CN103833166B - A kind of methyldiethanolamine (MDEA) process for treating industrial waste water - Google Patents
A kind of methyldiethanolamine (MDEA) process for treating industrial waste water Download PDFInfo
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- CN103833166B CN103833166B CN201210482462.2A CN201210482462A CN103833166B CN 103833166 B CN103833166 B CN 103833166B CN 201210482462 A CN201210482462 A CN 201210482462A CN 103833166 B CN103833166 B CN 103833166B
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Abstract
The present invention relates to a kind for the treatment of process of methyldiethanolamine trade effluent, comprising: methyldiethanolamine trade effluent is dosed in reactor by (1), regulate wastewater pH to be 2 ~ 5; (2) in reactor, add iron carbon material, aeration is carried out to waste water simultaneously; (3) when wastewater pH is 4, hydrogen peroxide is added; (4) abundant mixed waste water is incorporated into coagulant precipitation groove, adds alkaline coagulating agent simultaneously, regulate pH to be 9, carry out coagulant precipitation; (5) add oxidizing agent sodium hypochlorite wherein, then waste water is introduced into deodorizing reactor, react further, promote removal or the reduction of COD.The inventive method adopts iron-carbon micro-electrolysis technology to combine with class Fenton oxidation technology, be that chemical assistant works in coordination with the iron-carbon micro-electrolysis process promoting MDEA trade effluent with hydrogen peroxide, pH is regulated to combine with conventional coagulation technology, the COD clearance of MDEA waste water can reach more than 90%, and water outlet can reach national wastewater from chemical industry first discharge standard.
Description
Technical field
The present invention relates to green technology, be specifically related to the process for treating industrial waste water containing methyldiethanolamine.
Background technology
N methyldiethanol amine (also referred to as methyl glycol amine, being abbreviated as MDEA) is a kind of tertiary amines material.Molecular formula is CH
3n (CH
2cH
2oH)
2, molecular weight is 119.16, proportion 1.0418, boiling point 247 DEG C, and the viscosity 12 DEG C time is 101cP, Ning Gu Dian – 48 DEG C, can be all soluble in water.
At present, methyldiethanolamine is used widely as desulfurization solvent in selexol process, gasification desulfurization and refinery's desulfurization.MDEA is to H
2s has very high selectivity and lower energy consumption, is used to Crouse's unstripped gas concentrate, Scott method vent gas treatment, the processes such as low heating value gas desulfurization.
MDEA also has unique distinction on synthetic ammonia decarbonization process.The absorption CO of MDEA
2consuming energy comparatively with regeneration, monoethanolamine (MEA) is for low, and it is extremely low to the solubleness of non-polar gas as hydrogen, nitrogen, methyl alcohol, methane and other higher hydrocarbons compounds, and self loss seldom.MDEA and CO
2reaction only generates supercarbonate and does not generate carbamate, and absorption process is non-degradable, and daily magnitude of recruitment greatly reduces.
Methyldiethanolamine is used in a large number as emulsifying agent, acid gas absorbent, soda acid control agent, polyurethane foam catalyzer.It can remove carbonic acid gas in synthetic ammonia and hydrogen sulfide under activator booster action.But, in production application process, the life-time service of MDEA can cause heat exchanger tube fouling, produces large number of biological foundry loam, not only causes corrosion to equipment, and cause pipe leakage, and impact is produced.
MDEA has soluble in water, is not easily adsorbed, difficult for biological degradation, microorganism is had to the features such as certain toxicity.Should absorption method, oxidation style, flocculence and biological process etc. be adopted almost not to have effective effect by the trade effluent containing MDEA.
Summary of the invention
The present inventor finds through research, for the waste water containing methyldiethanolamine, by in same reactor, drop into iron carbon material and (class) Fenton's reaction material successively, via iron-carbon micro-electrolysis and (class) Fenton's reaction, methyldiethanolamine is removed in effective degraded, and then drop into alkaline coagulating agent and oxygenant successively, via coagulating and oxidizing reaction, iron ion in effective removal system and residual organic materials, thus the methyldiethanolamine removed expeditiously in waste water, and then complete the present invention.
The object of the present invention is to provide a kind for the treatment of process of methyldiethanolamine trade effluent, the method comprises the following steps:
(1) methyldiethanolamine trade effluent is dosed in reactor, regulates wastewater pH to be 2 ~ 4;
(2) in reactor, add iron carbon material, aeration is carried out to waste water simultaneously, methyldiethanolamine waste water is fully contacted with iron carbon, and the change of reaction system pH in Real-Time Monitoring reactor;
(3) when the pH of waste water in reactor is 4-5, in the waste water in reactor, add oxidants hydrogen peroxide with the ratio of 0.1-5%, fully mix;
(4) abundant mixed waste water is incorporated into coagulant precipitation groove, adds alkaline coagulating agent simultaneously, adjustment pH is 9-13, carries out coagulant precipitation;
(5) for the waste water carried out after coagulant precipitation, add oxidizing agent sodium hypochlorite wherein, then waste water is introduced into deodorizing reactor, react further, promote removal or the reduction of COD.
According to the inventive method, the difficult problem that methyldiethanolamine waste water is difficult to effectively process effectively can be solved, the method simple possible, can effective degrading high concentration methyldiethanolamine, cost is low, consumes low, and reaction material can repeatedly reuse.Specifically, the present invention has the following advantages:
(1) in the method according to the invention, with iron-carbon micro-electrolysis technical finesse methyldiethanolamine waste water, utilize the raw material that the iron ion produced in reaction process reacts as follow-up (class) Fenton oxidation, both the efficient degradation of methyldiethanolamine Pollutants in Wastewater had been facilitated, greatly reduce again the usage quantity of reaction mass, save processing cost;
(2) in the method according to the invention, iron-carbon micro-electrolysis reaction is carried out with reacting in same reactor of (class) Fenton oxidation process methyldiethanolamine, and technical process is simple, and processing efficiency is high;
(3) in the method according to the invention, after iron-carbon micro-electrolysis and (class) fragrant oxidizing reaction, directly add a small amount of alkaline coagulating agent, can interact with the iron ion that produces in micro-electrolysis reaction and enhanced flocculation effect occurs, the effect regulating reaction system pH can be played again;
(4) in the method according to the invention, iron-carbon micro-electrolysis reaction, the reaction of (class) Fenton oxidation and the combination process of coagulating, make the methyldiethanolamine waste water after processing can reach deodorizing and object up to standard after hypochlorite oxidation process;
(5) in the method according to the invention, for iron-carbon micro-electrolysis and (class) Fenton oxidation combination process, can plural serial stage use be carried out, high density methyldiethanolamine trade effluent can be processed, also can process lower concentration methyldiethanolamine trade effluent;
(6) according to the Technology of iron-carbon micro-electrolysis provided by the invention and (class) Fenton oxidation materialization combined treatment methyldiethanolamine trade effluent can with other water technology couplings.
Accompanying drawing explanation
Fig. 1 shows process flow diagram according to the preferred embodiment of the present invention.
description of reference numerals
1-waste water storage tank
2-aerating apparatus
3-pH on-line computing model
4-feeds in raw material volume pump
5-coagulant precipitation groove
6-feeds in raw material volume pump
7-feeds in raw material volume pump
8-deodorizing reactor
Embodiment
Below in conjunction with accompanying drawing, by illustrative embodiments, the present invention is described in detail.The features and advantages of the invention will illustrate along with these and become more explicit.
Word " exemplary " special here means " as example, embodiment or illustrative ".Here need not be interpreted as being better than or being better than other embodiment as any embodiment illustrated by " exemplary ".Although the various aspects of embodiment shown in the drawings, unless otherwise indicated, accompanying drawing need not be drawn in proportion.
In the method according to the invention, the effect of step (1) is the pH regulator of pending waste water to the scope being suitable for carrying out iron-carbon micro-electrolysis reaction, to carry out iron-carbon micro-electrolysis reaction smoothly, provide iron ion, so for follow-up (class) Fenton's reaction carry out smoothly provide basis.
In a preferred embodiment, in step (1), wastewater pH is regulated to be 2.5 ~ 4, more preferably 3 ~ 4, also more preferably from about about 3.
As reactor, in practice, waste water storage tank can be adopted, the stream of pending waste water can be saved like this, so cost-saving.
In the method according to the invention, the effect of step (2) is to carry out iron-carbon micro-electrolysis reaction, thus provides iron ion.
In the step (2) according to the inventive method, as iron carbon material, the part by weight of iron and carbon is in 1: 1-1: 5 scopes, and preferred iron carbon weight ratio is 1:1.For this iron carbon material, iron carbon dust or particle can be used, preferably use powder.
In the step (2) according to the inventive method, aeration can make waste water fully contact with iron carbon, thus promotes the carrying out of micro-electrolysis reaction.
In literary composition term used " aeration " be meant to instigate pending waste water fully contacts with air, promote that the oxygen in air is dissolved in pending waste water.
The object of aeration increases the dissolved oxygen in waste water, strengthens the contact of iron carbon and MDEA waste water, is conducive to the carrying out reacted.Aeration contributes to pharmaceutics wastewater reaction process, promotes carrying out fast of reaction.In practice, in order to carry out aeration, can aerating apparatus be adopted, mentioning such as jetted self-priming air type aerating apparatus.The preferred 1-10 hour of aeration time, more preferably 2-4 hour.
In the step (2) according to the inventive method, by the change of reaction system pH in Real-Time Monitoring reactor, the degree that monitoring micro-electrolysis reaction carries out can be checked.Abundant experimental results shows, when the pH of reaction system is changed to 3.5-5.0, preferably about 4 time, be suitable for carrying out follow-up (class) Fenton's reaction.
In order to the pH of Real-Time Monitoring system changes, pH on-line computing model can be used.
In the method according to the invention, the effect of step (3) is to carry out (class) Fenton's reaction smoothly, with the methyldiethanolamine of degrading in removal system.
In the step (3) according to the inventive method, the system pH being suitable for carrying out (class) Fenton's reaction is about about 4, now in system by volume with the ratio of 0.1-5%, preferably about 1.5% ratio add oxidants hydrogen peroxide, to carry out (class) Fenton's reaction.
In a preferred embodiment, the time of carrying out (class) Fenton's reaction in step (3) is 2-6 hour, preferred 3-4 hour, more preferably 3.5-4 hour.At this moment in scope, can guarantee that (class) Fenton's reaction carries out completely, not wasting the reaction times again.
In the method according to the invention, the effect of step (4) is the iron ion in coagulant precipitation system, simultaneously the pH value of regulation system, to carry out follow-up oxide treatment.
In the step (4) according to the inventive method, as alkaline coagulating agent, mention such as calcium oxide, sodium hydroxide, potassium hydroxide and sheet alkali etc.Wherein any one can be used, or combinationally use multiple.
In the method according to the invention, the effect of step (5) is the organic substance in removing system further, thus removes stink, and water quality is reached can emission standard.
In a preferred embodiment, for the waste water carried out after coagulant precipitation, be first separated, after separating lower sediment, add oxidizing agent sodium hypochlorite, ozone or chlorine water again, preferred clorox, this is because clorox also has deodouring effect concurrently except there being oxygenizement.Preferably, the addition of oxidizing agent sodium hypochlorite is 1/4000 of liquid volume.
In practice, process route chart as shown in Figure 1 can be adopted to implement method of the present invention.By pending storage of waste water in or be introduced in waste water storage tank, regulate the pH of waste water to desired value, then aeration under the effect of aerating apparatus, and add iron carbon dust and carry out micro-electrolysis reaction, by the pH of pH on-line computing model Real-Time Monitoring system, when the pH of system is 4, in system, add hydrogen peroxide carry out (class) Fenton's reaction, reacted waste water is entered in coagulant precipitation groove, add alkaline coagulating agent, carry out coagulant precipitation and regulation system pH, then upper strata waste water is introduced in deodorizing reactor, add oxidizing agent sodium hypochlorite wherein, carry out deodorizing.
The present invention is further described below by way of exemplary example.
Embodiment 1
1000mL methyldiethanolamine waste water is put into the there-necked flask of 2000mL, the COD=1000mg/L of this methyldiethanolamine waste water, regulate pH to 3,1g iron carbon dust is added under the condition of aeration, wherein, iron carbon dust to be speeded green technology Engineering Co., Ltd from Wu Xihai, production code member: HCW-007, (wherein iron is 0.49kg, carbon is 0.49kg), open peristaltic pump simultaneously, make waste water circulation, pH meter probe is placed in the middle part of reaction soln, the change of monitoring pH.When pH is 4, in reactor, add the superoxol 15mL that concentration is 30%, continue reaction 4h.After reaction terminates, leave standstill, supernatant liquor adds calcium oxide, regulates pH to 9, and coagulating sedimentation filters and obtains supernatant liquor, and after adding clorox, final outflow water COD=48mg/L, COD clearance reaches 98.1%.
Embodiment 2
The methyldiethanolamine waste water that 500LCOD is 1000mg/L is introduced in reactor, regulate wastewater pH to 2.5, utilize gas blower air-blowing, add 5kg iron carbon dust wherein, iron carbon dust to be speeded green technology Engineering Co., Ltd from Wu Xihai, production code member: HCW-007, (wherein, iron is 2.45kg, carbon is 2.45kg, wherein be mixed with trace copper, manganese and zinc), reach the object of gas mixing, make iron carbon dust and the abundant contact reacts of waste water.Utilize online pH monitor, the change of monitoring pH.As pH=4, utilize volume pump in reactor, add the superoxol 4.1L of 30% continuously, after reaction 4h, leave standstill, add calcium oxide in supernatant liquor and regulate pH to 9, coagulating sedimentation, supernatant liquor adds the water outlet COD=87mg/L after clorox, and COD clearance reaches 91.3%.
Embodiment 3
360L methyldiethanolamine waste water is introduced in reaction unit device, the COD=5000mg/L of this waste water, regulates pH to 3, adds 5kg iron carbon dust, wherein, iron carbon dust to be speeded green technology Engineering Co., Ltd from Wu Xihai, production code member: HCW-007, and (wherein iron is 2.45kg, carbon is 2.45kg), utilize gas blower air-blowing, reach the object of gas mixing, make iron carbon dust and the abundant contact reacts of waste water.Utilize online pH monitor, the change of monitoring pH.As pH=4, utilize volume pump in reactor, add the superoxol 4.2L of 30% continuously, after reaction 3.5h, leave standstill, add calcium oxide in supernatant liquor and regulate pH to 9, coagulating sedimentation, measure supernatant liquor water outlet COD=2076mg/L, COD clearance reaches 58.5%.
Embodiment 4
500L methyldiethanolamine waste water is introduced in reactor, the COD=15000mg/L of this waste water, regulates pH to 3, adds 7kg iron carbon dust, wherein, iron carbon dust to be speeded green technology Engineering Co., Ltd from Wu Xihai, production code member: HCW-007, and (wherein iron is 3.45kg, carbon is 3.45kg), utilize gas blower air-blowing, reach the object of gas mixing, make iron carbon dust and the abundant contact reacts of waste water.Utilize online pH monitor, the change of monitoring pH.As pH=4, utilize volume pump in reactor, add the superoxol 4.5L of 30% continuously, after reaction 4h, leave standstill, add calcium oxide and regulate pH to 9, coagulating sedimentation in supernatant liquor, measure supernatant liquor water outlet COD=9857mg/L, COD clearance reaches 34.3%.
Above by embodiment and exemplary example to invention has been detailed description, but these explanations are only illustrative, do not form any restriction to protection scope of the present invention.When not departing from the present invention's spirit and protection domain, those skilled in the art can carry out multiple improvement, equivalencing or modification to the present invention and embodiment thereof, and these all should fall within the scope of protection of the present invention.
The all documents mentioned in literary composition, incorporated herein by reference in full with it.
Claims (6)
1. a treatment process for methyldiethanolamine trade effluent, the method comprises the following steps:
(1) methyldiethanolamine trade effluent is dosed in reactor, regulates wastewater pH to be 2 ~ 4, wherein, use the pH change of pH on-line computing model Real-Time Monitoring system;
(2) in reactor, iron carbon material is added, aeration is carried out to waste water simultaneously, methyldiethanolamine waste water is fully contacted with iron carbon, and the change of reaction system pH in Real-Time Monitoring reactor, described iron carbon material is iron carbon dust within the scope of 1:1-1:5 of the part by weight of iron and carbon or iron carbon granule;
(3) when the pH of waste water in reactor is 4-5, in the waste water in reactor, add oxidants hydrogen peroxide with the ratio of 0.1-5%, fully mix;
(4) abundant mixed waste water is incorporated into coagulant precipitation groove, adds alkaline coagulating agent simultaneously, adjustment pH is 9-13, carries out coagulant precipitation, and wherein, described alkaline coagulating agent is calcium oxide, sodium hydroxide, potassium hydroxide;
(5) for the waste water carried out after coagulant precipitation, add oxidizing agent sodium hypochlorite wherein, then waste water is introduced into deodorizing reactor, react further, promote removal or the reduction of COD.
2. method according to claim 1, wherein, in step (1), regulates wastewater pH to be 2.5 ~ 4.
3. method according to claim 2, wherein, in step (1), regulates wastewater pH to be 3 ~ 4.
4. method according to claim 3, wherein, in step (1), regulates wastewater pH to be 3.
5. method according to claim 1, wherein, in step (2), the part by weight of iron and carbon is 1:1.
6. the method according to any one of claim 1-5, wherein, in step (2), aeration time is 1-10 hour.
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| CN104445711B (en) * | 2014-10-29 | 2016-08-24 | 浙江奇彩环境科技股份有限公司 | A kind of processing method of amino benzene analog waste water |
| CN104445807B (en) * | 2014-10-31 | 2019-05-31 | 中国石油化工股份有限公司 | A kind of wastewater treatment equipment and its treatment process containing methyl diethanolamine |
| CN107324559A (en) * | 2017-08-23 | 2017-11-07 | 哈尔滨工业大学 | A kind of processing method of industrial organic waste water |
| KR102085614B1 (en) * | 2018-11-28 | 2020-03-06 | 주식회사 포스코 | Wastewater treatment method and treatment device |
| CN110040901A (en) * | 2019-05-13 | 2019-07-23 | 上海明奥环保科技有限公司 | It is a kind of can sludge reuse light electrolysis/heterogeneous Fenton fluidized-bed process and device |
| CN111908569A (en) * | 2020-07-20 | 2020-11-10 | 广东石油化工学院 | Treatment method of diethanolamine wastewater |
| CN112759150A (en) * | 2020-12-31 | 2021-05-07 | 中国海洋大学 | Method for treating high-concentration methanol residual liquid wastewater |
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| CN101734817A (en) * | 2009-12-31 | 2010-06-16 | 江苏苏净集团有限公司 | Method for treating organic chemical waste water |
| CN102531247A (en) * | 2011-12-26 | 2012-07-04 | 浙江天蓝环保技术股份有限公司 | Treatment method for wastewater produced during flue gas desulphurization through alcohol-amine process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734817A (en) * | 2009-12-31 | 2010-06-16 | 江苏苏净集团有限公司 | Method for treating organic chemical waste water |
| CN102531247A (en) * | 2011-12-26 | 2012-07-04 | 浙江天蓝环保技术股份有限公司 | Treatment method for wastewater produced during flue gas desulphurization through alcohol-amine process |
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