CN102963943B - Method for treating nitrobenzene wastewater by natural pyrrhotite - Google Patents

Method for treating nitrobenzene wastewater by natural pyrrhotite Download PDF

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Publication number
CN102963943B
CN102963943B CN201210558731.9A CN201210558731A CN102963943B CN 102963943 B CN102963943 B CN 102963943B CN 201210558731 A CN201210558731 A CN 201210558731A CN 102963943 B CN102963943 B CN 102963943B
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pyrrhotite
nitrobenzene
treatment
wastewater
waste water
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CN102963943A (en
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李睿华
李�杰
张菁
孙茜茜
胡俊松
李爱民
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Nanjing University
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Nanjing University
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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

A kind of method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water
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 being 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 by oil of mirbane change into toxicity little, should biodegradable aniline, then by biological process by its permineralization, can make discharged wastewater met the national standard.Physical easily cause secondary pollution and processing costs higher, its widespread use is restricted.In practical application, the chemical methods that adopt carry out pre-treatment to high density nitrobenzene-containing waste water more, to reduce the impact load to biochemistry pool.
Since Agrawal in 1996 etc. propose Zero-valent Iron Reduction of Aromatic Nitro Compounds technology, Chinese scholars has been made large quantity research.The reparation to groundwater pollution in the higher ionogen iron of purity but they focus mostly on.Because the cost of ionogen iron is relatively high, therefore find the effective equivalent material of a kind of cheapness and there is important practical significance.Iron filings internal electrolysis has the advantages such as cost of material is cheap, wide material sources, successful, and by people are paid attention to, but the enforcement of this technology is also subject to the challenge of the following aspects: a large amount of aerations of the method, do not make full use of the reducing power of fe; The consumption of iron is large, and after reaction for some time, iron filings are easy to harden, thereby have reduced treatment effect; Be only applicable to the waste water that pH is low, in and waste water need a large amount of soda acid.
Chinese Patent Application No.: 2012100953696, open day: on 07 25th, 2012, disclose a the applicant is called a kind of method of utilizing Iron sulfuret pre-treatment nitrobenzene-containing waste water patent application document in the name of application on 04 01st, 2012, this patent discloses employing Iron sulfuret and has carried out the pretreated method of nitrobenzene waste water.The steps include: that it is 50-60 order that Iron sulfuret is crushed to granularity by (1), and it is stand-by to expose Iron sulfuret unsalted surface by washing or pickling; (2) Iron sulfuret after treatment is joined in reaction vessel; (3) nitrobenzene waste water is joined in above-mentioned reaction vessel, wherein in reaction vessel, Iron sulfuret is not less than 30:1 with the ratio of the mass concentration of oil of mirbane, and the mass concentration of Iron sulfuret is not less than 3.6 g/L; (4) reaction vessel is placed in to anaerobism or anaerobic environment, Iron sulfuret is mixed with nitrobenzene waste water, after hybrid reaction 60 ~ 180 min, complete the pre-treatment of nitrobenzene waste water.This patent provides the novel method of utilizing synthetic Iron sulfuret treatment of Nitrobenzene.But Iron sulfuret used 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 while using.And the pH value fluctuation ratio of general nitrobenzene waste water is larger, so being not suitable for big area, this method uses.Therefore need to find the method for the low and nitrobenzene waste water that treatable pH value fluctuation ratio is larger of a kind of cost.
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 5lattice development, has multiple crystalline form, wherein iron atom Fe the most in debt 7s 8have oblique crystal symmetry, some other intermediateness product and FeS have respectively hexagonal crystal and square crystal structure.The pyrrhotite of occurring in nature is usually the mixture of oblique crystal and hexagonal crystal, and owing to existing in crystalline structure, iron is in debt becomes complicated to its chemical property, and in crystalline structure, the deficit of iron causes lower crystal symmetry, thereby has strengthened its reactivity.In addition, in natural pyrrhotite, also there are some unvulcanised ferrous components such as ferric iron, can promote the formation of iron content active compound in natural pyrrhotite and oil of mirbane reaction process.Exactly because the crystalline structure of this uniqueness of natural pyrrhotite with become to be grouped into make it within the scope of wider pH, to there is stronger response capacity than Iron sulfuret, can react with oil of mirbane.Discarded pyrrhotite, in moistening oxidation that can be spontaneous with contact with air in the situation that, produces acid wastewater in mine, and the water surrounding in mine is caused to serious harm.Utilize the characteristic reduction nitrobenzene compounds of pyrrhotite not only can reduce its harm to mine environment, the method for a cheap pre-treatment nitrobenzene wastewater is also provided simultaneously.Utilize at present the research of natural pyrrhotite reduction nitrobenzene class pollutant and application has no bibliographical information and patent is open.
Summary of the invention
the problem solving
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 method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water, the steps include:
(1) natural pyrrhotite being crushed to granularity is 50-200 order, and it is stand-by to expose pyrrhotite unsalted surface by washing or pickling;
(2) regulating the pH value of nitrobenzene wastewater is 3-10, if the pH value of nitrobenzene wastewater between 3-10, does not need to regulate; The too low dissolving that will accelerate natural pyrrhotite of 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) natural pyrrhotite after treatment step (1) is mixed in a reactor with the nitrobenzene wastewater obtaining in step (2); After mixing, the mass concentration of pyrrhotite is not less than 50 g/L;
(4) the reaction vessel sealing in step (3) is placed on to hybrid reaction on vertical rotating rotating disk and is no less than 48 h, waste water after treatment is discharged.
Preferably, the natural pyrrhotite in described step (1), granularity is 60-80 order.More little the carrying out that is more conducive to reaction of granularity, but too little meeting causes the dissolving of natural pyrrhotite too fast, and reaction process is not easy to control.So consider, the granularity of natural pyrrhotite should be controlled the order into 50-200, and effect is better in the time that granularity is 60-80 order, and reaction process is easily controlled.
Preferably, in described step (2), the pH value of nitrobenzene wastewater is adjusted to 7.
Preferably, temperature is 15-60 DEG C when hybrid reaction in described step (4).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 processing speed faster, processing cost also increases.
Preferably, in described step (4), the rotating speed of vertical rotary turnplate is 10-60 r/min.
Preferably, in described step (4), the temperature of reaction of hybrid reaction is 27 DEG C.From treatment effect and cost, temperature of reaction be 27 DEG C the most reasonable.
beneficial effect
Adopt technical scheme provided by the invention, compared with existing known technology, there is following notable feature: a kind of method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water of the present invention, adopts cheap natural pyrrhotite pre-treatment nitrobenzene wastewater, to the strong adaptability of water inlet pH, nitrobenzene compound clearance can reach more than 90%, simple to operate, low for equipment requirements, adopt natural pyrrhotite, 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 50-60 order, and it is stand-by to expose pyrrhotite unsalted surface by washing or pickling;
(2) natural pyrrhotite after treatment step (1) being taken to 10 g mixes in a reactor with nitrobenzene wastewater; After mixing, the mass concentration of pyrrhotite is 50 g/L;
(3) the reaction vessel sealing in step (2) is placed on to hybrid reaction 3 d on 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 DEG C, and waste water after treatment is discharged.
The Nitrobenzene in Wastewater concentration of discharging after reaction is reduced to 2 mg/L, and oil of mirbane clearance is 90%.
embodiment 2
For the processing of 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 60-80 order, after natural pyrrhotite mixes with dinitrobenzene waste water, natural pyrrhotite mass concentration is 55 g/L, the rotating speed of vertical rotating rotating disk is 60 r/min, and the temperature of reaction of hybrid reaction is 15 DEG C, and the reaction times is 2 d.
In waste water after treatment 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 150-200 order, after natural pyrrhotite mixes with dinitrobenzene waste water, natural pyrrhotite mass concentration is 60 g/L, the rotating speed of vertical rotating rotating disk is 10 r/min, the temperature of reaction of hybrid reaction is 60 DEG C, and the reaction times is 2 d.
In waste water after treatment, nitro-chlorobenzene concentration is reduced to 1.9 mg/L, and 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 70-90 order, and it is stand-by to expose pyrrhotite unsalted surface by washing or pickling;
(2) regulating the pH value of nitrotoluene class waste water is 3;
(3) natural pyrrhotite after treatment step (1) is mixed in a reactor with the nitrotoluene class waste water obtaining in step (2); After mixing, the mass concentration of pyrrhotite is 51 g/L;
(4) the reaction vessel sealing in step (3) 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 DEG C, and waste water after treatment is discharged.The Nitrobenzene in Wastewater concentration of discharging is reduced to 2.1 mg/L, and nitrotoluene clearance is 92%.
embodiment 5
For the processing of nitro-chlorobenzene waste water, 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: it is 10 that step (2) regulates the pH value of nitro-chlorobenzene waste water; In step (4), the reaction vessel sealing in step (3) 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 DEG C, and waste water after treatment is discharged.In the waste water of getting rid of, nitro-chlorobenzene concentration is reduced to 2.5 mg/L, and nitrotoluene clearance is 93%.

Claims (5)

1. a method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water, the steps include:
(1) natural pyrrhotite being crushed to granularity is 50-200 order, and it is stand-by to expose pyrrhotite unsalted surface by washing or pickling;
(2) regulating the pH value of nitrobenzene wastewater is 3-10, if the pH value of nitrobenzene wastewater between 3-10, does not need to regulate;
(3) natural pyrrhotite after treatment step (1) is mixed in a reaction vessel with the nitrobenzene wastewater obtaining in step (2); After mixing, the mass concentration of pyrrhotite is not less than 50g/L;
(4) the reaction vessel sealing in step (3) is placed on to hybrid reaction on vertical rotating rotating disk and is no less than 48h, when hybrid reaction, temperature is 15-60 DEG C, and waste water after treatment is discharged.
2. a kind of method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water according to claim 1, is characterized in that, the natural pyrrhotite in described step (1), and granularity is 60-80 order.
3. a kind of method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water according to claim 1, is characterized in that, in described step (2), the pH value of nitrobenzene wastewater is adjusted to 7.
4. a kind of method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water according to claim 1, is characterized in that, in described step (4), the rotating speed of vertical rotary turnplate is 10-60r/min.
5. a kind of method of utilizing natural pyrrhotite treatment of Nitrobenzene class waste water according to claim 4, is characterized in that, in described step (4), the temperature of reaction of hybrid reaction is 27 DEG C.
CN201210558731.9A 2012-12-21 2012-12-21 Method for treating nitrobenzene wastewater by natural pyrrhotite Expired - Fee Related CN102963943B (en)

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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
CN109052641B (en) * 2018-09-05 2020-12-18 南京大学 Coupling filler autotrophic denitrification biological filter and application

Citations (4)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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

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