CN105566176A - Improved 6-nitro-1-diazo-2-naphthol-4-sulphonic acid production process - Google Patents
Improved 6-nitro-1-diazo-2-naphthol-4-sulphonic acid production process Download PDFInfo
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- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
Abstract
The invention discloses an improved 6-nitro-1-diazo-2-naphthol-4-sulphonic acid (hereinafter referred to as 6nitro) production process. The process includes preparation of 1,2,4 acid, preparation of 1-diazo-2-naphthol-4-sulphonic acid and preparation of 6-nitro-1-diazo-2-naphthol-4-sulphonic acid and particularly includes steps: step 1, treating 6nitro wastewater through a diffusion dialysis membrane to recover acid and obtain diffusion dialysis treatment fluid; step 2, treating the diffusion dialysis treatment fluid to obtain treatment fluid by at least one of means of neutralization and sedimentation, microelectrolysis, Fenton oxidation, flocculation, wet oxidation, adsorption and extraction; step 3, treating the treatment fluid obtained at the step 2 by bipolar membrane electrodialysis to obtain an acid solution and an alkaline solution for recycling in 6nitro production process. By introduction of diffusion dialysis and bipolar membrane electrodialysis to the 6nitro production process, acid recovery is realized while acid and alkali input cost is reduced.
Description
Technical field
The present invention relates to the sour oxysome production technical field of 6-nitro-1,2,4, be specifically related to a kind of production technique of the sour oxysome of 6-nitro-1,2,4 of improvement.
Background technology
The sour oxysome of 6-nitro-1,2,4 is 6-nitro-DNSA by name entirely, also known as 6 nitre, is the intermediate manufacturing matching stain.
The production technique of 6 nitre oxysomes is divided into three sections, i.e. 1,2,4 acid preparation workshop section A, 1, and 2,4 sour oxysomes prepare workshop section B and the sour oxysome of 6-nitro-1,2,4 prepares workshop section C.In workshop section A, bisnaphthol obtains 1,2 through nitrosification-addition-sulfonation, and 4 acid, produce reducing waste water I simultaneously; In workshop section B, 1,2,4 acid, through diazonium-acid out, obtain 1,2,4 sour oxysomes, simultaneously output oxysome waste water II; In workshop section C, bisnaphthol 1,2,4 sour oxysomes, through nitrated-segregation, obtain the sour oxysome of 6-nitre-1,2,4, produce nitre body waste water III simultaneously.
From above-mentioned technique, in 6 nitre production processes, acid consumption is large, and in the waste water of generation, acid content is also higher.All containing naphthene sulfonic acid type organic in three strands of waste water, common treatment process has: Coagulation Method, resin method, extraction process.But coagulant sedimentation produces a large amount of difficult solid waste utilized, and resin method consumption alkali is many, and extraction process acid consumpting alkali amount is large, and all floor space is large, complicated operation, cost are high, the difficult recovery of resource for two kinds of methods.
For addressing this problem, the application is studied 6 nitre waste water, is devoted to find a kind of method of wastewater treatment that is novel, resource utilization, improves, excavate a kind of more clean, more economical technique to 6 nitre production technique.
Summary of the invention
The invention provides a kind of production technique of the sour oxysome of 6-nitro-1,2,4 of improvement, the waste water produced in the sour oxysome production technique of 6-nitro-1,2,4 is recovered to acid by diffusion dialysis film, film water outlet qualified discharge after treatment.
A kind of production technique of the sour oxysome of 6-nitro-1,2,4 of improvement, comprises 1,2, the preparation, 1 of 4 acid, the preparation of 2,4 sour oxysomes and 6-nitro-1,2, the preparation of 4 sour oxysomes, is characterized in that, also comprise the step processed the 6 nitre waste water produced in production process, concrete steps are as follows:
Step (1): 6 nitre waste water, through the process of diffusion dialysis film, are recovered to acid, obtain diffusion dialysis treatment solution;
Step (2): at least one in the optional following processing mode of diffusion dialysis treatment solution carries out pre-treatment, obtains brackish water:
Mode 2-a, filters after neutralization precipitation;
Mode 2-b, light electrolysis and filtration: be under the acidic conditions of 2 ~ 5 at pH, light electrolysis carried out to the diffusion dialysis treatment solution that step (1) obtains, then filters;
Mode 2-c, Fenton oxidation: be under the acidic conditions of 2 ~ 5 at pH, at 40 ~ 60 DEG C, adds hydrogen peroxide, molysite and/or ferrous salt, carries out Fenton oxidation in the diffusion dialysis treatment solution that step (1) obtains;
Mode 2-d, flocculation and filtration: add flocculation agent in the diffusion dialysis treatment solution that step (1) obtains, then regulates pH to 8 ~ 10, filters after flocculation;
Mode 2-e, wet oxidation: the diffusion dialysis treatment solution that step (1) obtains 100 ~ 300 DEG C, carry out wet oxidation under the condition of 0.5 ~ 10MPa;
Mode 2-f, absorption: add sorbent material in the diffusion dialysis treatment solution that step (1) obtains, filter after whip attachment;
Mode 2-g, extraction: the diffusion dialysis treatment solution that step (1) obtains carries out complexometric extraction, is separated and obtains treatment solution;
Step (3): the brackish water that step 2 obtains, by bipolar membrane electrodialysis process, obtains bronsted lowry acids and bases bronsted lowry; Bronsted lowry acids and bases bronsted lowry reuse to 1, in the preparation of 2,4 acid preparations and/or 1,2,4 sour oxysomes.
Diffusion dialysis and electrodialytic technique are incorporated in the sour oxysome technique of 6-nitro-1,2,4 by the present invention, have both reclaimed acid, reduce again the input cost of soda acid or salt.
The waste water acid content produced in 6 nitre production processes is higher, about 10-30%, mainly sulfuric acid.In ordinary method, usually to first neutralize.When adopting limestone vegetation, obtain solid waste, containing many organism in solid waste, belonging to danger useless, the high and waste resource of processing costs; To adopt in sodium hydroxide, sodium carbonate, potassium sulfate, salt of wormwood, ammoniacal liquor etc. and time, obtain soluble salt, rear concentration and recovery salt, but alkali consumption is large, the salt quality be recovered to differs, and utility value is poor.In addition, in the reducing waste water produced in 6 nitre production processes outside sulfuric acid, the sodium sulfate salt of 5-10% is also had; Containing a small amount of copper sulfate in oxysome waste water; Containing a small amount of nitric acid in nitre body waste water.
As preferably, step (1) is front also comprises absorption.In waste water, add 0.1-2% (taking wastewater quality as benchmark) sorbent material, after whip attachment 30-90min, filter.Or waste water at the uniform velocity by adsorption column, obtains out post liquid.Described sorbent material is one or more in gac, diatomite, activated coke, wilkinite, molecular sieve; In described adsorption column, weighting material is one or more in activated carbon granule, activated coke, molecular sieve, activated alumina.Further preferably, the post speed excessively of waste water is 0.5-10BV/h.Preferred again, the post speed excessively of waste water is 1-2BV/h.
In step 1,6 nitre waste water pass through the process of diffusion dialysis film, in sour reuse to the 6 nitre production technique obtained.Such as, the acid obtained is used for preparation diluted acid (massfraction is 50%), and reuse to 1, in the nitrosification of 2,4 sour synthesizing sections and/or sulfonation process.
As preferably, in mode 2-a, neutralization precipitation adopts sodium hydroxide, sodium carbonate, sodium bicarbonate or alkaline sulfides.Preferred again, adopt in sodium hydroxide, sodium carbonate, sodium bicarbonate one or more to be neutralized to pH be after 6-9, then continue to react by one or more in sodium sulphite, Sodium sulfhydrate.
In mode 2-b, Fe/C reaction principle is as follows:
Following electrochemical reaction is there is after waste water contacts with iron carbon:
Anode: Fe-2e-→ Fe
Negative electrode: 2H
++ 2e-→ H
2
Under the condition of aeration Fuyang, also there is following reaction:
O
2+4H
++4e-→2H
2O
O
2+2H
2O+4e-→4OH
-
4Fe
2++O
2+4H+→2H
2O+4Fe
3+
In reaction process, owing to producing OH-, so the pH of system constantly rises; Meanwhile, the Fe2+ of generation or Fe3+ and OH-combines, and produces flco and precipitation, the pollutent in effective adsorption-condensation water, strengthening water treatment effect.
As preferably, the light electrolysis in mode 2-b: with the quality of pending liquid for benchmark, adds light electrolysis reagent in pending liquid, and the dosage of iron is 0.5 ~ 4%, and the mass ratio of iron and carbon is 2 ~ 20:1, carries out light electrolysis; Or add iron carbon reagent in pending liquid, aerated reaction 1 ~ 6h, the volume ratio of iron carbon reagent and pending liquid is 1:2 ~ 9.
Preferred again, the light electrolysis in mode 2-b: with the quality of pending liquid for benchmark, adds iron and the carbon of 0.5 ~ 2% in pending liquid, and the mass ratio of iron and carbon is 5 ~ 10:1, carries out light electrolysis; Or the volume ratio of iron carbon reagent and pending liquid is 1:1 ~ 5.
The light electrolysis time in mode 2-b is selected as required, and preferably, the light electrolysis time is 1 ~ 6h.In whole microelectrolysis process, the pH value of maintenance system is constant.Further preferably, the light electrolysis time is 2 ~ 4h.
As preferably, mode 2-c, with the quality of pending liquid for benchmark, molysite and/or the ferrous salt (total add-on of molysite and/or ferrous salt is 0.5 ~ 5%) of 0.5 ~ 5% is added in pending liquid, and the hydrogen peroxide of 0.5 ~ 30%, the massfraction of hydrogen peroxide is 27 ~ 30%, carries out Fenton oxidation.
Molysite and ferrous salt adopt water-soluble salt, and such as, molysite adopts ferric sulfate, iron(ic) chloride usually, and ferrous salt adopts ferrous sulfate, iron protochloride usually.
In mode 2-c, Fenton reaction principle is as follows:
Fe
2++H
2O
2→Fe
3++OH
-+·OH(1)
Fe
3++H
2O
2→Fe
2++HO
2·+H
+(2)
Fe
2++·OH→Fe
3++OH
-(3)
Fe
3++HO
2·→Fe
2++O
2+H
+(4)
·OH+H
2O
2→H
2O+HO
2·(5)
Fe
2++HO
2·→Fe
3++HO
2 -(6)
RH+·OH→R·+H
2O(7)
R·+Fe
3+→R
++Fe
2+(8)
R·+H
2O
2→OH+·OH(9)
The reaction of whole system is very complicated, and its key passes through Fe
2+or Fe
3+play in the reaction and excite and transmission effect, and H
2o
2then play oxygenizement, generate the hydroxyl radical free radical OH with extremely strong oxidation capacity, thus the organism in oxidized waste water.
In the process of Fenton oxidation, carry out Keep agitation, the Fenton oxidation time is 1 ~ 10h, needs to add hydrogen peroxide, add Fe simultaneously in Fenton oxidation process
2+, Fe
3+in at least one.
Further preferably, mode 2-c, with the quality of pending liquid for benchmark, adds molysite and/or the ferrous salt of 0.5 ~ 4% in pending liquid, and the hydrogen peroxide of 0.5 ~ 15%, and the massfraction of hydrogen peroxide is 27 ~ 30%, carries out Fenton oxidation.
As preferably, the flocculation in mode 2-d, after adding flocculation agent, then adds polyacrylamide and/or sorbent material in pending liquid, then regulates pH to 8 ~ 10, flocculates.Keep agitation in flocculation process, flocculation time is 30 ~ 60min.
As preferably, described flocculation agent is FeSO
47H
2one or more in O, polyaluminium sulfate, iron protochloride, polymerize aluminum chloride, PAFS, poly-ferric chloride.
With the quality of pending liquid for benchmark, the add-on of flocculation agent is 0.2-4%, and the add-on of polyacrylamide is 0.0001 ~ 0.005%, and the add-on of sorbent material is 0.02 ~ 0.5%.Further preferably, the add-on of flocculation agent is 0.2-2%, and the add-on of polyacrylamide is 0.0001 ~ 0.001%, and the add-on of sorbent material is 0.1 ~ 0.5%.
As preferably, in mode 2-f, sorbent material is one or more in activity charcoal powder/particle, diatomite, and with the quality of pending liquid for benchmark, the dosage of sorbent material is 0.02 ~ 2%.
As preferably, in mode 2-f, sorbent material is adsorption column, and filler is one or more in gac, activated coke, molecular sieve, wilkinite, quartz sand.The volume ratio of pending liquid and sorbent material filler is 1 ~ 5:1.Preferred again, the volume ratio of pending liquid and sorbent material is 1 ~ 2:1.
As preferably, in method 2-g, the mixed volume ratio of extraction agent and thinner is 1:1-6, and water oil ratio is 1:1-8, and wastewater pH is 0.5-4.
Further preferably, in method 2-g, extraction agent is trioctylamine, and thinner is the one in toluene, ethylene dichloride, sulfonated kerosene.
In order to obtain better pretreating effect, obtaining clean brackish water, various pretreatment mode can be carried out coupling when carrying out pre-treatment to diffusion dialysis treatment solution, preferably, adopt following either type to carry out pre-treatment:
Mode A, carries out mode 2-b, mode 2-d successively;
Mode B, carries out mode 2-e, mode 2-a, mode 2-f successively;
Mode C, carries out mode 2-b, mode 2-c, mode 2-d, mode 2-f successively;
Mode D, carries out mode 2-g, mode 2-a successively;
Further preferably, mode A is as follows:
Mode 2-b, light electrolysis: be under the acidic conditions of 2 ~ 5 at pH, add light electrolysis reagent in diffusion dialysis treatment solution, stirring reaction 2 ~ 6h, after reaction terminates, standing separation, obtains clear liquid;
Mode 2-d, flocculation: add flocculation agent in above-mentioned clear liquid, then regulates pH to 8 ~ 10, filters after flocculation.
Mode B is as follows:
Mode 2-e, wet oxidation: diffusion dialysis treatment solution, under 180-250 DEG C, 0.5-4MPa condition, makees oxygenant with oxygen or air, carries out 40-180min oxidizing reaction, obtains wet oxidation treatment solution;
Mode 2-a, neutralization precipitation, by the pH regulator to 8 of wet oxidation treatment solution ~ 10, filters and obtains filtrate I;
Mode 2-f, absorption: add sorbent material in filtrate I, agitation and filtration, obtain treatment solution.
As preferably, catalyzer can be added in described wet oxidation reaction, described catalyzer is one or more in soluble copper salt, molysite, nickel salt, cobalt salt etc., and the dosage of catalyzer is 0.1-2.5% (to participate in the quality of the waste water of wet oxidation for benchmark).
Preferred again, in the mode 2-a of mode B, in wet oxidation treatment solution, add reducible sulfur compound, stirring reaction 30-90min, filter and obtain filtrate.
Further preferably, first use one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate, after wet oxidation treatment solution pH regulator to 6-9, then add reducible sulfur compound wherein.Described reducible sulfur compound is one or more in sodium sulphite, Sodium sulfhydrate, and dosage is 1-1.5 times of the molar content of the effective constituent of catalyzer.
The molar content effective constituent of described catalyzer is the molar content of metallic element.
Mode C is as follows:
Mode 2-b, light electrolysis: be under the acidic conditions of 2 ~ 5 at pH, add light electrolysis reagent in diffusion dialysis treatment solution, reaction 2 ~ 6h, then filters, obtains filtrate II;
Mode 2-c, Fenton oxidation: filtrate II heating and thermal insulation, to 40-60 DEG C, adds 0.5-2% hydrogen peroxide (massfraction is 27-30%, with the quality of filtrate II for benchmark), stirring reaction 0.5-2h, terminates reaction;
Mode 2-d, flocculation: add flocculation agent in Fenton oxidation product, then regulates pH to 8 ~ 10, stirs flocculation 30 ~ 60min, filters, obtain filtrate III after flocculation;
Mode 2-f, absorption: add sorbent material in filtrate III, agitation and filtration, obtain treatment solution.
Preferred again, in mode C, also comprise neutralization precipitation after flocculation, add one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate in filtrate III, being neutralized to pH is 6-8.
Mode D is as follows:
Mode 2-g, extraction: be that under the acidic conditions of 0.5 ~ 4, diffusion dialysis treatment solution carries out complexometric extraction at pH, the ratio of extraction agent and thinner is 1:1-8, and water oil ratio is 1:1-8, stirring reaction 10-60min, and standing separation, obtains subnatant;
Mode 2-a, neutralization precipitation: it is 8-10 that above-mentioned subnatant is neutralized to pH, stirring reaction 10-60min, filters and obtains filtrate IV;
Preferred again, in mode D, after mode 2-a, also comprise absorption, in filtrate IV, add 0.05-0.5% sorbent material, whip attachment 30-90min, filter and obtain treatment solution.
As preferably, the electrodialysis described in step (3) comprises bipolar membrane electrodialysis and common electrodialysis.
Bipolar Membrane is a kind of novel ion-exchange composite membranes, and under DC electric field effect, Bipolar Membrane by hydrolytic dissociation, can obtain hydrogen ion and hydroxide ion in film both sides respectively.Bipolar membrane electrodialysis technology utilizes this feature, Bipolar Membrane is combined with common electrodialysis, when not introducing new component, the salt in the aqueous solution is converted into corresponding bronsted lowry acids and bases bronsted lowry.This technology can be widely used in the fields such as food-processing, chemical industry synthesis and environment protection, and due to its technical advance, Economic competitive and environment friendly, bipolar membrane electrodialysis technology is described as a kind of Sustainable development technology.
The treatment solution that step (2) obtains is the aqueous solution of main contains sodium sulfate, and this treatment solution passes in the compartment be made up of anion-exchange membrane and cationic exchange membrane, under DC electric field effect, and Na
+by the OH that cationic exchange membrane and Bipolar Membrane dissociate water produce
-combine in alkali room and generate NaOH; SO
4 2-by the H that anion-exchange membrane and Bipolar Membrane dissociate water produce
+combine in sour room and generate H
2sO
4.
As preferably, in step (3), before bipolar membrane electrodialysis process is carried out to brackish water, first electrodialysis is carried out to brackish water and concentrate, obtain the brackish water of high density.This high density brackish water again by bipolar membrane electrodialysis recovered acid or alkali, or concentrates further, and crystallization obtains crystalline salt.
Further preferably, common electrodialysis adopt saltiness be the conductive soln of 2 ~ 5% as pole liquid, current density is 50 ~ 500A/m
2.
When electrodialysis is carried out to brackish water, adopt heterogeneous membrane or half homogeneous membrane, the treatment solution that step (2) obtains is passed into the freshwater room of electrodialysis system, not saliferous or the low water of saltiness is entered in dense hydroecium, after electrodialysis, the dense water obtained be concentrated after salts solution, the fresh water obtained mixes with the brackish water obtained after next batch pre-treatment and again carries out electrodialysis.Obtain after electrodialysis process concentrated after salts solution carry out bipolar membrane electrodialysis process.
As preferably, the inorganic salt in above-mentioned conductive soln are one or more in sodium sulfate, potassium sulfate, sodium-chlor, ammonium sulfate.Preferred again, the inorganic salt in above-mentioned conductive soln are one or more in sodium sulfate, potassium sulfate.
As preferably, when step 3 carries out bipolar membrane electrodialysis process, adopt titanium to be coated with ruthenium as electrode, current density is 100 ~ 700A/m
2.
During bipolar membrane electrodialysis, adopt saltiness be the inorganic salt solution of 0.1 ~ 5% as pole liquid, weak brine reuse is after treatment to electrodialysis step.
Run after for some time, functional quality mark be 2 ~ 5% hydrochloric acid soln Bipolar Membrane system is cleaned.
Compared with the prior art, the present invention has the following advantages:
Diffusion dialysis and electrodialytic membranes technology are incorporated in 6 nitre production technique, can process the waste water that technique produces, the acid simultaneously obtained and alkali or salt are back in technique again, have both solved the process problem of waste water, can reduce again the input cost of soda acid.Present invention process flow process is succinct, simple to operate, mild condition, and the salt while process waste water in energy recycling waste water, realizes cleaner production.
Accompanying drawing explanation
Fig. 1 is the production technological process of 6 nitre that the present invention improves.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and do not play any restriction effect.
If be not particularly limited temperature in the present invention, then at room temperature carry out.
Technical process of the present invention as shown in Figure 1.
Embodiment 1
Produce in 6 nitre production processes 1,2,4 sour waste water, aobvious dark red, COD is about 28790mg/L, and sulfuric acid content is 11%, contains sodium sulfate, S-WAT in waste water, the inorganic componentss such as sulfurous acid iron.
(1) acid recovery: after adding 0.4% gac whip attachment 60min in above-mentioned waste water, the COD obtaining filtrate is about 17090mg/L.By diffusion dialysis film, obtain acid solution and organic waste water.Recording acid content in acid solution is that 10%, COD is about 20mg/L; 18800mg/L is about containing acid 1.1%, COD in organic waste water.
(2) treatment of Organic Wastewater: the organic waste water that step (1) obtains is heated to 60 DEG C, adds 0.2%FeSO
47H
2o, evenly adds 11% hydrogen peroxide (massfraction of hydrogen peroxide is 28%) in 4h, and limit edged stirs, after adding, and insulation reaction 30min.Add calcium oxide wherein and regulate pH to 8.5, stir flocculation 100min, filter and obtain filtrate.Filtrate shows slightly yellow, and COD is 200mg/L, contains sodium sulfate 10%.
(3) soda acid is recycled: the filtrate that step (2) obtains is by bipolar membrane electrodialysis system, and adjustment current density is 700A/m
2, temperature is 30 DEG C, obtains the sodium hydroxide of 8.3% and the sulfuric acid of 10%, and the water outlet of saliferous 0.68%.Sulfuric acid is used for the dilute sulphuric acid of preparation 50%, for 1, and the nitrosation step of 2,4 acid production processes; Sodium hydroxide is used for the dissolving of bisnaphthol in nitrosification, and water outlet is used for dissolving sodium bisulfite.
Embodiment 2
In described in embodiment 11,2,4 sour method of wastewater treatment, step (1) is constant, and other steps are as follows:
Step (2): the organic waste water that step (1) obtains extracts, extraction agent is trioctylamine, thinner is sulfonated kerosene, extraction agent and thinner by volume 1:4 mix and are made into oil phase, water oil ratio is 1:1, after stirring extraction 30min, be separated through water-and-oil separator, obtain subnatant and show slightly yellow.Subnatant adds liquid caustic soda and regulates pH to 8, adds 0.2% (with the quality of subnatant for benchmark) gac, whip attachment 30min, filters and obtains filtrate.Filtrate is almost colourless transparent, and recording its COD is 56mg/L, contains sodium sulfate 11%.
Step (3): above-mentioned filtrate is concentrated by MVR, obtains sodium sulfate salt, meets industrial salt standard, reuse to 1,2, the sulfonation process of 4 acid production processes; The phlegma be recovered to is with to recovered acid in step (1); The concentrated solution obtained shows slightly yellow, and COD is 409mg/L, continues concentrated with extraction after the subnatant mixing and absorption process obtained.
Embodiment 3
Produce in 6 nitre production processes 1,2,4 sour oxysome waste water, aobvious scarlet, COD is about 16570mg/L, and sulfuric acid content is 15%, contains sodium sulfate about 3% in waste water, copper about 0.18%.
(1) filter after adding 0.2% gac whip attachment 60min in above-mentioned waste water, the COD obtaining filtrate is about 14599mg/L.Filtrate, by diffusion dialysis film, obtains acid solution and organic waste water.Recording acid content in acid solution is that 14%, COD is about 47mg/L; Record organic waste water COD and be about 15098mg/L.
(2) organic waste water that step (1) obtains carries out complexometric extraction, water oil ratio is 1:2 (volume ratio, be made into oil phase by trioctylamine and ethylene dichloride with 1:3 volume mixture, stir extraction 1h at 50 DEG C, standing separation obtains upper organic phase and subnatant.The COD recording subnatant is about 202mg/L, and content of copper ion is 0.31%.
(3) sodium sulphite 0.18% (with subnatant quality for benchmark) is added in the subnatant that step (2) obtains, the pH regulating clear liquid is 8-9, filter after stirring reaction 0.5h, 0.1% gac is added in the filtrate obtained, after whip attachment 30min, filter and obtain filtrate.
(4) filtrate that step (3) obtains is concentrated by electrodialytic membranes, and the current density of electrodialysis system is 400A/m2, and temperature is 30 DEG C.Obtain the salt solution that saliferous is 10%.This salt solution, through bipolar membrane electrodialysis system, obtains the sulphuric acid soln of 9% and the sodium hydroxide solution of 7.5%, and the water outlet of saliferous 0.9%.
(5) enter electrodialysis system after the filtrate that the water outlet of above-mentioned electrodialysis freshwater room and Bipolar Membrane water outlet obtain with step (3) again mixes and continue concentration.The bronsted lowry acids and bases bronsted lowry reuse to 1 again that step (4) obtains, 2,4 acid synthesis and 1,2,4 sour oxysome synthesis steps in.
(6) step (2) processes the upper organic phase that obtains after sodium hydroxide back extraction, the strip liquor obtained passes through electrodialysis process, obtain organic liquid waste and brackish water, the filtrate that brackish water and step (3) obtain mixes and enters electrodialysis system again and continue to process.After testing, wherein containing two kinds of materials, the content of material 1 is 95% to the organic liquid waste obtained, the content of material 2 is 4%.Further detection finds that material 1 is intermediate product, and material 2 is by product.Organic liquid waste can reuse in products production.Be applied to by organic liquid waste in products production, the product quality of output is without obvious decline.
Embodiment 4
Oxysome method of wastewater treatment described in embodiment 3, step (1) is constant, and other steps are as follows:
(2) pumped into by waste water in one-level iron carbon pond, the volume ratio of iron carbon reagent and waste water is 1:2, after aerated reaction 2h, standing separation, adds 0.4% diatomite in the clear liquid obtained, the pH regulating clear liquid with calcium oxide is 8, stirring reaction 30min, press filtration obtains filtrate; It is in 3 rear inflow secondary iron carbon ponds that filtrate is adjusted to pH, the volume ratio of iron carbon reagent and waste water is 1:4, after aerated reaction 1h, standing separation, add 0.2% gac in the clear liquid obtained, being adjusted to pH with liquid caustic soda is 8, stirring reaction 40min, press filtration obtains yellow filtrate, records COD=1450mg/L; Add the sodium sulphite of 0.05% wherein, filter after stirring reaction 30min, then in filtrate, add the diatomite of 0.5%, whip attachment 40min, filter that to obtain filtrate almost colourless transparent, COD is about 569mg/L, copper content is about 0.01%, saltiness is 7%.
(3) filtrate that obtains of step (2) is through bipolar membrane electrodialysis system, and adjustment current density is 400A/m
2, the obtained sulphuric acid soln of 8% and the sodium hydroxide solution of 7.5%, and the water outlet of saliferous 0.9%.
(4) enter electrodialysis system after the filtrate that above-mentioned Bipolar Membrane water outlet obtains with step (3) again mixes and continue concentration.The bronsted lowry acids and bases bronsted lowry reuse to 1 again that step (4) obtains, 2,4 acid synthesis and 1,2,4 sour oxysome synthesis steps in.
Embodiment 5
Oxysome waste water described in embodiment 3, processes by the following method:
(1) filter after adding 0.2% gac whip attachment 60min in waste water, the COD obtaining filtrate is about 14599mg/L.Filtrate, by diffusion dialysis film, obtains acid solution and organic waste water.Recording acid content in acid solution is that 14%, COD is about 47mg/L; Record organic waste water COD and be about 15098mg/L.
(2) in waste water, add the gac of 2% reduced iron powder and 0.3%, after 30 DEG C of reaction 2h, standing separation, the clear liquid obtained is heated to 60 DEG C, in 4h, evenly add 5% hydrogen peroxide (quality of the organic waste water obtained with step (1) is for benchmark), then react 30min, add alkali and regulate pH to 9, stir flocculation 60min, filter and obtain filtrate displaing yellow, COD=1000mg/L; Add the sodium sulphite of 0.08% wherein, filter after stirring reaction 30min, in filtrate, add the diatomite of 0.5%, whip attachment 40min, filter that to obtain filtrate almost colourless transparent, COD is about 509mg/L, copper content is about 0.03%, saltiness is 5%.
(3) filtrate that step (2) obtains is concentrated by electrodialytic membranes, and the current density of electrodialysis system is 600A/m
2, temperature is 30 DEG C.Dense room and the water inlet of light room are the filtrate that step (2) obtains, and obtaining saliferous is the dense water of 11% and the fresh water of saliferous 0.5%.Dense water, through bipolar membrane electrodialysis system, obtains the sulphuric acid soln of 9% and the sodium hydroxide solution of 7.5%, and the water outlet of saliferous 0.9%.
(4) enter electrodialysis system after the filtrate that the water outlet of above-mentioned electrodialysis freshwater room and Bipolar Membrane water outlet obtain with step (3) again mixes and continue concentration.The bronsted lowry acids and bases bronsted lowry reuse to 1 again that step (4) obtains, 2,4 acid synthesis and 1,2,4 sour oxysome synthesis steps in.
Embodiment 6
The nitration waste water produced in 6 nitre production processes, in bright red, is with a little white opacity thing, COD=8000mg/L; Ammonia-nitrogen content 190mg/L; Sulfuric acid content 23%; Nitric acid content 0.017% (spectrophotometer test).
(1) filter after adding 0.5% gac whip attachment 45min in above-mentioned waste water, liquor C OD is about 6800mg/L.Filtrate, by diffusion dialysis film, obtains acid solution and organic waste water.Recording acid content in acid solution is that 22%, COD is about 40mg/L; The COD of organic waste water is about 7170mg/L.
(2) organic waste water that step (1) obtains adds alkali, and to be neutralized to pH be 8, filters and obtain filtrate.
(3) filtrate that step (2) obtains is concentrated by electrodialytic membranes, and electrodialytic current density is 550A/m2, and temperature is 28 DEG C.Obtain the dope of saliferous 8.7% and the light liquid of saliferous 0.78%.After dope concentrates further, Crystallization Separation obtains sodium sulfate crystal.Reuse to 1, in 2,4 sour synthesis steps, fresh water reuse is to the isolation step of nitration processes.
(4) organic waste water that step (1) obtains can be used to make water reducer.
Embodiment 5
6 nitre production technique are improved in the following manner.
1,1,2,4 acid preparations
1.1 to mix with 300kg water with the sodium hydroxide solution that 300kg massfraction is 9% after dissolve 100kg bisnaphthol, be heated to 80 DEG C of stirring and dissolving, obtain the beta naphthal solution of pH=10.7; Be cooled to 0-5 DEG C, add 48kg sodium nitrite solution (massfraction is 40%), at being incubated 0 ~ 10 DEG C, sulphuric acid soln 150kg (sulfuric acid of be made into by 4.6 methods 50%) is evenly added in 4 hours, congo-red test paper is surveyed in acid, during the micro-blue look of potassium iodide starch paper, and insulation reaction 1h, filter, obtain waste water 580kg.
1.2 above-mentioned filter cakes add the making beating of 1500L water, be adjusted to congo-red test paper just disappear with the liquid caustic soda that step 4.5 is obtained.At 15-20 DEG C, add 170kg sodium metabisulfite solution (massfraction is 60%), react 1 hour.Filtration obtains filtrate.
1.3 add 100kg sodium sulfate in above-mentioned filtrate, after stirring and dissolving, add 100kg sulfuric acid, are heated to 55-60 DEG C, filter after standing and reacting 8h, obtain 1,2 in 3h, 4 sour finished product 166kg and 1,2,4 sour waste water 2577kg.
2,1,2,4 sour oxysome preparations
2.1 above-mentioned 1,2,4 sour finished products add the making beating of 550kg water, and the liquid caustic soda obtained by step 4.5 is neutralized to pH=4, adds 1.7kg cupric sulfate pentahydrate, are on the rocksly down to 15 DEG C, add 132kg sodium nitrite solution (massfraction is 40%).Under temperature 25 ~ 30 DEG C, starch potassium iodide paper are micro-blue condition, stirring reaction 1 hour.
2.2 are heated to 40 ~ 45 DEG C, filtered while hot, and the filtrate obtained slowly added 228kg sulphuric acid soln (sulfuric acid of be made into by 4.6 methods 50%) in 3 ~ 4 hours, press filtration after insulation reaction 1h, obtain 1,2,4-acid oxysome finished product 136kg, and 1,2,4 sour oxysome waste water 784kg.
3,6 taws are standby
210kg nicotinic acid is cooled to 0-15 DEG C by 3.1, slowly adds oxysome, then between 30 ~ 35 DEG C, then adds 85kg nicotinic acid, stirring reaction 30 minutes.Add 100kg nitration mixture (nitric acid and nicotinic acid mass ratio are 1:2) under 15 ~ 20 DEG C of conditions, keep 18 ~ 25 DEG C to react 5 hours.In 800kg frozen water, slowly put into nitrification liquid under 0 ~ 5 DEG C of condition, the adjustment reactant total mass that adds water after discharging is 1300kg, and insulated and stirred reacts 30 minutes, leaves standstill 5 hours.
3.2 press filtrations, dry up, and obtain finished product 130kg.Produce waste water 1130kg simultaneously.
4, wastewater treatment
4.1 waste water produced step (1)-(3) are 5000kg altogether, and after mixing, waste water shows black, has a small amount of suspended substance.COD is 20977mg/L, acid content 18%, sodium sulphate content 5%, cupric 0.08%.
In waste water, add 0.3% gac, whip attachment 60min, filter and obtain filtrate.It is general red that filtrate shows black, and COD is about 18070mg/L.By filtrate by the process of diffusion dialysis film, do absorption liquid with the sulphuric acid soln that 14000kg massfraction is 9.5%, obtain containing the sulphuric acid soln 15000kg of the acid 15% and organic waste water 4100kg containing acid 0.8%;
4.2 above-mentioned organic waste waters, at 200 DEG C, under 1MPa condition, make oxygenant with oxygen, and high-temperature high-voltage reaction 60min obtains wet oxidation treatment solution, and 3800kg, COD are about 5670mg/L, cupric 0.21% altogether to record treatment solution;
4.3 sodium sulphite adding 0.06% (with wet oxidation treatment solution quality for benchmark) in wet oxidation treatment solution, and regulate pH to 9, agitation and filtration obtains filtrate, and in filter residue, copper sulfide content is 98.5%, makees catalyzer again after can selling or be oxidized with in 2.1;
4.4 add 0.4% gac, agitation and filtration in filtrate I, and obtain treatment solution 3200kg, treatment solution is almost colourless transparent, and COD is about 319mg/L, and sodium sulphate content is 12%.
4.5 above-mentioned treatment solutions are by the bipolar membrane electrodialysis of three compartments, and the fresh water that treatment solution feed chamber, electrodialysis obtain enters sour room and light room respectively, and current density is 550A/m
2, obtain the sodium hydroxide solution 2250kg of the sulphuric acid soln 2800kg and 9% of 9.5%, and the water outlet 2780kg of saliferous about 0.6%.
4.6 to 290kg massfractions are slowly add the vitriol oil that 210kg massfraction is 98% in the sulphuric acid soln of 15%, are made into the sulfuric acid that 500kg massfraction is 50%, and for the production of in technique, the sulfuric acid of 9.5% does the absorption liquid of diffusion dialysis; With 300kg massfraction be 9% sodium hydroxide solution mix with 300kg water after dissolve bisnaphthol, for regulating the alkali lye of pH to be 20kg, all the other are for absorbing the sulfurous gas overflowed in 1.2-1.3; By electrodialysis, concentrated (electrodialysis current density is 400A/m2 in Bipolar Membrane water outlet, dense room and light room is reverse enters Bipolar Membrane water outlet), obtaining 150kg massfraction is the dense water of 10% and the fresh water of 2600kg saliferous 0.4%, fresh water is intake as bipolar acid room, dense water mixes with the waste water after absorption, enters Bipolar Membrane process.
Claims (8)
1. the production technique of the sour oxysome of 6-nitro-1,2,4 improved, comprises 1,2, the preparation, 1 of 4 acid, the preparation of 2,4 sour oxysomes and 6-nitro-1,2, the preparation of 4 sour oxysomes, is characterized in that, also comprise the step processed the 6 nitre waste water produced in production process, concrete steps are as follows:
Step (1): 6 nitre waste water, through the process of diffusion dialysis film, are recovered to acid, obtain diffusion dialysis treatment solution;
Step (2): at least one in the optional following processing mode of diffusion dialysis treatment solution carries out pre-treatment, obtains brackish water:
Mode 2-a, filters after neutralization precipitation;
Mode 2-b, light electrolysis and filtration: be under the acidic conditions of 2 ~ 5 at pH, light electrolysis carried out to the diffusion dialysis treatment solution that step (1) obtains, then filters;
Mode 2-c, Fenton oxidation: be under the acidic conditions of 2 ~ 5 at pH, at 40 ~ 60 DEG C, adds hydrogen peroxide, molysite and/or ferrous salt, carries out Fenton oxidation in the diffusion dialysis treatment solution that step (1) obtains;
Mode 2-d, flocculation and filtration: add flocculation agent in the diffusion dialysis treatment solution that step (1) obtains, then regulates pH to 8 ~ 10, filters after flocculation;
Mode 2-e, wet oxidation: the diffusion dialysis treatment solution that step (1) obtains 100 ~ 300 DEG C, carry out wet oxidation under the condition of 0.5 ~ 10MPa;
Mode 2-f, absorption: add sorbent material in the diffusion dialysis treatment solution that step (1) obtains, filter after whip attachment;
Mode 2-g, extraction: the diffusion dialysis treatment solution that step (1) obtains extracts, is separated and obtains treatment solution;
Step (3): the brackish water that step 2 obtains, by bipolar membrane electrodialysis process, obtains bronsted lowry acids and bases bronsted lowry; Bronsted lowry acids and bases bronsted lowry reuse to 1, in the preparation of 2,4 acid preparations and/or 1,2,4 sour oxysomes.
2. the production technique of the sour oxysome of 6-nitro-1,2,4 of a kind of improvement as claimed in claim 1, is characterized in that, in step (2), diffusion dialysis treatment solution adopts following either type to carry out pre-treatment:
Mode A, carries out mode 2-b, mode 2-d successively;
Mode B, carries out mode 2-e, mode 2-a, mode 2-f successively;
Mode C, carries out mode 2-b, mode 2-c, mode 2-d, mode 2-f successively;
Mode D, carries out mode 2-g, mode 2-a successively.
3. the 6-nitro-1 of a kind of improvement as claimed in claim 1,2, the production technique of 4 sour oxysomes, it is characterized in that, light electrolysis in mode 2-b: with the quality of pending liquid for benchmark, adds light electrolysis reagent in pending liquid, and wherein the dosage of iron is 0.5 ~ 4%, the mass ratio of iron and carbon is 2 ~ 20:1, carries out light electrolysis; Or add iron carbon reagent in pending liquid, aerated reaction 1 ~ 4h, the volume ratio of iron carbon reagent and pending liquid is 1:2 ~ 9.
4. the 6-nitro-1 of a kind of improvement as claimed in claim 1,2, the production technique of 4 sour oxysomes, it is characterized in that, Fenton oxidation in mode 2-c: with the quality of pending liquid for benchmark, molysite and/or the ferrous salt of 0.5 ~ 5% is added in pending liquid, and the hydrogen peroxide of 0.5 ~ 30%, carry out Fenton oxidation.
5. the production technique of the sour oxysome of 6-nitro-1,2,4 of a kind of improvement as claimed in claim 1, it is characterized in that, the flocculation in mode 2-d: add flocculation agent in pending liquid after, then add polyacrylamide and/or sorbent material, then regulate pH to 8 ~ 10, flocculate.
6. the 6-nitro-1 of a kind of improvement as claimed in claim 1,2, the production technique of 4 sour oxysomes, it is characterized in that, absorption in mode 2-f: described sorbent material is one or more in gac, diatomite, activated coke, molecular sieve, with the quality of pending liquid for benchmark, the dosage of sorbent material is 0.02 ~ 2%.
7. the 6-nitro-1 of a kind of improvement as claimed in claim 1,2, the production technique of 4 sour oxysomes, it is characterized in that, in step (3): before bipolar membrane electrodialysis process is carried out to brackish water, first carry out electrodialysis to brackish water to concentrate, electrodialysis is concentrated adopt saltiness be the conductive soln of 2 ~ 5% as pole liquid, current density is 50 ~ 500A/m
2.
8. the production technique of the sour oxysome of 6-nitro-1,2,4 of a kind of improvement as claimed in claim 1, is characterized in that, when step (3) carries out electrodialysis process, current density is 100 ~ 700A/m
2.
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