CN102976514A - Reduction mother solution treatment method in production process of dinitrodiazophenol - Google Patents

Reduction mother solution treatment method in production process of dinitrodiazophenol Download PDF

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Publication number
CN102976514A
CN102976514A CN2012104856712A CN201210485671A CN102976514A CN 102976514 A CN102976514 A CN 102976514A CN 2012104856712 A CN2012104856712 A CN 2012104856712A CN 201210485671 A CN201210485671 A CN 201210485671A CN 102976514 A CN102976514 A CN 102976514A
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liquor
acid
mother
alkali
tank
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CN2012104856712A
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张文艺
戴如娟
李仁霞
占明飞
郑泽鑫
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Changzhou University
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Changzhou University
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Abstract

The invention relates to a reduction mother solution treatment method in a production process of dinitrodiazophenol. The method comprises the following steps: firstly adjusting pH (Potential of Hydrogen) of a reduction mother solution to 3-4; adding FeSO4*7H2O and H2O2 to react; respectively entering a neutralizing tank along the mother solution, wherein a substance for adjusting an alkali in the link is carbide slag which takes calcium hydroxide as a main component; adjusting the pH to 7-8 and staying for 5-7 minutes; entering a sedimentation basin; and carrying out further treatment on liquid supernatant in the sedimentation basin and discharging after the standard is achieved; enabling sediment to enter a sediment concentration tank; reflowing a concentrated solution in the sedimentation basin to an acid-alkali adjusting tank; enabling concentrated sludge to enter a horizontal spiral type centrifuge to dehydrate; doping the dehydrated sludge into power coal to carry out combustion treatment; and reflowing the separation liquid into the acid-alkali adjusting tank. The reduction mother solution treatment method has the advantages of small occupied area, high treating efficiency and the like.

Description

Mother-liquor treatment process in a kind of dinitrodiazophenol production process
Technical field
The invention belongs to the disposal of waste gas, water and industrial residue technical field of dinitrodiazophenol production process, be specifically related to a kind of dinitrodiazophenol production process mother-liquor treatment process.
Background technology
Mechanical sensitivity is low, flame sensitivity good because having for dinitrodiazophenol, the excellent property of detonating, chemical safety high, raw material sources are wide and low cost and other advantages, has become the industrial detonator priming explosive that China's civil area is most widely used.Dinitrodiazophenol in the market adopts sodium salt method production technique mostly, but this production method waste water generation is larger, and every production 1kg dinitrodiazophenol product approximately produces the high chroma mother liquor that 200kg~300kg contains poisonous objectionable impurities.It is complicated that dinitrodiazophenol is produced mother liquor composition, derive from the mother-liquor that produces when sodium sulphite reduces picric acid in the first step production process, contain the hazardous contaminants such as a large amount of nitro-compounds, sodium sulfate, sodium hydroxide, Sulfothiorine, COD and colourity are up to 5.0 * 10 4~ 6.0 * 10 4Mg/L and 6.0 * 10 4~ 7.0 * 10 4Doubly, biodegradability is poor, and the alkalescence of mother liquor own is larger in addition, if it is larger effectively not process its harm to environment.
At present, the dinitrodiazophenol mother-liquor adopts dilution method to carry out pre-treatment mostly both at home and abroad, namely in mother liquor, add a large amount of process waters, with its dilution 10-50 doubly, make the COD of mother-liquor be diluted to about 500-1000mg/L, colourity be diluted to 3000-5000 doubly about, be referred to as reducing waste water.These reducing waste waters are taked mainly to comprise that the technology such as physico-chemical processes, biological process, advanced oxidation processes process.These treatment processs all exist technique comparatively complicated, and treatment effect is not good, is difficult to the deficiencies such as qualified discharge and cost of investment are higher, processing costs is larger, makes manufacturing enterprise be difficult to bear.Simultaneously in treating processes, dinitrodiazophenol in the waste water usually possesses blast characteristics (even dinitrodiazophenol is also very easily blasted) because of deposition, crystallization in water, cause many enterprises in the process of processing this type of mother liquor, the accidental explosion accident to occur, cause certain loss of life and personal injury and financial loss.Therefore seek efficiently, dinitrodiazophenol mother-liquor treatment technology is significant economically and reasonably.
The Fenton method is a kind of advanced oxidation processes, can effectively process difficult for biological degradation and the general reluctant organic waste waters of physico-chemical process such as phenols, arylamine class, aromatic hydrocarbons, agricultural chemicals and nuke rubbish.Though the processing costs of Fenton reagent is high, as pre-treatment, can improve the biodegradability of waste water, its water outlet can directly enter the municipal wastewater pipeline through suitable processing again, and the secondary comprehensive treating process is carried out in unification, can be like this enterprise and saves civil engineering and other working costs.Therefore, utilize such mother-liquor of Fenton agent treated in the certain condition scope, to have certain actual application prospect.
Summary of the invention
The objective of the invention is for effectively solving nitro-compound and the synchronous a kind of pre-treatment process of degrading and proposing of inorganic sulphide in the dinitrodiazophenol production process mother-liquor, COD and colourity realizing effectively removing when nitro-compound and inorganic sulphide are removed synchronously in the mother-liquor realize efficient, the safe handling of such mother-liquor.
Technical scheme of the present invention is implemented successively as follows: first the mother-liquor that produces in the dinitrodiazophenol production process is collected through the acid-alkali accommodation pond respectively and homogeneous, equal amounts, regulating mother liquor pH is 3-4; Inject reaction tank by sump pump again, in reaction tank, add FeSO 47H 2O and mass concentration are 30% H 2O 2, H 2O 2With FeSO 47H 2The O mol ratio is 40:1, and temperature remains on 15-35 ℃, and the residence time is 2h; Mother liquor enters respectively neutralization tank subsequently, transfers the alkali material to be the carbide slag take calcium hydroxide as main component in this link, regulates pH to 7-8, and the residence time is 5-7min; Enter at last settling tank, sedimentation time 20-35min, qualified discharge was carried out in water outlet after supernatant liquor entered activated carbon adsorber and does further processing in this pond.Throw out then enters the precipitation concentration basin; Concentrated solution is back to the acid-alkali accommodation pond in the concentration basin, and thickened sludge enters Horizontal helical type centrifuge and dewaters, and the mud after the dehydration mixes and carries out burn processing in the steam coal, and parting liquid is back to the acid-alkali accommodation pond, finally reaches effective removal of COD and colourity.Mother-liquor water outlet COD and colourity after the method is processed all reach " weapon industry pollution discharge standard Charge of ammunitions " (GB 14470.3-2002) emission request.
Cardinal principle of the present invention is to utilize H 2O 2With FeSO 47H 2O forms Fenton reagent under acidic conditions, with inorganic sulphide, from the elementary sulfur to sulfide, the oxygenate of sulphur and hydrogen sulfide all are oxidized to vitriol, and reaction equation is as follows:
S 2-+4H 2O 2→SO 4 2-+4H 2O
And under acidic conditions with NO 2 -Be converted into NO 3 -, while NO 3 -Reduction reaction occurs generate H 2O and NO;
In acidic medium,
H 2O 2→O 2+2H ++2e -
Fe 2+→Fe 3++e -
NO 3 -Reduction reaction occurs:
NO 3 -+4H ++3e -→2H 2O+NO
NO in mother liquor 2 -Base is converted into NO 3 -:
NO 2 -+H 2O→NO 3 -+2H ++2e -
Simultaneously, OH, the HO of reaction generation 2Deng free radical can with mother-liquor in organism react and make it decompose the effective removal finally reach COD and colourity, reaction equation is as follows:
Fe 2++H 2O 2→Fe 3++OH -+·OH
Fe 3++H 2O 2→Fe 2++·HO 2+H +
·OH+H 2O 2→H 2O+·HO 2
·HO 2→·O 2 -+H +
·O 2 -+H 2O 2→O 2+·OH+OH -
OH than other oxygenant commonly used (such as MnO 4 -, ClO 2) have a higher electrode potential:
·HO+H +→H 2O Eo=2.80V
So, OH, HO 2Deng free radical can with mother liquor in organism react, make its decomposition
·OH+RH→R·+H 2O
R+O 2→ ROO → ROOH → degradation production+OH
The present invention has that floor space is little, the processing efficiency advantages of higher.
Description of drawings
Fig. 1 is process flow sheet of the present invention
Among the figure: 1. acid-alkali accommodation pond; 2. lift pump; 3. reaction tank; 4. neutralization tank; 5. settling tank; 6. activated carbon adsorber; 7. precipitation concentration basin; 8. Horizontal helical type centrifuge.
Embodiment
The present invention is with FeSO 47H 2O and H 2O 2For medicament forms Fenton agent treated dinitrodiazophenol production process mother-liquor, utilize H 2O 2High these characteristics of rate of oxidation all are oxidized to vitriol with inorganic sulphide, and under acidic conditions with NO 2 -Be converted into NO 3 -, while NO 3 -Reduction reaction occurs generate H 2O and NO, simultaneously two kinds of OH, HO that the medicament reaction produces 2Deng free radical can with mother-liquor in organism react and make it decompose the effective removal finally reach COD and colourity; In neutralization tank, add carbide slag, regulate pH to 7-8, make to form Fe (OH) 3And CaCO 3Precipitation; After the settling tank precipitation, supernatant liquor enters activated carbon adsorber qualified discharge after adsorption treatment.Throw out enters the precipitation concentration basin, and concentrated solution is back to the acid-alkali accommodation pond, and thickened sludge enters Horizontal helical type centrifuge and dewaters, and the mud after the dehydration mixes and carries out burn processing in the coal, and parting liquid is back to the acid-alkali accommodation pond.
Its concrete treatment scheme such as Fig. 1, method is as follows: first the mother-liquor that produces in the dinitrodiazophenol production process 1 is collected and homogeneous, equal amounts through the acid-alkali accommodation pond respectively, it is 3-4 that acid adding is regulated mother liquor pH; Inject reaction tank 3 by sump pump 2 again, in reaction tank 3, add FeSO 47H 2O and mass concentration are 30% H 2O 2, H 2O 2With FeSO 47H 2The O mol ratio is 40:1.Temperature remains on 15-35 ℃, and the residence time is 2h; Mother liquor enters respectively neutralization tank 4 subsequently, adds carbide slag again and regulates pH to 7-8, and the residence time is 5-7min; Enter at last settling tank 5, sedimentation time 20-35min, the supernatant liquor gravity flow enters activated carbon adsorber 6, the water outlet qualified discharge after the adsorption treatment.Supernatant C OD and colourity all reach " weapon industry pollution discharge standard Charge of ammunitions " (GB 14470.3-2002) emission request, and colourity and COD clearance on average can reach more than 99.0% and 93.8%.Throw out then enters precipitation concentration basin 7; Concentrated solution is back to acid-alkali accommodation pond 1 in this pond, thickened sludge enters Horizontal helical type centrifuge 8 and dewaters, and centrifuge speed is 1500-1800r/min, centrifugation 5-8min, mud after the dehydration mixes and carries out burn processing in the steam coal, and parting liquid is back to acid-alkali accommodation pond 1.
3 embodiment of the present invention below are provided:
Embodiment 1
Mother-liquor 3.0m 3, initial pH value is 12.0, and 1 collects and homogeneous, equal amounts through the acid-alkali accommodation pond, and it is 3 that acid adding is regulated mother liquor pH; Inject reaction tank 3 by sump pump 2 again, in reaction tank 3, add FeSO 47H 2O and mass concentration are 30% H 2O 2, H 2O 2With FeSO 47H 2The O mol ratio is 40:1, and temperature remains on 15-35 ℃, and the residence time is 2h; Mother liquor enters respectively neutralization tank 4 subsequently, adds alkali (being carbide slag) again and regulates pH to 7, and the residence time is 5-7min; Enter at last settling tank 5, sedimentation time 20min, the supernatant liquor gravity flow enters activated carbon adsorber 6, the water outlet qualified discharge after the adsorption treatment.Inlet COD concentration is down to 94.7mg/L from 1367.5mg/L, colourity is down to 60 times from 6250 times, COD and colourity all reach " weapon industry pollution discharge standard Charge of ammunitions " (GB 14470.3-2002) emission request, and colourity and COD clearance are 95.2% and 90.1%.Throw out then enters precipitation concentration basin 7; Concentrated solution is back to acid-alkali accommodation pond 1 in this pond, thickened sludge enters Horizontal helical type centrifuge 8 and dewaters, and centrifuge speed is 1500-1800r/min, centrifugation 7min, mud after the dehydration mixes and carries out burn processing in the steam coal, and parting liquid is back to acid-alkali accommodation pond 1.
Embodiment 2
Mother-liquor 5.0m 3, initial pH value is 13.0, and 1 collects and homogeneous, equal amounts through the acid-alkali accommodation pond, and it is 3 that acid adding is regulated mother liquor pH; Inject reaction tank 3 by sump pump 2 again, in reaction tank 3, add FeSO 47H 2O and mass concentration are 30% H 2O 2, H 2O 2With FeSO 47H 2The O mol ratio is 40:1, and temperature remains on 15-35 ℃, and the residence time is 2h; Mother liquor enters respectively neutralization tank 4 subsequently, adds alkali (being carbide slag) again and regulates pH to 7.5, and the residence time is 5-7min; Enter at last settling tank 5, sedimentation time 35min, the supernatant liquor gravity flow enters activated carbon adsorber 6, the water outlet qualified discharge after the adsorption treatment.Inlet COD concentration is down to 94.3mg/L from 1532.1mg/L, colourity is down to 60 times from 6800 times, COD and colourity all reach " weapon industry pollution discharge standard Charge of ammunitions " (GB 14470.3-2002) emission request, and colourity and COD clearance are 99.1% and 93.8%.Throw out then enters precipitation concentration basin 7; Concentrated solution is back to acid-alkali accommodation pond 1 in this pond, thickened sludge enters Horizontal helical type centrifuge 8 and dewaters, and centrifuge speed is 1500-1800r/min, centrifugation 8min, mud after the dehydration mixes and carries out burn processing in the steam coal, and parting liquid is back to acid-alkali accommodation pond 1.
Embodiment 3
Mother-liquor 9.0m 3, initial pH value is 14.0, and 1 collects and homogeneous, equal amounts through the acid-alkali accommodation pond, and it is 4 that acid adding is regulated mother liquor pH; Inject reaction tank 3 by sump pump 2 again, in reaction tank 3, add FeSO 47H 2O and mass concentration are 30% H 2O 2, H 2O 2With FeSO 47H 2The O mol ratio is 40:1, and temperature remains on 15-35 ℃, and the residence time is 2h; Mother liquor enters respectively neutralization tank 4 subsequently, adds alkali (being carbide slag) again and regulates pH to 8, and the residence time is 5-7min; Enter at last settling tank 5, sedimentation time 35min, the supernatant liquor gravity flow enters activated carbon adsorber 6, the water outlet qualified discharge after the adsorption treatment.Inlet COD concentration is down to 84.6mg/L from 1680.0mg/L, colourity is down to 50 times from 6540 times, COD and colourity reach respectively " weapon industry pollution discharge standard Charge of ammunitions " (GB 14470.3-2002) emission request, and colourity and COD clearance are 99.2% and 94.9%.Throw out then enters precipitation concentration basin 7; Concentrated solution is back to acid-alkali accommodation pond 1 in this pond, thickened sludge enters Horizontal helical type centrifuge 8 and dewaters, and centrifuge speed is 1500-1800r/min, centrifugation 8min, mud after the dehydration mixes and carries out burn processing in the steam coal, and parting liquid is back to acid-alkali accommodation pond 1.

Claims (1)

1. mother-liquor treatment process in the dinitrodiazophenol production process comprises the steps: first the mother-liquor that produces in the dinitrodiazophenol production process to be collected through the acid-alkali accommodation pond respectively and homogeneous, equal amounts, and regulating mother liquor pH is 3-4; Inject reaction tank by sump pump again, in reaction tank, add FeSO 47H 2O and mass concentration are 30% H 2O 2, H 2O 2With FeSO 47H 2The O mol ratio is 40:1, and temperature remains on 15-35 ℃, and the residence time is 2h; Mother liquor enters respectively neutralization tank subsequently, transfers the alkali material to be the carbide slag take calcium hydroxide as main component in this link, regulates pH to 7-8; Enter at last settling tank, sedimentation time 20-35min, qualified discharge was carried out in water outlet after supernatant liquor entered activated carbon adsorber and does further processing in the settling tank; Throw out then enters respectively the precipitation concentration basin; Concentrated solution is back to the acid-alkali accommodation pond in the concentration basin, and thickened sludge enters Horizontal helical type centrifuge and dewaters, and the mud after the dehydration mixes and carries out burn processing in the steam coal, and parting liquid is back to the acid-alkali accommodation pond.
CN2012104856712A 2012-11-26 2012-11-26 Reduction mother solution treatment method in production process of dinitrodiazophenol Pending CN102976514A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109019962A (en) * 2018-08-16 2018-12-18 北方工程设计研究院有限公司 A kind of processing method of refinery alkaline sewage
CN114163057A (en) * 2021-12-23 2022-03-11 南京信息工程大学 Method for catalytically degrading organic matters in waste water containing nitrosyl sulfuric acid dye by using tungsten oxide

Citations (1)

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Publication number Priority date Publication date Assignee Title
CN1562818A (en) * 2004-04-01 2005-01-12 广东省三○九厂 Method for treating wastewater of dinitrodiazophenol

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1562818A (en) * 2004-04-01 2005-01-12 广东省三○九厂 Method for treating wastewater of dinitrodiazophenol

Non-Patent Citations (2)

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Title
王焕珠等: "用聚合铝铁-Fenton试剂-活性炭处理DDNP生产废水的方法探讨", 《煤矿环境保护》 *
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109019962A (en) * 2018-08-16 2018-12-18 北方工程设计研究院有限公司 A kind of processing method of refinery alkaline sewage
CN114163057A (en) * 2021-12-23 2022-03-11 南京信息工程大学 Method for catalytically degrading organic matters in waste water containing nitrosyl sulfuric acid dye by using tungsten oxide
CN114163057B (en) * 2021-12-23 2023-04-18 南京信息工程大学 Method for catalytically degrading organic matters in waste water containing nitrosyl sulfuric acid dye by using tungsten oxide

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Application publication date: 20130320