CN103977777B - The method of modifying of zeolite for sewage disposal - Google Patents
The method of modifying of zeolite for sewage disposal Download PDFInfo
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- CN103977777B CN103977777B CN201410198405.0A CN201410198405A CN103977777B CN 103977777 B CN103977777 B CN 103977777B CN 201410198405 A CN201410198405 A CN 201410198405A CN 103977777 B CN103977777 B CN 103977777B
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Abstract
The method of modifying of zeolite for sewage disposal, it comprises the following steps: 1), pulverize after, sorting; 2), react with hydrochloric acid solution, reaction finishes after washing dry; 3), with Nacl hybrid reaction, reaction finishes after washing dry; 4), with fishes and shrimps oxygenation agent mix and blend; 5), the filling finished product that is; Compared with prior art, it is simpler that the present invention has preparation process, and the zeolite activity after the lower and modification of production cost is feature relatively preferably.
Description
Technical field
The present invention relates to the method for modifying of a kind of sewage disposal zeolite.
Background technology
At present, although there are many methods can effectively remove ammonia nitrogen, as physical method has distillation, counter-infiltration, pulsed discharge etc.Gas ions technology, ultrasonic wave and soil irrigation etc.; Chemical method has ammonia stripping, chemical precipitation method, breakpoint chlorination, electrodialysis etc.;The selective exchange adsorption method of physical chemistry method, catalytic oxidation, electrochemical oxidation technology etc.; Biological method has biological nitration, solidSurely change biotechnology, algal culture etc., if but be applied to the removal of ammonia nitrogen in municipal sewage plant's secondary biochemical effluent, necessaryHave that application is convenient, the advantage such as waste water quality and price economy is stablized, is adapted to handling property.
Biochemical process is removed ammonia nitrogen and is required there is the required sufficient carbon source of growth of microorganism, but goes out at municipal sewage plant's secondary biochemicalIn water, COD concentration is lower, and select biochemical process to remove ammonia nitrogen just need additional carbon, and this makes the operating cost increase of technique,Add that microbial acclimation time and start-up cycle are longer; In physical-chemical process, adopt break point chlorination method except chlorine dosage andOutside chlorine bad control time of contact, because chlorine dosage is larger, cause the concentration of DBPs in water to increase, thereby increasedThe risk of " three cause "; Chemical precipitation method need to be adjusted the pH of sewage, and alkali consumption is huge, and has a large amount of precipitations, makes follow-up workAmount increases greatly; And artificial swamp method floor space is large, and in real work, be infeasible as the treatment process increasing;In exchange adsorption method, widely distributed as the natural zeolite of ion-exchanger, cheap, and also equipment is simple, operation fortuneAccommodating, therefore at present major part is all to adopt zeolite to process, zeolite needs modification, the natural zeolite after modification not only to ammonia fromSon has higher selective and ion-exchange capacity, and fast than natural zeolite of its resolution speed.
Prior art is carried out natural zeolite the method for modification, and if publication number is CN102527330, name is called modified clinoptiloliteThe preparation method of ion-exchanger; Publication number is CN101716489, and it is anti-that name is called a kind of denitrogenation dephosphorizing for reused water processingThe compound material for water treatment of bacterium, the disclosed natural zeolite method of modifying of above-mentioned these two open files, modifying process is more loaded down with trivial details, producesCost is higher, and zeolite activity after modification is relatively poor.
Summary of the invention
The present invention is directed to above problem provides a kind of preparation process simpler, and the zeolite activity after the lower and modification of production cost is relativeThe method of modifying of zeolite for sewage disposal preferably.
The present invention overcomes the above problems technical scheme used: the method for modifying of a kind of sewage disposal zeolite is provided, and it comprisesFollowing steps:
1), dry natural zeolite is pulverized after, sorting, the standard of sorting is for being more than or equal to 200 orders;
2), by step 1) zeolite is put into hydrochloric acid solution after sorting, the reaction time is 0.5～1.5 hour, the concentration of hydrochloric acid solutionBe 8 ‰～12 ‰, reaction finishes after washing dry;
3), by step 2) process after zeolite and Nacl hybrid reaction, the reaction time is 20～40 minutes, reaction temperature is1500～1800 DEG C, the ratio of Nacl and zeolite is 0.8～1.5: 1, and reaction finishes after washing dry;
4), by step 3) zeolite after treatment and fishes and shrimps oxygenation agent mix and blend, stir the adding of fishes and shrimps oxygenation agent 2～20 minutesEntering amount is 20%～60% of zeolite weight;
5), step 4) the rear filling finished product that is of processing.
Adopt after above method, compared with prior art, the present invention first adopts hydrochloric acid pretreatment, and after activating by Nacl,Mix with fishes and shrimps oxygenation agent, whole process operation is simpler again, and hydrochloric acid, Nacl and fishes and shrimps oxygenation agent are the large of commercially available routineThe product of amount application, cost is lower, and the zeolite after modification has higher selective and ion-exchange capacity to ammonia nitrogen like this,To the ammonia nitrogen removal better effects if (ammonia nitrogen removal frank is high) in waste water, can remove the ammonia nitrogen of trace in water body, make ammonia nitrogenThe Natural Water exceeding standard reaches the standard of national drinking water, and can also remove removing fluorine in water and arsenic; Zeolite after modification simultaneouslyValue changes, and can remove chlorine residue, manganese and iron in hand, and the heavy metal of excess; The municipal sewage after two stage treatment is through modificationZeolite filler after, can effectively reduce the content of nitrogen phosphorus and heavy metal; Moreover zeolite after modification and active carbon be while being used in combination,Active carbon can make up zeolite to removing the lower defect of organic matter ability, can effectively remove organic molecule and nothing in water bodyMachine thing ion, filter effect is better. Therefore to have preparation process simpler in the present invention, the zeolite after the lower and modification of production costActivity is feature relatively preferably.
As preferably, described step 2) in reaction time be 1 hour, the concentration of hydrochloric acid solution is 10 ‰.
As preferably, described step 3) in reaction time be 30 minutes, reaction temperature is 1600 DEG C, Nacl and zeoliteRatio be 0.8～1.2: 1.
As preferably, described step 4) in mixing time be 2～8 minutes, fishes and shrimps oxygenation agent addition is 40%～60%.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
A method of modifying for zeolite for sewage disposal, it comprises the following steps:
1), dry natural zeolite is pulverized after, sorting, the standard of sorting is for being more than or equal to 200 orders;
2), by step 1) zeolite is put into hydrochloric acid solution after sorting, the reaction time is 1.5 hours, the concentration of hydrochloric acid solution is 8‰, reaction finishes after washing dry;
3), by step 2) process after zeolite and Nacl hybrid reaction, the reaction time is 40 minutes, reaction temperature is 1500 DEG C,The ratio of Nacl and zeolite is 0.8: 1, and reaction finishes after washing dry;
4), by step 3) zeolite after treatment and fishes and shrimps oxygenation agent mix and blend, stir the adding of fishes and shrimps oxygenation agent 20 minutesAmount is 20% of zeolite weight;
5), step 4) the rear filling finished product that is of processing.
Embodiment 2
A method of modifying for zeolite for sewage disposal, it comprises the following steps:
1), dry natural zeolite is pulverized after, sorting, the standard of sorting is for being more than or equal to 200 orders;
2), by step 1) zeolite is put into hydrochloric acid solution after sorting, the reaction time is 0.5 hour, the concentration of hydrochloric acid solution is 12‰, reaction finishes after washing dry;
3), by step 2) process after zeolite and Nacl hybrid reaction, the reaction time is 20 minutes, reaction temperature is 1800 DEG C,The ratio of Nacl and zeolite is 1.5: 1, and reaction finishes after washing dry;
4), by step 3) zeolite after treatment and fishes and shrimps oxygenation agent mix and blend, stir the addition of fishes and shrimps oxygenation agent 2 minutesFor 60% of zeolite weight;
5), step 4) the rear filling finished product that is of processing.
Embodiment 3
A method of modifying for zeolite for sewage disposal, it comprises the following steps:
1), dry natural zeolite is pulverized after, sorting, the standard of sorting is for being more than or equal to 200 orders;
2), by step 1) zeolite is put into hydrochloric acid solution after sorting, the reaction time is 1 hour, the concentration of hydrochloric acid solution is 10‰, reaction finishes after washing dry;
3), by step 2) process after zeolite and Nacl hybrid reaction, the reaction time is 30 minutes, reaction temperature is 1600 DEG C,The ratio of Nacl and zeolite is 1: 1, and reaction finishes after washing dry;
4), by step 3) zeolite after treatment and fishes and shrimps oxygenation agent mix and blend, stir the addition of fishes and shrimps oxygenation agent 5 minutesFor 50% of zeolite weight;
5), step 4) the rear filling finished product that is of processing.
Embodiment 4
A method of modifying for zeolite for sewage disposal, it comprises the following steps:
1), dry natural zeolite is pulverized after, sorting, the standard of sorting is for being more than or equal to 200 orders;
2), by step 1) zeolite is put into hydrochloric acid solution after sorting, the reaction time is 1 hour, the concentration of hydrochloric acid solution is 11‰, reaction finishes after washing dry;
3), by step 2) process after zeolite and Nacl hybrid reaction, the reaction time is 35 minutes, reaction temperature is 1650 DEG C,The ratio of Nacl and zeolite is 1.2: 1, and reaction finishes after washing dry;
4), by step 3) zeolite after treatment and fishes and shrimps oxygenation agent mix and blend, stir the addition of fishes and shrimps oxygenation agent 8 minutesFor 40% of zeolite weight;
5), step 4) the rear filling finished product that is of processing.
Embodiment 5
A method of modifying for zeolite for sewage disposal, it comprises the following steps:
1), dry natural zeolite is pulverized after, sorting, the standard of sorting is for being more than or equal to 200 orders;
2), by step 1) zeolite is put into hydrochloric acid solution after sorting, the reaction time is 1.2 hours, the concentration of hydrochloric acid solution is 9‰, reaction finishes after washing dry;
3), by step 2) process after zeolite and Nacl hybrid reaction, the reaction time is 25 minutes, reaction temperature is 1700 DEG C,The ratio of Nacl and zeolite is 0.9: 1, and reaction finishes after washing dry;
4), by step 3) zeolite after treatment and fishes and shrimps oxygenation agent mix and blend, stir the adding of fishes and shrimps oxygenation agent 10 minutesAmount is 50% of zeolite weight;
5), step 4) the rear filling finished product that is of processing.
While washing in above-described embodiment, the water of employing is pure water or deionized water; The equipment adopting is commercially available conventional equipment;The composition adding is also commercially available conventional commodity.
Above embodiment is only preferred embodiment of the present invention, and the present invention is not limited only to above embodiment and has also allowed other to change, allIn rights to independence claimed range of the present invention, change, all belong to protection domain of the present invention.
Claims (3)
1. a method of modifying for zeolite for sewage disposal, is characterized in that: it comprises the following steps:
1), dry natural zeolite is pulverized after, sorting, the standard of sorting is for being more than or equal to 200 orders;
2), by step 1) zeolite is put into hydrochloric acid solution after sorting, the reaction time is 0.5～1.5 hour, the concentration of hydrochloric acid solutionBe 8 ‰～12 ‰, reaction finishes after washing dry;
3), by step 2) process after zeolite and Nacl hybrid reaction, the reaction time is 20～40 minutes, reaction temperature is1500～1800 DEG C, the ratio of Nacl and zeolite is 0.8～1.5: 1, and reaction finishes after washing dry;
4), by step 3) zeolite after treatment and fishes and shrimps oxygenation agent mix and blend, stir the adding of fishes and shrimps oxygenation agent 2～8 minutesAmount is 40%～60% of zeolite weight;
5), step 4) the rear filling finished product that is of processing.
2. the method for modifying of zeolite for sewage disposal according to claim 1, is characterized in that: described step 2) in anti-Between seasonable, be 1 hour, the concentration of hydrochloric acid solution is 10 ‰.
3. the method for modifying of zeolite for sewage disposal according to claim 1, is characterized in that: described step 3) in anti-Between seasonable, be 30 minutes, reaction temperature is 1600 DEG C, and the ratio of Nacl and zeolite is 0.8～1.2: 1.
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| CN86100413A (en) * | 1986-02-01 | 1987-09-30 | 浙江省丽水地区工业科学研究所 | A kind of zeolite detergent auxiliary agent preparation technology |
| CN102641744B (en) * | 2011-02-16 | 2014-07-09 | 中国环境科学研究院 | Catalytic oxidation active medium for removing nitrobenzene pollutant |
| CN102423684B (en) * | 2011-10-28 | 2015-08-12 | 广西博世科环保科技股份有限公司 | A kind of modified zeolite ammonia nitrogen adsorbent and use thereof and renovation process |
| CN102583827B (en) * | 2012-03-01 | 2013-07-24 | 中国环境科学研究院 | Repairing system for double-layer permeable reaction wall, preparation method and application |
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