CN103539300B - A kind of method processing Oxidative Dehydrogenation of Butene into Butadiene waste water - Google Patents
A kind of method processing Oxidative Dehydrogenation of Butene into Butadiene waste water Download PDFInfo
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- CN103539300B CN103539300B CN201210253351.4A CN201210253351A CN103539300B CN 103539300 B CN103539300 B CN 103539300B CN 201210253351 A CN201210253351 A CN 201210253351A CN 103539300 B CN103539300 B CN 103539300B
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Abstract
The invention provides a kind of method processing Oxidative Dehydrogenation of Butene into Butadiene waste water, first butadiene waste water is stripped in stripper, remove low boiling component in butadiene waste water, then treatment of wastewater from stripping is carried out pH value regulation, add fenton reagent, stirring carries out oxidation reaction, add flocculant, stirring, stand, filter, filtrate is neutralized to neutrality with alkali liquor, again filtrate is distilled and obtain the COD the entered boiler less than 100 and the water white transparency water sample of circulation, the present invention carries out deep oxidation to waste water, non-secondary pollution, simple to operate, have efficiently, economical, environment amenable feature.
Description
Technical field
The present invention relates to a kind of Oxidative Dehydrogenation of Butene into Butadiene method of wastewater treatment.
Background technology
Butadiene is a kind of important basic petrochemical Organic Ingredients and synthetic rubber monomer, at synthetic rubber and
The aspect tools such as organic synthesis have been widely used.The source of butadiene mainly mixing from ethylene cracker by-product
Close and C 4 fraction extracts and obtains from oil plant C 4 fraction butylene oxidation-dehydrogenation.In Oxidative Dehydrogenation of Butene fourth two
In alkene production process, wastewater source is guarantee safety in production, and a large amount of water vapour introduced in reaction raw materials are de-
Hydrogen water generation reaction and product washings, producing 1 ton of butadiene just has 16 tons of waste water to produce, and contains in waste water
The components such as acetone, furan, acetaldehyde, acetic acid, acrylic aldehyde, methylacrolein, butane, butadiene, butylene,
Concentration is high, have butadiene waste water hypertoxic, difficult to be treated as Oxidative Dehydrogenation of Butene into Butadiene produces work
One of industrialized the biggest problem of skill.
Oxidative Dehydrogenation of Butene into Butadiene waste water processes and has no that method is reported, the processing method master of current organic wastewater
Have: membrane separation process, absorption method, extraction, the way of distillation, oxidizing process, bioanalysis, burning method, bleaching powder
Or photocatalysis, metal catalytic etc., Oxidative Dehydrogenation of Butene into Butadiene waste water is processed, these single methods are all
Difficulty reaches treatment effect, and processing cost is high, processes not thorough, produces secondary pollution etc..
Summary of the invention
The invention aims to solve Oxidative Dehydrogenation of Butene into Butadiene waste water and process a difficult problem, it is provided that Yi Zhongding
Alkene oxidative dehydrogenation butadiene method of wastewater treatment, the advantage utilizing the processing method of current organic wastewater, respectively take
The chief, improves treatment effeciency, processing procedure non-secondary pollution, and energy consumption is low, simple to operate, has efficient, warp
Ji, environment amenable feature.
In order to achieve the above object, the technical scheme that the present invention takes is as follows:
Butadiene waste water is stripped in stripper, removes low boiling component in butadiene waste water；After stripping
Treatment of wastewater from stripping dilute sulfuric acid and sodium hydroxide carry out pH value regulation, regulation pH value is between 2.5～4.5；
Then adding fenton reagent in waste water, stirring carries out oxidation reaction；Add flocculant, stirring, quiet
Putting, filter, filtrate is neutralized to neutrality with sodium hydroxide lye, then filtrate carries out distillation obtains COD and be less than
The water of 100.
Butadiene waste water of the present invention carries out the steam stripped time in stripper and is generally 1～4h.
The time of oxidation reaction of the present invention is generally 30min～4h.
Oxidative Dehydrogenation of Butene into Butadiene waste water of the present invention is a kind of containing acetone, furan, acetaldehyde, second
The organic waste water such as acid, acrylic aldehyde, methylacrolein, butane, butadiene, butylene, its COD 1500～
Between 8000.
The ferrous sulfate concentration used in fenton reagent of the present invention is 5～30%, and hydrogen peroxide concentration is
In 10～40%, fenton reagent, ferrous sulfate is (0.05～0.5) relative to the mass ratio of butadiene waste water:
In 100, fenton reagent, hydrogen peroxide is (0.1～5.0) relative to the mass ratio of butadiene waste water: 100.
Flocculant aqueous solution of the present invention be mass concentration be 0.01%～5% PAMC,
PAMA, non-ionic polyacrylamide, aluminium polychlorid, iron chloride, aluminium iron sulfate aqueous solution
In any one or the combination of any two kinds of arbitrary proportions；The addition of flocculant is relative to butadiene wastewater flow rate
1～10ppm.
The present invention has the following technical effect that
Butadiene waste water is stripped in stripper, makes low boiling component in butadiene waste water separate, reach
The purpose of pretreatment, alleviates oxidation processes pressure；Fenton reagent is used to carry out deep oxidation, at ferrous iron
Under ionic catalysis effect, hydrogen peroxide can produce active hydroxyl radical free radical, thus causes radical chain reaction, adds
Fast Organic substance and the oxidation of reducing substances, generate carbon dioxide and water, effectively reduces the COD of waste water；Add
Flocculant flocculation can accelerate sedimentation, reduces the sedimentation time of staying；Filtrate is carried out distillation and obtains COD less than 100
Water white transparency water, can qualified discharge or after further treatment after use as circulating cooling make-up water or demineralized water.
The method of the present invention Organic substance in water removal efficiency that gives up butadiene reaches more than 99%, and COD declines more than 95%.
The method treatment effeciency of the present invention is high, non-secondary pollution, and energy consumption is low, simple to operate, has efficient, warp
Ji, environmentally friendly.
Detailed description of the invention
The present invention will be further described by the following examples, but not thereby limit the present invention.
Embodiment 1: butadiene waste water used is with useless produced by Oxidative Dehydrogenation of Butene into Butadiene waste water pilot scale
Water is for processing object, containing acetone, furan, acetaldehyde, acetic acid, acrylic aldehyde, methylacrolein, fourth in waste water
The Organic substances such as alkane, butadiene, butylene, wherein COD is 2781mg/L.
A kind of method processing Oxidative Dehydrogenation of Butene into Butadiene waste water, comprises the following steps:
Butadiene waste water is stripped in stripper, removes low boiling component in butadiene waste water；
Treatment of wastewater from stripping dilute sulfuric acid and sodium hydroxide after stripping carry out pH value regulation, regulate pH value 3.5；
Then adding fenton reagent in treatment of wastewater from stripping, the ferrous sulfate concentration used in fenton reagent is
10%, hydrogen peroxide concentration is 27%, and in fenton reagent, ferrous sulfate relative to the mass ratio of butadiene waste water is
In 0.12: 100, fenton reagent, hydrogen peroxide is 0.9: 100 relative to the mass ratio of butadiene waste water, stirring
Carry out oxidation reaction, oxidation time 50min；
Adding relative to the mass ratio of butadiene waste water is 1ppm flocculant, stirs 30min, stands 3h,
Filtering, flocculant is PAMC and the combination of polyaluminium aluminum water solution of 5% of 0.01%, sun
Cationic polyacrylamide and polyaluminium aluminum water solution mass ratio be 0.09: 1.
Filtrate is neutralized to neutrality with 10% sodium hydroxide lye；
Filtrate is carried out air-distillation；
After stripping, aoxidize, flocculate, filter, distilling, butadiene waste water quality index is clearly better,
Water sample water white transparency, COD is 70.2.
Embodiment 2: butadiene waste water used is with useless produced by Oxidative Dehydrogenation of Butene into Butadiene waste water pilot scale
Water is for processing object, containing acetone, furan, acetaldehyde, acetic acid, acrylic aldehyde, methylacrolein, fourth in waste water
The Organic substances such as alkane, butadiene, butylene, wherein COD is 4119mg/L.
A kind of method processing Oxidative Dehydrogenation of Butene into Butadiene waste water, comprises the following steps:
Butadiene waste water is stripped in stripper, removes low boiling component in butadiene waste water；
Treatment of wastewater from stripping dilute sulfuric acid and sodium hydroxide after stripping carry out pH value regulation, regulate pH value 3.6；
Then adding fenton reagent in treatment of wastewater from stripping, the ferrous sulfate concentration used in fenton reagent is
10%, hydrogen peroxide concentration is 27%, and in fenton reagent, ferrous sulfate relative to the mass ratio of butadiene waste water is
In 0.26: 100, fenton reagent, hydrogen peroxide is 2.5: 100 relative to the mass ratio of butadiene waste water, stirring
Carry out oxidation reaction, oxidation time 90min；
Adding relative to the mass ratio of butadiene waste water is 2ppm flocculant, stirs 20min, stands 5h,
Filtering, flocculant is non-ionic polyacrylamide and the combination of polyaluminium aluminum water solution of 1% of 0.01%, sun
Cationic polyacrylamide and polyaluminium aluminum water solution mass ratio be 0.6: 1.
Filtrate is neutralized to neutrality with 10% sodium hydroxide lye；
Filtrate is carried out air-distillation；
After stripping, aoxidize, flocculate, filter, distilling, butadiene waste water quality index is clearly better,
Water sample water white transparency, COD is 58.6.
Embodiment 3: butadiene waste water used is with useless produced by Oxidative Dehydrogenation of Butene into Butadiene waste water pilot scale
Water is for processing object, containing acetone, furan, acetaldehyde, acetic acid, acrylic aldehyde, methylacrolein, fourth in waste water
The Organic substances such as alkane, butadiene, butylene, wherein COD is 4119mg/L.
A kind of method processing Oxidative Dehydrogenation of Butene into Butadiene waste water, comprises the following steps:
Butadiene waste water is stripped in stripper, removes low boiling component in butadiene waste water；
Treatment of wastewater from stripping dilute sulfuric acid and sodium hydroxide after stripping carry out pH value regulation, regulate pH value 3.5；
Then adding fenton reagent in treatment of wastewater from stripping, the ferrous sulfate concentration used in fenton reagent is
10%, hydrogen peroxide concentration is 27%, and in fenton reagent, ferrous sulfate relative to the mass ratio of butadiene waste water is
In 0.35: 100, fenton reagent, hydrogen peroxide is 3.5: 100 relative to the mass ratio of butadiene waste water, stirring
Carry out oxidation reaction, oxidation time 30min；
Adding relative to the mass ratio of butadiene waste water is 5ppm flocculant, stirs 30min, stands 1.5h,
Filtering, flocculant is PAMA and the combination of polyaluminium aluminum water solution of 2% of 0.05%, sun
Cationic polyacrylamide and polyaluminium aluminum water solution mass ratio be 0.8: 1.
Filtrate is neutralized to neutrality with 10% sodium hydroxide lye；
Filtrate is carried out air-distillation；
After stripping, aoxidize, flocculate, filter, distilling, butadiene waste water quality index is clearly better,
Water sample water white transparency, COD is 31.5.
Embodiment 4: butadiene waste water used is with useless produced by Oxidative Dehydrogenation of Butene into Butadiene waste water pilot scale
Water is for processing object, containing acetone, furan, acetaldehyde, acetic acid, acrylic aldehyde, methylacrolein, fourth in waste water
The Organic substances such as alkane, butadiene, butylene, wherein COD is 4400mg/L.
A kind of method processing Oxidative Dehydrogenation of Butene into Butadiene waste water, comprises the following steps:
Butadiene waste water is stripped in stripper, removes low boiling component in butadiene waste water；
Treatment of wastewater from stripping dilute sulfuric acid and sodium hydroxide after stripping carry out pH value regulation, regulate pH value 3.7；
Then adding fenton reagent in treatment of wastewater from stripping, the ferrous sulfate concentration used in fenton reagent is
10%, hydrogen peroxide concentration is 27%, and in fenton reagent, ferrous sulfate relative to the mass ratio of butadiene waste water is
In 0.45: 100, fenton reagent, hydrogen peroxide is 5.0: 100 relative to the mass ratio of butadiene waste water, stirring
Carry out oxidation reaction, oxidation time 30min；
Adding relative to the mass ratio of butadiene waste water is 6ppm flocculant, stirs 30min, stands 12h,
Filtering, flocculant is the ferric chloride in aqueous solution of 1%.
Filtrate is neutralized to neutrality with 10% sodium hydroxide lye；
Filtrate is carried out air-distillation；
After stripping, aoxidize, flocculate, filter, distilling, butadiene waste water quality index is clearly better,
Water sample water white transparency, COD is 90.0.
Embodiment 5: butadiene waste water used is with useless produced by Oxidative Dehydrogenation of Butene into Butadiene waste water pilot scale
Water is for processing object, containing acetone, furan, acetaldehyde, acrylic aldehyde, acetic acid, methylacrolein, fourth in waste water
The Organic substances such as alkane, butadiene, butylene, wherein COD is 4400mg/L.
A kind of method processing Oxidative Dehydrogenation of Butene into Butadiene waste water, comprises the following steps:
Butadiene waste water is stripped in stripper, removes low boiling component in butadiene waste water；
Treatment of wastewater from stripping dilute sulfuric acid and sodium hydroxide after stripping carry out pH value regulation, regulate pH value 3.5；
Then adding fenton reagent in treatment of wastewater from stripping, the ferrous sulfate concentration used in fenton reagent is
10%, hydrogen peroxide concentration is 27%, and in fenton reagent, ferrous sulfate relative to the mass ratio of butadiene waste water is
In 0.5: 100, fenton reagent, hydrogen peroxide is 4.5: 100 relative to the mass ratio of butadiene waste water, stirring
Carry out oxidation reaction, oxidation time 120min；
Adding relative to the mass ratio of butadiene waste water is 10ppm flocculant, stirs 30min, stands 15h,
Filtering, flocculant is the ferric aluminium sulfate aqueous solution of 1%.
Filtrate is neutralized to neutrality with 10% sodium hydroxide lye；
Filtrate is carried out air-distillation；
After stripping, aoxidize, flocculate, filter, distilling, butadiene waste water quality index is clearly better,
Water sample water white transparency, COD is 94.0.
Claims (1)
1. the method processing Oxidative Dehydrogenation of Butene into Butadiene waste water, it is characterised in that:
Butadiene waste water is stripped in stripper, removes the low boiling group in butadiene waste water
Point；Treatment of wastewater from stripping dilute sulfuric acid and sodium hydroxide after stripping carry out pH value regulation, regulate pH
Value is between 2.5～4.5；Then adding fenton reagent in waste water, it is anti-that stirring carries out oxidation
Should；Add flocculant, stirring, stand, filter, filtrate is neutralized to sodium hydroxide lye
Neutrality, then filtrate is distilled the water obtaining COD less than 100；Described butadiene gives up
Water is a kind of containing acetone, furan, acetaldehyde, acrylic aldehyde, methylacrolein, butane, fourth two
The organic waste water of alkene, butylene, its COD is between 1500～8000；Described butadiene
It is 1～4h that waste water carries out the steam stripped time in stripper；The time of oxidation reaction is
30min～4h；The ferrous sulfate concentration used in described fenton reagent is 5～30%, double
Oxygen water concentration is 10～40%, and in fenton reagent, ferrous sulfate is relative to the matter of butadiene waste water
Amount ratio is for (0.05～0.5): in 100, fenton reagent, hydrogen peroxide is relative to butadiene waste water
Mass ratio is (0.9～5.0): 100；Described flocculant aqueous solution is that mass concentration is
The PAMC of 0.01%～5%, PAMA, nonionic polypropylene
Any one or any two kinds in amide, aluminium polychlorid, iron chloride, aluminium iron sulfate aqueous solution
The combination of arbitrary proportion；The addition of flocculant is relative to butadiene wastewater flow rate
1～10ppm；Described filtrate is distilled obtain COD less than 100 water white transparency water reach
Mark discharge or after further treatment after use as circulating cooling make-up water or demineralized water.
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| KR101783517B1 (en) | 2014-12-04 | 2017-09-29 | 주식회사 엘지화학 | Method for producing conjugated diene |
| KR101785146B1 (en) * | 2015-03-24 | 2017-10-12 | 주식회사 엘지화학 | Method for producing conjugated diene and an apparatus |
| CN105293807A (en) * | 2015-11-18 | 2016-02-03 | 武汉致衡环境安全工程技术有限公司 | Organosilicone waste water purifying processing system and method thereof |
| US10647639B2 (en) * | 2016-02-04 | 2020-05-12 | Basf Se | Method for preparing 1,3-butadiene from N-butenes by oxidative dehydrogeneation |
| CN107311370A (en) * | 2016-04-26 | 2017-11-03 | 中国石油化工股份有限公司 | A kind of processing method of glycol production waste water |
| CN109851179B (en) * | 2019-04-09 | 2021-12-10 | 岳阳天河环保科技有限公司 | Acrolein production wastewater treatment process |
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