CN101402503A - Treatment method for wastewater from dinitrobenzene production with benzene mixed acid nitrification - Google Patents
Treatment method for wastewater from dinitrobenzene production with benzene mixed acid nitrification Download PDFInfo
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- CN101402503A CN101402503A CNA2008101217212A CN200810121721A CN101402503A CN 101402503 A CN101402503 A CN 101402503A CN A2008101217212 A CNA2008101217212 A CN A2008101217212A CN 200810121721 A CN200810121721 A CN 200810121721A CN 101402503 A CN101402503 A CN 101402503A
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- dinitrobenzene
- acid
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000002351 wastewater Substances 0.000 title claims abstract description 69
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000002253 acid Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000002829 reductive effect Effects 0.000 claims abstract description 20
- 238000004062 sedimentation Methods 0.000 claims abstract description 18
- 230000003311 flocculating effect Effects 0.000 claims abstract description 6
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 90
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 229910052742 iron Inorganic materials 0.000 claims description 43
- 239000003610 charcoal Substances 0.000 claims description 36
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 238000005189 flocculation Methods 0.000 claims description 21
- 230000016615 flocculation Effects 0.000 claims description 20
- 238000006722 reduction reaction Methods 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229920002401 polyacrylamide Polymers 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 4
- 229910001018 Cast iron Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- 238000000710 polymer precipitation Methods 0.000 claims description 2
- 229920003176 water-insoluble polymer Polymers 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 24
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 abstract description 18
- 238000006396 nitration reaction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 230000005494 condensation Effects 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 235000019256 formaldehyde Nutrition 0.000 description 10
- 229960004279 formaldehyde Drugs 0.000 description 10
- -1 nitro aromatic compound Chemical class 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 6
- 239000012028 Fenton's reagent Substances 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 description 1
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical class OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
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- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
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- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
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Images
Abstract
The invention provides a method for treating dinitrobenzene wastewater generated by the nitration of benzene mixed acid, wherein the method comprises the following steps: (1) acidification; (2) iron-carbon reduction; (3) condensation; (4) flocculating sedimentation; and (5) general biochemical treatment of sedimentation water. When the dinitrobenzene wastewater generated by the nitration of benzene mixed acid is treated by the method, the contents of the matters of nitrobenzene, nitrophenol and the COD in the wastewater are greatly reduced; after further biochemical treatment, the wastewater can easily meet the water discharge standard; and compared with the prior treatment technique, the method has the advantages of low cost and good effect.
Description
(1) technical field
The present invention relates to the method for wastewater treatment in a kind of dinitrobenzene (DNB) preparation process, particularly, relate to a kind of benzene mixed acid nitrification prepare dinitrobenzene in and the treatment process of washes.
(2) background technology
Industrial circle, dinitrobenzene (DNB, between containing, adjacent, to three kinds of isomer) production generally carry out nitration reaction with nitration mixture (preparing) and obtain by sulfuric acid and nitric acid by oil of mirbane, or directly undertaken and the nitration reaction preparation by benzene and nitration mixture, the nitration product standing demix divides the mineral acid layer mutually of leaving away, and obtaining organic layer is thick DNB, wherein containing nitrophenol, sulfuric acid, nitric acid, nitrous acid etc. has dysgenic impurity to quality product, needs the neutralization of water and alkaline liquid, washing purifying.Produce washes with washing among the thick DNB, waste water is weakly alkaline, wherein except that the dinitrobenzene that contains trace, also contain with nitrated by products such as the monohydric phenol of a plurality of nitros and polyphenol, 2.85 inorganic salt such as～4.6% yellow soda ash, sodium sulfate, SODIUMNITRATE, Sodium Nitrite, COD5000 ~ 10000mg/L.Because dinitrobenzene and nitrophenol content height in the waste water have toxicity to bacterium, biochemical treatment is difficult to prove effective.The toxicity of nitro-compound is bigger, and there is strict regulation in country to the content of nitro-aromatic and nitrophenol in the waste water of discharging, and the processing with washes in the dinitrobenzene itrated compound has realistic meanings to the protection of ecotope and the development of relevant enterprise.
The treatment technology that contains nitro aromatic compound and nitrophenol wastewater according to the characteristic of pollutent in the waste water, adopts the combination of one or more treatment processs in the methods such as catalyzed oxidation, extraction, charcoal absorption, chemical reduction, biochemical treatment, incineration more.
Improvement for Meta-dinitrobenzene waste water, previous research is almost all pointed to and is adopted the refining dinitrobenzene of process for sulfonation to produce the waste water that takes place in the Meta-dinitrobenzene process, the ortho para dinitrobenzene is converted into neighbour/p-nitrophenyl sulfonate, pollutent is except that nitro-aromatic in the waste water, be mainly the nitrobenzene-sulfonic acid salts substances, there were significant differences with the present invention relates to field of wastewater.
Chinese patent application ZL94103021.0 has disclosed the step-by-step processing method that nitroaromatic and nitro-phenolic compound in the waste water are removed in a kind of processing, this method earlier with hydrogen peroxide oxidation to remove most of nitrophenol and partial nitro aromatic hydrocarbons, then with charcoal absorption to remove the technology of oil of mirbane and nitrophenol.Because the oxidation program has removed most nitro-aromatic and nitrophenol in advance, the volume of unit weight activated carbon treatment waste water improves greatly.
At in the dinitrobenzene itrated compound and the improvement of washes, " little electrolysis-catalyzed oxidation-absorption method is handled wastewater from dinitrobenzene " (fourth Central Military Commission etc., industrial safety and environmental protection, 2006 the 32nd the 6th phases of volume) the tertiary treatment flow process that adopts scrap iron carbon micro-electrolysis, Fenton reagent oxidation, charcoal absorption to handle has been proposed.
Because of the oxidation effectiveness of Fenton reagent p-nitrophenyl a little less than, and oil of mirbane has metathesis to the nitrophenol of charcoal absorption in the charcoal adsorption process, above-mentioned document focuses on and remove wherein a kind of component before charcoal absorption, to reduce the consumption of adsorption process gac.The hydrogen peroxide oxidation target is to remove a large amount of nitrophenol and partial nitro aromatic hydrocarbons, microelectrolysis process mainly is converted into aniline category matter with oil of mirbane so that the Fenton reagent oxidation, but in general, for organic pollutant, all higher dinitrobenzene nitration waste water of COD content, use Fenton reagent oxidation, charcoal absorption as the waste water physicochemical treatment process, processing cost is obviously higher.
(3) summary of the invention
The invention provides a kind of treatment process of nitration waste water, improve the biodegradability of sewage, reduce the cost that sewage is handled fully.
The technical solution used in the present invention is: a kind of treatment process of wastewater from dinitrobenzene production with benzene mixed acid nitrification, described method comprises the steps:
(1) acidifying: with benzene mixed acid nitrification produce produce in the dinitrobenzene technology in and the washing soda wastewater, with inorganic acid adjust pH 2.0～4.0, acid waste water;
(2) iron charcoal reduction: the acid waste water adding is equipped with in the iron charcoal reactor of capacity iron and charcoal, and acid material fully contacts with charcoal with iron and carries out reduction reaction, and nitro aromatic compound changes into aniline, and nitrophenol changes into amino phenol; Reaction finishes, and separating ferrum and carbon get reduced liquid, and described iron is iron filings, and described charcoal is the chip of coke or gac;
(3) polycondensation: in iron carbon reaction solution, add short poly-agent, fully stir down, make amino phenol and the most of and short poly-agent generation polycondensation of aniline in the above-mentioned reduction material, generate water-insoluble polymer;
(4) flocculating settling: the reaction mass flocculation that step (3) is obtained, transfer pH value to 7.5～9.0, flocculation makes the polycondensate sedimentation in the reaction mass, separates and removes water-insoluble, obtains the sedimentation water outlet.
(5) the sedimentation water outlet is through adopting biochemical treatment (carry out two kinds of technologies of anoxic and aerobic treatment or anaerobism and aerobic treatment all can).
The treatment process of wastewater from dinitrobenzene production with benzene mixed acid nitrification of the present invention,
Strong acid can especially can use the separating obtained sulfuric acid adjust pH of nitrifying process self with sulfuric acid or hydrochloric acid in the described step (1); Acidity strengthens the raising that helps follow-up reduction effect, but acid too high meeting increases the adjusting acid amount that pH value consumed and the consumption of iron powder, increases processing cost, and preferred pH value scope is 2～4.
In the affiliated step (2), common iron reductive agent adopts cast iron filing, mechanical workout steel scrap iron filings etc., and described charcoal is coke or gac chip; Reactor generally includes the reactor that iron/charcoal fixed-bed reactor, iron/charcoal are in suspended state, need adopt stirring to guarantee solid particulate uniform distribution in solution for the latter, reaction solution needs to separate through centrifugal or filtering mode, removing iron filings, breeze, and makes it to return the previous reaction device; The quality of the iron filings that add in the reactor answers 2～5% of acid waste water quality to be advisable to be not less than, and excess is excessive all can filtered and recycled, the few reduction of amount not exclusively, iron/charcoal mass ratio 1～12: 1, the iron/charcoal of optimization is than 3～8: 1; The iron of the fixed bed/disposable adding of charcoal weighting material, according to reaction consumes situation each time, regular replenishment iron filings, filling again, as using the reactor of suspended state, the iron filings in the reactor then can add in good time; Be reflected under the normal temperature state and can normally carry out, suitable heating is carried out favourable to reaction, and suitable temperature of reaction is 20～55 ℃; The reaction times prolongation helps improving transformation efficiency, 60～240 minutes suitable reaction times; Usually under above-mentioned reaction conditions, nitryl aromatic hydrocarbon conversion rate 80～96%, nitrophenol transformation efficiency 90～100%;
The short poly-agent of described step (3) adding makes it under the whipped state and polyamino benzene and the polyamino phenol and short poly-agent thorough mixing reaction of step (2) gained reduced liquid through iron/charcoal reduction generation, removes to generate water-fast polycondensate; Available short poly-agent has aromatic diisocyanate or formaldehyde etc., from treatment effect, processing cost with avoid the waste water introducing consideration such as other difficult impurity, the preferred formaldehyde that uses can use industrial formol or not contain the formaldehyde waste liquid of other compositions that are unfavorable for subsequent disposal; Usually detect the amount of aniline category matter in the reduced liquid earlier in the concrete described step of operation process (3), the short poly-agent and the aniline category matter mass ratio that add of control is 8～25% again.
The suitable reaction conditions of step (3) control comprises the add-on of the pH and the formaldehyde of reaction solution, step (2) iron/charcoal reduction reaction liquid pH value will raise to some extent than step (1), generally do not need to regulate separately pH value, the pH value 5.5～6.5 of preferred control reaction solution, the amount of the short poly-agent formaldehyde that adds is according to the amount of aromatic multi-amine in the reduced liquid and amino phenol, the formaldehyde that control adds and the mass ratio of aniline category matter are 8～25%, and preferable range is 12～20%; Reaction times 30～100min;
Described step (4) is a flocculating settling, so that the polycondensate of step (3) reaction is settlement separate; In step (3) reaction solution, add alkaline matter, can use unslaked lime, calcium hydroxide, liquid caustic soda etc., reconcile the pH value 7.5～9.0 of reaction solution; Because the Fe that the iron carbon reduction generates
2+Hydrolysate adsorption-flocculation ability is stronger, can directly bring into play the effect of flocculation agent, for quickening coagulation, also can add an amount of flocculation agent, described additional flocculating agents is a Synergist S-421 95 one of one of following or following and separately: polyacrylamide, polymerize aluminum chloride, iron trichloride, poly-ferric chloride, bodied ferric sulfate; Sedimentation mud can be after dewatering burning disposal; Through step (3), (4), the aniline category matter decreasing ratio can reach 90～98% after the coagulation water outlet; The reaction mass volume ratio that flocculation agent and step (3) obtain is 1: 3000～5000.Also can not add flocculation agent in addition, even add, also be seldom to measure, and do not do metering usually, plays auxiliary throwing out.The preferred flocculation agent of the present invention is a polyacrylamide.
Described step (5), by the above-mentioned steps pre-treatment, nitro aromatic compound, nitrophenol are significantly cut down in the dinitrobenzene factory effluent, the BOD/COD of waste water can reach 0.4～0.6, wastewater biodegradability significantly improves, carry out biochemical conventional processing after follow-up can suitably the dilution, as carry out anoxic and aerobic treatment, or anaerobism and aerobic treatment, also can combine with the measure of Fenton reagent oxidation, make waste water be handled fully, oil of mirbane and aniline category matter content can drop to below the 5mg/L in the waste water, and COD is less than 500mg/L.
Concrete, the present invention recommends the treatment process of following wastewater from dinitrobenzene production with benzene mixed acid nitrification:
(1) acidifying: with benzene mixed acid nitrification produce that dinitrobenzene produces in and the washing soda wastewater, transfer pH value 2～4 with sulfuric acid, acid waste water;
(2) iron charcoal reduction: acid waste water is incorporated with cast iron filing, gac, and iron/charcoal ratio is 3～8: 1 reactor, and the quality of iron is 2～5% of an acid waste water, 20～55 ℃ of reactions of controlled temperature 60～180 minutes; Filtering separation iron/charcoal gets reduced liquid;
(3) polycondensation: detect the quality of aniline category matter in the reduced liquid, the pH value 5.5～6.5 of control reaction solution adds short poly-agent formaldehyde to reduced liquid, stirs, and makes aniline category matter generation polycondensation, generates polymer precipitation; The formaldehyde that is added and the mass ratio of aniline category matter are 12～20%, reaction times 30～100min;
(4) flocculating settling: in the reaction mass that step (3) obtains, add lime or liquid caustic soda, regulate pH value 7.5～9.0,1: 3000～1: 5000 the ratio of reaction mass volume ratio that obtains in flocculation agent and step (3) adds flocculation agent simultaneously, make the polycondensate sedimentation, separate water-insoluble, obtain clarifying the sedimentation water outlet; Described flocculation agent optimization polypropylene acid amides; It is fewer that flocculation agent is used, and adds a small amount of throwing out that can play and get final product, and do not measure usually during operation;
(5) step (4) sedimentation water outlet through with sanitary sewage etc. do not contain nitro thing waste water by dilution in minimum 1: 1 after, further adopt biochemical treatment, oil of mirbane and aniline category matter content are less than below the 5mg/L in the waste water, COD is less than 500mg/L.
The invention has the beneficial effects as follows: through wastewater from dinitrobenzene production with benzene mixed acid nitrification, processing by the inventive method, can cut down the content of nitrobenzene, nitropheneol material and COD in the waste water in a large number, now further carry out to reach easily after the biochemical treatment standard of discharge water, compare treatment technology in the past, cost is low, and height produces effects.
(4) description of drawings
Fig. 1 is the wastewater treatment process figure in the dinitrobenzene preparation process of the present invention.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1
(benzene feeds intake: nitric acid: sulfuric acid=1: 1.05: 1.3) carry out two nitrated reactions of benzene for benzene and mixed acid nitration, control 30～97 ℃ of each section temperature of reaction, the nitrated material that goes out nitrator leaves standstill, be separated into the acid layer of organic layer and sulfuric acid concentration～69%, organic layer is the thick dinitrobenzene that nitration reaction generates, wherein contain neighbour based on Meta-dinitrobenzene,, by products such as nitrophenol that three kinds of isomer and reaction are generated, nitrous acid, also be dissolved with a small amount of nitric acid and sulfuric acid.Use 10% sodium carbonate solution, water washing organic layer (thick dinitrobenzene) respectively, leave standstill, separate organic layer (dinitrobenzene) and water layer, obtain in the dinitrobenzene of purifying and the alkalescence and washes.In the alkalescence and in the washes, CODcr content 6670g/L after testing, pH value 8.5.Sampling, with gas-chromatography gentle-matter connection instrument detects the content of nitro aromatic compound and nitrophenol in the waste water, detects dinitrobenzene content 352mg/L in the waste water, nitrophenol 1933mg/L.
Get in the above-mentioned alkalescence of 300ml and washes, under the monitoring of PH meter, with 85% sulfuric acid adjusting waste water pH value to 2.8; Get acid waste water;
Acid waste water is placed high-order bottle, and high-order bottle is inserted the waters, regulates 40 ℃ of control reaction temperature by the waters;
Acid waste water continuously flows in the internal diameter 25mm Glass tubing, casing pack steel scrap iron filings and activated carbon granule, and iron/charcoal ratio is 8: 1; The quality of steel scrap iron filings is 12 grams.
Adjustment of acidity waste liquid add-on makes waste liquid and iron/charcoal reaction time reach 150min, filters, collect water outlet, reduced liquid, the reduced liquid that takes a morsel with gas-chromatography gentle-matter connection instrument detects nitro aromatic compound and nitrophenol content in the waste water, gained the results are shown in Table 1;
Nitro thing and aniline category matter content in table 1 iron/charcoal reducing waste water
Get the 200ml reduced liquid, detect aniline category matter in the reductive water, 1285mg/L, nitro thing content (dinitrobenzene+nitrophenol) is 80.3mg/L, adding in the round neck flask that the 200ml band stirs, is 10% industrial formol 0.4ml to flask adding quality percentage composition, stirring reaction 1h; In reaction solution, add calcium hydroxide emulsion, regulate pH value to 8, add the polyacrylamide solution of 0.1ml2 ‰ (volume ratio) again, stir, leave standstill, filter; The water body clarification of filter back detects water outlet nitro thing and aniline category matter content and COD index.Wherein, phenyl amines content 31.6mg/L, aniline category matter decreasing ratio 97.6%; Nitro thing (containing nitro-aromatic and nitrophenol) content 65.7mg/L, COD1890mg/L.
The sedimentation water outlet is through pressing 1: 1 mixed with sanitary wastewater (COD350mg/L), the biochemical system that employing is made up of anoxic section and aerobic section carries out the biochemical treatment at intermittence, two sections residence time meter 24h, water outlet COD can reach 475mg/L, nitrobenzene 4.2mg/L, aniline category matter content 3.9mg/L.
Embodiment 2
Get as in the alkalescence of embodiment 1 and washes, through the sulfuric acid acidation pH value is that 3.0 acid waste water 300ml adds in the round neck flask that band stirs, cast iron filing and active breeze are housed in the flask, the heavy 7.5g of iron filings, iron/charcoal ratio is 3: 1, stir speed (S.S.) 150rpm, 50 ℃ of temperature of reaction, reaction times 180min; Leave standstill after reaction is finished, filter.Filtering iron filings and active breeze get reduced liquid;
Nitro thing content in table 2 iron/charcoal reducing waste water
Get filtrate 200ml, add in the round neck flask of band stirring, add 5% formaldehyde solution 1.1ml, stirring reaction 60min;
It is 8 that reaction solution is regulated pH value with 30% liquid caustic soda, leaves standstill, settlement separate;
Get supernatant liquor and detect nitro thing and aniline category matter content and COD index in the waste water, nitrobenzene content 65.6mg/L, aniline category matter content 25.3mg/L, COD1970mg/L, aniline category matter decreasing ratio 98.1%.
The sedimentation water outlet is through pressing 1: 1 mixed with sanitary wastewater (COD328mg/L), adopt the biochemical system by anoxic section and aerobic section formed identical to carry out the biochemical treatment at intermittence with embodiment 1, two sections residence time meter 24h, water outlet COD432mg/L, nitrobenzene 3.8mg/L, aniline category matter content 3.5mg/L.
Embodiment 3
Other condition and embodiment 1 are identical, and the flocculation agent polyacrylamide is replaced to polymerize aluminum chloride, and final outflow water COD can reach 471mg/L, nitrobenzene 4.0mg/L, aniline category matter content 3.4mg/L.
Embodiment 4
Other condition and embodiment 1 are identical, and the flocculation agent polyacrylamide is replaced to iron trichloride, and final outflow water COD can reach 465mg/L, nitrobenzene 4.3mg/L, aniline category matter content 3.6mg/L.
Embodiment 5
Other condition and embodiment 1 are identical, and the flocculation agent polyacrylamide is replaced to poly-ferric chloride, and final outflow water COD can reach 471mg/L, nitrobenzene 3.9mg/L, aniline category matter content 3.5mg/L.
Embodiment 6
Other condition and embodiment 1 are identical, and the flocculation agent polyacrylamide is replaced to bodied ferric sulfate, and final outflow water COD can reach 467mg/L, nitrobenzene 4.1mg/L, aniline category matter content 3.9mg/L.
Claims (10)
1, a kind of treatment process of wastewater from dinitrobenzene production with benzene mixed acid nitrification is characterized in that described method comprises the steps:
(1) acidifying: with benzene mixed acid nitrification produce produce in the dinitrobenzene technology in and the washing soda wastewater, with inorganic acid adjust pH 2.0～4.0, acid waste water;
(2) iron charcoal reduction: the acid waste water adding is equipped with in the iron charcoal reactor of capacity iron and charcoal, and acid material fully contacts with iron and charcoal and carries out reduction reaction, and reaction finishes, separating ferrum and carbon, get reduced liquid, described iron is iron filings, and described charcoal is the chip of coke or gac;
(3) polycondensation: in reduced liquid, add short poly-agent, fully stir down, generate water-insoluble polymer;
(4) flocculating settling: the reaction mass that step (3) obtains is transferred pH value to 7.5～9.0, and flocculation makes the polycondensate sedimentation in the reaction mass, separates the insolubles that anhydrates, and obtains the sedimentation water outlet;
(5) the sedimentation water outlet is through conventional biochemical treatment.
2, the treatment process of wastewater from dinitrobenzene production with benzene mixed acid nitrification as claimed in claim 1, after it is characterized in that the first reaction mass that described step (3) is obtained of step (4) is transferred pH value to 7.5～9.0, in reaction mass, add the flocculation agent flocculation again, make the polycondensate sedimentation in the reaction mass, described flocculation agent is a Synergist S-421 95 one of one of following or following and separately: polyacrylamide, polymerize aluminum chloride, iron trichloride, poly-ferric chloride or bodied ferric sulfate.
3, the treatment process of wastewater from dinitrobenzene production with benzene mixed acid nitrification as claimed in claim 2 is characterized in that the described flocculation agent of described step (4) is a polyacrylamide.
4, the treatment process of wastewater from dinitrobenzene production with benzene mixed acid nitrification as claimed in claim 1 is characterized in that the described short poly-agent of described step (3) is a formaldehyde.
5, the treatment process of wastewater from dinitrobenzene production with benzene mixed acid nitrification as claimed in claim 1 is characterized in that described step (3) detects the amount of aniline category matter in the reduced liquid earlier, and short poly-agent and aniline category matter mass ratio that control adds are 8～25%.
6, the treatment process of wastewater from dinitrobenzene production with benzene mixed acid nitrification as claimed in claim 1 is characterized in that the iron described in the described step (2), charcoal mass ratio are 1～12: 1.
7, the treatment process of wastewater from dinitrobenzene production with benzene mixed acid nitrification as claimed in claim 1, the quality that it is characterized in that described in the described step (2) adding iron be no less than acid waste water quality 2～5%;
8, the treatment process of wastewater from dinitrobenzene production with benzene mixed acid nitrification as claimed in claim 1 is characterized in that the described reduction reaction of step (2) is 20～55 ℃ in temperature; Reacted 60～240 minutes.
9, the treatment process of wastewater from dinitrobenzene production with benzene mixed acid nitrification as claimed in claim 1 is characterized in that the described inorganic acid of step (1) is sulfuric acid or hydrochloric acid.
10, the treatment process of wastewater from dinitrobenzene production with benzene mixed acid nitrification as claimed in claim 1 is characterized in that described step is as follows:
(1) acidifying: with benzene mixed acid nitrification produce that dinitrobenzene produces in and the washing soda wastewater, transfer pH value 2～4 with sulfuric acid, acid material;
(2) iron charcoal reduction: acid material is incorporated with the iron carbon reactor of cast iron filing and gac, and iron, charcoal mass ratio are 3～8: 1, and the quality of iron is 2～5% of an acid material, 20～55 ℃ of reactions of control reaction temperature 60～240 minutes; Filter reduced liquid;
(3) polycondensation: the quality that detects aniline category matter in the reduced liquid, the pH value 5.5～6.5 of control reaction solution, in reduced liquid, add formaldehyde, the formaldehyde that control adds and the mass ratio of aniline category matter are 12～20%, stirring reaction 30～100min, make amino phenol and aniline generation polycondensation, generate polymer precipitation;
(4) flocculating settling: the reaction mass that step (3) obtains is with lime or liquid caustic soda adjust pH to 7.5～9.0, add polyacrylamide, make the polycondensate sedimentation, the reaction mass volume ratio that polyacrylamide and step (3) obtain is 1: 3000～5000), separate the insolubles that anhydrates, obtain the sedimentation water outlet;
(5) the sedimentation water outlet is through conventional biochemical treatment, and discharge back up to standard.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101531430B (en) * | 2009-04-22 | 2011-05-04 | 南京大学 | Method for releasing biological toxicity of mixed acid nitrified wastewater |
| CN105152445A (en) * | 2015-09-25 | 2015-12-16 | 浙江奇彩环境科技有限公司 | Treatment method of organic wastewater of nitrobenzene category |
| CN106477769A (en) * | 2016-10-26 | 2017-03-08 | 浙江奇彩环境科技股份有限公司 | A kind of processing method of nitrobenzene compounds waste water |
| CN113104946A (en) * | 2021-04-01 | 2021-07-13 | 时代沃顿科技有限公司 | Method for treating wastewater containing polyamino aromatic compounds |
| CN114605041A (en) * | 2022-04-01 | 2022-06-10 | 扬州工业职业技术学院 | Environment-friendly purification device and method for purifying industrial high-alkalinity wastewater |
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- 2008-10-23 CN CN 200810121721 patent/CN101402503B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531430B (en) * | 2009-04-22 | 2011-05-04 | 南京大学 | Method for releasing biological toxicity of mixed acid nitrified wastewater |
| CN105152445A (en) * | 2015-09-25 | 2015-12-16 | 浙江奇彩环境科技有限公司 | Treatment method of organic wastewater of nitrobenzene category |
| CN106477769A (en) * | 2016-10-26 | 2017-03-08 | 浙江奇彩环境科技股份有限公司 | A kind of processing method of nitrobenzene compounds waste water |
| CN113104946A (en) * | 2021-04-01 | 2021-07-13 | 时代沃顿科技有限公司 | Method for treating wastewater containing polyamino aromatic compounds |
| CN114605041A (en) * | 2022-04-01 | 2022-06-10 | 扬州工业职业技术学院 | Environment-friendly purification device and method for purifying industrial high-alkalinity wastewater |
| CN114605041B (en) * | 2022-04-01 | 2022-12-06 | 扬州工业职业技术学院 | Environment-friendly purification device and method for purifying industrial high-alkalinity wastewater |
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