CN105566176B - A kind of production technology of the sour oxysome of improved 6- nitros -1,2,4 - Google Patents

A kind of production technology of the sour oxysome of improved 6- nitros -1,2,4 Download PDF

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CN105566176B
CN105566176B CN201510835629.2A CN201510835629A CN105566176B CN 105566176 B CN105566176 B CN 105566176B CN 201510835629 A CN201510835629 A CN 201510835629A CN 105566176 B CN105566176 B CN 105566176B
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sour
acid
obtains
oxysomes
treatment fluid
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CN105566176A (en
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张云保
张静
吕伏建
梁伟
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Zhejiang Qicai Eco Technology Co Ltd
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Zhejiang Qicai Eco Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/42—Separation; Purification; Stabilisation; Use of additives
    • C07C303/44—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air

Abstract

The invention discloses a kind of improved sour oxysomes of 6 nitro 1,2,4（Hereinafter referred to as 6 nitre）Production technology, include the preparation of 1,2,4 acid, the preparation of 1,2,4 sour oxysomes and the preparation of the sour oxysome of 6 nitro 1,2,4, further include：Step 1,6 nitre waste water pass through diffusion dialysis film process, are recovered to acid, obtain diffusion dialysis treatment fluid；Step 2, at least one of optionally following processing mode of diffusion dialysis treatment fluid is handled, and obtains treatment fluid：Neutralization precipitation, light electrolysis, Fenton oxidation, flocculation, wet oxidation, absorption, extraction；Step 3, the treatment fluid that step 2 obtains is handled using bipolar membrane electrodialysis, in obtained acid solution and alkaline solution reuse to 6 nitre production technologies.Diffusion dialysis and bipolar membrane electrodialysis technology are introduced into 6 nitro production technologies by the present invention, have not only recycled acid, but also reduce the input cost of soda acid.

Description

A kind of production technology of the sour oxysome of improved 6- nitros -1,2,4
Technical field
The present invention relates to 6- nitros -1,2,4 sour oxysome production technical fields, and in particular to a kind of improved 6- nitro -1, The production technology of 2,4 sour oxysomes.
Background technology
6- nitros -1,2,4 sour oxysomes entitled 6- nitros -1-diazo-2-naphthol-4-sulfonic acid, also known as 6 nitre entirely, are manufacture acid The intermediate of property dyestuff.
The production technology of 6 nitre oxysomes is divided into three sections, i.e., 1, and 2,4 acid prepare workshop section A, 1,2,4 sour oxysomes prepare workshop section B and 6- The sour oxysome of nitro -1,2,4 prepares workshop section C.In workshop section A, bisnaphthol obtains 1,2,4 acid by nitrosation-addition-sulfonation, simultaneously Generate reducing waste water I；In workshop section B, 1,2,4 acid obtains 1,2,4 sour oxysomes, while output oxysome waste water II through diazonium-acid out； In workshop section C, the sour oxysome of bisnaphthol 1,2,4 obtains 6- nitre -1,2,4 sour oxysomes, while generate nitre body waste water III through nitrification-isolation.
From the process above it is found that in 6 nitre production processes, acid consumption is big, and acid content is also higher in the waste water of generation.Three strands useless Containing naphthalene sulfonic acids type organic in water, common processing method has：Coagulation Method, resin method, extraction.But coagulating sedimentation Method generates the solid waste that a large amount of difficulties utilize, and resin method consumption alkali is more, and extraction acid consumpting alkali amount is big, moreover, both of which floor space Greatly, complicated for operation, of high cost, the difficult recycling of resource.
To solve the problems, such as this, the application studies 6 nitre waste water, is dedicated to finding a kind of novel, recycling Wastewater treatment method, 6 nitre production technologies are improved, excavate it is a kind of more cleaning, more economical technique.
Invention content
The present invention provides a kind of improved 6- nitros -1,2, the production technology of 4 sour oxysomes, 6- nitros -1,2,4 sour oxysomes The waste water generated in production technology is recovered to acid by diffusion dialysis film, and film is discharged qualified discharge after treatment.
A kind of improved 6- nitros -1,2, the production technology of 4 sour oxysomes, the preparation including 1,2,4 acid, 1,2,4 sour oxysomes Preparation and 6- nitros -1,2, the preparation of 4 sour oxysomes, which is characterized in that further include to the 6 nitre waste water generated in production process into It the step of row processing, is as follows：
Step (1)：6 nitre waste water pass through diffusion dialysis film process, are recovered to acid, obtain diffusion dialysis treatment fluid；
Step (2)：At least one of optionally following processing mode of diffusion dialysis treatment fluid is pre-processed, and obtains saliferous Water：
Mode 2-a is filtered after neutralization precipitation；
Mode 2-b, light electrolysis and filtering：In the case where pH is 2~5 acid condition, at the diffusion dialysis that is obtained to step (1) It manages liquid and carries out light electrolysis, be then filtered；
Mode 2-c, Fenton oxidation：In the case where pH is 2~5 acid condition, at 40~60 DEG C, obtained to step (1) Hydrogen peroxide, molysite and/or ferrous salt are added in diffusion dialysis treatment fluid, carries out Fenton oxidation；
Mode 2-d, flocculation and filtering：Flocculant is added in the diffusion dialysis treatment fluid obtained to step (1), is then adjusted PH to 8~10 is filtered after flocculation；
Mode 2-e, wet oxidation：Diffusion dialysis treatment fluid that step (1) obtains is in 100~300 DEG C, 0.5~10MPa Under the conditions of carry out wet oxidation；
Mode 2-f, absorption：Add in adsorbent in the diffusion dialysis treatment fluid obtained to step (1), mistake after stirring and adsorbing Filter；
Mode 2-g, extraction：The diffusion dialysis treatment fluid that step (1) obtains carries out complexometric extraction, isolated treatment fluid；
Step (3)：The brackish water that step 2 obtains is handled by bipolar membrane electrodialysis, obtains bronsted lowry acids and bases bronsted lowry；Bronsted lowry acids and bases bronsted lowry reuse is extremely In 1,2,4 acid preparations and/or the preparation of 1,2,4 sour oxysomes.
Diffusion dialysis and electrodialytic technique are introduced into 6- nitros -1,2 by the present invention, in 4 sour oxysome techniques, are both recycled Acid, and reduce the input cost of soda acid or salt.
The waste water acid content generated in 6 nitre production processes is higher, about 10-30%, mainly sulfuric acid.In conventional method, lead to Chang Yaoxian is neutralized.Using in lime and when, obtain solid waste, contain in solid waste there are many organic matter, belong to dangerous waste, processing cost it is high and Waste of resource；Using sodium hydroxide, sodium carbonate, potassium sulfate, potassium carbonate, ammonium hydroxide when neutralizations, soluble-salt is obtained, is concentrated back afterwards Salt is received, but alkali consumption is big, the salt quality being recovered to differs, and utility value is poor.In addition, the reduction generated in 6 nitre production processes In waste water outside sulfuric acid, the also sodium sulfate salt of 5-10%；Contain a small amount of copper sulphate in oxysome waste water；Containing few in nitre body waste water Measure nitric acid.
Preferably, further include absorption before step (1).0.1-2% (on the basis of wastewater quality) is added in into waste water to inhale Attached dose, after stirring and adsorbing 30-90min, filtering.Or, waste water obtains out column liquid at the uniform velocity by adsorption column.The adsorbent is lives One or more of property charcoal, diatomite, activated coke, bentonite, molecular sieve；Filler is activated carbon in the adsorption column One or more of grain, activated coke, molecular sieve, activated alumina.Further preferably, the column speed of crossing of waste water is 0.5- 10BV/h.Further preferably, the column speed of crossing of waste water is 1-2BV/h.
In step 1,6 nitre waste water are by diffusion dialysis film process, in obtained sour reuse to 6 nitre production technologies.For example, To acid be used for preparing diluted acid (mass fraction 50%), nitrosation and/or sulfonation process of the reuse to 1,2,4 sour synthesizing sections In.
Preferably, in mode 2-a, neutralization precipitation uses sodium hydroxide, sodium carbonate, sodium bicarbonate or alkaline sulfides. Further preferably, after one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate is used to be neutralized to pH as 6-9, then with vulcanized sodium, The reaction was continued for one or more of NaHS.
In mode 2-b, Fe/C reaction principles are as follows：
Following electrochemical reaction occurs after waste water is contacted with iron carbon:
Anode：Fe-2e-→Fe
Cathode：2H++2e-→H2
It is aerated under the conditions of Fuyang, following react also occurs:
O2+4H++4e-→2H2O
O2+2H2O+4e-→4OH-
4Fe2++O2+4H+→2H2O+4Fe3+
In reaction process, due to generating OH-, so the pH of system constantly rises；Meanwhile the Fe2+ or Fe3+ of generation with OH- is combined, generation flco and precipitation, and the pollutant in effective adsorption-condensation water strengthens water treatment effect.
Preferably, the light electrolysis in mode 2-b：On the basis of the quality of pending liquid, added in into pending liquid micro- Reagent is electrolysed, the dosage of iron is 0.5~4%, and the mass ratio of iron and carbon is 2~20:1, carry out light electrolysis；Or to pending The volume ratio of addition iron carbon reagent in liquid, 1~6h of aeration reaction, iron carbon reagent and pending liquid is 1:2~9.
Further preferably, the light electrolysis in mode 2-b：On the basis of the quality of pending liquid, into pending liquid plus 0.5~ The mass ratio of 2% iron and carbon, iron and carbon is 5~10:1, carry out light electrolysis；Or the volume ratio of iron carbon reagent and pending liquid It is 1:1~5.
The light electrolysis time in mode 2-b is selected as needed, it is preferable that the light electrolysis time is 1~6h.Entire In microelectrolysis process, the pH value of maintenance system is constant.Further preferably, the light electrolysis time is 2~4h.
Preferably, mode 2-c, on the basis of the quality of pending liquid, 0.5~5% iron is added in into pending liquid Salt and/or ferrous salt (total addition of molysite and/or ferrous salt is 0.5~5%) and 0.5~30% hydrogen peroxide, dioxygen The mass fraction of water is 27~30%, carries out Fenton oxidation.
Molysite and ferrous salt use water soluble salt, for example, molysite generally use ferric sulfate, iron chloride, ferrous salt are usually adopted With ferrous sulfate, frerrous chloride.
In mode 2-c, Fenton reaction principles are as follows：
Fe2++H2O2→Fe3++OH-+·OH (1)
Fe3++H2O2→Fe2++HO2·+H+ (2)
Fe2++·OH→Fe3++OH- (3)
Fe3++HO2·→Fe2++O2+H+ (4)
·OH+H2O2→H2O+HO2· (5)
Fe2++HO2·→Fe3++HO2 - (6)
RH+·OH→R·+H2O (7)
R·+Fe3+→R++Fe2+ (8)
R·+H2O2→OH+·OH (9)
The reaction of whole system is sufficiently complex, and key is to pass through Fe2+Or Fe3+Play excitation and transmission in the reaction, And H2O2Then play oxidation, hydroxyl radical free radical OH of the generation with extremely strong oxidability, so as to organic in oxidized waste water Object.
Carried out during Fenton oxidation continue stirring, the Fenton oxidation time be 1~10h, Fenton oxidation mistake Cheng Zhongxu adds in hydrogen peroxide, while adds in Fe2+、Fe3+At least one of.
Further preferably, on the basis of the quality of pending liquid, 0.5~4% is added in into pending liquid by mode 2-c Molysite and/or ferrous salt and 0.5~15% hydrogen peroxide, the mass fraction of hydrogen peroxide is 27~30%, carries out Fenton oxygen Change.
Preferably, the flocculation in mode 2-d, after adding in flocculant into pending liquid, add polyacrylamide and/ Or adsorbent, pH to 8~10 is then adjusted, is flocculated.It is persistently stirred in flocculation process, flocculation time is 30~60min.
Preferably, the flocculant is FeSO4·7H2O, polyaluminium sulfate, frerrous chloride, aluminium polychloride, polymerised sulphur One or more of sour ferro-aluminum, poly-ferric chloride.
On the basis of the quality of pending liquid, the addition of flocculant is 0.2-4%, and the addition of polyacrylamide is 0.0001~0.005%, the addition of adsorbent is 0.02~0.5%.Further preferably, the addition of flocculant is 0.2- 2%, the addition of polyacrylamide is 0.0001~0.001%, and the addition of adsorbent is 0.1~0.5%.
Preferably, in mode 2-f, adsorbent is one or more of active powdered carbon/particle, diatomite, to wait to locate On the basis of the quality for managing liquid, the dosage of adsorbent is 0.02~2%.
Preferably, in mode 2-f, adsorbent is adsorption column, filler is activated carbon, activated coke, molecular sieve, bentonite, One or more of quartz sand.The volume ratio of pending liquid and adsorbent filler is 1~5:1.Further preferably, pending liquid is with inhaling Attached dose of volume ratio is 1~2:1.
Preferably, in method 2-g, the mixed volume ratio of extractant and diluent is 1:1-6, oil-water ratio 1:1-8, Wastewater pH is 0.5-4.
Further preferably, in method 2-g, extractant is trioctylamine, and diluent is toluene, in dichloroethanes, sulfonated kerosene One kind.
In order to obtain better pretreating effect, clean brackish water is obtained, is located in advance to diffusion dialysis treatment fluid Various pretreatment modes can be combined during reason, it is preferable that pre-processed using following either type：
Mode A, successively ways of carrying out 2-b, mode 2-d；
Mode B, successively ways of carrying out 2-e, mode 2-a, mode 2-f；
Mode C, successively ways of carrying out 2-b, mode 2-c, mode 2-d, mode 2-f；
Mode D, successively ways of carrying out 2-g, mode 2-a；
Further preferably, mode A is as follows：
Mode 2-b, light electrolysis：In the case where pH is 2~5 acid condition, light electrolysis examination is added in diffusion dialysis treatment fluid Agent is stirred to react 2~6h, and after reaction, standing separation obtains clear liquid；
Mode 2-d, flocculation：Flocculant is added in into above-mentioned clear liquid, pH to 8~10 is then adjusted, is carried out after flocculation Filtering.
Mode B is as follows：
Mode 2-e, wet oxidation：Diffusion dialysis treatment fluid is under the conditions of 180-250 DEG C, 0.5-4MPa, with oxygen or sky Gas makees oxidant, carries out 40-180min oxidation reactions, obtains wet oxidation treatment fluid；
The pH of wet oxidation treatment fluid is adjusted to 8~10, filtrate I is obtained by filtration by mode 2-a, neutralization precipitation；
Mode 2-f, absorption：Adsorbent is added in into filtrate I, agitation and filtration obtains treatment fluid.
Preferably, can add catalyst in the wet oxidation reaction, the catalyst is soluble copper salt, molysite, nickel One or more of salt, cobalt salt etc., the dosage of catalyst are 0.1-2.5% (to participate in the quality of the waste water of wet oxidation On the basis of).
Further preferably, in the mode 2-a of mode B, reducible sulfur compound is added in into wet oxidation treatment fluid, is stirred to react Filtrate is obtained by filtration in 30-90min.
Further preferably, first wet oxidation is handled with one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate Liquid pH is adjusted to 6-9, then adds in reducible sulfur compound thereto.The reducible sulfur compound is vulcanized sodium, in NaHS One or more, 1-1.5 times of molar content for the active ingredient of catalyst of dosage.
The molar content active ingredient of the catalyst is the molar content of metallic element.
Mode C is as follows：
Mode 2-b, light electrolysis：In the case where pH is 2~5 acid condition, light electrolysis examination is added in diffusion dialysis treatment fluid Agent reacts 2~6h, is then filtered, obtains filtrate II；
Mode 2-c, Fenton oxidation：II heating and thermal insulation of filtrate adds in 0.5-2% hydrogen peroxide (mass fractions to 40-60 DEG C For 27-30%, on the basis of the quality of filtrate II), 0.5-2h is stirred to react, reaction was completed；
Mode 2-d, flocculation：Flocculant is added in into Fenton oxidation product, then adjusts pH to 8~10, stirring flocculation 30~60min is filtered after flocculation, obtains filtrate III；
Mode 2-f, absorption：Adsorbent is added in into filtrate III, agitation and filtration obtains treatment fluid.
Further preferably, in mode C, flocculation later further include neutralization precipitation, into filtrate III add in sodium hydroxide, sodium carbonate, One or more of sodium bicarbonate is neutralized to pH as 6-8.
Mode D is as follows：
Mode 2-g, extraction：In the case where pH is 0.5~4 acid condition, diffusion dialysis treatment fluid carries out complexometric extraction, extraction The ratio of agent and diluent is 1:1-8, oil-water ratio 1:1-8, is stirred to react 10-60min, and standing separation obtains subnatant；
Mode 2-a, neutralization precipitation：Above-mentioned subnatant is neutralized to pH as 8-10, is stirred to react 10-60min, is obtained by filtration Filtrate IV；
Further preferably, in mode D, absorption is further included after mode 2-a, 0.05-0.5% adsorbents are added in into filtrate IV, are stirred Absorption 30-90min is mixed, treatment fluid is obtained by filtration.
Preferably, the electrodialysis described in step (3) includes bipolar membrane electrodialysis and common electrodialysis.
Bipolar Membrane is a kind of novel ion-exchange composite membranes, under DC electric field effect, Bipolar Membrane can by hydrolytic dissociation, Film both sides respectively obtain hydrogen ion and hydroxide ion.Bipolar membrane electrodialysis technology utilizes this feature, by Bipolar Membrane and commonly Electrodialysis is combined, and the salt in aqueous solution is converted into corresponding bronsted lowry acids and bases bronsted lowry in the case where not being introduced into new component.The technology can To be widely used in the fields such as food processing, chemical industry synthesis and environmental protection, due to its technical advance, Economic competitive and ring Border friendly, bipolar membrane electrodialysis technology are known as a kind of sustainable development technology.
The treatment fluid that step (2) obtains is the aqueous solution of main sulfur acid sodium, which is passed through by anion-exchange membrane In the compartment formed with cation-exchange membrane, under DC electric field effect, Na+Water is dissociated by cation-exchange membrane and Bipolar Membrane The OH of generation-Generation NaOH is combined in alkali room；SO4 2-The H of water generation is dissociated by anion-exchange membrane and Bipolar Membrane+In sour room knot Symphysis is into H2SO4。
Preferably, in step (3), before bipolar membrane electrodialysis processing is carried out to brackish water, first to brackish water into Row electrodialysis concentrates, and obtains the brackish water of high concentration.The high concentration brackish water again by bipolar membrane electrodialysis recovery acid or alkali or Person further concentrates, and crystallization obtains crystalline salt.
Further preferably, it is 2~5% conducting solution as pole liquid that common electrodialysis, which uses salt content, and current density is 50~500A/m2。
When carrying out electrodialysis to brackish water, using heterogeneous membrane or half homogeneous membrane, the treatment fluid that step (2) obtains is passed through The freshwater room of electrodialysis system, into the low water of not saliferous or salt content in concentrated water room, after electrodialysis, obtained concentrated water is Salting liquid after concentration, the brackish water that obtained fresh water obtains after being pre-processed with next group mixes carries out electrodialysis again.Electric osmose Salting liquid after the concentration obtained after analysis processing carries out bipolar membrane electrodialysis processing.
Preferably, the inorganic salts in above-mentioned conducting solution are sodium sulphate, one kind in potassium sulfate, sodium chloride, ammonium sulfate It is or several.Further preferably, the inorganic salts in above-mentioned conducting solution are one or more of in sodium sulphate, potassium sulfate.
Preferably, when step 3 carries out bipolar membrane electrodialysis processing, ruthenium is applied as electrode, current density 100 using titanium ~700A/m2。
During bipolar membrane electrodialysis, it is 0.1~5% inorganic salt solution as pole liquid to use salt content, after processing dilute Brine reuse is to electrodialysis step.
After running a period of time, the hydrochloric acid solution that use quality score is 2~5% cleans bipolar membranous system.
Compared with the prior art, the present invention has the following advantages：
Diffusion dialysis and electrodialytic membranes technology are introduced into 6 nitre production technologies, the waste water that technique generates can be carried out Processing, while obtained acid is back in technique again with alkali or salt, has not only solved the process problem of waste water, but also can reduce soda acid Input cost.Present invention process flow is succinct, easy to operate, mild condition, and energy recycling gives up while handling waste water Salt in water realizes clean manufacturing.
Description of the drawings
Fig. 1 is the production technological process of improved 6 nitre of the present invention.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples, it should be pointed out that reality as described below It applies example to be intended to convenient for the understanding of the present invention, without playing any restriction effect.
If being not particularly limited in the present invention to temperature, carry out at room temperature.
The technological process of the present invention is as shown in Figure 1.
Embodiment 1
1,2, the 4 sour waste water generated in 6 nitre production processes, show dark red, COD about 28790mg/L, sulfuric acid content is 11%, the inorganic constituents such as sulfur acid sodium, sodium sulfite, iron sulfite in waste water.
(1) acid recovery：After 0.4% activated carbon stirring and adsorbing 60min is added in above-mentioned waste water, the COD for obtaining filtrate is about 17090mg/L.By diffusion dialysis film, acid solution and organic wastewater are obtained.It is 10%, COD about 20mg/ to measure acid content in acid solution L；1.1%, the COD containing acid is about 18800mg/L in organic wastewater.
(2) treatment of Organic Wastewater：The organic wastewater that step (1) obtains is heated to 60 DEG C, adds in 0.2%FeSO4·7H2O, 11% hydrogen peroxide (mass fraction of hydrogen peroxide is 28%) is uniformly added into 4h, it is stirring while adding, after adding, insulation reaction 30min.Calcium oxide is added in thereto and adjusts pH to 8.5, and filtrate is obtained by filtration in stirring flocculation 100min.Filtrate shows slightly yellow, COD is 200mg/L, sulfur acid sodium 10%.
(3) soda acid recycles：By bipolar membrane electrodialysis system, adjust current density is the filtrate that step (2) obtains 700A/m2, temperature is 30 DEG C, obtains the water outlet of 8.3% sodium hydroxide and 10% sulfuric acid and saliferous 0.68%.Sulfuric acid is used 50% dilute sulfuric acid is prepared, for the nitrosation step of 1,2,4 acid production process；Sodium hydroxide is used for bisnaphthol in nitrosation Dissolving, water outlet be used for dissolve sodium hydrogensulfite.
Embodiment 2
In described in embodiment 11,2,4 sour wastewater treatment methods, step (1) is constant, other steps are as follows：
Step (2)：The organic wastewater that step (1) obtains is extracted, and extractant is trioctylamine, and diluent is sulfonated coal Oil, extractant and diluent by volume 1:4 mixing are made into oil phase, oil-water ratio 1:After 1, stirring extraction 30min, by grease Separator detaches, and obtains subnatant and shows slightly yellow.Subnatant liquid feeding alkali adjusts pH to 8, adds in 0.2% (with subnatant Quality on the basis of) activated carbon, filtrate is obtained by filtration in stirring and adsorbing 30min.Filtrate is almost colourless transparent, measures its COD and is 56mg/L, sulfur acid sodium 11%.
Step (3)：Above-mentioned filtrate is concentrated by MVR, obtains sodium sulfate salt, meets industrial salt standard, reuse to 1,2,4 The sulfonation process of acid production process；The condensate liquid being recovered to is with to recovery acid in step (1)；Obtained concentrate shows slightly yellow, COD is 409mg/L, continues to concentrate after handling with the subnatant mixing and absorption being obtained by extraction.
Embodiment 3
1,2, the 4 sour oxysome waste water generated in 6 nitre production processes, show peony, COD about 16570mg/L, sulfuric acid content is 15%, sulfur acid sodium 3% or so in waste water, copper about 0.18%.
(1) it is filtered after 0.2% activated carbon stirring and adsorbing 60min is added in above-mentioned waste water, the COD for obtaining filtrate is about 14599mg/L.Filtrate obtains acid solution and organic wastewater by diffusion dialysis film.Acid content is measured in acid solution as 14%, COD about 47mg/L；Measure organic wastewater COD about 15098mg/L.
(2) organic wastewater that step (1) obtains carries out complexometric extraction, oil-water ratio 1:2 (volume ratios, by trioctylamine and two Chloroethanes is with 1:3 volume mixtures are made into oil phase, and in 50 DEG C of stirring extraction 1h, standing separation obtains upper organic phase and lower floor is clear Liquid.Measure the COD about 202mg/L of subnatant, content of copper ion 0.31%.
(3) vulcanized sodium 0.18% (on the basis of subnatant quality) is added in the subnatant that step (2) obtains, is adjusted The pH of clear liquid is 8-9, is filtered after being stirred to react 0.5h, 0.1% activated carbon, stirring and adsorbing 30min are added in obtained filtrate Afterwards, filtrate is obtained by filtration.
(4) filtrate that step (3) obtains is concentrated by electrodialytic membranes, and the current density of electrodialysis system is 400A/ M2, temperature are 30 DEG C.Obtain the brine that saliferous is 10%.The brine passes through bipolar membrane electrodialysis system, and obtained 9% sulfuric acid is molten The water outlet of liquid and 7.5% sodium hydroxide solution and saliferous 0.9%.
(5) above-mentioned electrodialysis fresh water room water outlet and Bipolar Membrane water outlet enter electricity after being mixed again with the filtrate that step (3) obtains Electrodialysis system continues concentration.Reuse to 1,2,4 acid synthesis and 1,2,4 sour oxysomes synthesize the bronsted lowry acids and bases bronsted lowry that step (4) obtains again In step.
(6) for the upper organic phase that step (2) processing obtains after sodium hydroxide is stripped, obtained strip liquor passes through electrodialysis Processing, obtains organic liquid waste and brackish water, and brackish water is mixed with the filtrate that step (3) obtains to be entered back into electrodialysis system and continue to locate Reason.After testing, wherein containing there are two types of substances, the content of substance 1 is 95% to obtained organic liquid waste, the content of substance 2 is 4%. Further detection finds that substance 1 is intermediate product, and substance 2 is by-product.Organic liquid waste can be in reuse to production.It will be organic Waste liquid is applied in production, and the product quality of output is without being decreased obviously.
Embodiment 4
Oxysome wastewater treatment method described in embodiment 3, step (1) is constant, other steps are as follows：
(2) waste water is pumped into level-one iron carbon pond, the volume ratio of iron carbon reagent and waste water is 1:It is quiet after 2, aeration reaction 2h Separation is put, 0.4% diatomite is added in obtained clear liquid, the pH that clear liquid is adjusted with calcium oxide is 8, is stirred to react 30min, press filtration Obtain filtrate；Filtrate is adjusted to pH to flow into two level iron carbon pond after 3, and the volume ratio of iron carbon reagent and waste water is 1:4, aeration is anti- After answering 1h, standing separation adds in 0.2% activated carbon in obtained clear liquid, and it is 8 to be adjusted with liquid caustic soda to pH, is stirred to react 40min, Press filtration obtains yellow filtrate, measures COD=1450mg/L；0.05% vulcanized sodium is added in thereto, is stirred to react mistake after 30min Filter, then 0.5% diatomite is added in into filtrate, stirring and adsorbing 40min is obtained by filtration that filtrate is almost colourless transparent, and COD is about 569mg/L, copper content are about 0.01%, salt content 7%.
(3) filtrate that step (2) obtains passes through bipolar membrane electrodialysis system, and adjusting current density is 400A/m2, it is made The water outlet of 8% sulfuric acid solution and 7.5% sodium hydroxide solution and saliferous 0.9%.
(4) above-mentioned Bipolar Membrane water outlet continues into electrodialysis system at concentration after being mixed again with the filtrate that step (3) obtains Reason.The bronsted lowry acids and bases bronsted lowry that step (4) obtains is again in reuse to 1,2,4 acid synthesis and 1,2,4 sour oxysome synthesis steps.
Embodiment 5
Oxysome waste water described in embodiment 3, is handled by the following method：
(1) it is filtered after 0.2% activated carbon stirring and adsorbing 60min is added in waste water, the COD for obtaining filtrate is about 14599mg/ L.Filtrate obtains acid solution and organic wastewater by diffusion dialysis film.It is 14%, COD about 47mg/L to measure acid content in acid solution；It surveys Obtain organic wastewater COD about 15098mg/L.
(2) 2% reduced iron powder and 0.3% activated carbon are added in into waste water, after 30 DEG C are reacted 2h, standing separation obtains Clear liquid be heated to 60 DEG C, 5% hydrogen peroxide is uniformly added into 4h, and (quality of organic wastewater obtained using step (1) is base It is accurate), then 30min is reacted, alkali is added to adjust pH to 9, filtrate displaing yellow, COD=1000mg/L is obtained by filtration in stirring flocculation 60min； 0.08% vulcanized sodium is added in thereto, is filtered after being stirred to react 30min, 0.5% diatomite is added in into filtrate, and stirring is inhaled Attached 40min, is obtained by filtration that filtrate is almost colourless transparent, and COD is about 509mg/L, copper content is about 0.03%, salt content 5%.
(3) filtrate that step (2) obtains is concentrated by electrodialytic membranes, and the current density of electrodialysis system is 600A/ m2, temperature is 30 DEG C.Dense room and the water inlet of light room are the filtrate that step (2) obtains, and obtain the concentrated water and saliferous that saliferous is 11% 0.5% fresh water.Concentrated water passes through bipolar membrane electrodialysis system, and 9% sulfuric acid solution and 7.5% sodium hydroxide solution is made, And the water outlet of saliferous 0.9%.
(4) above-mentioned electrodialysis fresh water room water outlet and Bipolar Membrane water outlet enter electricity after being mixed again with the filtrate that step (3) obtains Electrodialysis system continues concentration.Reuse to 1,2,4 acid synthesis and 1,2,4 sour oxysomes synthesize the bronsted lowry acids and bases bronsted lowry that step (4) obtains again In step.
Embodiment 6
The nitration waste water generated in 6 nitre production processes, in cerise, 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) it is filtered after 0.5% activated carbon stirring and adsorbing 45min is added in above-mentioned waste water, liquor C OD about 6800mg/L.Filter Liquid obtains acid solution and organic wastewater by diffusion dialysis film.It is 22%, COD about 40mg/L to measure acid content in acid solution；Organic waste The COD of water is about 7170mg/L.
(2) organic wastewater that step (1) obtains add alkali neutralization to pH be 8, filtrate is obtained by filtration.
(3) filtrate that step (2) obtains is concentrated by electrodialytic membranes, and electrodialytic current density is 550A/m2, and temperature is 28℃.Obtain the dope of saliferous 8.7% and the light liquid of saliferous 0.78%.For dope further after concentration, Crystallization Separation obtains sulfuric acid Sodium crystal.In reuse to 1,2,4 sour synthesis step, the isolation step of fresh water reuse to nitration processes.
(4) organic wastewater that step (1) obtains can be used to make water-reducing agent.
Embodiment 5
6 nitre production technologies are improved in the following manner.
1st, prepared by 1,2,4 acid
1.1 sodium hydroxide solutions that 300kg mass fractions is used to be 9% dissolve 100kg bisnaphthols after being mixed with 300kg water, 80 DEG C of stirring and dissolvings are heated to, obtain the beta naphthal solution of pH=10.7；0-5 DEG C is cooled to, adds in 48kg sodium nitrite solutions (mass fraction 40%) at 0~10 DEG C of heat preservation, sulfuric acid solution 150kg was uniformly added into 4 hours and (is made by 4.6 methods 50% sulfuric acid), Congored test paper is surveyed in acidity, and during the micro- blue of potassium iodide starch paper, insulation reaction 1h, filtering obtains waste water 580kg。
1.2 above-mentioned filter cakes add 1500L water to be beaten, and the liquid caustic soda made from step 4.5, which is adjusted to Congored test paper, just to have disappeared. At 15-20 DEG C, 170kg sodium metabisulfite solutions (mass fraction 60%) are added in, are reacted 1 hour.Filtrate is obtained by filtration.
1.3 add in 100kg sodium sulphate into above-mentioned filtrate, after stirring and dissolving, 100kg sulfuric acid are added in 3h, is heated to It 55-60 DEG C, is filtered after standing reaction 8h, obtains 1,2,4 acid finished product 166kg and 1,2,4 sour waste water 2577kg.
2nd, prepared by 1,2,4 sour oxysomes
2.1 above-mentioned 1,2,4 sour finished products add 550kg water to be beaten, and the liquid caustic soda made from step 4.5 is neutralized to pH=4, adds in 1.7kg cupric sulfate pentahydrates, it is on the rocks to be down to 15 DEG C, add in 132kg sodium nitrite solutions (mass fraction 40%).Temperature 25~ 30 DEG C, starch potassium iodide paper in it is micro- blue under the conditions of, be stirred to react 1 hour.
2.2 are heated to 40~45 DEG C, filter while hot, and it is molten that obtained filtrate was slowly added into 228kg sulfuric acid in 3~4 hours Liquid (50% sulfuric acid being made by 4.6 methods), after insulation reaction 1h press filtration to get 1,2,4- acid oxysome finished product 136kg and 1,2,4 sour oxysome waste water 784kg.
3rd, 6 nitrates are standby
210kg niacin is cooled to 0-15 DEG C by 3.1, is slowly added to oxysome, then between 30~35 DEG C, then adds 85kg cigarettes Acid is stirred to react 30 minutes.Under the conditions of 15~20 DEG C plus 100kg nitration mixture (nitric acid and niacin mass ratio are 1:2) 18~25, are kept DEG C reaction 5 hours.Nitrification liquid is slowly put into 800kg ice water under the conditions of 0~5 DEG C, after discharging plus water adjusts the total matter of reactant It measures as 1300kg, insulated and stirred reaction 30 minutes, standing 5 hours.
3.2 press filtrations, drying, obtain finished product 130kg.Generate waste water 1130kg simultaneously.
4th, wastewater treatment
The 4.1 common 5000kg of waste water for generating step (1)-(3), waste water shows black after mixing, there is a small amount of suspended matter.COD For 20977mg/L, acid content 18%, sodium sulphate content 5%, cupric 0.08%.
0.3% activated carbon is added in into waste water, filtrate is obtained by filtration in stirring and adsorbing 60min.It is general red that filtrate shows black, COD About 18070mg/L.By filtrate by diffusion dialysis film process, make and absorb of the sulfuric acid solution that 14000kg mass fractions are 9.5% Liquid obtains the sulfuric acid solution 15000kg containing the acid 15% and organic wastewater 4100kg containing acid 0.8%；
4.2 above-mentioned organic wastewaters are at 200 DEG C, under the conditions of 1MPa, make oxidant with oxygen, high-temperature high-voltage reaction 60min is obtained To wet oxidation treatment fluid, it is about 5670mg/L to measure treatment fluid common 3800kg, COD, cupric 0.21%；
4.3 add in the vulcanized sodium of 0.06% (on the basis of wet oxidation treatment fluid quality) into wet oxidation treatment fluid, And pH to 9 is adjusted, agitation and filtration obtains filtrate, and copper sulfide content is 98.5% in filter residue, again with to 2.1 after can selling or aoxidizing In make catalyst；
4.4 add in 0.4% activated carbon into filtrate I, and agitation and filtration obtains treatment fluid 3200kg, and treatment fluid is almost colourless Transparent, COD is about 319mg/L, sodium sulphate content 12%.
4.5 above-mentioned treatment fluids pass through the bipolar membrane electrodialysis of three compartments, the fresh water that treatment fluid feed space, electrodialysis obtain point Not into sour room and light room, current density 550A/m2, obtain the sodium hydroxide solution of 9.5% sulfuric acid solution 2800kg and 9% The water outlet 2780kg of 2250kg and saliferous about 0.6%.
4.6 are slowly added to the dense sulphur that 210kg mass fractions are 98% into the sulfuric acid solution that 290kg mass fractions are 15% Acid is made into the sulfuric acid that 500kg mass fractions are 50%, in production technology, 9.5% sulfuric acid to do the absorption of diffusion dialysis Liquid；Bisnaphthol is dissolved after being mixed with the sodium hydroxide solution that 300kg mass fractions are 9% with 300kg water, for adjusting the alkali of pH Liquid is 20kg, remaining is used to absorb the sulfur dioxide overflowed in 1.2-1.3；Bipolar Membrane water outlet concentrates (electrodialysis by electrodialysis Current density is 400A/m2, and dense room and light room inversely enter Bipolar Membrane and be discharged), obtain the concentrated water that 150kg mass fractions are 10% With the fresh water of 2600kg saliferous 0.4%, fresh water is intake as Bipolar Membrane sour room, and concentrated water is mixed with the waste water after adsorbing, into double Pole film process.

Claims (4)

1. a kind of improved 6- nitros -1,2, the production technology of 4 sour oxysomes, the preparation including 1,2,4 acid, 1,2,4 sour oxysomes Preparation and 6- nitros -1,2, the preparation of 4 sour oxysomes, which is characterized in that further include and the 6 nitre waste water generated in production process are carried out The step of processing, is as follows：
Step（1）：6 nitre waste water pass through diffusion dialysis film process, are recovered to acid, obtain diffusion dialysis treatment fluid；
Step（2）：Diffusion dialysis treatment fluid follows the steps below pretreatment, obtains brackish water：
2-a, wet oxidation：Step（1）Obtained diffusion dialysis treatment fluid carries out under conditions of 100 ~ 300 DEG C, 0.5 ~ 10MPa Wet oxidation；
2-b is filtered after neutralization precipitation；
2-c, absorption：Adsorbent is added in filtrate, is filtered after stirring and adsorbing；
Step（3）：The brackish water that step 2 obtains is handled by bipolar membrane electrodialysis, obtains bronsted lowry acids and bases bronsted lowry；Bronsted lowry acids and bases bronsted lowry reuse to 1,2, In 4 acid preparations and/or the preparation of 1,2,4 sour oxysomes.
2. a kind of improved 6- nitros -1,2 as described in claim 1, the production technology of 4 sour oxysomes, which is characterized in that 2-c In absorption：The adsorbent is one or more of activated carbon, diatomite, activated coke, molecular sieve, with the matter of pending liquid On the basis of amount, the dosage of adsorbent is 0.02 ~ 2%.
3. a kind of improved 6- nitros -1,2 as described in claim 1, the production technology of 4 sour oxysomes, which is characterized in that step （3）In, before carrying out bipolar membrane electrodialysis processing to brackish water, electrodialysis concentration, electrodialysis concentration are carried out to brackish water first Using the conducting solution that salt content is 2 ~ 5%, current density is 50 ~ 500A/m as pole liquid2。
4. a kind of improved 6- nitros -1,2 as described in claim 1, the production technology of 4 sour oxysomes, which is characterized in that step （3）When carrying out electrodialysis process, current density is 100 ~ 700A/m2。
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