CN102151546B - Modified zeolite as well as preparation method and application thereof - Google Patents
Modified zeolite as well as preparation method and application thereof Download PDFInfo
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- CN102151546B CN102151546B CN 201110030919 CN201110030919A CN102151546B CN 102151546 B CN102151546 B CN 102151546B CN 201110030919 CN201110030919 CN 201110030919 CN 201110030919 A CN201110030919 A CN 201110030919A CN 102151546 B CN102151546 B CN 102151546B
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Abstract
The invention discloses a modified zeolite as well as a preparation method and application thereof. The modified zeolite is prepared by mixing, roasting and cooling natural zeolite and magnesium oxide. Particularly, the preparation method comprises the steps of: taking natural zeolite and magnesium oxide as raw materials; mixing the natural zeolite and the magnesium oxide in mass ratio of (3-6): 1; roasting at a constant temperature of 100-600 DEG C for 2-6h; and naturally cooling to obtain the modified zeolite. The modified zeolite can be applied to the pre-treatment process of removing ammonia nitrogen in biological treatment aquaculture wastewater and used as an adsorbent for adsorbing the high-strength ammonia nitrogen in the aquaculture wastewater. The modified zeolite is strong in ability of adsorbing ammonia nitrogen, good in ammonia nitrogen adsorption effect, low in preparation cost, environmental-friendly and regenerative.
Description
Technical field
The present invention relates to a kind of zeolite and preparation thereof and application, relate in particular to a kind of modified zeolite and its preparation method and application.
Background technology
The core processing technology of breeding wastewater is the microbiological treatment technology, i.e. nitration denitrification effect by microorganism, mineralized nitrogen is nitrite, nitrate after, be further converted to again nitrogen and reach the ammonia nitrogen removal purpose.Because ammonia nitrogen is dense in the breeding wastewater, usually can cause activity of activated sludge to descend, strengthen processing load and the impact load of microorganism, suppress normally carrying out of biological treatment process, but also limited the regeneration of processing water outlet.In addition, the breeding wastewater content of organic matter is low, usually needs additional carbon in the microbiological treatment process, and then has increased the sewage disposal expense.Therefore, before adopting biological treatment, need to carry out the ammonia nitrogen removal preliminary treatment to breeding wastewater.
At present, often adopt blow-off method to carry out the ammonia nitrogen removal preliminary treatment, but the gaseous nitrogen that blow-off method produces is discharged into and easily cause secondary pollution in the atmospheric environment; In addition, the pretreated investment operating cost of existing ammonia nitrogen removal is expensive, and stripping also can't normally move under the cryogenic conditions.Adopt ion-exchange or adsorption method to carry out the ammonia nitrogen removal preliminary treatment, become gradually the inevitable choice of domestic and international high ammonia-nitrogen content wastewater treatment.Wherein, utilize the natural minerals zeolite as ion-exchange, the absorption ammonia nitrogen removal technology of sorbing material, at home and abroad paid close attention to widely in the sewage treatment area.
Natural zeolite is a kind of crystalline hydrate aluminosilicate mineral, has porous crystal structure, higher cation exchange capacity and huge specific area, and the cation in the duct has very large electrostatic attraction to ammonia nitrogen.Therefore, natural zeolite has certain adsorption capacity and ion-exchange capacity, also can adsorb certain organic matter in the absorption ammonia nitrogen, thereby reduce the concentration of ammonia nitrogen in the breeding wastewater, and alleviate to a certain extent the stench of breeding wastewater.Yet because the inner duct of natural zeolite and surface texture are easily blocked, and contain more water-soluble residual matter and inorganic impurity, this can not reach the purpose of efficient removal polluter so that the ion-exchange capacity of natural zeolite and adsorption capacity are relatively low.Therefore, be necessary to adopt chemistry or physical method that natural zeolite is carried out modification, to improve the ability of its absorption ammonia nitrogen.
The natural zeolite modification is more, generally is divided into solution and soaks modification and high-temperature roasting modification two large classes.It is to adopt inorganic acid solution, inorganic alkali solution or inorganic salt solution that natural zeolite is soaked that solution soaks modification, these class methods can be removed part water-soluble residue and inorganic impurity in natural zeolite surface and the endoporus, improved to a certain extent the ionic adsorption exchange capacity of zeolite, the modification soak time is long, the ammonia nitrogen absorption capacity promotes the shortcomings such as amplitude is little but exist, and is difficult to remove and is combined firmly dirt with zeolite.High-temperature calcination can larger limit this class impurity of removal, improve porosity, strengthen zeolite surface activity and adsorption capacity, but single carries out modification with natural zeolite by high-temperature calcination, usually need 600 ℃～800 ℃ high temperature, energy consumption is higher, and easily cause zeolite structured destruction, make it lose absorption and ion exchange.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide that a kind of ammonia nitrogen absorption ability is strong, ammonia nitrogen absorption is effective, preparation cost is low and the modified zeolite of environmental protection reproducible utilization and application thereof, the preparation method of the modified zeolite that a kind of sintering temperature is low, firing cycle is short, technological operation is easy also is provided.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of modified zeolite, and described modified zeolite is to be mixed with magnesia by roasting, cooling by natural zeolite to prepare.
In the above-mentioned modified zeolite, described natural zeolite and magnesian mass ratio are preferably (3～6): 1.
As a total technical conceive, the present invention also provides a kind of preparation method of above-mentioned modified zeolite, may further comprise the steps: take natural zeolite and magnesia as raw material, with described natural zeolite and magnesia according to (3～6): 1 mass ratio mixes, then heat temperature raising carries out constant temperature calcining to mixture, temperature during roasting is controlled at 100 ℃～600 ℃ (being preferably 150 ℃～400 ℃), and roasting time is controlled at 2h～6h, naturally obtains modified zeolite after the cooling.
As a total technical conceive, the present invention also provides a kind of application of above-mentioned modified zeolite, specifically described modified zeolite is used for the ammonia nitrogen removal preprocessing process of biological treatment breeding wastewater, and as the adsorbent that adsorbs high-strength ammonium nitrogen in the breeding wastewater.
In the above-mentioned application, addition when described modified zeolite is used as adsorbent is preferably every liter of breeding wastewater and adds 5g～60g (most preferably being 15g/L), the pH value of breeding wastewater preferably is controlled at 6.5～9.0 (most preferably being 7.0～8.0) in the described preprocessing process, ammonia nitrogen concentration in the breeding wastewater preferably is controlled at 600mg/L～1200mg/L, and temperature is controlled at 25 ℃～31 ℃ (most preferably being 27 ℃).
In the above-mentioned application, described stirring condition is preferably: first rotating speed rapid stirring 1min with 300r/min, and then with the rotating speed low rate mixing 10min of 130r/min, last quiet heavy 30min.
Compared with prior art, the invention has the advantages that: the present invention is directed to the deficiency of existing natural zeolite method of modifying, the heat modification method by the roasting supported magnesium oxide has prepared the modified zeolite that a kind of microstructure and composition are different from natural zeolite; In the whole preparation process, sintering temperature is relatively low, and roasting time and cycle are shorter, fully contacts in reaction tank through the modified zeolite after the modification and breeding wastewater and stirs to carry out the absorption of ammonia nitrogen.We adsorb the index of ammonia nitrogen ability as investigation modified zeolite of the present invention to the adsorption capacity of ammonia nitrogen with the unit mass modified zeolite, by detecting the ammonia nitrogen concentration after the initial ammonia nitrogen concentration of breeding wastewater and the adsorption equilibrium, we find that the zeolite after modification of the present invention can bring up to original 140%～200% to the equilibrium adsorption capacity of ammonia nitrogen.As seen, the performance of modified zeolite absorption ammonia nitrogen of the present invention is stronger, and the adsorption and sedimentation performance is good, and moisture percentage in sewage sludge is low, and is comparatively desirable to the Adsorption effect of high-strength ammonium nitrogen.
In addition, modified zeolite modification technology provided by the invention is simple to operate, can effectively in conjunction with traditional water treatment technology (as: SBR, UASB etc.), have good actual application value and industrialization prospect.
Description of drawings
Fig. 1 is the process chart of modified zeolite of the present invention when being applied to carry out a biological disposal upon breeding wastewater.
The specific embodiment
The invention will be further described below in conjunction with Figure of description and specific embodiment.
Embodiment: a kind of modified zeolite of the present invention and its preparation method and application.
A kind of modified zeolite of the present invention, it is to be mixed with magnesia by roasting, cooling by natural zeolite to prepare.
Preparation method's concrete operations of modified zeolite are as follows in the present embodiment: take natural zeolite and magnesia as raw material, natural zeolite and the magnesia mass ratio according to 4: 1 is mixed, then heat temperature raising carries out constant temperature calcining to mixture, change temperature control condition (value in 100 ℃～600 ℃ scopes) during roasting, roasting time is controlled at 4.5h (2h～6h all can), naturally obtains the modified zeolite under the different temperature control conditions after the cooling.
The modified zeolite that natural zeolite and the present embodiment are made is applied in the ammonia nitrogen removal preprocessing process of biological treatment breeding wastewater as shown in Figure 1, and as the adsorbent that adsorbs high-strength ammonium nitrogen in the breeding wastewater, simultaneously its performance of adsorbing ammonia nitrogen in breeding wastewater is investigated.
Take by weighing respectively 15g natural zeolite and etc. the modified zeolite of quality, be placed on respectively in the serial reaction pond of the breeding wastewater sample that the known ammonia nitrogen concentration of 1000mL (844mg/L) is housed, the pH value of breeding wastewater is 7.5, temperature is controlled at 27 ℃, then adopting mixing agitator to carry out stirring at normal temperature fully contacts it, stirring condition is: 300r/min rapid stirring 1min, then 130r/min low rate mixing 10min, at last quiet heavy 30min.Get supernatant, ammonia nitrogen concentration in the water outlet after the employing nessler reagent spectrophotometry adsorption equilibrium, the adsorbance Q that adopts following formula (1) to calculate zeolite (is that the unit mass modified zeolite is to the adsorption capacity of ammonia nitrogen, unit: mg/g), with judge with relatively using natural clinoptilolite and the control of different sintering temperatures under modified zeolite of the present invention to the absorption property of ammonia nitrogen.
In the formula (1):
C
0Be breeding wastewater sample ammonia nitrogen initial concentration (unit: mg/L);
C is the final concentration (unit: mg/L) of ammonia nitrogen in the water outlet after the adsorption equilibrium;
M is zeolite powder consumption (unit: g);
V is the volume (unit: mL) of breeding wastewater sample.
The comparing result of absorption property sees the following form 1 in the above-mentioned Application Example.
Table 1: the performance comparison table of zeolite powder absorption ammonia nitrogen
Can be found out by upper table 1, modified zeolite of the present invention all is better than using natural clinoptilolite to the absorption property of ammonia nitrogen, and wherein the modified zeolite under 150 ℃ of roasting conditions is best to the absorption property of ammonia nitrogen, and 150 ℃～400 ℃ is preferred sintering temperature scope.
Effectively in conjunction with traditional water treatment technology (aerobic SBR), make the final qualified discharge of breeding wastewater through above-mentioned pretreated breeding wastewater.
Claims (3)
1. the application of a modified zeolite is characterized in that, described modified zeolite is to be mixed with magnesia by roasting, cooling by natural zeolite to prepare; Its preparation specifically may further comprise the steps: take natural zeolite and magnesia as raw material, with described natural zeolite and magnesia according to (3～6): 1 mass ratio mixes, then heat temperature raising carries out constant temperature calcining to mixture, temperature during roasting is controlled at 100 ℃～600 ℃, roasting time is controlled at 2h～6h, naturally obtains modified zeolite after the cooling;
The ammonia nitrogen removal preprocessing process that described modified zeolite is used for the biological treatment breeding wastewater, and as the adsorbent that adsorbs high-strength ammonium nitrogen in the breeding wastewater;
Addition when described modified zeolite is used as adsorbent is that every liter of breeding wastewater adds 5g～60g, the pH value of breeding wastewater is controlled at 6.5～9.0 in the described preprocessing process, ammonia nitrogen concentration in the breeding wastewater is 600mg/L～1200mg/L, and temperature is controlled at 25 ℃～31 ℃;
Stirring condition in the described ammonia nitrogen removal preprocessing process is: first rotating speed rapid stirring 1min with 300r/min, and then with the rotating speed low rate mixing 10min of 130r/min, last quiet heavy 30min.
2. application according to claim 1 is characterized in that, the temperature during described roasting is controlled at 150 ℃～400 ℃.
3. application according to claim 1 and 2 is characterized in that, the addition when described modified zeolite is used as adsorbent is that every liter of breeding wastewater adds 15g, and the pH value of breeding wastewater is controlled at 7.0～8.0 in the described preprocessing process, and temperature is controlled at 27 ℃.
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| CN102527331B (en) * | 2012-01-09 | 2013-12-25 | 上海海洋大学 | Hydroxyapatite-modified zeolite composite material adsorbent, and preparation method and application thereof |
| CN102527330A (en) * | 2012-01-30 | 2012-07-04 | 中国地质大学（武汉） | Preparation method of modified clinoptilolite ion exchanger |
| CN102755913B (en) * | 2012-06-28 | 2014-07-23 | 燕山大学 | Method for improving ammonium exchange capacity of natural zeolite ammonium |
| CN103043742A (en) * | 2012-11-30 | 2013-04-17 | 姜英杰 | Environment-friendly and energy-saving ammonia nitrogen removal process |
| CN104645932B (en) * | 2015-01-30 | 2016-09-14 | 暨南大学 | A kind of composite modified zeolite of iron and manganese oxides and preparation method and application |
| CN105036470A (en) * | 2015-07-21 | 2015-11-11 | 常州大学 | Pig farm waste water and manure processing system |
| CN106362681A (en) * | 2016-09-29 | 2017-02-01 | 上海海洋大学 | Phosphorus adsorbent, and preparation method and application thereof |
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| CN108970586A (en) * | 2017-05-31 | 2018-12-11 | 南京博络金环保科技有限公司 | A method of utilizing low-concentration ammonia-nitrogen in biological adsorption removing water body |
| CN108752951A (en) * | 2018-06-01 | 2018-11-06 | 界首市静峰新型建材有限公司 | A kind of asphalt material preparation method with decomposing automobile exhaust function |
| CN109046238B (en) * | 2018-07-18 | 2021-06-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method and regeneration method of compound ammonia nitrogen adsorbent |
| CN108940190A (en) * | 2018-07-26 | 2018-12-07 | 中国大唐集团科学技术研究院有限公司西北分公司 | A kind of preparation method and applications of modified zeolite |
| CN111268758A (en) * | 2020-03-04 | 2020-06-12 | 安徽晋煤中能化工股份有限公司 | Treatment method of phenol wastewater |
| CN112777744A (en) * | 2021-01-14 | 2021-05-11 | 镇江市和云工业废水处置有限公司 | Industrial ammonia nitrogen organic wastewater treating agent and preparation method thereof |
| CN113443794B (en) * | 2021-08-11 | 2022-09-27 | 南通固润环保科技有限公司 | Landfill leachate treatment system |
| CN114950350A (en) * | 2022-06-28 | 2022-08-30 | 电子科技大学中山学院 | Low-concentration ammonia-nitrogen wastewater advanced treatment composite adsorption material and preparation method thereof |
| CN116605968B (en) * | 2023-06-08 | 2024-03-12 | 株洲稷维环境科技有限公司 | Treatment method of ammonia nitrogen in industrial wastewater |
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Address after: 410082 School of environmental science and engineering, Hunan University, Changsha, Hunan, Gansu Province, Patentee after: HUNAN University Patentee after: HUNAN HYSO ENVIRONMENT BIOTECHNOLOGY Co.,Ltd. Address before: 410082 School of environmental science and engineering, Hunan University, Changsha, Hunan, Gansu Province, Patentee before: HUNAN University Patentee before: HUNAN HYSO ENVIRONMENTAL BIOTECHNOLOGY Co.,Ltd. |
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