CN109970127A - A method of recycling butyl acetate from antibiotic production wastewater - Google Patents
A method of recycling butyl acetate from antibiotic production wastewater Download PDFInfo
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- CN109970127A CN109970127A CN201910299374.0A CN201910299374A CN109970127A CN 109970127 A CN109970127 A CN 109970127A CN 201910299374 A CN201910299374 A CN 201910299374A CN 109970127 A CN109970127 A CN 109970127A
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- butyl acetate
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- film evaporator
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 title claims abstract description 88
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000002351 wastewater Substances 0.000 title claims abstract description 66
- 238000004064 recycling Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 54
- 239000010409 thin film Substances 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000002699 waste material Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001704 evaporation Methods 0.000 claims description 13
- 230000008020 evaporation Effects 0.000 claims description 13
- 239000000498 cooling water Substances 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000003242 anti bacterial agent Substances 0.000 claims description 4
- 229940088710 antibiotic agent Drugs 0.000 claims description 4
- 230000007613 environmental effect Effects 0.000 claims description 4
- 238000013517 stratification Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 238000010626 work up procedure Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 32
- 238000005265 energy consumption Methods 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000005292 vacuum distillation Methods 0.000 abstract description 2
- OAIYNRAQCIOEBD-UHFFFAOYSA-N butyl acetate;hydrate Chemical compound O.CCCCOC(C)=O OAIYNRAQCIOEBD-UHFFFAOYSA-N 0.000 abstract 1
- 238000004886 process control Methods 0.000 abstract 1
- 238000007790 scraping Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 230000006837 decompression Effects 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 238000010025 steaming Methods 0.000 description 9
- 229930194936 Tylosin Natural products 0.000 description 7
- 239000004182 Tylosin Substances 0.000 description 7
- WBPYTXDJUQJLPQ-VMXQISHHSA-N tylosin Chemical compound O([C@@H]1[C@@H](C)O[C@H]([C@@H]([C@H]1N(C)C)O)O[C@@H]1[C@@H](C)[C@H](O)CC(=O)O[C@@H]([C@H](/C=C(\C)/C=C/C(=O)[C@H](C)C[C@@H]1CC=O)CO[C@H]1[C@@H]([C@H](OC)[C@H](O)[C@@H](C)O1)OC)CC)[C@H]1C[C@@](C)(O)[C@@H](O)[C@H](C)O1 WBPYTXDJUQJLPQ-VMXQISHHSA-N 0.000 description 7
- 229960004059 tylosin Drugs 0.000 description 7
- 235000019375 tylosin Nutrition 0.000 description 7
- 230000009977 dual effect Effects 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229950007634 kitasamycin Drugs 0.000 description 3
- XYJOGTQLTFNMQG-KJHBSLKPSA-N leucomycin V Chemical compound CO[C@H]1[C@H](O)CC(=O)O[C@H](C)C\C=C\C=C\[C@H](O)[C@H](C)C[C@H](CC=O)[C@@H]1O[C@H]1[C@H](O)[C@@H](N(C)C)[C@H](O[C@@H]2O[C@@H](C)[C@H](O)[C@](C)(O)C2)[C@@H](C)O1 XYJOGTQLTFNMQG-KJHBSLKPSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- -1 alkanes compound Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 208000036828 Device occlusion Diseases 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/08—Thin film evaporation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The method that the invention discloses a kind of to recycle butyl acetate from antibiotic production wastewater, it include: the antibiotic production wastewater containing butyl acetate, through the direct Hybrid Heating of steam to after 55~85 DEG C, vacuum distillation separation is carried out into scrapper thin film evaporator, the vacuum degree that removal process controls scrapper thin film evaporator is -0.05~-0.095MPa.After being recycled using this method, in waste water butyl acetate content can descend to 0.05% hereinafter, the butyl acetate rate of recovery up to 90% or more.It is compared with traditional rectifying column recycling, the present invention uses and the energy consumption that can significantly reduce removal process is recovered under reduced pressure；Feed liquid fouling in removal process can be well solved using steam direct heating and scraping plates system and block up tower problem.
Description
Technical field
The invention belongs to antibiotic medicine production fields, and in particular to one kind recycles acetic acid fourth from antibiotic production wastewater
The method of ester.
Background technique
Butyl acetate is a kind of excellent extractant, during antibiotics production, usually can using butyl acetate from
Effective component is extracted in antibiotic fermentation filtrate.But since butyl acetate and water have certain mutual solubility, in raffinate waste liquid
It can the butyl acetate residual containing about 1% (wt%, the butyl acetate concentration being mentioned below all is mass percent).Although production
The content of butyl acetate is very low in waste water, but since wastewater flow rate is very big, daily up to several hundred tons, if not considering, recycling will be will cause
Serious waste.On the other hand, butyl acetate will will increase the COD value of waste water, according to theoretical calculation, 1% butyl acetate pair
The contribution margin of COD is up to 22000, if great difficulty will be brought to environmental protection treatment by not recycling.And the waste water gas containing butyl acetate
Taste is very big, will cause serious environmental pollution.
In order to separate and recover the butyl acetate in antibiotic waste water, most widely used at present is rectification method.However due to
Butyl acetate content in waste water is too low, there are many drawbacks in actual production.Firstly, using energy needed for rectifying column recycling
Consumption is very big, and waste water is heated to 100 DEG C and is separated and recovered by its a large amount of energy consumption of needs；Feed liquid temperature is greater than after rectifying column processing
90 DEG C, and environment-protection wastewater processing requirement feed liquid temperature is not above 40 DEG C, so needing a large amount of energy consumption to feed liquid after recycling again
Cool down.Secondly, some foreign proteins, calcium salt in feed liquid can be precipitated in feed liquid heating process, causes column plate to block, make
The operational efficiency for obtaining rectifying column is low, and the care and maintenance task of rectifying column is very arduous.
The drawbacks of in order to solve rectifying column recycling butyl acetate, in industry develop a series of new method.
Song K H etc. has reported the technology (Vapor using modified aluminum oxide UF membrane recycling butyl acetate
permeation of ethyacetate,propyl acetate,and butyl acetate with hydrophobic
inorganic membrane[J].Sep PurifTechnol,2003,30:169-176.)；Wojciech C etc., which has been reported, to be adopted
With technology (the Siloxane-urethane membranes for removal of polyurethane composite membrane separation and recovery butyl acetate
of volatile organic solvents by pervaporation[J].Desalination,2004,163:207-
214.).But do not investigate influence and film device of the complicated ingredient of waste water to membrane flux and membrane module service life investment operation at
This is higher, is very restricted in practical applications.
Patent CN 1534012A discloses a kind of method using butyl acetate in resin adsorption method recycling waste water, can be with
Significantly save recycling energy consumption.But this method is complicated for operation, and the complexity of antibiotic waste water ingredient easilys lead to adsorbent
It is contaminated.
Patent CN 1238262C has reported a kind of side for separating and recovering minim organic solvent from waste water using ionic liquid
Method.Methylimidazole and brominated alkanes compound are prepared into hexafluoro and close alkyl acid phosphate imidazole ion liquid by this method, by ionic liquid
Body and waste water mixing, so that the butyl acetate in waste water is enriched in ionic liquid, then are isolated by way of vacuum distillation
Butyl acetate in ionic liquid.This method equipment investment is low, easy to operate, but extraction yield is relatively low, the two-stage tandem rate of recovery
Can be only achieved 90%, and the impurity in waste water is easily accessible ionic liquid system, to after contaminated systematic difference and maintenance
Lack further evaluation.
Summary of the invention
The present invention provides a kind of method that butyl acetate is recycled from antibiotic production wastewater.This method can significantly drop
The energy consumption of low Sewage treatment process improves since macromolecular complex polymerize caused device blockage during Sewage treatment.It should
The technical solution of method is as follows:
A method of recycling butyl acetate from antibiotic production wastewater, comprising the following steps:
(1) enter after the antibiotic production wastewater containing butyl acetate and the direct Hybrid Heating of steam scrapper thin film evaporator into
Row is evaporated under reduced pressure, and obtains overhead vapours and tower bottom waste liquid；
(2) overhead vapours is condensed, and condensate liquid obtains light phase butyl acetate by stratification；
(3) further work-up is carried out after tower bottom waste collection.
In the above method, the ratio that tower top outflow flow quantity accounts for feed rate is 3%~15%.
Preferably, the scrapper thin film evaporator controls pressure, the decompression by pressure reducer in step (1)
The cooling of device uses circulation, and recirculated water returns in production waste water and recycles butyl acetate again.
Preferably, the feeding temperature in the step (1) can control at 50~85 DEG C；The work of scrapper thin film evaporator
Making temperature is 45~65 DEG C；The vacuum degree control of scrapper thin film evaporator is in -0.05~-0.085MPa.
Preferably, being cooled down in step (2) using tubular heat exchanger, cooling water temperature is lower than 15 DEG C.
Preferably, the light phase after layering is re-applied as butyl acetate finished product in antibiotics production in step (2),
Heavy phase recycle enters wastewater collection tank and recycles butyl acetate again.
Preferably, if the butyl acetate in tower bottom waste liquid meets discharge standard, (general butyl acetate contains in step (3)
Measure down to 0.05% or less), it is cooled to 40 DEG C or less and enters environmental protection progress wastewater treatment；
If the butyl acetate in tower bottom waste liquid is unsatisfactory for discharge standard, tower bottom waste liquid enters two-stage scraper thin film evaporator
Carry out secondary pressure evaporation.
Present invention employs reduced pressure distillation techniques to compare with traditional rectifying column separation, considerably reduces the place of feed liquid
Temperature is managed, heating energy consumption has been saved.Synchronous, the drop temperature of tower bottom waste liquid is also considerably reduced, since environmental protection treatment is wanted
Ask the temperature of waste water no more than 40 DEG C, it means therefore that the energy consumption to cool down to waste water is greatly saved.
Scrapper thin film evaporator is suitble to processing high viscosity, easy crystallization, easy fouling, containing suspended matter due to the presence of scraper plate
Feed liquid overcomes rectifying column and is easy blocked defect.In addition, this system is by the way of the direct Hybrid Heating of steam to feed liquid
The problem of heating up, avoiding tubular heat exchanger easy fouling blockage.
Preferably, removal process carries out under continuous limit, the antibiotic production wastewater is mixed with steam
It is continuously passed through the scrapper thin film evaporator afterwards to be evaporated under reduced pressure, overhead vapours and tower bottom waste liquid are continuously available；
The flow of the antibiotic production wastewater is 1.0~3.0m3/h。
Vacuum pump is cooled down using recirculated water, and cooling water is imported butyl acetate recovery system, can to avoid because
During butyl acetate recycling by vacuum take away and caused by loss.System is substantially increased to the rate of recovery of butyl acetate.
The working principle of scrapper thin film evaporator is single-stage pressure reducing distillation.Under normal conditions, single-stage distillation is for two components
The separative efficiency of system be it is not high, be extremely difficult to 90% or more separating degree.We are under study for action it has surprisingly been found that antibiotic
Micro butyl acetate present in waste water, it is easy to be separated well in such a way that heating in vacuum is volatilized, containing 1%
Butyl acetate waste water, content only remains 0.05% after 5min is evaporated under 65 DEG C of vacuum condition.The easy fouling of combination antibiotic waste water
Characteristic, we have selected scrapper thin film evaporator.
Under the preferred conditions, the butyl acetate rate of recovery of the invention can achieve 95% or more and traditional rectifying column
Technology is compared, and energy consumption can save 50% or more.
Detailed description of the invention
Fig. 1 is the process flow chart of recycling butyl acetate of the invention, in figure, 001, wastewater collection tank；002: mixer；
003, scrapper thin film evaporator；004, tower bottom collecting tank；005, pressure reducer；006, tubular heat exchanger, 007, storage tank.
Specific embodiment
Below with reference to embodiment, the content of the present invention will be explained in more detail.It should be appreciated that implementation of the invention is not limited to
In the following examples, the accommodation in any form and/or change made to the present invention fall within the scope of the present invention.
Fig. 1 is the process flow chart of recycling butyl acetate of the invention, as shown in Figure 1, the antibiosis in wastewater collection tank 001
Plain waste water is squeezed into mixer 002 by transfer tube；Meanwhile steam is passed through into mixer 002, directly mixed；Then
It is passed through scrapper thin film evaporator 003 again to be evaporated under reduced pressure, pressure reducer 005 is communicated on scrapper thin film evaporator 003 for controlling
Vacuum degree processed enters tubular heat exchanger 006 in the overhead vapours that tower top obtains and exchanges heat, then again after being evaporated under reduced pressure
Stratification is carried out into storage tank 007；Light phase after layering is re-applied as butyl acetate finished product in antibiotics production, heavy phase
It is recycled into wastewater collection tank and recycles butyl acetate again；Tower bottom waste liquid enters tower bottom collecting tank 004, according to its butyl acetate
Content is different, and (discharge or double evaporation-cooling) is further processed respectively.
Wherein, the cooling of pressure reducer uses circulation, and recirculated water access wastewater collection tank recycles butyl acetate again,
To improve the rate of recovery of butyl acetate.
Embodiment 1
Kitasamycin produces waste water, and butyl acetate content is 0.83%, flow 1.5m3/ h, the direct Hybrid Heating of steam
About to entering scrapper thin film evaporator after 65 DEG C.The vacuum degree of control scrapper thin film evaporator is that -0.091MPa carries out decompression steaming
It evaporates.It is collected after 15 DEG C of water condensation of overhead vapours and is layered the butyl acetate for obtaining recycling.54 DEG C of tower bottom feed liquid drop temperature,
40 DEG C or less discharges are cooled to through heat exchanger.It is 0.03% through detection tower bottom feed liquid butyl acetate content, theoretical recovery is
96.4%.Since in actual production system recovery system can be used using vacuum pump recirculated cooling water set, so acetic acid fourth
The actual recovered rate of ester can be close to theoretical recovery.Waste water COD drops to 10592mg/L from original 16675mg/L after recycling.
It is compared with original rectifying column absorption method, after flash distillation recycling, heating temperature can drop to 65 from 100 DEG C
℃；Heavy-fluid temperature drops to 55 DEG C from 90 DEG C after recycling.4.2kJ/kg/ DEG C of the specific heat capacity of water, in heating link, waste water per ton can
To save energy 4.2 × 1000 × (100-65)=147000KJ, being counted as 0.5Mpa steam is 53.2kg.In cooling link, often
Ton waste water can save cooling capacity 4.2 × 1000 × (90-54)=151000KJ, can about save 20 DEG C of circulating water for cooling 2
Ton.So steam 53.2kg can be saved by handling waste water per ton, 20 DEG C about 2 tons of circulating water for cooling.
Embodiment 2
Kitasamycin produces waste water, and butyl acetate content is 0.79%, flow 1.0m3/ h, the direct Hybrid Heating of steam
About to entering scrapper thin film evaporator after 70 DEG C.The vacuum degree of control scrapper thin film evaporator is that -0.085MPa carries out decompression steaming
It evaporates.It is collected after 15 DEG C of water condensation of overhead vapours and is layered the butyl acetate for obtaining recycling.59 DEG C of tower bottom feed liquid drop temperature,
40 DEG C or less discharges are cooled to through heat exchanger.It is 0.05% through detection tower bottom feed liquid butyl acetate content, theoretical recovery is
93.7%.Since in actual production system recovery system can be used using vacuum pump recirculated cooling water set, so acetic acid fourth
The actual recovered rate of ester can be close to theoretical recovery.Waste water COD drops to 11547mg/L from original 17136mg/L after recycling.
Embodiment 3
Kitasamycin produces waste water, and butyl acetate content is 0.86%, flow 1.0m3/ h, the direct Hybrid Heating of steam
About to entering scrapper thin film evaporator after 80 DEG C.The vacuum degree of control scrapper thin film evaporator is that -0.074MPa carries out decompression steaming
It evaporates.It is collected after 15 DEG C of water condensation of overhead vapours and is layered the butyl acetate for obtaining recycling.71 DEG C of tower bottom feed liquid drop temperature,
40 DEG C or less discharges are cooled to through heat exchanger.It is 0.07% through detection tower bottom feed liquid butyl acetate content, theoretical recovery is
91.8%.Since in actual production system recovery system can be used using vacuum pump recirculated cooling water set, so acetic acid fourth
The actual recovered rate of ester can be close to theoretical recovery.Waste water COD drops to 12547mg/L from original 18316mg/L after recycling.
Embodiment 4
Tylosin produces waste water, and butyl acetate content is 0.75%, flow 1.0m3/ h, the direct Hybrid Heating of steam
About to entering scrapper thin film evaporator after 60 DEG C.The vacuum degree of control scrapper thin film evaporator is that -0.089MPa carries out decompression steaming
It evaporates.It is collected after 15 DEG C of water condensation of overhead vapours and is layered the butyl acetate for obtaining recycling.Tower bottom feed liquid drop temperature is 55
DEG C, 40 DEG C or less discharges are cooled to through heat exchanger.It is 0.06% through detection tower bottom feed liquid butyl acetate content, theoretical recovery is
92.0%.Since in actual production system recovery system can be used using vacuum pump recirculated cooling water set, so acetic acid fourth
The actual recovered rate of ester can be close to theoretical recovery.Waste water COD drops to 11690mg/L from original 17123mg/L after recycling.
Embodiment 5
Tylosin produces waste water, and butyl acetate content is 0.69%, flow 1.0m3/ h, the direct Hybrid Heating of steam
About to entering scrapper thin film evaporator after 85 DEG C.The vacuum degree of control scrapper thin film evaporator is that -0.051MPa carries out decompression steaming
It evaporates.It is collected after 15 DEG C of water condensation of overhead vapours and is layered the butyl acetate for obtaining recycling.Tower bottom feed liquid drop temperature is 74
DEG C, 40 DEG C or less discharges are cooled to through heat exchanger.It is 0.11% through detection tower bottom feed liquid butyl acetate content, theoretical recovery is
84.1%.Since in actual production system recovery system can be used using vacuum pump recirculated cooling water set, so acetic acid fourth
The actual recovered rate of ester can be close to theoretical recovery.Waste water COD drops to 12130mg/L from original 15897mg/L after recycling.
Embodiment 6
Tylosin produces waste water, and butyl acetate content is 0.70%, flow 2.0m3/ h, the direct Hybrid Heating of steam
About to entering scrapper thin film evaporator after 65 DEG C.The vacuum degree of control scrapper thin film evaporator is that -0.091MPa carries out decompression steaming
It evaporates.It is collected after 15 DEG C of water condensation of overhead vapours and is layered the butyl acetate for obtaining recycling.Tower bottom feed liquid drop temperature is 52
DEG C, 40 DEG C or less discharges are cooled to through heat exchanger.It is 0.02% through detection tower bottom feed liquid butyl acetate content, theoretical recovery is
97.2%.Since in actual production system recovery system can be used using vacuum pump recirculated cooling water set, so acetic acid fourth
The actual recovered rate of ester can be close to theoretical recovery.Waste water COD drops to 11038mg/L from original 16921mg/L after recycling.
It is compared with rectifying column recycling, this process material liquid heating temperature drops to 65 DEG C from 100 DEG C, and feed liquid temperature declines from 90 DEG C after recycling
To 52 DEG C, heating and cooling required energy consumption are drastically reduced.
Embodiment 7
Tylosin produces waste water, and butyl acetate content is 0.75%, flow 3.0m3/ h, the direct Hybrid Heating of steam
About to entering scrapper thin film evaporator after 75 DEG C.The vacuum degree of control scrapper thin film evaporator is that -0.091MPa carries out decompression steaming
It evaporates.It is collected after 15 DEG C of water condensation of overhead vapours and is layered the butyl acetate for obtaining recycling.Tower bottom feed liquid carries out two-stage scraper
Thin film evaporation, feed liquid is heated to 60 DEG C when dual evaporation, remaining control condition is as level-one.Tower bottom feed liquid goes out after dual evaporation
Material temperature degree is 49 DEG C, cools to 40 DEG C or less discharges.It is less than 0.01% through detection tower bottom feed liquid butyl acetate content.Acetic acid fourth
Ester theoretical recovery is greater than 98%, due to that can use recycling system using vacuum pump recirculated cooling water set in actual production system
System, so the actual recovered rate of butyl acetate can be close to theoretical recovery.Waste water COD is under original 16154mg/L after recycling
Drop to 9805mg/L.
Embodiment 8
Tylosin produces waste water, and butyl acetate content is 0.68%, flow 3.0m3/ h, the direct Hybrid Heating of steam
About to entering scrapper thin film evaporator after 65 DEG C.The vacuum degree of control scrapper thin film evaporator is that -0.091MPa carries out decompression steaming
It evaporates.It is collected after 15 DEG C of water condensation of overhead vapours and is layered the butyl acetate for obtaining recycling.Tower bottom feed liquid carries out two-stage scraper
Thin film evaporation, feed liquid is heated to 55 DEG C when dual evaporation, remaining control condition is as level-one.Tower bottom feed liquid goes out after dual evaporation
Material temperature degree is 48 DEG C, cools to 40 DEG C or less discharges.It is less than 0.01% through detection tower bottom feed liquid butyl acetate content.Acetic acid fourth
Ester theoretical recovery is greater than 98%, due to that can use recycling system using vacuum pump recirculated cooling water set in actual production system
System, so the actual recovered rate of butyl acetate can be close to theoretical recovery.Waste water COD is under original 15008mg/L after recycling
Drop to 8260mg/L.
Embodiment 9
Tylosin produces waste water, and butyl acetate content is 0.76%, flow 3.0m3/ h, the direct Hybrid Heating of steam
About to entering scrapper thin film evaporator after 65 DEG C.The vacuum degree of control scrapper thin film evaporator is that -0.091MPa carries out decompression steaming
It evaporates.It is collected after 15 DEG C of water condensation of overhead vapours and is layered the butyl acetate for obtaining recycling.Tower bottom feed liquid carries out two-stage scraper
Thin film evaporation, feed liquid does not heat (temperature 50 C) when dual evaporation, remaining control condition is as level-one.Tower bottom after dual evaporation
Feed liquid drop temperature is 43 DEG C, cools to 40 DEG C or less discharges.It is less than 0.01% through detection tower bottom feed liquid butyl acetate content.
Butyl acetate theoretical recovery is greater than 98%, due to that can be used using vacuum pump recirculated cooling water set in actual production system
Recovery system, so the actual recovered rate of butyl acetate can be close to theoretical recovery.Waste water COD is from original after recycling
18108mg/L drops to 9806mg/L.
After system is run three months, recycling butyl acetate efficiency is without being decreased obviously.
Comparative example 1
Tylosin produces waste water, and butyl acetate content is 0.69%, and control flow is 13~20m3/ h, steam are heated to
90~95 DEG C enter rectifying column, by adjusting 92~99 DEG C of temperature, 99~102 DEG C of column bottom temperature of feed liquid flow control tower top.Tower
Top efflux is collected after cooling, and tower bottom waste liquid is cooled to 40 DEG C of discharges through tubular heat exchanger.Through detecting tower bottom feed liquid acetic acid fourth
Ester content is 0.01%.
Fouling is serious after system is run 3 months, and system recycling butyl acetate efficiency is decreased obviously.
Claims (8)
1. a kind of method for recycling butyl acetate from antibiotic production wastewater, which comprises the following steps:
(1) antibiotic production wastewater containing butyl acetate is subtracted with after the direct Hybrid Heating of steam into scrapper thin film evaporator
Pressure evaporation, obtains overhead vapours and tower bottom waste liquid；
(2) overhead vapours is condensed, and condensate liquid obtains light phase butyl acetate by stratification；
(3) further work-up is carried out after tower bottom waste collection.
2. the method according to claim 1, wherein the scrapper thin film evaporator is by subtracting in step (1)
Depressor controls pressure, and the pressure reducer is cooled down using circulation, and recirculated water is returned in production waste water and returned again
Receive butyl acetate.
3. subtracting the method according to claim 1, wherein the temperature after step (1) Hybrid Heating is 50~85 DEG C
The vacuum degree of pressure evaporation is -0.05~-0.085MPa.
4. cold the method according to claim 1, wherein condensed in step (2) using tubular heat exchanger
It coagulates cooling water temperature used and is lower than 15 DEG C.
5. the method according to claim 1, wherein in step (2), light phase after layering as butyl acetate at
Product are re-applied in antibiotics production, and heavy phase recycle enters wastewater collection tank and recycles butyl acetate again.
6. the method according to claim 1, wherein in step (3), if the butyl acetate in tower bottom waste liquid meets
Discharge standard is cooled to 40 DEG C or less and enters environmental protection progress wastewater treatment；
If the butyl acetate in tower bottom waste liquid is unsatisfactory for discharge standard, tower bottom waste liquid enters the progress of two-stage scraper thin film evaporator
Secondary pressure evaporation.
7. the method according to claim 1, wherein the operating temperature of scrapper thin film evaporator is 45~65 DEG C.
8. described the method according to claim 1, wherein removal process carries out under continuous limit
Antibiotic production wastewater is continuously passed through the scrapper thin film evaporator after mixing with steam and is evaporated under reduced pressure, and is continuously available tower top
Steam and tower bottom waste liquid；
The flow of the antibiotic production wastewater is 1.0~3.0m3/h。
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