CN101333047B - Advanced waste treatment process in process of production of long chain dibasic acid by fermentation method - Google Patents
Advanced waste treatment process in process of production of long chain dibasic acid by fermentation method Download PDFInfo
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- CN101333047B CN101333047B CN2008100540127A CN200810054012A CN101333047B CN 101333047 B CN101333047 B CN 101333047B CN 2008100540127 A CN2008100540127 A CN 2008100540127A CN 200810054012 A CN200810054012 A CN 200810054012A CN 101333047 B CN101333047 B CN 101333047B
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Abstract
The invention discloses a deep treatment method for the wastewater from the technique for producing long-chain dibasic acids by fermentation method. In the method, acid is used for adjusting the pH value of the wastewater to be discharged; after sedimentation, supernatant fluid is added with proper amount of oxidizing agent, precipitate is separated from the solution once more, oxidizing agent isadded again in the supernatant fluid obtained by separation for deep chemical oxidation until the COD of the treated water solution meets the requirements. Then alkali is used for neutralizing the water solution to neutrality and after iron sludge is separated out, the water can be discharged into a second-grade pipe network. The method can recycle about 80% of organic dibasic acid by controllingthe adding amount of the oxidizing agent, and has short wastewater treatment time, low dosage of the oxidizing agent and little emission amount of CO2 waste gas. The recycled dibasic acid can be usedfor preparing fine chemical products such as cold resistant plasticizer, high class lubricating oil, high temperature dielectric medium, high-grade hot-melt adhesives, high-grade paint, and the like;and the iron sludge produced can be used for producing iron series pigments.
Description
[technical field]
The present invention relates to the wastewater treatment of resource and environment and utilize the field, particularly a kind of advanced waste treatment method of process in process of production of long chain dibasic acid by fermentation.
[background technology]
Long-chain biatomic acid is the fine-chemical intermediate that a class has extensive use, can be used for the speciality chemical of a series of high added values such as synthetic extraordinary nylon, spices, cold resistant plasticizer, senior lubricant, high temperature dielectric medium, high-grade hot melt adhesive and high grade paint.In its multiple production method, biological fermentation process has great superiority than chemical synthesis aspect synthetic difficulty or ease and the economy, and therefore the production technique of newly-built long-chain biatomic acid all adopts bio-fermentation process.With the tridecanyldicarboxylic acid is example, and biological fermentation process is to be raw material with the n-tridecane hydrocarbon, obtains tridecanyldicarboxylic acid concentration by fermentation and is about 6% fermented liquid, more after filtration, operation such as acid out, crystallization, filtration obtains high-quality tridecanyldicarboxylic acid.
Although it is good that biological fermentation process has selectivity than chemical synthesis, the yield height, outstanding advantages such as technology cleaning have still been discharged a large amount of waste liquids inevitably in the production process.In the waste liquid of discharging, diprotic acid content still reaches about 0.8%, causes yield losses about 15%, produces yield and generally is lower than 85%.In order to cut the waste, improve yield, reduce cost, reduce environmental pollution simultaneously, be necessary the processing wastewater of its discharging is recycled research.
[summary of the invention]
The objective of the invention is to economize on resources, protect the needs of environment simultaneously, and a kind of advanced waste treatment method of process in process of production of long chain dibasic acid by fermentation is provided in order to satisfy.This method is at first regulated the pH value of waste discharge with acid, through leaving standstill, post precipitation, in the supernatant liquor that separation obtains, add an amount of oxygenant, solution is separated out precipitation once more, continue to add oxygenant and carry out degree of depth chemical oxidation in the supernatant liquor that separation obtains, the COD of the aqueous solution after handling reaches necessary requirement.Neutralize this aqueous solution to neutral with alkali afterwards, and the water behind the separating ferrum mud can enter secondary network.
For achieving the above object, the invention discloses a kind of advanced waste treatment method of process in process of production of long chain dibasic acid by fermentation, it is characterized in that may further comprise the steps:
(1) with sour pH to 1.0～3.0 of regulating institute's emission treatment waste water;
(2) product that step (1) is obtained leaves standstill, and precipitation is separated out mixed dibasic acid;
(3) product that step (2) is obtained separates, and adds oxygenant in the supernatant liquor that separation obtains; Described oxygenant is ferrous iron reagent and superoxol; The consumption of described ferrous iron reagent is: 0.1-100gFe
2+/ every liter of waste water; The consumption of described superoxol is: 1-200g H
2O
2/ every liter of waste water.The consumption of best described ferrous iron reagent is: 1-30gFe
2+/ every liter of waste water; The consumption of described superoxol is: 1-50g H
2O
2/ every liter of waste water.Superoxol is that concentration is 10%～80% aqueous hydrogen peroxide solution.
(4) solution left standstill that step (3) is obtained is separated out the mixed dibasic acid precipitation;
(5) product that step (4) is obtained separates, and continues to add oxygenant in the supernatant liquor that separation obtains, and reaches emission standard until the COD of waste water;
(6) solution that obtains with alkali neutralization procedure (5) is to pH 7～10;
(7) separation of iron mud.
The advanced waste treatment method of process in process of production of long chain dibasic acid by fermentation of the present invention can be used for administering trade effluent.
The invention has the beneficial effects as follows: developed a kind of advanced waste treatment method that adopts process in process of production of long chain dibasic acid by fermentation, this method is taken into account resources conservation and environment protection simultaneously.
The present invention and long processing period, organism can not be recycled, CO
2The biological treatment that the waste gas burst size is big is compared, and has the add-on by control Fenton reagent, recyclable about 80% organic dibasic acid, and the wastewater treatment time is short, and the oxygenant consumption is few, CO
2The waste gas burst size is few, and the diprotic acid that is reclaimed can be used for preparing the fine chemicals of a series of high added values such as cold resistant plasticizer, senior lubricant, high temperature dielectric medium, high-grade hot melt adhesive and high grade paint.The iron mud that produces can be used for the production of iron serial pigment.Therefore can not cause secondary pollution, compliance with environmental protection requirements is a kind of environmentally friendly treatment process.This technology can be widely used in the process field of process in process of production of long chain dibasic acid by fermentation waste water, promptly is applicable to the wastewater treatment in the water-insoluble C8-C18 representative examples of saturated aliphatic di-carboxylic acid production.
This method also can be united use with other method of wastewater treatment such as biological treatment, ozonation process, physisorphtions, with the consumption of further minimizing Fenton reagent.
[embodiment]
Described ferrous iron reagent of the present invention is ferrous sulfate, iron protochloride, iron protoxide, iron powder or iron block, Z 250, or their mixture.
The treatment temp of each step of described method helps to separate out precipitation normally at 0～80 ℃ more in 35～70 ℃.
The mode that described oxygenant adds can be to add ferrous iron reagent in pending product earlier, adds superoxol then; Perhaps in pending product, add superoxol earlier, add ferrous iron reagent then; Perhaps in pending product, add ferrous iron reagent and superoxol simultaneously.Described is that the time that oxygenant carries out chemical oxidation treatment is 0.1-4 hour with Fenton reagent.
There is throw out to separate out in step (3) process.
Embodiment 1: get the filtered wastewater (COD about 22000mg/L) of 500mL from the fermentative Production tridecanyldicarboxylic acid, under fully stirring, transfer its pH value to 1 with the vitriol oil.Allow its standing sedimentation.Obtain 0.67g mixing acid.Get 200mL supernatant liquor (the about 9912mg/L of COD), under fully stirring, add 10mL 25%H
2O
2Solution added in about 0.5 hour and contains 4g FeSO
4Ferrous iron solution.After finishing, solution is warming up to 70～75 ℃, produces the floss precipitation in this process, and when precipitation reached maximum value, post precipitation (obtaining 0.1 gram blended solid acid approximately) was isolated in cooling, and supernatant liquor (the about 3752mg/L of COD) continues to drip H
2O
2(in this process, materials in good time,, press the COD that GB11914-89 " the mensuration potassium dichromate process of hydrochemistry oxygen requirement " measures solution) with the sample after the neutralization.Behind the COD＜1000mg/L of solution, add sodium hydroxide and transfer pH value of solution value 9～10.Separate the iron mud that this process produces, the waste liquid after the processing can be used as process water, or discharging.
Embodiment 2: get the filtered wastewater (COD about 22000mg/L) of 500mL from the fermentative Production tridecanyldicarboxylic acid, under abundant stirring and room temperature, transfer its pH value to 3 with the vitriol oil.Allow its standing sedimentation, separate obtaining about 0.6g mixing acid.Get 200mL supernatant liquor (the about 11805mg/L of COD), add 6g solid FeSO
47H
2O after treating all to dissolve, slowly adds 10mL35%H under fully stirring
2O
2Solution, the reinforced time is about 1.5 hours.Solution is warming up to 50～55 ℃ automatically, has the floss precipitation to produce in this process, isolates post precipitation, and supernatant liquor (the about 4731mg/L of COD) continues to drip 20mLH
2O
2(in this process, materials in good time,, press the COD that GB11914-89 " the mensuration potassium dichromate process of hydrochemistry oxygen requirement " measures solution) with the sample after the neutralization.At last, add sodium hydroxide and transfer pH value of solution value 7～8.After separating the iron mud that produces, the COD of gained solution is 1288mg/L.The content of tridecanyldicarboxylic acid, SL-AH and 11 carbon dicarboxylic acids is respectively 92.0,6.5 and 0.3% in the mixed dibasic acid that reclaims.
Embodiment 3: get the filtered wastewater (COD about 22000mg/L) of 500mL from the fermentative Production hendecane dicarboxylic acid, fully stir and 10 ℃ under, transfer its pH value to 2 with the vitriol oil.Allow its standing sedimentation, separate obtaining about 0.65g mixing acid.Get 200mL supernatant liquor (the about 10228mg/L of COD), add 10g solid FeSO
47H
2O after treating all to dissolve, slowly adds 6mL30%H under fully stirring
2O
2Solution, the reinforced time is about 1.5 hours.Solution is warming up to 40～45 ℃, has the floss precipitation to produce in this process, isolates post precipitation, continues to drip 15mL35%H
2O
2Solution.At last, add sodium hydroxide and transfer pH value of solution value 7～8.After separating the iron mud that produces, the COD of gained solution is about 1088mg/L, and the content of tridecanyldicarboxylic acid, SL-AH and 11 carbon dicarboxylic acids is respectively 92.7,5.2 and 0.6% in the mixed dibasic acid of recovery.
Embodiment 4: get the filtered wastewater (COD about 22000mg/L) of 500mL from the fermentative Production hendecane dicarboxylic acid, fully stir and 25 ℃ under, transfer its pH value to 1.2 with the vitriol oil.Allow its standing sedimentation, separate obtaining the acid of about 0.65g blended solid.Get 200mL supernatant liquor (the about 10228mg/L of COD), add 8g solid FeSO
47H
2O, treat all dissolvings after, slowly add 4mL30%H in room temperature with under fully stirring
2O
2Solution, the reinforced time is about 1.0 hours.Solution is warming up to 40～45 ℃, has the floss precipitation to produce in this process, isolates post precipitation, continues to drip 10mLH
2O
2At last, add sodium hydrate regulator solution pH value 7～8.After separating the iron mud that produces, the COD of gained solution is about 798mg/L.The content that separates tridecanyldicarboxylic acid, SL-AH and 11 carbon dicarboxylic acids in the mixed dibasic acid that obtains is respectively 93.1,2.3 and 3.48%.
Embodiment 5: get the filtered wastewater (COD about 22000mg/L) of 500mL from the fermentative Production hendecane dicarboxylic acid, fully stir and 40 ℃ under, transfer its pH value to 2 with the vitriol oil.Allow its standing sedimentation.Get 200mL supernatant liquor (the about 10228mg/L of COD), add 8g solid FeSO
47H
2O, treat all dissolvings after, slowly add 4mL35%H in room temperature with under fully stirring
2O
2Solution, the reinforced time is about 1.0 hours.Have the floss precipitation to produce in this process, isolate post precipitation, supernatant liquor (the about 3967mg/L of COD) continues to drip 15mLH
2O
2At last, add sodium hydrate regulator solution pH to 7～8.Behind the separation of iron mud, the COD of solution is about 578mg/L.The content that separates tridecanyldicarboxylic acid, SL-AH and 11 carbon dicarboxylic acids in the mixed dibasic acid that obtains is respectively 88.1,4.8 and 6.1%.
Embodiment 6: get the filtered wastewater (COD about 22000mg/L) of 500mL from the fermentative Production hendecane dicarboxylic acid, fully stir and 30 ℃ under, transfer its pH value to 2 with the vitriol oil.Allow its standing sedimentation.Get 200mL supernatant liquor (the about 10228mg/L of COD), under abundant stirring and room temperature, add 6mL30%H
2O
2, in about 0.5 hour, add and contain 5gFeCl
2Solution.After finishing, solution is warming up to 70～75 ℃, has the floss precipitation to produce in this process, when precipitation reached maximum value, post precipitation was isolated in cooling, continued to drip 15mLH
2O
2, add sodium hydrate regulator solution pH value 9～10 afterwards.Separate the iron mud that this process produces, the waste liquid COD after the processing is about 620mg/L.
Embodiment 7: get the filtered wastewater (COD about 22000mg/L) of 500mL from the fermentative Production hendecane dicarboxylic acid, under fully stirring, transfer its pH value to 2 with the vitriol oil.Allow its standing sedimentation.Get supernatant liquor (the about 10228mg/L of COD), in 2 hours, slowly add Fenton reagent (50mL 30%H
2O
2Solution and 5mL contain 10 gram FeSO
4The aqueous solution also adds), will produce floss in this process, when reaching maximum value, precipitation suspends dropping Fenton reagent, isolate post precipitation, continue to add Fenton reagent.
Embodiment 8: get the filtered wastewater (COD about 22000mg/L) of 500mL from the fermentative Production hendecane dicarboxylic acid, fully stir and 40 ℃ under, transfer its pH value to 2 with the vitriol oil.Allow its standing sedimentation.Get 200mL supernatant liquor (the about 10228mg/L of COD), add 15g solid FeO, 50 ℃ and fully stir under slowly add 20mL 30%H
2O
2Solution, the reinforced time is about 1.5 hours.There is the floss precipitation to produce in this process, isolates post precipitation, continue to drip 20mLH
2O
2At last, add sodium hydrate regulator solution pH to 7～8.Behind the separation of iron mud, the COD of solution is about 815mg/L.
Embodiment 9: get the filtered wastewater (COD about 22000mg/L) of 500mL from the fermentative Production hendecane dicarboxylic acid, fully stir and 40 ℃ under, transfer its pH value to 2 with the vitriol oil.Allow its standing sedimentation.Get 200mL supernatant liquor (the about 10228mg/L of COD), add 1.0g Fe powder, after waiting to dissolve, slowly add 3mL40%H in envrionment temperature with under fully stirring
2O
2Solution, the reinforced time is about 2.0 hours.There is the floss precipitation to produce in this process, isolates post precipitation, continue to drip 12mL H
2O
2At last, add sodium hydrate regulator solution pH to 7～8.Behind the separation of iron mud, the COD of solution is about 802mg/L.
Embodiment 10: get the filtered wastewater (COD about 22000mg/L) of 500mL from the fermentative Production hendecane dicarboxylic acid, under fully stirring, transfer its pH value to 3 with the vitriol oil.Allow its standing sedimentation.Get supernatant liquor (the about 11805mg/L of COD), add 15g FeSO
47H
2O after treating all to dissolve, slowly adds 2mL 40%H under fully stirring
2O
2Solution feeds ozone gas simultaneously, and this process will temporarily stop to add H with the sedimentary generation of floss when precipitation reaches maximum value
2O
2, isolate post precipitation, continue to drip 9mL H
2O
2With the feeding ozone gas.At last, add sodium hydrate regulator solution pH to 7～8.Behind the separation of iron mud, the COD of solution is about 946mg/L.
Embodiment 11: get the filtered wastewater (COD about 22000mg/L) of 500mL from the fermentative Production hendecane dicarboxylic acid, fully stir and 40 ℃ under, transfer its pH value to 2 with the vitriol oil.Allow its standing sedimentation.Get 200mL supernatant liquor (the about 10228mg/L of COD), add the 4.0g iron rust, after waiting to dissolve, slowly add 6mL20%H in envrionment temperature with under fully stirring
2O
2Solution, the reinforced time is about 1.0 hours.There is the floss precipitation to produce in this process, isolates post precipitation, continue to drip 9mL H
2O
2At last, add sodium hydrate regulator solution pH to 7～8.Behind the separation of iron mud, the COD of solution is about 896mg/L.
Embodiment 12: get the filtered wastewater (COD about 20000mg/L) of 500mL from the fermentative Production dodecanedioic acid, under abundant stirring and envrionment temperature, transfer its pH value to 2 with the vitriol oil.Allow its standing sedimentation.Get 200mL supernatant liquor (the about 10000mg/L of COD), add 20g solid FeSO
47H
2O, treat all dissolvings after, 20 ℃ and fully stir under slowly add 5mL 30%H
2O
2Solution, the reinforced time is about 0.5 hour.There is the floss precipitation to produce in this process, isolates post precipitation, continue to drip 15mLH
2O
2At last, add sodium hydrate regulator solution pH to 7～8.Behind the separation of iron mud, the COD of solution is about 972mg/L.
Claims (9)
1. the advanced waste treatment method of a process in process of production of long chain dibasic acid by fermentation is characterized in that may further comprise the steps:
(1) with sour pH to 1.0～3.0 of regulating the waste water of handling;
(2) product that step (1) is obtained leaves standstill, and precipitation is separated out mixed dibasic acid;
(3) product that step (2) is obtained separates, and adds oxygenant in the supernatant liquor that separation obtains; Described oxygenant is ferrous iron reagent and superoxol; The consumption of described ferrous iron reagent is: 0.1-100gFe
2+/ every liter of waste water; The consumption of described superoxol is: 1-200g H
2O
2/ every liter of waste water, superoxol are that concentration is 10%～80% aqueous hydrogen peroxide solution;
(4) solution left standstill that step (3) is obtained is separated out the mixed dibasic acid precipitation;
(5) product that step (4) is obtained separates, and continues to add oxygenant in the supernatant liquor that separation obtains, and reaches emission standard until the COD of waste water;
(6) solution that obtains with alkali neutralization procedure (5) is to pH 7～10;
(7) separation of iron mud.
2. in accordance with the method for claim 1, it is characterized in that described each step carries out under 0～80 ℃ of temperature.
3. according to claim 1 or 2 described methods, it is characterized in that described ferrous iron reagent is ferrous sulfate, iron protochloride, iron protoxide or their mixture.
4. in accordance with the method for claim 1, it is characterized in that the mode that oxygenant adds in described step (3) and (5) is to add ferrous iron reagent in pending product earlier, add superoxol then.
5. in accordance with the method for claim 1, it is characterized in that the mode that oxygenant adds in described step (3) and (5) is to add superoxol in pending product earlier, add ferrous iron reagent then.
6. in accordance with the method for claim 1, it is characterized in that the mode that oxygenant adds in described step (3) and (5) is to add ferrous iron reagent and superoxol in pending product simultaneously.
7. according to claim 1 or 4,5,6 described methods, it is characterized in that the time with the oxygenant chemical oxidation treatment is 0.1-4 hour in described step (3) and (5).
8. in accordance with the method for claim 1, it is characterized in that described step (3) process has throw out to separate out.
9. in accordance with the method for claim 1, the consumption that it is characterized in that described ferrous iron reagent is: 1-30gFe
2+/ every liter of waste water; The consumption of described superoxol is: 1-50g H
2O
2/ every liter of waste water.
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| CN110305006A (en) * | 2019-06-12 | 2019-10-08 | 江苏达成生物科技有限公司 | The processing method of long carbochain biatomic acid purification waste liquid |
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