CN101073762A - Arsenic-removing adsorbent containing lanthanum mesic-porous molecular sieve and its production - Google Patents
Arsenic-removing adsorbent containing lanthanum mesic-porous molecular sieve and its production Download PDFInfo
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- CN101073762A CN101073762A CN 200710042509 CN200710042509A CN101073762A CN 101073762 A CN101073762 A CN 101073762A CN 200710042509 CN200710042509 CN 200710042509 CN 200710042509 A CN200710042509 A CN 200710042509A CN 101073762 A CN101073762 A CN 101073762A
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Abstract
The invention is concerned with a kind of mesoporous molecular sieve sorbent and its production with lanthanum to get rid of arsenic. The sorbent is made up of two unattached sets mesoporous silica MCM-48 with three dimensional passage and lanthanum on it. The weight contain of lanthanum is 1.17 to 9.80 percent, the surface is 202 to 732 m2/g, the even aperture is 2.7 to 3.2 nm, and the hole volume is 0.2 to 0.7 ml/g. This molecular sieve has large specific surface area, narrow aperture distributing of hole, high stability and good performance. It has high content, selectivity, adsorption and machine intensity for reusing with easy process and low cost.
Description
Technical field
The present invention relates to a kind of arsenic-removing adsorption agent and preparation method thereof, specifically be meant can effectively remove arsenic in the water contain the lanthanum mesic-porous molecular sieve sorbing material.
Background technology
The soluble compound of arsenic and arsenic is poisonous.As arsenic, white arsenic is exactly arsenic trioxide.Occurring in nature mainly exists with compound form, or become simple substance to exist, mispickel (FeAsS), realgar (As are arranged
2S
2), orpiment (As
2S).Contain arsenide in many nonferrous metals ores, so in nonferrous metallurgical process,, all have arsenide (as white arsenic) to discharge as the ore roast.
Arsenide is used for making the hair remover and the anticorrisive agent of carbide alloy, arsenate medicine, pesticide, rat poison (being generally arsenic acid, arsenite), glass industry decolorizer, fur industry more.So industry such as metallurgy, sulfuric acid, chemical fertilizer, leather, agricultural chemicals all have arsenic contamination.Arsenic can enter human body by approach such as breathing, skin contact, diet.Arsenic can combine with the sulfydryl in protein and the enzyme, suppresses a lot of biochemical processes in the body, particularly combines with the sulfydryl of pyruvate oxidase, and it is lost activity, and causes the serious disorder of cellular metabolism.Arsenic is 0.02～0.052 gram to people's toxic dose, and lethal dose is 0.06～0.2 gram.Find also that in recent years in workman that matter containing arsenic often contacts, the incidence of disease of cutaneum carcinoma and lung cancer is higher than other industry.
The World Health Organization considered to have issued that the content range of arsenic is 7～10ppb the water from health in 1993." drinking water sanitary standard " regulation of Ministry of Construction's issuing and implementation in 1986, the content of arsenic must not surpass 50ppb.Content according to China's regulation arsenic from July, 2006 water in June, 2005 water quality safety drinking water standard also drops to 10ppb by 50ppb.
Therefore, the problem that high arsenic drinking water is handled to reduce its content has important practical usage.Arsenic in traditional removal water all adopts active carbon adsorption, and is remarkable to high arsenic waste water effect, if but only with activated carbon arsenic content in the water to be dropped to 10ppb be unrealistic.The method of arsenic removal mainly contains lime softening method in the drinking water at present, charcoal filtering, and the iron sulfide filter bed, ferric sulfate condenses, and iron chloride condenses, the ferric hydroxide precipitate method.Wherein, with the research of the compound absorption arsenic removal of the synthetic unformed Powdered iron of coprecipitation do many, but experimental results show that it is very difficult filtering behind its arsenic-adsorbing from solution.So the someone studies and is prepared into particulate iron oxide or carries out iron oxide coatings on the surface of sand, is used for arsenic removal, its effect is more satisfactory.But the specific area of this sorbing material is little, has limited it and has used widely.In a word, the material that can satisfy the adsorbent that can be used for adsorbent bed of arsenic removal should satisfy simultaneously: grain shape, remove As (III) or As (V) all effectively, high power capacity, high selection and high adsorption rate, high mechanical properties (being difficult for decomposing), reproducible utilization, low cost, non-environmental-pollution at water.Chinese invention patent application " remove arsenic in the water composite adsorbing material and preparation method thereof " application number is apparent in view for the effect of removing arsenic of 200510027898.2 sorbing materials that provide, but, prolongation along with adsorption time, the iron oxide on surface has the phenomenon of decay, has limited the long-play of this material.Also have Chinese patent application " to carry the preparation method of iron activated carbon arsenic-removing adsorption agent " though application number for 200510110226.8 sorbing materials that provide make moderate progress, still has similar shortcoming.People such as Fryxell have synthesized the mesopore silicon oxide that is fixed with copper chelate and ethylenediamine, and its high-adsorption-capacity to arsenic is approximately 140mg (As)/g.People such as Yoshitake have synthesized MCM-41, SBA-1 and the MCM-48 of amino silane functionalization, wherein each all complexing cross Fe
3+, Co
2+, Ni
2+, Cu
2+Or H
+When the initial concentration of arsenic is lower than 100mg/l, complexing Fe
3+The MCM-41 of amino silane functionalization arsenic is had the highest adsorption capacity 2.5mmol
As/ g.But these two examples have all been used expensive and poisonous chemical substance.
Summary of the invention
The objective of the invention is to disclose a kind of arsenic-removing adsorbent containing lanthanum mesic-porous molecular sieve, to overcome the above-mentioned defective that prior art exists;
Further object of the present invention is the preparation method who discloses described arsenic-removing adsorption agent, so that suitability for industrialized production.
The arsenic-removing adsorbent containing lanthanum mesic-porous molecular sieve that the present invention proposes is characterized in that, is made up of mesopore silicon oxide MCM-48 and load lanthanum thereon with the mutual disjunct three-dimensional open-framework of two covers, and the weight content of lanthanum is 1.17～9.80%.
This arsenic-removing adsorption agent has three-dimensional open-framework, and nitrogen determining adsorption BET surface area is 202-732m
2/ g, average pore size is 2.7-3.2nm, pore volume is 0.2-0.7ml/g;
Document C.T.Kresge specifically seen in term " the mesopore silicon oxide MCM-48 of the mutual disjunct three-dimensional open-framework of two covers ", M.E.Leonowicz, and W.J.Roth, J.C.Vartuli, J.S.Beck, Nature359 (1992) 710.
The preparation method of arsenic-removing adsorbent containing lanthanum mesic-porous molecular sieve of the present invention comprises the steps:
(1) with the mixture of silicon source, alkali source, lanthanum source, template agent and water, at 25～40 ℃, under preferred 30～37 ℃, reacted 40～60 minutes, reaction mixture;
(2) then with the reaction mixture of step (1) gained, reacted 10～24 hours at 100～150 ℃ of hydrothermal crystallizings, again that the product washing of hydrothermal crystallizing reaction is extremely neutral, dry, 450～550 ℃ of roastings 2～6 hours, get object;
Said silicon source is silica gel, Ludox or tetraalkyl silicic acid fat, and preferred silicon source is a tetraalkyl acid fat, and most preferred is four C
1～C
4Alkyl silicic acid fat, the best are tetraethyl silicic acid fat [Si (OC
2H
5)
4];
Said alkali source is alkali-metal hydroxide, and preferred alkali source is potassium hydroxide or NaOH;
Said lanthanum source is lanthanum nitrate or lanthanum chloride;
Said template agent is the cetyl trimethyl ammonia bromide;
Silicon source: alkali source: template agent: water: lanthanum source=1.0: 0.45～0.50: 0.62～0.65: 60～62: x, mol ratio;
X=0.004～0.05; Preferred 0.005～0.04
Advantage that the present invention has and effect:
Because of the present inventionly contain that the lanthanum mesic-porous molecular sieve specific area is big, pore-size distribution is narrow, stability is high, functional, have the advantage of high power capacity, high selection and high adsorption rate, high mechanical properties, reproducible utilization.
2. because the lanthanum mesic-porous molecular sieve that contains of the present invention is once to be prepared from by hydro-thermal method, and crystallization temperature is lower than 150 ℃, so the present invention's simple, easy to operate advantage that has technology;
3. lanthanum is a most cheap a kind of rare earth element, and it is nontoxic, and and environmental friendliness, so the lanthanum mesic-porous molecular sieve non-environmental-pollution that contains of the present invention, the advantage that preparation cost is cheap;
4. improve absorption arsenic removal efficient and enlarged the scope of application simultaneously.Sorbing material of the present invention can be used as the adsorbent of adsorbent bed and removes arsenic other heavy metals in addition.
Description of drawings
Fig. 1 is the variation relation of the adsorption concentration of arsenic with lanthanum content (La/Si) among the La-MCM-48.
Fig. 2 is the arsenic removal experiment isothermal curve of arsenic-removing adsorbent containing lanthanum mesic-porous molecular sieve of the present invention.
The specific embodiment
10 milliliters of tetraethyl silicate resins are mixed with 50 ml deionized water, mixture was stirring 40 minutes under 35 ℃ of conditions, NaOH with 0.9 gram joins in the mixture then, add lanthanum source and silicon source subsequently, continue to stir after 40 minutes, the cetyl trimethyl ammonia bromide of 10.6 grams is added in the mixture, continue to stir to change over to after 60 minutes in the polytetrafluoroethylene (PTFE) autoclave and after 24 hours the product of crystallization gained is washed to neutral 120 ℃ of hydrothermal crystallizing reactions, oven dry can prepare cubic mesoporous La-MCM-48 in 4 hours with the product after the oven dry 550 ℃ of roastings.
| | Embodiment | 1 | | | |
| Phase | Cube phase | Cube phase | Cube phase | Cube phase | |
| Lanthanum nitrate addition (gram) | 0.0485 | 0.0970 | 0.1940 | 0.3880 | |
| Tetraethyl silicic acid fat (gram) | 4.665 | 4.665 | 4.665 | 4.665 | |
| La/Si | 0.005 | 0.01 | 0.02 | 0.04 |
Adopt following method that the materialization data of adsorbent of the present invention are measured: the arsenic-removing adsorption agent that weighing 1g prepares with the present invention, totally 24 parts, add 24 bottles of different preliminary examination respectively and contain in the solution of arsenic concentration and at room temperature stir, sway, 48 hours backsights are adsorption equilibrium.With the aperture is 0.45 μ m membrane filtration, gets its supernatant.With model is the effect of atom absorption fluophotometer (place of production Japan) the mensuration absorption back arsenic removal of 508-0182.Adopt the condition of work of the concentration of the arsenic in the water after atomic absorption fluorescence is measured processing to be: laboratory temperature (18 ℃), negative high voltage PMT (270V), A road lamp current (40mA), B road lamp current (0mA), height of observation (8mm), reading mode (Peak Area), time delay (2s), experimental temperature (30 ℃), heating-up temperature (200 ℃), carrier gas flux (400ml/min), shield gas flow amount (800ml/min), measuring method (Std Curve), is measured number of repetition (3 times) at the reading duration (7s).
As can be seen from Figure 1, when the initial concentration of arsenic is 4mmol/L, slowly increase after the increase elder generation fast rise of the adsorption concentration of arsenic with the mol ratio of La/Si.
Fig. 2 is that La/Si is 0.04 La-MCM-48 arsenic removal experiment isothermal curve, and the adsorbance of arsenic increases with the increase of initial concentration, and the adsorption effect of arsenic-removing adsorbent containing lanthanum mesic-porous molecular sieve of the present invention is very good.This material is a more satisfactory absorption arsenic removal adsorbent.
Embodiment 5
10 milliliters of tetraethyl silicate resins are mixed with 50 ml deionized water, mixture was stirring 40 minutes under 35 ℃ of conditions, potassium hydroxide with 1.3 grams joins in the mixture then, add lanthanum source and silicon source subsequently, continue to stir after 45 minutes, the cetyl trimethyl ammonia bromide of 10.4 grams is added in the mixture, continue to stir to change over to after 60 minutes in the polytetrafluoroethylene (PTFE) autoclave and after 10 hours the product of crystallization gained is washed to neutral 150 ℃ of hydrothermal crystallizing reactions, oven dry can prepare a cube mesopore La-MCM-48 with the product after the oven dry in 6 hours 450 ℃ of roastings.
| | Embodiment | 1 | | | |
| Phase | Cube phase | Cube phase | Cube phase | Cube phase | |
| Lanthanum chloride addition (gram) | 0.0396 | 0.0792 | 0.1584 | 0.3168 | |
| Tetraethyl silicic acid fat (gram) | 4.665 | 4.665 | 4.665 | 4.665 | |
| La/Si | 0.005 | 0.01 | 0.02 | 0.04 |
Adopt embodiment 1 identical method to measure, its result is basic identical.
Claims (8)
1. arsenic-removing adsorbent containing lanthanum mesic-porous molecular sieve is characterized in that, is made up of mesopore silicon oxide MCM-48 and load lanthanum thereon with the mutual disjunct three-dimensional open-framework of two covers, and the weight content of lanthanum is 1.17～9.80%.
2. arsenic-removing adsorbent containing lanthanum mesic-porous molecular sieve according to claim 1 is characterized in that, this arsenic-removing adsorption agent surface area is 202-732m
2/ g, average pore size is 2.7-3.2nm, pore volume is 0.2-0.7ml/g.
3. prepare the method for claim 1 or 2 described arsenic-removing adsorbent containing lanthanum mesic-porous molecular sieves, comprise the steps:
(1) with the mixture of silicon source, alkali source, lanthanum source, template agent and water,, reacted 40～60 minutes, get reaction mixture at 25～40 ℃;
(2) then with the reaction mixture of step (1) gained, reacted 10～24 hours at 100～150 ℃ of hydrothermal crystallizings, again that the product washing of hydrothermal crystallizing reaction is extremely neutral, dry, 450～550 ℃ of roastings 2～6 hours, get object.
4. method according to claim 3 is characterized in that, said silicon source is silica gel, Ludox or tetraalkyl silicic acid fat;
Said alkali source is alkali-metal hydroxide;
Said lanthanum source is lanthanum nitrate or lanthanum chloride;
Said template agent is the cetyl trimethyl ammonia bromide.
5. method according to claim 4 is characterized in that, said silicon source is a tetraalkyl acid fat, and alkali source is potassium hydroxide or NaOH.
6. method according to claim 5 is characterized in that, said silicon source is four C
1～C
4Alkyl silicic acid fat.
7. method according to claim 6 is characterized in that, said silicon source is a tetraethyl silicic acid fat.
8. according to each described method of claim 3～6, it is characterized in that silicon source: alkali source: template agent: water: lanthanum source=1.0: 0.45～0.50: 0.62～0.65: 60～62: x, mol ratio;
x＝0.004～0.05。
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101804321A (en) * | 2010-04-15 | 2010-08-18 | 山东科技大学 | Novel silica gel compound adsorption and separation material and preparation method thereof |
| CN101559954B (en) * | 2009-05-26 | 2011-01-19 | 上海大学 | Method for preparing mesoporous molecular sieve with high hydrothermal stability by taking ionic liquid as template agent |
| CN102350302A (en) * | 2011-09-05 | 2012-02-15 | 青岛理工大学 | Novel arsenic removal material and preparation method thereof |
| CN102397775A (en) * | 2011-11-21 | 2012-04-04 | 中国科学院化学研究所 | Arsenic-removal adsorbent as well as preparation method and application thereof |
| CN104891615A (en) * | 2015-05-27 | 2015-09-09 | 福建洋屿环保科技股份有限公司 | Flocculating agent and preparation method thereof |
| CN104971699A (en) * | 2015-07-27 | 2015-10-14 | 南京大学 | Modified zeolite organic matter composite agent for synchronous nitrogen and phosphorus removal of sewage, and preparation method, application and application method of modified zeolite organic matter composite agent |
| CN109603785A (en) * | 2018-12-18 | 2019-04-12 | 安徽工业大学 | It is a kind of to remove arsenic, phosphorus adsorbent and preparation method thereof in water removal simultaneously |
| CN114367267A (en) * | 2022-01-19 | 2022-04-19 | 中国科学院赣江创新研究院 | Mesoporous composite material and preparation method and application thereof |
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2007
- 2007-06-22 CN CN200710042509A patent/CN100594975C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559954B (en) * | 2009-05-26 | 2011-01-19 | 上海大学 | Method for preparing mesoporous molecular sieve with high hydrothermal stability by taking ionic liquid as template agent |
| CN101804321A (en) * | 2010-04-15 | 2010-08-18 | 山东科技大学 | Novel silica gel compound adsorption and separation material and preparation method thereof |
| CN101804321B (en) * | 2010-04-15 | 2012-08-22 | 山东科技大学 | Novel silica gel compound adsorption and separation material and preparation method thereof |
| CN102350302A (en) * | 2011-09-05 | 2012-02-15 | 青岛理工大学 | Novel arsenic removal material and preparation method thereof |
| CN102397775A (en) * | 2011-11-21 | 2012-04-04 | 中国科学院化学研究所 | Arsenic-removal adsorbent as well as preparation method and application thereof |
| CN102397775B (en) * | 2011-11-21 | 2013-06-26 | 中国科学院化学研究所 | Arsenic-removal adsorbent as well as preparation method and application thereof |
| CN104891615A (en) * | 2015-05-27 | 2015-09-09 | 福建洋屿环保科技股份有限公司 | Flocculating agent and preparation method thereof |
| CN104971699A (en) * | 2015-07-27 | 2015-10-14 | 南京大学 | Modified zeolite organic matter composite agent for synchronous nitrogen and phosphorus removal of sewage, and preparation method, application and application method of modified zeolite organic matter composite agent |
| CN109603785A (en) * | 2018-12-18 | 2019-04-12 | 安徽工业大学 | It is a kind of to remove arsenic, phosphorus adsorbent and preparation method thereof in water removal simultaneously |
| CN114367267A (en) * | 2022-01-19 | 2022-04-19 | 中国科学院赣江创新研究院 | Mesoporous composite material and preparation method and application thereof |
| CN114367267B (en) * | 2022-01-19 | 2023-11-28 | 中国科学院赣江创新研究院 | Mesoporous composite material and preparation method and application thereof |
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