CN101172725A - Method for processing waste alkali liquid in butyl octanol production - Google Patents

Method for processing waste alkali liquid in butyl octanol production Download PDF

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Publication number
CN101172725A
CN101172725A CN 200610150167 CN200610150167A CN101172725A CN 101172725 A CN101172725 A CN 101172725A CN 200610150167 CN200610150167 CN 200610150167 CN 200610150167 A CN200610150167 A CN 200610150167A CN 101172725 A CN101172725 A CN 101172725A
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treatment
water
treatment process
process according
oxygenant
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程学文
刘正
栾金义
宋惠琴
杜蓓
王宜军
刘襄渝
张申
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention provides a treatment method of the waste alkali liquor produced in the production process of butyl alcohol. The treatment method comprises the steps as follows: the pH value of waste alkali liquor is adjusted into acidity at normal temperature and normal pressure, and the oil phase and the water phase are separated after the waste alkali liquor is settled and layered; and the water phase is catalyzed and oxidized by taking Fe2+ as the catalyst and H<2>O<2> as the oxidizer; the waste water is adjusted into neutral for accomplishing a neutralization reaction and then is accomplished with a solid-liquid separation process. The COD removing rate of the invention reaches more than 97 percent, therefore, the invention has good treatment effect and has the advantages of mild operation condition, flexible operation mode and stable and reliable operation.

Description

The treatment process of the waste lye that produces during a kind of fourth octanol is produced
Technical field
The present invention relates to a kind of Chemical Manufacture wastewater treatment method, particularly relate to a kind of treatment process that contains organic chemical industry's factory effluent of high density alcohols, aldehyde material.
Background technology
In fourth octanol production process, n butyraldehyde aldolization generates the reaction needed of octenal to carry out under the effect of alkaline catalysts, owing to there is water to generate in the reaction process, concentration for alkaline catalysts in the maintenance system, must continuously from system, discharge alkaline waste water, this alkaline waste water not only pH is very high, and organic content is very high, its COD is generally at 40000～50000mg/L, principal pollutant comprise alcohols and aldehyde materials such as butanols, butyraldehyde, octenal, octanol, are more unmanageable at present a kind of waste water.
Because hazardous and noxious substances is more in the fourth octanol production waste lye, concentration is higher, and independent pretreated difficulty is bigger, and enterprise does not generally carry out pre-treatment to it at present, but the method for taking directly to enter biochemical treatment apparatus after diluting is handled.
On the one hand, along with the raising of national wastewater discharge standard, the pressure of scale wastewater treatment qualified discharge constantly increases the weight of; On the other hand, country is for the purpose of protection water resources, and water rate raises, and can impel enterprise to improve constantly the water saving level, and the dilution water yield when reducing wastewater biochemical and handling has so also increased the difficulty of discharged wastewater met the national standard.Therefore, need a kind of effective fourth octanol of exploitation to produce the pretreatment process of waste lye, reduce waste water COD, alleviate the processing load and the water burden of subsequent processes.
In the prior art, CN1124230C provides the method for a kind of acidifying from the extraction treatment octanol waste lye.This method is at first carried out acidification with the vitriol oil to waste lye; Carry out extraction treatment with the organic phase of separating out after the acidifying as extraction agent then.Through said process, the COD clearance that the fourth octanol is produced waste lye is about 50%.
Though prior art has reduced the COD concentration of waste lye to a certain extent, but the place to go effect is bad, can not satisfy the requirement that reduces follow-up biochemical processing pressure, minimizing biochemical treatment load, reduces the dilution water consumption, and, owing to adopt extraction treatment technology, bring secondary pollution easily.
Summary of the invention
In order to overcome the deficiencies in the prior art, improve the treatment effect of waste lye, reduce secondary pollution, the invention provides a kind of fourth octanol and produce the treatment process of waste lye, effectively reduce waste water COD, alleviate the load of subsequent disposal, reach the purpose that improves the biochemical treatment effect, reduces the dilution water consumption.
Treatment process of the present invention is achieved in that
The treatment process of the waste lye that produces during a kind of fourth octanol is produced, described waste lye are alkalescence, contain alcohols material and aldehyde materials such as butanols, butyraldehyde, and this treatment process may further comprise the steps successively:
A. the pH that regulates described waste lye is to acid, and the sedimentation layering separates organic phase and water then;
B. described water is carried out catalytic oxidation treatment, catalyzer is a ferrous salt, and oxygenant is a hydrogen peroxide.
In the specific implementation, in steps A, the pH that regulates described waste lye is 1.0～6.0, and preferred pH is 2.0～5.0; The acid that is used to regulate pH is that sulfuric acid is or/and hydrochloric acid; The stratified treatment time of sedimentation is 10～30min, and the preferred treatment time is 15～25min.
In the specific implementation, in step B, the H of described oxygenant 2O 2With the weight ratio of aqueous phase COD be 0.5～3.5, preferred weight ratio is 1.0～3.0; Described catalyzer is ferrous sulfate, wherein Fe 2+With H in the oxygenant 2O 2Weight ratio be 0.04～0.20, preferred weight ratio is 0.08～0.16; The treatment temp of catalyzed oxidation is 40～80 ℃, and preferred treatment temp is 50～70 ℃; The treatment time of catalyzed oxidation is 30～180min, and the preferred time of handling is 60～150min.
In the specific implementation, in order further to improve treatment effect, in step C, the water pH that regulates process step B processing carries out neutralization reaction to neutrality or weakly alkaline, carries out solid-liquid separation then.The alkali that is used to regulate waste lye pH is sodium hydroxide; The pH that regulates waste lye is 6.0～9.0, and preferred pH is 7.0～8.0; The temperature of reaction of neutralization reaction is 30～80 ℃, and preferred temperature of reaction is 40～60 ℃; The reaction times of neutralization reaction is 5～30min, and the preferred reaction times is 10～25min.
The treatment process that produces waste lye in the preferred fourth octanol production may further comprise the steps successively:
A. add sulfuric acid in described waste lye or/and hydrochloric acid, regulating its pH is 2.0～5.0, handles through 15～25min sedimentation layering, separates organic phase and water then.
B. adopting ferrous sulfate is that catalyzer, hydrogen peroxide are oxygenant, and the water that steps A is obtained carries out catalytic oxidation treatment.The H of described oxygenant 2O 2With the weight ratio of aqueous phase COD be 1.0～3.0, the Fe of described catalyzer 2+With H in the oxygenant 2O 2Weight ratio be 0.08～0.16, the treatment temp of catalyzed oxidation is that 50～70 ℃, treatment time are 60～150min.
C. add sodium hydroxide at the aqueous phase of handling through step B, regulating its pH is 7.0～8.0, carries out neutralization reaction, and the temperature of reaction of neutralization reaction is that 40～60 ℃, reaction times are 10～25min, carries out solid-liquid separation then.
Because the strong alkaline condition of waste lye has solubilization effect to organism such as alcohol, aldehyde, under normal temperature and pressure conditions, the pH regulator of waste lye is extremely acid or neutral, and the organic form that exists changes in the water, solubleness diminishes, and partial organic substances can be separated out from water.
When pH is reduced to a certain degree, the organism that can separate out from water is separated out fully substantially, continues to reduce pH and has not had clear meaning, takes all factors into consideration factors such as treatment effect and sour consumption, determines the scope of adjusting pH.
Because waste lye pH is very high,, regulate the appropriate to the occasion concentrated acid of using of pH from reducing the acid solution volume and reducing water organic solvency action is considered.Operable acid is more, from effect and cost consideration, and preferably sulfuric acid and hydrochloric acid.
When carrying out organic phase and aqueous phase separation,, can adopt conventional gravity method settlement separate,, separate organic phase and water through the sedimentation layering of certain hour because the proportion of organic phase is significantly less than water.
Through above-mentioned treating processes, not only reclaimed most of organism in the waste lye, and the COD of waste lye can drop to 13000～18000mg/L by 40000～50000mg/L, the COD clearance reaches 70%.
The present invention adopts the homogeneous catalysis oxidation style that the water that the sedimentation layering obtains is further handled.Oxygenant is a hydrogen peroxide, preferred 30% or 27.5% hydrogen peroxide; Catalyzer is a ferrous salt, and preferably sulfuric acid is ferrous.
In catalyzed oxidation, the consumption of oxygenant is the important factor that influences treatment effect.Relation between oxygenant consumption and the treatment effect neither linear neither be dull, when the oxygenant consumption more after a little while, along with the increase of oxygenant consumption, water treatment effect obviously improves thereupon; When the oxygenant consumption was increased to a certain degree, along with the increase of oxygenant consumption, water treatment effect can't obviously change; When the oxygenant consumption continues to be increased to a certain degree, continue to increase the oxygenant consumption and can worsen water treatment effect on the contrary.
Catalyst consumption also is an important factor that influences treatment effect.Relation between catalyst levels and the treatment effect is not dull, and when catalyst levels within the specific limits the time, along with the increase of catalyst levels, treatment effect can improve thereupon; But after catalyst levels increased to a certain degree, along with the increase of catalyst levels, treatment effect is variation on the contrary.
It is that this system has very strong oxidation capacity as oxygenant, ferrous salt as a major reason of catalyzer that the present invention selects hydrogen peroxide for use, can effectively remove pollutants in waste water under lower temperature and pressure condition.
The pressure of catalytic oxidation is normal pressure, and temperature is 40～80 ℃, and preferred temperature is 50～70 ℃.When reaction temperature is spent when low, speed of response is slower, and reaching the ideal treatment effect needs long reaction times or mean residence time, and after temperature of reaction is elevated to certain value, continuing to heat up has not had obvious effect to improving treatment effect, and can increase the intensification expense.
The reaction times of catalyzed oxidation or mean residence time are 30～180min, are preferably 60～150min.When the reaction times is less than 30min, H 2O 2Can not fully react, not only influenced treatment effect but also caused the waste of oxygenant, and the reaction times be long, can increase the expense of treatment facility.
Through catalytic oxidation treatment, waste lye COD can drop to 4000～5000mg/L, and total clearance can reach 90%.
It is acid that the water outlet of catalytic oxidation is, and wherein residual have free state iron, also H may residually be arranged 2O 2, in order to reduce of the influence of these materials, add the pH that alkali is regulated water outlet to follow-up biochemical treating processes, carry out neutralization reaction.Through neutralization reaction, most free state iron are separated out H in the water with precipitation forms 2O 2Be reduced, pass through solid-liquid separation again, separate water outlet and can enter follow-up biochemical treatment apparatus.
In neutralization reaction, regulate pH and can use sodium hydroxide, also can under the prerequisite that guarantees treatment effect, use undressed waste lye.
In order to ensure H residual in the water 2O 2Can decompose fully, behind the adjusting pH, neutralization reaction is carried out 5～30min, preferred 10～25min, and the temperature of reaction of neutralization reaction is 30～80 ℃, preferred temperature of reaction is 40～60 ℃.
In neutralization reaction, residual ferrous ion in the water can play certain throwing out, the effect of solid-liquid separation after improving, and can further reduce COD in the water.The method of solid-liquid separation can adopt conventional method, such as filtering or press filtration.
Handle through neutralization reaction, waste lye COD further drops to 1200～1500mg/L, and total COD clearance can reach 97%.
Treatment process of the present invention, not only treatment effect is good, and have operational condition gentleness, flexible operation mode, characteristics such as processing is reliable and stable, processing costs is low.
Embodiment
Be described in further detail technical scheme of the present invention below in conjunction with embodiment, protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The COD that certain fourth octanol is produced waste lye is 48520mg/L.
With the pH regulator to 2.0 of 98% sulfuric acid with waste lye, sedimentation layering 25min.After the layering, the upper strata is an organic phase, and lower floor is a water, and water COD is 15080mg/L, and waste lye COD clearance is 69%.
Then, water is carried out the homogeneous catalysis oxide treatment, the catalytic oxidation treatment condition is as follows: temperature of reaction is 60 ℃, and reaction pressure is a normal pressure; Add 30% hydrogen peroxide, wherein H at water 2O 2With the weight ratio of water COD be 2.5; Add Fe at water 2+Concentration is the copperas solution of 20g/L, wherein Fe 2+With H in the oxygenant 2O 2Weight ratio be 0.12; Reaction time is 90min.
Then, with 20%NaOH solution the pH of catalyzed oxidation water outlet is transferred to 7.2, controlled temperature is 60 ℃, stops 15min, carries out solid-liquid separation afterwards.The COD of solid-liquid separation water outlet is 1260mg/L, and the total clearance of waste lye COD is 97%.
Embodiment 2～9/ Comparative Examples 1～2
The COD that certain fourth octanol is produced waste lye is 48520mg/L.
The treating processes of waste lye is identical with embodiment 1, and operational condition and treatment effect that its acidifying sedimentation processing, catalytic oxidation treatment, neutralization reaction are handled see Table 1.
Table 1
Figure A20061015016700081
Continuous table 1
Figure A20061015016700091
Can draw by the foregoing description and Comparative Examples, the treatment effect that treatment process of the present invention is produced waste lye for the fourth octanol is good, and treating processes is simple, is a kind of effective pretreatment process.

Claims (11)

1. the treatment process of the waste lye of generation during a fourth octanol is produced, described waste lye is alkalescence, contains alcohols material and aldehyde materials such as butanols, butyraldehyde, and this treatment process may further comprise the steps successively:
A. the pH that regulates described waste lye is to acid, and the sedimentation layering separates organic phase and water then;
B. described water is carried out catalytic oxidation treatment, catalyzer is a ferrous salt, and oxygenant is a hydrogen peroxide.
2. treatment process according to claim 1 is characterized in that:
In steps A, the pH that regulates described waste lye is 1.0～6.0, and the acid that is used to regulate pH is that sulfuric acid is or/and hydrochloric acid.
3. treatment process according to claim 2 is characterized in that:
The pH that regulates described waste lye is 2.0～5.0.
4. treatment process according to claim 1 is characterized in that:
In steps A, the stratified treatment time of sedimentation is 10～30min.
5. treatment process according to claim 4 is characterized in that:
The stratified treatment time of sedimentation is 15～25min.
6. treatment process according to claim 1 is characterized in that:
In step B, the H of described oxygenant 2O 2With the weight ratio of aqueous phase COD be 0.5～3.5; Described catalyzer is ferrous sulfate, wherein Fe 2+With H in the oxygenant 2O 2Weight ratio be 0.04～0.20; The treatment temp of catalyzed oxidation is 40～80 ℃, and the treatment time is 30～180min.
7. treatment process according to claim 6 is characterized in that:
The H of described oxygenant 2O 2With the weight ratio of aqueous phase COD be 1.0～3.0; The Fe of described catalyzer 2+With H in the oxygenant 2O 2Weight ratio be 0.08～0.16; The treatment temp of catalyzed oxidation is 50～70 ℃, and the treatment time is 60～150min.
8. treatment process according to claim 1 is characterized in that:
After step B, increase step C:
C. the water pH that regulates process step B processing carries out neutralization reaction to neutrality or weakly alkaline, carries out solid-liquid separation then.
9. treatment process according to claim 8 is characterized in that:
In step C, the alkali that is used to regulate described water pH is sodium hydroxide; The pH that regulates water is 6.0～9.0; The temperature of reaction of neutralization reaction is that 30～80 ℃, reaction times are 5～30min.
10. treatment process according to claim 9 is characterized in that:
In step C, the pH that regulates described water is 7.0～8.0; The temperature of reaction of neutralization reaction is that 40～60 ℃, reaction times are 10～25min.
11. treatment process according to claim 1 is characterized in that:
In steps A, in described waste lye, add sulfuric acid or/and hydrochloric acid, regulating its pH is 2.0～5.0, sedimentation layering 15～25min separates organic phase and water then;
In step B, the H of described oxygenant 2O 2With the weight ratio of described aqueous phase COD be 1.0～3.0, described catalyzer is a ferrous sulfate, its Fe 2+With H in the oxygenant 2O 2Weight ratio be 0.08～0.16, the treatment temp of catalyzed oxidation is that 50～70 ℃, treatment time are 60～150min.
Add sodium hydroxide at the aqueous phase of handling through step B, regulating its pH is 7.0～8.0, carries out neutralization reaction, and the temperature of reaction of neutralization reaction is that 40～60 ℃, reaction times are 10～25min, carries out solid-liquid separation then.
CN 200610150167 2006-10-31 2006-10-31 Method for processing waste alkali liquid in butyl octanol production Pending CN101172725A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101892066A (en) * 2010-01-27 2010-11-24 杨保利 Production technology for cracking butyl octanol residual liquid into C4 and C8 by means of alkaline liquid cracking agent
CN101423455B (en) * 2008-12-03 2011-08-31 南京福昌化工残渣处理有限公司 Butanol-octanol waste oil and 2-PH waste oil resource treatment method
CN103936212A (en) * 2014-04-14 2014-07-23 鲁西化工集团股份有限公司 Butyl octanol wastewater treatment method
CN105198066A (en) * 2014-06-25 2015-12-30 中国石油化工股份有限公司 Catalytic oxidation method for methanol-to-olefin waste lye
CN105217830A (en) * 2014-06-25 2016-01-06 中国石油化工股份有限公司 A kind of method for oxidation of methanol-to-olefins waste lye
CN105330048A (en) * 2014-06-25 2016-02-17 中国石油化工股份有限公司 Pretreatment method of olefin waste lye prepared by methanol
CN105439309A (en) * 2014-06-25 2016-03-30 中国石油化工股份有限公司 Treatment method of methanol-to-olefin (MTO) waste alkali liquid
CN110171875A (en) * 2019-01-28 2019-08-27 内蒙古荣信化工有限公司 Activated sludge maintenance object and preparation method thereof, system are prepared using fusel oil

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101423455B (en) * 2008-12-03 2011-08-31 南京福昌化工残渣处理有限公司 Butanol-octanol waste oil and 2-PH waste oil resource treatment method
CN101892066A (en) * 2010-01-27 2010-11-24 杨保利 Production technology for cracking butyl octanol residual liquid into C4 and C8 by means of alkaline liquid cracking agent
CN101892066B (en) * 2010-01-27 2013-01-23 杨保利 Production technology for cracking butyl octanol residual liquid into C4 and C8 by means of alkaline liquid cracking agent
CN103936212A (en) * 2014-04-14 2014-07-23 鲁西化工集团股份有限公司 Butyl octanol wastewater treatment method
CN103936212B (en) * 2014-04-14 2015-05-13 鲁西化工集团股份有限公司 Butyl octanol wastewater treatment method
CN105198066A (en) * 2014-06-25 2015-12-30 中国石油化工股份有限公司 Catalytic oxidation method for methanol-to-olefin waste lye
CN105217830A (en) * 2014-06-25 2016-01-06 中国石油化工股份有限公司 A kind of method for oxidation of methanol-to-olefins waste lye
CN105330048A (en) * 2014-06-25 2016-02-17 中国石油化工股份有限公司 Pretreatment method of olefin waste lye prepared by methanol
CN105439309A (en) * 2014-06-25 2016-03-30 中国石油化工股份有限公司 Treatment method of methanol-to-olefin (MTO) waste alkali liquid
CN105439309B (en) * 2014-06-25 2018-01-23 中国石油化工股份有限公司 A kind of processing method of methanol-to-olefins spent lye
CN110171875A (en) * 2019-01-28 2019-08-27 内蒙古荣信化工有限公司 Activated sludge maintenance object and preparation method thereof, system are prepared using fusel oil

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