid absorbent continues to add deionized water washing 3-4 time, isolate adsorbent after, be placed in the baking oven and dried by the fire 9 hours down in 65 ℃, be warming up to 150 ℃ and kept 6 hours, promptly get aluminium manganese composite oxide/adsorbent of molecular sieve sample 4.
The preparation of embodiment 5 aluminium manganese composite oxide/adsorbent of molecular sieve: aluminium polychloride and the manganese chloride mixed solution of configuration 200ml, the mol ratio that makes aluminium manganese salt is 9: 1.Under quick stirring condition, in aluminium manganese mixed salt solution, add an amount of liquid chlorine solution, the mol ratio that makes oxidant and manganese salt is 1: 1, continuation stirring 2h, and be 6-8 with sodium hydroxide solution (0.01M-5M) regulator solution concentration; The 13X type molecular sieve that with the 200g particle diameter is 1.5mm-1.7mm then joins in the mixed liquor, and vibration 12h leaves standstill, room temperature ageing 24 hours then.Through ageing, skim supernatant, add a small amount of sig water again and be neutralized to neutrality, add the 200ml deionized water then, stir, washed 10 minutes, carry out Separation of Solid and Liquid with filter method, solid absorbent continues to add deionized water washing 3-4 time, isolate adsorbent after, be placed in the baking oven and dried by the fire 6 hours down in 75 ℃, be warming up to 180 ℃ and kept 3 hours, promptly get aluminium manganese composite oxide/adsorbent of molecular sieve sample 5.
The preparation of embodiment 6 aluminium manganese composite oxide/adsorbent of molecular sieve: aluminium chloride and the manganese chloride mixed solution of configuration 200ml, the mol ratio that makes aluminium manganese salt is 18: 1.Under quick stirring condition, in aluminium manganese mixed salt solution, add an amount of postassium hypochlorite solution, the mol ratio that makes oxidant and manganese salt is 1: 1, continuation stirring 2h, and be 6-8 with potassium hydroxide solution (0.01M-5M) regulator solution concentration; The HY type molecular sieve that with the 200g particle diameter is 1.7mm-2.0mm then joins in the mixed liquor, and vibration 12h leaves standstill, room temperature ageing 24 hours then.Through ageing, skim supernatant, add a small amount of sig water again and be neutralized to neutrality, add the 200ml deionized water then, stir, washed 10 minutes, carry out Separation of Solid and Liquid with filter method, solid absorbent continues to add deionized water washing 3-4 time, isolate adsorbent after, be placed in the baking oven and dried by the fire 6 hours down in 75 ℃, be warming up to 180 ℃ and kept 3 hours, promptly get aluminium manganese composite oxide/adsorbent of molecular sieve sample 5.
The application of embodiment 7 aluminium manganese composite oxide/adsorbent of molecular sieve in arsenic-containing waste water is handled: the used reactor of the present invention is a glass packed column, wherein be filled with the aluminium Mn oxide/adsorbent of molecular sieve particle of preparation, the high about 0.8m of post, diameter 5cm, packing volume 750cm
3Certain arsenic-containing waste water, trivalent arsenic As (III) concentration 100 μ g/L, pH=7.2.From the water inlet of packed column below, upper end water outlet, flow of inlet water 50ml/min, results of regular determination water outlet arsenic concentration.Flow through behind about 5400 times of packing volumes, arsenic concentration just is higher than 10 μ g/L in the water outlet.
The in-situ regeneration of embodiment 8 aluminium manganese composite oxide/adsorbent of molecular sieve: when arsenic concentration is higher than water quality requirement in the packed column water outlet, stop into water, in the emptying post behind the water, slowly pumping into from the below of packed column and being added with alkali lye 100ml concentration is 30% liquor natrii hypochloritis, slowly add the sodium hydroxide solution of 100ml 0.5mol/L then from the packed column top, flow velocity is 1ml/min.Finish, water is emitted in static ageing 4 hours then, uses the deionized water rinsing packed column, and the concentration of dissolubility aluminium manganese ion is lower than water quality requirement in water outlet.
Should be understood that, for those of ordinary skills, can be improved according to the above description or conversion, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (9)
1. the preparation method of an aluminium manganese composite oxide modified molecular screen, it is characterized in that: the mixed solution of preparation aluminium salt and manganese salt, under even stirring condition, in aluminium salt and manganese mixed salt solution, slowly add an amount of oxidizing agent solution, continue to stir 15min-2h to guarantee abundant reaction, add appropriate alkaline liquor regulator solution pH value afterwards and be 6-8, adding an amount of molecule then is sieved in the solution, fully vibration earlier, still aging again 2-24h takes out molecular sieve at last and prepares and get through washing and dry run.
2. the preparation method of aluminium manganese composite oxide modified molecular screen according to claim 1 is characterized in that: described aluminum salt solution comprises a kind of in aluminum sulfate, aluminium chloride, polyaluminium sulfate, aluminium polychloride, the alum or it is arbitrarily than mixture; Described manganese salt is selected from a kind of in manganese chloride, manganese sulfate, the manganese nitrate or it is arbitrarily than mixture.
3. the preparation method of aluminium manganese composite oxide modified molecular screen according to claim 1 is characterized in that: it is 1: 1 to 18: 1 that described aluminium salt and manganese salt satisfy aluminium manganese mol ratio, and the reaction time behind the adding oxidant is 15min to 2h.
4. the preparation method of aluminium manganese composite oxide modified molecular screen according to claim 1 is characterized in that: used alkali lye is the mixture of a kind of or its any ratio in NaOH, potassium hydroxide, sodium carbonate, the potash.
5. the preparation method of aluminium manganese composite oxide modified molecular screen according to claim 1 is characterized in that: described oxidant is a permanganate, and the mol ratio of oxidant and described manganese salt is 2: 3.
6. the preparation method of aluminium manganese composite oxide modified molecular screen according to claim 1 is characterized in that: described oxidant is a kind of in hypochlorite, hydrogen peroxide, the liquid chlorine etc., and the mol ratio of oxidant and manganese salt is 1: 1.
7. the preparation method of aluminium manganese composite oxide modified molecular screen according to claim 1, it is characterized in that: described load matrix is selected from the molecular sieve of particle size range 0.2mm-2mm, and its kind is one or more any combination in 3A type, 4A type, 5A type, 13X type and the HY type.
8. the preparation method of aluminium manganese composite oxide modified molecular screen according to claim 1 is characterized in that: after molecular sieve added mixed liquor, duration of oscillation was 0.5-12h, and the temperature of described aging step is that room temperature, digestion time are 2-24 hour.
9. the preparation method of aluminium manganese composite oxide modified molecular screen according to claim 1 is characterized in that: described drying steps is under 50-75 ℃ of condition dry 6-24 hour, is warming up to afterwards 90-180 ℃ of dry 3-12 hour again.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102580670A (en) * | 2012-02-20 | 2012-07-18 | 中国地质大学（武汉） | Arsenic removal material of nanometer ferrimanganic binary oxide loaded by zeolite and preparation method of arsenic removal material |
| CN109592720A (en) * | 2018-11-23 | 2019-04-09 | 湖南中伟新能源科技有限公司 | Ternary precursor solution purification method |
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| US20030017936A1 (en) * | 2000-11-01 | 2003-01-23 | Kyung-Byung Yoon | Zeolite-substrate composite comprising a patterned zeolite layer on a substrate and preparation thereof |
| CN1632061A (en) * | 2004-12-01 | 2005-06-29 | 中国石油天然气股份有限公司 | Selective cracking catalyst for producing low carbon olefin |
| CN101579638A (en) * | 2009-06-29 | 2009-11-18 | 清华大学 | Catalyst for preparing ethylene by ethanol dehydration and preparation method thereof |
| CN101628242A (en) * | 2009-08-10 | 2010-01-20 | 大唐国际化工技术研究院有限公司 | Molecular sieve catalyst for preparing low-carbon olefin and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6042731A (en) * | 1997-01-31 | 2000-03-28 | The University Of South Florida | Method of removing arsenic species from an aqueous medium using modified zeolite minerals |
| US20030017936A1 (en) * | 2000-11-01 | 2003-01-23 | Kyung-Byung Yoon | Zeolite-substrate composite comprising a patterned zeolite layer on a substrate and preparation thereof |
| CN1632061A (en) * | 2004-12-01 | 2005-06-29 | 中国石油天然气股份有限公司 | Selective cracking catalyst for producing low carbon olefin |
| CN101579638A (en) * | 2009-06-29 | 2009-11-18 | 清华大学 | Catalyst for preparing ethylene by ethanol dehydration and preparation method thereof |
| CN101628242A (en) * | 2009-08-10 | 2010-01-20 | 大唐国际化工技术研究院有限公司 | Molecular sieve catalyst for preparing low-carbon olefin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102580670A (en) * | 2012-02-20 | 2012-07-18 | 中国地质大学（武汉） | Arsenic removal material of nanometer ferrimanganic binary oxide loaded by zeolite and preparation method of arsenic removal material |
| CN102580670B (en) * | 2012-02-20 | 2014-03-26 | 中国地质大学（武汉） | Arsenic removal material of nanometer ferrimanganic binary oxide loaded by zeolite and preparation method of arsenic removal material |
| CN109592720A (en) * | 2018-11-23 | 2019-04-09 | 湖南中伟新能源科技有限公司 | Ternary precursor solution purification method |
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