CN102963943A - Method for treating nitrobenzene wastewater by natural pyrrhotite - Google Patents
Method for treating nitrobenzene wastewater by natural pyrrhotite Download PDFInfo
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- CN102963943A CN102963943A CN2012105587319A CN201210558731A CN102963943A CN 102963943 A CN102963943 A CN 102963943A CN 2012105587319 A CN2012105587319 A CN 2012105587319A CN 201210558731 A CN201210558731 A CN 201210558731A CN 102963943 A CN102963943 A CN 102963943A
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- pyrrhotite
- nitrobenzene
- waste water
- wastewater
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Abstract
The invention discloses a method for treating nitrobenzene wastewater by natural pyrrhotite, which belongs to the field of wastewater treatment. The method comprises the steps of: (1) smashing natural pyrrhotite to granularity of 50-200 meshes and washing pyrrhotite by water or acid to expose fresh surfaces for later use; (2) adjusting pH value of nitrobenzene wastewater to 3-10; (3) mixing the natural pyrrhotite treated in the step (1) with nitrobenzene wastewater obtained in the step (2) in a reactor, wherein the mass concentration of pyrrhotite mixed is not smaller than 50g/L; and (4) sealing the reactor in the step (3) and placing the reactor on a vertical spiral turntable for mixed reaction for no less than 48 hours, and discharging treated wastewater. According to the method for treating nitrobenzene wastewater by natural pyrrhotite provided by the invention, cheap natural pyrrhotite is used to pre-treat nitrobenzene wastewater, the adaptability to pH of inflow is strong, and the removing rate of nitrobenzene wastewater can reach 90% above. The operation is simple, the requirement on the device is low, and the treatment cost can be greatly reduced.
Description
Technical field
The invention belongs to technical field of sewage, specifically, relate to a kind of method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water.
Background technology
Nitrobenzene compounds is serious environment pollution and the objectionable impurities that is detrimental to health, its BOD
5/ COD
CrRatio is lower, and biodegradability is poor, and waste water treatment is difficulty comparatively.If by physico-chemical processes with oil of mirbane change into toxicity little, should biodegradable aniline, again by biological process with its permineralization, can make discharged wastewater met the national standard.Physical causes secondary pollution and processing costs higher easily, and its widespread use is restricted.The chemical methods that adopt carry out pre-treatment to high density nitrobenzene-containing waste water more in the practical application, to reduce the impact load to biochemistry pool.
Since the proposition Zero-valent Iron Reduction of Aromatic Nitro Compounds technology such as Agrawal in 1996, Chinese scholars has been made large quantity research.But they focus mostly in the reparation of the higher ionogen iron of purity to groundwater pollution.Because the cost of ionogen iron is relatively high, therefore seeking the effective equivalent material of a kind of cheapness has important practical significance.The iron filings internal electrolysis has the advantages such as cost of material is cheap, wide material sources, successful, paid attention to by people, but the enforcement of this technology also is subject to the challenge of the following aspects: a large amount of aerations of the method do not take full advantage of the reducing power of fe; The consumption of iron is large, and iron filings are easy to harden after reaction for some time, thereby have reduced treatment effect; Be only applicable to the low waste water of pH, in and waste water need a large amount of soda acids.
Chinese patent application number: 2012100953696, open day: on 07 25th, 2012, disclose a the applicant and be called a kind of patent application document that utilizes the method for Iron sulfuret pre-treatment nitrobenzene-containing waste water in the name of application on 04 01st, 2012, this patent disclosure the employing Iron sulfuret carry out the pretreated method of nitrobenzene waste water.The steps include: that (1) is crushed to granularity with Iron sulfuret is the 50-60 order, and it is stand-by to expose the Iron sulfuret unsalted surface by washing or pickling; (2) Iron sulfuret after will processing joins in the reaction vessel; (3) nitrobenzene waste water is joined in the above-mentioned reaction vessel, wherein the ratio of Iron sulfuret and the mass concentration of oil of mirbane is not less than 30:1 in the reaction vessel, and the mass concentration of Iron sulfuret is not less than 3.6 g/L; (4) reaction vessel is placed anaerobism or anaerobic environment, Iron sulfuret is mixed with nitrobenzene waste water, behind hybrid reaction 60 ~ 180 min, finish the pre-treatment of nitrobenzene waste water.This patent provides the novel method of utilizing synthetic Iron sulfuret treatment of Nitrobenzene.But used Iron sulfuret is chemical products, and cost is higher.Using method is intermittently batch use, uses and is limited to, and pH is had relatively high expectations when using.And the pH value fluctuation ratio of general nitrobenzene waste water is larger, uses so this method is not suitable for big area.Therefore need to seek the method for the larger nitrobenzene waste water of the low and treatable pH value of a kind of cost fluctuation ratio.
In fact, FeS is on earth with pyrrhotite (Fe
(1-x)S, x is between 0～0.1) form exist, it is natural mineral widely distributed, cheap and easy to get on the earth.Natural pyrrhotite main component is Iron sulfuret, and still wherein the ratio of iron and sulphur is usually less than 1:1, and compositing range is Fe
7S
8～Fe
11S
12, its structure is the NiA from standard
5The lattice development has multiple crystalline form, wherein iron atom Fe the most in debt
7S
8Have the oblique crystal symmetry, some other intermediateness product and FeS then have respectively hexagonal crystal and square crystal structure.The pyrrhotite of occurring in nature usually is the mixture of oblique crystal and hexagonal crystal, and its chemical property is owing to exist the iron deficit and complicated in the crystalline structure, and the deficit of iron causes lower crystal symmetry in the crystalline structure, thereby has strengthened its reactivity.In addition, also there are some unvulcanised ferrous components such as ferric iron in the natural pyrrhotite, can promote the formation of iron content active compound in natural pyrrhotite and the oil of mirbane reaction process.Exactly because the crystalline structure of this uniqueness of natural pyrrhotite with become to be grouped into so that it has stronger response capacity than Iron sulfuret in wider pH scope, can react with oil of mirbane.Discarded pyrrhotite moistening and with the situation of contact with air under can be spontaneous oxidation, produce acid wastewater in mine, to the water surrounding harm in mine.Utilize the characteristic reduction nitrobenzene compounds of pyrrhotite not only can reduce it to the harm of mine environment, the method for the pre-treatment nitrobenzene wastewater of a cheapness also is provided simultaneously.Utilize at present research and the application of natural pyrrhotite reduction nitrobenzene class pollutant to have no bibliographical information and patent disclosure.
Summary of the invention
The problem that solves
Processing cost for prior art treatment of Nitrobenzene class waste water is high, the problem of pH narrow application range, the invention provides a kind of method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water, is a kind of method of pre-treatment nitrobenzene-containing waste water simply effective, with low cost.
Technical scheme
In order to address the above problem, the technical solution adopted in the present invention is as follows:
A kind of method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water the steps include:
(1) natural pyrrhotite being crushed to granularity is the 50-200 order, and it is stand-by to expose the pyrrhotite unsalted surface by washing or pickling;
(2) the pH value of adjusting nitrobenzene wastewater is 3-10, if the pH value of nitrobenzene wastewater then need not regulated between 3-10; The too low dissolving that will accelerate natural pyrrhotite of the pH value of nitrobenzene wastewater, the too high oxides-containing iron that will form at Surface of Pyrrhotite similar patina of pH value, all be difficult to form the surface bonding iron system with reduction characteristic, realize the reduction of p-nitrophenyl compounds;
(3) nitrobenzene wastewater that obtains in the natural pyrrhotite after step (1) is processed and the step (2) mixes in a reactor; The mass concentration of pyrrhotite is not less than 50 g/L after mixing;
(4) reaction vessel in the step (3) sealing is placed on hybrid reaction is no less than 48 h on the vertical rotating rotating disk, the waste water after the processing is discharged.
Preferably, the natural pyrrhotite in the described step (1), granularity is the 60-80 order.Granularity is more little more to be conducive to the carrying out that react, but too little meeting causes the dissolving of natural pyrrhotite too fast, and reaction process is not easy control.So consider, the granularity of natural pyrrhotite should be controlled to be the 50-200 order, and effect is better when granularity is the 60-80 order, and reaction process is controlled easily.
Preferably, in the described step (2) the pH value of nitrobenzene wastewater is adjusted to 7.
Preferably, in the described step (4) during hybrid reaction temperature be 15-60 ℃.The transformation efficiency of nitrobenzene compounds raises along with the rising of temperature of reaction, and the too low nitrobenzene compounds clearance of temperature is lower, is difficult to apply, although higher temperature may obtain faster processing speed, processing cost also increases.
Preferably, the rotating speed of vertical rotary turnplate is 10-60 r/min in the described step (4).
Preferably, the temperature of reaction of hybrid reaction is 27 ℃ in the described step (4).On treatment effect and cost, temperature of reaction be 27 ℃ the most reasonable.
Beneficial effect
Adopt technical scheme provided by the invention, compare with existing known technology, have following notable feature: a kind of method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water of the present invention, adopt cheap natural pyrrhotite pre-treatment nitrobenzene wastewater, strong adaptability to water inlet pH, the nitrobenzene compound clearance can reach more than 90%, and is simple to operate, low for equipment requirements, adopt natural pyrrhotite, the pyrrhotite source is wide, cheap, can greatly reduce processing costs.
Embodiment
Describe the present invention below in conjunction with specific embodiment.
Embodiment 1
For the processing of nitrobenzene waste water, nitrobenzene waste water is prepared by oil of mirbane and distilled water, water sample pH=6.56, and initial nitro phenenyl concentration is 20 mg/L.Its treatment step is:
(1) natural pyrrhotite being crushed to granularity is the 50-60 order, and it is stand-by to expose the pyrrhotite unsalted surface by washing or pickling;
(2) the natural pyrrhotite after step (1) processing being taken by weighing 10 g mixes in a reactor with nitrobenzene wastewater; The mass concentration of pyrrhotite is 50 g/L after mixing;
(3) sealing of the reaction vessel in the step (2) is placed on hybrid reaction 3 d on the vertical rotating rotating disk, the rotating speed of vertical rotating rotating disk is 40 r/min, and the temperature of reaction of hybrid reaction is 27 ℃, and the waste water after the processing is discharged.
The Nitrobenzene in Wastewater concentration of discharging after the reaction is reduced to 2 mg/L, and the oil of mirbane clearance is 90%.
Embodiment 2
Processing for wastewater from dinitrobenzene, dinitrobenzene waste water is by 1,3-dinitrobenzene and distilled water preparation, water sample pH=6.75, initial 1,3-dinitrobenzene concentration is 102 mg/L, and its treatment process is with embodiment 1, and difference is: the granularity of natural pyrrhotite is the 60-80 order, natural pyrrhotite mass concentration was 55 g/L after natural pyrrhotite mixed with dinitrobenzene waste water, the rotating speed of vertical rotating rotating disk is 60 r/min, and the temperature of reaction of hybrid reaction is 15 ℃, and the reaction times is 2 d.
In the waste water after the processing 1,3-dinitrobenzene concentration is reduced to 10.5mg/L, and 1,3-dinitrobenzene clearance is 90%.
Embodiment 3
For the processing of nitro-chlorobenzene waste water, nitro-chlorobenzene waste water is prepared by nitro-chlorobenzene and distilled water, water sample pH=7.0, and initial nitro-chlorobenzene concentration is 96 mg/L.Treatment step is with embodiment 1, difference is, the granularity of natural pyrrhotite is the 150-200 order, natural pyrrhotite mass concentration was 60 g/L after natural pyrrhotite mixed with dinitrobenzene waste water, the rotating speed of vertical rotating rotating disk is 10 r/min, the temperature of reaction of hybrid reaction is 60 ℃, and the reaction times is 2 d.
Nitro-chlorobenzene concentration is reduced to 1.9 mg/L in the waste water after the processing, and the nitro-chlorobenzene clearance is 98%.
Embodiment 4
For the processing of methyl nitrobenzene waste water, nitrotoluene class wastewater source is in Nanjing factory, water sample pH=2.0, and initial nitrotoluene concentration is 25 mg/L.Its treatment step is:
(1) natural pyrrhotite being crushed to granularity is the 70-90 order, and it is stand-by to expose the pyrrhotite unsalted surface by washing or pickling;
(2) the pH value of adjusting nitrotoluene class waste water is 3;
(3) the nitrotoluene class waste water that obtains in the natural pyrrhotite after step (1) is processed and the step (2) mixes in a reactor; The mass concentration of pyrrhotite is 51 g/L after mixing;
(4) reaction vessel in the step (3) sealing being placed at rotating speed is hybrid reaction 8 d on the vertical rotating rotating disk of 40 r/min, and temperature of reaction is controlled between 20-30 ℃, and the waste water after the processing is discharged.The Nitrobenzene in Wastewater concentration of discharging is reduced to 2.1 mg/L, and the nitrotoluene clearance is 92%.
Embodiment 5
For the processing of nitro-chlorobenzene waste water, the nitro-chlorobenzene wastewater source is in Suzhou factory, water sample pH=11, and initial nitro-chlorobenzene is 35 mg/L.Its treatment step is with embodiment 4, and difference is: the pH value that step (2) is regulated nitro-chlorobenzene waste water is 10; In the step (4) reaction vessel in the step (3) sealing being placed at rotating speed is hybrid reaction 4 d on the vertical rotating rotating disk of 50 r/min, and temperature of reaction is controlled between 30-35 ℃, and the waste water after the processing is discharged.Nitro-chlorobenzene concentration is reduced to 2.5 mg/L in the waste water of getting rid of, and the nitrotoluene clearance is 93%.
Claims (6)
1. a method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water the steps include:
(1) natural pyrrhotite being crushed to granularity is the 50-200 order, and it is stand-by to expose the pyrrhotite unsalted surface by washing or pickling;
(2) the pH value of adjusting nitrobenzene wastewater is 3-10, if the pH value of nitrobenzene wastewater then need not regulated between 3-10;
(3) nitrobenzene wastewater that obtains in the natural pyrrhotite after step (1) is processed and the step (2) mixes in a reactor; The mass concentration of pyrrhotite is not less than 50 g/L after mixing;
(4) reaction vessel in the step (3) sealing is placed on hybrid reaction is no less than 48 h on the vertical rotating rotating disk, the waste water after the processing is discharged.
2. require 1 described a kind of method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water according to letter of authorization, it is characterized in that, the natural pyrrhotite in the described step (1), granularity is the 60-80 order.
3. require 1 described a kind of method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water according to letter of authorization, it is characterized in that the pH value with nitrobenzene wastewater in the described step (2) is adjusted to 7.
4. require 1 described a kind of method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water according to letter of authorization, it is characterized in that, temperature is 15-60 ℃ during the middle hybrid reaction of described step (4).
5. require 1 or 4 described a kind of methods of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water according to letter of authorization, it is characterized in that the rotating speed of vertical rotary turnplate is 10-60 r/min in the described step (4).
6. require 4 described a kind of methods of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water according to letter of authorization, it is characterized in that, the temperature of reaction of hybrid reaction is 27 ℃ in the described step (4).
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| CN201210558731.9A CN102963943B (en) | 2012-12-21 | 2012-12-21 | Method for treating nitrobenzene wastewater by natural pyrrhotite |
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|---|---|---|---|
| CN201210558731.9A CN102963943B (en) | 2012-12-21 | 2012-12-21 | Method for treating nitrobenzene wastewater by natural pyrrhotite |
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| CN102963943A true CN102963943A (en) | 2013-03-13 |
| CN102963943B CN102963943B (en) | 2014-07-30 |
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| CN201210558731.9A Expired - Fee Related CN102963943B (en) | 2012-12-21 | 2012-12-21 | Method for treating nitrobenzene wastewater by natural pyrrhotite |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109052641A (en) * | 2018-09-05 | 2018-12-21 | 南京大学 | A kind of coupling filler autotrophic denitrification biofilter and application |
| CN109133190A (en) * | 2018-08-03 | 2019-01-04 | 武钢资源集团有限公司 | The processing method of magnetic iron ore |
| CN115417483A (en) * | 2022-09-16 | 2022-12-02 | 中国地质大学（武汉） | Method for treating sulfide ore mine wastewater by using pyrite |
Citations (4)
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|---|---|---|---|---|
| EP0503387A1 (en) * | 1991-03-13 | 1992-09-16 | BASF Aktiengesellschaft | Process for decomposition of aromatic nitro compounds contained in waste water |
| CN1170776C (en) * | 1998-04-08 | 2004-10-13 | Basf公司 | Breaking down aromatic nitro compounds in wastewaters |
| CN100425550C (en) * | 2003-07-11 | 2008-10-15 | 斯图加特大学 | Method for the biological breakdown of effluent containing nitroaromatics |
| CN102603050A (en) * | 2012-04-01 | 2012-07-25 | 南京大学 | Method for preprocessing nitrobenzene-contained waste water by ferrous sulfide |
-
2012
- 2012-12-21 CN CN201210558731.9A patent/CN102963943B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0503387A1 (en) * | 1991-03-13 | 1992-09-16 | BASF Aktiengesellschaft | Process for decomposition of aromatic nitro compounds contained in waste water |
| CN1170776C (en) * | 1998-04-08 | 2004-10-13 | Basf公司 | Breaking down aromatic nitro compounds in wastewaters |
| CN100425550C (en) * | 2003-07-11 | 2008-10-15 | 斯图加特大学 | Method for the biological breakdown of effluent containing nitroaromatics |
| CN102603050A (en) * | 2012-04-01 | 2012-07-25 | 南京大学 | Method for preprocessing nitrobenzene-contained waste water by ferrous sulfide |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133190A (en) * | 2018-08-03 | 2019-01-04 | 武钢资源集团有限公司 | The processing method of magnetic iron ore |
| CN109133190B (en) * | 2018-08-03 | 2020-12-29 | 武钢资源集团大冶铁矿有限公司 | Processing method of pyrrhotite |
| CN109052641A (en) * | 2018-09-05 | 2018-12-21 | 南京大学 | A kind of coupling filler autotrophic denitrification biofilter and application |
| CN115417483A (en) * | 2022-09-16 | 2022-12-02 | 中国地质大学（武汉） | Method for treating sulfide ore mine wastewater by using pyrite |
| CN115417483B (en) * | 2022-09-16 | 2024-04-02 | 中国地质大学（武汉） | Method for treating sulfide ore mine wastewater by using pyrite |
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| CN102963943B (en) | 2014-07-30 |
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