CN105084657B - Methionine produces the Biochemical pretreatment method of waste water - Google Patents
Methionine produces the Biochemical pretreatment method of waste water Download PDFInfo
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- CN105084657B CN105084657B CN201510487792.4A CN201510487792A CN105084657B CN 105084657 B CN105084657 B CN 105084657B CN 201510487792 A CN201510487792 A CN 201510487792A CN 105084657 B CN105084657 B CN 105084657B
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Abstract
The present invention relates to the biochemical processing method that a kind of methionine produces waste water, comprise the following steps：1) waste water is extracted with extractant, organic phase and water phase is obtained after separation；2) water stripping phase, deviates from partial organic substances；3) formaldehyde of the water phase is removed by mashing system；4) again by lowering the temperature the water phase biochemical treatment.Using method of the present invention treatment methionine production waste water, energy consumption is significantly reduced compared with prior art, improve material utilization.
Description
Technical field
The present invention relates to chemical process system and method, and in particular to the processing method and processing system of industrial wastewater.
Background technology
Methionine is one of base unit of composition protein, and it is widely used, can be as medicine, nutriment, food
Additive, feed addictive etc..
Often producing one ton of methionine can produce about 0.5 ton of waste water, wherein containing organic acid (such as acrylic acid, acetic acid, horse
Come sour), the organic matter such as aldehyde (such as methacrylaldehyde, formaldehyde) and allyl alcohol, hydroquinones.Total organic content can reach 5-20%
Left and right.
This industrial wastewater cannot be processed with microbial method because its COD is too high, or organic matter concentration
It is too high, and fractions have bactericidal action so that and biochemical effects substantially reduce even failure.Existing processing method be by
Waste water incineration, i.e. waste water is sprayed into combustion zone by high-pressure nozzle, burns the organic matter in waste water.Due in waste water it is main into
It is water to divide, and thoroughly burning organic matter can also vaporize water therein, can consume substantial amounts of natural gas, anxious in the China of energy shortage
A kind of method compared with low energy consumption is needed to process methionine production waste water.
Applicant is in recent study, it is intended to extracts organic matter as much as possible from the production waste water, and will contain low
The waste water of concentration organic carries out biochemical treatment.But which kind of extractant no matter is selected, it is still not low containing mass concentration in water phase
In 1% low-carbon (LC) aldehyde, such as formaldehyde, methacrylaldehyde etc..The latter can seriously suppress biochemical treatment link in being present in water in high concentration
In microorganism activity, or even kill microorganism.
The existing advance method for removing formaldehyde in waste water mainly has the sulfonated method of formaldehyde, methenamine method and saccharification
Method.Wherein, the sulfonated method of formaldehyde is to adding sodium hydrogensulfite in waste water, formaldehyde is changed into rongalite
(sodium formaldehyde sulfoxylate；rongalite).The advantage of the method is that formaldehyde clearance is high, without adding
Heat, product biodegradability is good, but high cost, is only applicable to the formaldehyde of low concentration.Methenamine method is added in waste water
Ammoniacal liquor, formaldehyde is converted into hexamethylenetetramine, is commonly called as methenamine (English name：Hexamethylenetetramine), this
Method formaldehyde removal effect is good, higher than 99%；Exothermic reaction；Reaction speed is fast；But due to the addition of ammonia nitrogen, during subsequent treatment
The control difficulty of ammonia nitrogen concentration is increased.Comparatively, mashing system is reacted with limewash and formaldehyde, be translated into bacterium without
Harmful sugar.According to the technique of current report, this method can remove up to 80% formaldehyde, but, the existing skill of the method
There is the unmanageable defect of saccharification degree in art, if excessively saccharification, can produce the polysaccharide degree of polymerization of high polymerization degree, it is difficult to micro-
Biology is degraded.
The content of the invention
The present invention proposes that a kind of methionine produces the Biochemical pretreatment method of waste water, to solve existing method high energy consumption, thing
The low problem of matter utilization rate.
The processing method of methionine production waste water of the invention comprises the steps：1) waste water is extracted with extractant,
Organic phase and water phase are obtained after separation；2) water stripping phase, deviates from partial organic substances；3) first of the water phase is removed by mashing system
Aldehyde；4) biochemical treatment is carried out after the water is mutually lowered the temperature.
Preferably, water stripping to deviate from partial organic substances is carried out in gas tower, is entered the control of tower pH value of water solution and is existed
3-4。
Preferably, pH value is controlled in 10-12 with NaOH as mixing saccharifying agent with NaOH and calcium hydroxide
Scope, is subsequently adding calcium hydroxide, and the mass ratio of formaldehyde and calcium hydroxide is 10:1 to 1:3 scope, saccharification temperature is in 100-
In the range of 120 DEG C.
It is highly preferred that the saccharification is carried out in stripper.
It is highly preferred that formaldehyde is adjusted to 5 with the mass ratio of calcium hydroxide:1 to 1:2 scope.
It is highly preferred that the height in the column plate section about 3/10 to 4/10 of stripper introduces NaOH water in the way of spraying
Solution.
It is highly preferred that introducing sodium hydrate aqueous solution in the way of spraying.
It is highly preferred that the bottom of towe in stripper adds calcium hydroxide aqueous solution.
By this method, 99.9% formaldehyde can be removed in stripping link, and the condensation product for obtaining is substantially
It is hexose, it is easy to degraded by Institute of Micro-biology, efficiently solves saccharification degree and be difficult to control to, it is to avoid the height of excessively saccharification generation gathers
Right polymer is difficult to the problem of biochemical degradation, compared with prior art with prominent advantage.
Specific embodiment
In general, the method for the present invention includes that the formaldehyde extract, strip, going to remove water in phase and biochemical treatment gained are useless
Four steps of water.
Extraction
In extraction step, waste water is separated with organic matter therein, most of acrylic acid is not only reclaimed, also by major part
Other organic matters are taken out of from water, mitigate the homework burden of follow-up water process.It is preferred that, for extractant of the invention
Can be from methyl iso-butyl ketone (MIBK) (MIBK), DIBK, ethyl acetate, isopropyl acetate, isobutyl acetate, acrylic acid first
Selected in ester, ethyl acrylate, butyl acrylate, dimethylbenzene, toluene, heptane, hexahydrotoluene and isobutyl ether.Wherein, it is optimal
Choosing uses MIBK.
Extraction is carried out in extraction tower.Extraction conditions can be：Extractant and useless water weight ratio 1:3-10:1；Extraction temperature
Degree：10-60℃；Mixing time：15-150 minutes；Time of repose：15-150min；The number of times of extraction：1-5 times.Preferred condition
It is extractant and useless water weight ratio 1:2-3, is carried out at a temperature of 10-30 DEG C, and stirring 15-20min stands 15-30min again every time,
It is preferred that repeating 3-5 times.
Using above-mentioned preferred extraction conditions and MIBK, by extraction, formaldehyde all stays in water phase, does not almost have in organic phase
Have, organic acid has distribution in water phase and organic phase.
Stripping
Stripping step is carried out in stripper.Heating medium (such as water vapour) heats stripper by heat exchanger,
Water vapor in tower reactor, drives organic matter to rise to tower top and separate.In a preferred embodiment of the invention, in extraction step
Using MIBK as extractant.The extractant can form azeotropic mixture with water, and so, water can will remain in the extraction in water phase
Agent band in the form of azeotropic mixture, to tower top, is divided into organic phase and water phase after overhead condensation, and extraction tower, water are removed in discharging to organic phase entirely
Phase infinite reflux；
Preferably, the column bottom temperature of stripper is 80-120 DEG C, preferably 85-115 DEG C.In the present invention, will preferably enter
Tower pH value of water solution is controlled in 3-4..
Formaldehyde is saccharified
Hexose is converted to alkali, formaldehyde is added in waste water.Alkali serves not only as catalyst, also serves as reactant, hydroxyl
Also it is consumed in the reaction that is saccharified.The alkali that can be used includes calcium hydroxide, potassium hydroxide and NaOH, wherein it is preferred that using
NaOH and calcium hydroxide are controlled in 10-12 scopes pH value with NaOH as mixing saccharifying agent, are subsequently adding consumption
The calcium hydroxide of amount.Formaldehyde can be 10 with the mass ratio of calcium hydroxide:1 to 1:10th, most preferably 5:1 to 1:2 scope.Sugar
Change temperature be preferably controlled in 60-120 DEG C, most preferably in the range of 100-120 DEG C, saccharificatinn period can be 20-170min, excellent
Select 20~70min.Using these conditions that are most preferably saccharified, more than 99% formaldehyde can be removed.
In a kind of more preferred implementation method, stripping and formaldehyde is saccharified and carry out simultaneously.In this embodiment,
The pH value being saccharified is controlled in 10-12 scopes with NaOH, the mass ratio of formaldehyde and NaOH can be adjusted to 5:1 to
1:2 scope.It is highly preferred that the height in the column plate section about 3/10 to 4/10 of stripper introduces sodium hydrate aqueous solution, preferably
Introduced in the form of spraying, it is highly preferred that the bottom of towe in stripper adds calcium hydroxide aqueous solution.By this method, in vapour
Drop handle section can remove 99.9% formaldehyde, and the condensation product for obtaining substantially hexose, it is easy to be dropped by Institute of Micro-biology
Solution, compared with prior art with prominent advantage, method for saccharifying of the prior art is difficult to control to, and can obtain excessively being saccharified
Macromolecular polysaccharide, the polysaccharide is difficult to biochemical method and thoroughly degrades.
Biochemical treatment water phase
Waste water after PARA FORMALDEHYDE PRILLS(91,95) saccharification possesses the preliminary condition of biochemical treatment, makes the material such as first being harmful to biochemical treatment
Aldehyde, acrylic acid concentration is reduced to acceptable scope, then adjusts temperature, pH value, N/P ratio, oxygen demand to routine biochemistry
Handling process.
The present invention extracts methionine and produces waste water by extraction, and has mutually carried out above-mentioned treatment to the water after extraction,
So that the formaldehyde in water phase is substantially completely removed, follow-up biochemical treatment efficiency, and produced polysaccharide polymerization are not interfered with
Degree is not high, it is easy to degraded by Institute of Micro-biology.
Claims (8)
1. a kind of methionine produces the Biochemical pretreatment method of waste water, comprises the following steps：
1) waste water is extracted with extractant, organic phase and water phase is obtained after separation；
2) water stripping phase, deviates from partial organic substances；
3) formaldehyde of the water phase is removed by mashing system；
4) biochemical treatment is carried out after the water is mutually lowered the temperature.
2. the Biochemical pretreatment method described in claim 1, in saccharification step, with NaOH and calcium hydroxide as mixing
Saccharifying agent, is controlled in 10-12 scopes pH value with NaOH, is subsequently adding the quality of calcium hydroxide, formaldehyde and calcium hydroxide
Than 2:1 to 1:3 scope, saccharification temperature is in the range of 100-120 DEG C.
3. the Biochemical pretreatment method described in claim 2, wherein, the saccharification is carried out in stripper.
4. the Biochemical pretreatment method described in claim 3, wherein, saccharification temperature is in the range of 70-100 DEG C.
5. the Biochemical pretreatment method described in claim 3, wherein, formaldehyde is adjusted to 5 with the mass ratio of calcium hydroxide:1 to 1:2
Scope.
6. the Biochemical pretreatment method described in claim 3, wherein, enter the control of tower pH value of water solution in 3-4.
7. the Biochemical pretreatment method described in claim 4, wherein, introduced in the position of the column plate section about 1/5 to 2/5 of stripper
Sodium hydrate aqueous solution, calcium hydroxide aqueous solution is added in the bottom of towe of stripper.
8. the Biochemical pretreatment method described in claim 7, wherein, introduce sodium hydrate aqueous solution in the way of spraying.
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| CN112661682B (en) * | 2020-12-21 | 2023-08-01 | 宁夏紫光天化蛋氨酸有限责任公司 | Method for producing DL-methionine |
| CN112661683A (en) * | 2020-12-22 | 2021-04-16 | 宁夏紫光天化蛋氨酸有限责任公司 | DL-methionine production method without discharged wastewater |
| CN112679399A (en) * | 2020-12-22 | 2021-04-20 | 宁夏紫光天化蛋氨酸有限责任公司 | Methionine crystallization mother liquor post-treatment method and separation equipment |
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| CN102491581B (en) * | 2011-11-14 | 2013-11-27 | 中国海洋石油总公司 | Advanced treatment method for production waste water of acrylic acid and ester device |
| CN102910761B (en) * | 2012-11-06 | 2015-03-11 | 绍兴汉青环保科技有限公司 | Extraction method for reducing emission of chemical oxygen demand (COD) in pure terephthalic acid (PTA) wastewater |
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