CN109824135A - A kind of method of catalytic wet oxidation processing cephalo-type waste water - Google Patents
A kind of method of catalytic wet oxidation processing cephalo-type waste water Download PDFInfo
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- CN109824135A CN109824135A CN201711182519.6A CN201711182519A CN109824135A CN 109824135 A CN109824135 A CN 109824135A CN 201711182519 A CN201711182519 A CN 201711182519A CN 109824135 A CN109824135 A CN 109824135A
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- waste water
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- wet oxidation
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Abstract
The present invention relates to a kind of methods of catalytic wet oxidation processing cephalo-type waste water.Cephalosporin analog antibiotic is a kind of antibiotic being most widely used, and abuse and pollution remnants of antibiotic etc. make bacterium produce drug resistance, threaten human health.The present invention is under conditions of reaction pressure is 3.5~8.0Mpa, reaction temperature is 200~300 DEG C, using air by cephalo-type waste water in reactor packed with catalyst internal oxidition.After catalytic wet oxidation is handled, cephalo-type waste water TOC removal rate, 90%~99% or so, significantly improves wastewater biodegradability in 80%~98% or so, TN removal rate, substantially reduces subsequent processing difficulty up to standard.The method is efficient and without secondary pollution, is the ideal chose for solving the pollution of water body antibiotic.
Description
Technical field
The present invention relates to pharmacy wastewater treatment fields, and in particular to a kind of catalytic wet oxidation processing cephalo-type waste water
Method.
Background technique
China is antibiotics production big country, while being also antibiotic usage big country.Cephalosporin analog antibiotic be in antibiotic most
It is representative, while being also to be most widely used.Cephalo-type waste component complexity, Biostatic height, COD high, ammonia nitrogen
High, salt content height, solids concentration are big, and biological method is difficult to handle.
Zhuhai Li Zhu synthesis pharmaceutical Co., Ltd is in CN201510031012.5 using repeatedly extraction point under different condition
From organic phase, then the method that water phase is aoxidized to 60~90min under the conditions of active carbon-UV ozone is given up to handle ceftriaxone
Water, this method is only suitable for handling ultrahigh concentration COD waste water, but processed waste water COD is still very high, is further processed difficulty still
It is very big, and processing middle and high concentration COD waste water is not suitable for.ATK Holding Group Co., Ltd. is in CN201210349360.3
In disclose anaerobic hydrolysis acidification-iron-carbon micro-electrolysis-Membrane Bioreactor for Wastewater Treatment cephalosporins medicine production waste water method, this
The method residence time is long, takes up a large area, is influenced by variation water quality and environmental change, and final outflow water ammonia nitrogen and total phosphorus are not
Discharge standard can be reached.
Good treatment effect directly can not be obtained with Biochemical method cephalo-type waste water, and catalytic wet oxidation is special
Door is greatly improved the biodegradability of waste water for the difficult biochemical industrial wastewater of this high concentration is handled.Catalytic wet oxidation skill
Art (CWAO) is a kind of pair of high concentration, high murder by poisoning, a kind of particularly effective method of dark colour treatment of Organic Wastewater.It is in height
Under the conditions of warm (125~320 DEG C) high pressure (0.5~20MPa), air or oxygen as oxidant, by waste water organic matter and
Ammonia nitrogen distinguishes oxygenolysis into small organic molecule, CO2, the innocuous substances such as water and nitrogen process.The industrialization of CWAO is answered
With extensive, can be used to handle pulp-making waste-water, dyeing waste water, refinery(waste) water, winery waste water, aluminium oxide refining wastewater, food
Industrial wastewater, waste water in leather industry, pharmacy waste water, municipal waste etc..Catalytic wet oxidation technology is a kind of efficient, green, section
Energy, method for treating water without secondary pollution.
Summary of the invention
The present invention is to handle cephalosporin analog antibiotic waste water using catalytic wet oxidation technology, is urged in high temperature and pressure and multiphase
Under the action of agent, the organic matter and ammonia nitrogen removal frank in cephalo-type waste water are higher, and secondary dirt will not be generated in treatment process
Dye is a kind of wastewater treatment method efficiently, stable, operating cost is moderate and safe.
In order to solve the problems, such as cephalosporin analog antibiotic waste water, the present invention provides the following technical scheme that
Intermittent reaction: cephalo-type waste water is fitted into reaction kettle, and 2~20g of catalyst, Xiang Fanying are added in every liter of waste water
It is 1.5~3.5Mpa that pure oxygen to pressure is poured in kettle, and low whipping speed is 300~700r/min, and reaction temperature is 200~300
30~180min of isothermal reaction at DEG C；
Or,
Successive reaction: carrying out successive reaction in the reactor, and reaction pressure is 3.5~8.0Mpa, reaction temperature 200
~300 DEG C, cephalo-type waste water is with 0.5~3.0h of liquid hourly space velocity (LHSV)-1By catalyst bed, oxygen flux control is in wastewater flow
With 1.2 times or so of COD product.
Cephalo-type waste water TOC is 3000~10000mg/L, TN is 600~2500mg/L.
Above-mentioned method for preparing catalyst is that carrier calcination temperature is 400~1000 DEG C, and calcining time is 2~8h；Dipping is lived
Property component rear catalyst calcination temperature be 400~800 DEG C, calcination time be 2~8h.
Catalyst carrier is active carbon, in titanium dioxide, zirconium dioxide, aluminum oxide, silica, molecular sieve
One or more combinations.
Catalyst activity component is one of ruthenium, rhodium, palladium, silver, platinum, cerium, lanthanum, neodymium or a variety of noble metals or rare earth gold
Belong to combination, weight accounts for the 1%~5% of catalyst overall weight.
Catalyst mesh number is 20~60 mesh in intermittent reaction；Catalyst particle diameter is 2~5mm, length 2 in successive reaction
The cylindrical body of~10mm.
Compared with prior art, the present invention has the advantage that the present invention is without being added any chemical agent, with oxygen
For oxidant, the COD and ammonia nitrogen of cephalo-type waste water can be removed simultaneously in the presence of a catalyst, generate harmless carbon dioxide, water
With nitrogen etc., water outlet biodegradability is greatly improved.Reaction process is the heat supply that exothermic process can realize itself.This is
A kind of energy saving, processing cephalo-type waste water technology without secondary pollution.
Detailed description of the invention
The continuous CWAO reaction TOC of yielding water of Fig. 1 cephalo-type waste water and TN removal rate change curve.
Specific embodiment
In order to be easier to understand the present invention, present invention is further elaborated in following combination specific embodiment, but this is not
It can limit the scope of protection of the present invention.
Using the CJF-0.5 type permanent magnetism rotating batch-type autoclave and bubbling bed of the sensible reaction kettle factory production in Dalian
Continuous reaction apparatus carries out CWAO experiment.The TOC-V produced using Shimadzu CorporationCPH/CPNAnalysis-e/or determining waste water TOC and TN.
The preparation of catalyst LC-CAT: the activity of 80 parts of titanium dioxide and 19.9 parts of aluminum oxide and 0.1 part is taken
Charcoal is sufficiently mixed, and is shaped to long 3mm, it is roasted 6h at 600 DEG C by the cylinder of diameter 3mmm；Carrier after roasting is isometric
Impregnate Nd (NO3)3·6H2O and RhCl3Solution, 600 DEG C of calcining 6h prepare required catalyst, and activity component load quantity is
2wt.%.
In following embodiment, intermittent reaction used catalyst is that LC-CAT wears into 50 mesh powder, and successive reaction is prepared
LC-CAT catalyst.
Water sample used in following embodiment derives from Shandong pharmaceutical factory (specific company is inconvenient to reveal), analyzes waste water TOC
For 8520mg/L, TN 2130mg/L.
Embodiment 1
It takes 200mL cephalo waste water to be added in reaction kettle, and 2g catalyst fines is added into reaction kettle, into reaction kettle
Pure oxygen 2MPa is poured, isothermal reaction 2 hours at 210 DEG C, mixing speed 600r/min measures TOC after reaction end cooling
Removal rate is 80.3%, TN removal rate is 92.6%.
Embodiment 2
It takes 200mL cephalo waste water to be added in reaction kettle, pure oxygen 2MPa is poured into reaction kettle, the isothermal reaction at 260 DEG C
3 hours, mixing speed 600r/min, reaction measured that TOC removal rate is 78.1%, TN removal rate is after terminating cooling
47.2%.
Embodiment 3
It takes 200mL cephalo waste water to be added in reaction kettle, and 2g catalyst fines is added into reaction kettle, into reaction kettle
Pure oxygen 2MPa is poured, isothermal reaction 3 hours at 260 DEG C, mixing speed 600r/min measures TOC after reaction end cooling
Removal rate is 91.8%, TN removal rate is 96.5%.
Embodiment 4
Cephalo waste water is passed into tubular fixed-bed reactor and carries out successive reaction, catalyst granules loads 10mL, liquid
When air speed SV=1.0h-1, reaction temperature is set as 260 DEG C, reaction pressure 6.5MPa, air mass flow 40mL/min.It is continuous to survey
Measure a couple of days water outlet result such as Fig. 1.
Embodiment 5
Cephalo waste water is passed into tubular fixed-bed reactor and carries out successive reaction, catalyst granules loads 10mL, liquid
When air speed SV=2.0h-1, reaction temperature is set as 280 DEG C, reaction pressure 7.2MPa, air mass flow 40mL/min.Continuously go out
Water TOC removal rate, which is stablized, to be stablized in 94% or so, TN removal rate 97% or so.
Embodiment 6
Cephalo waste water is passed into tubular fixed-bed reactor and carries out successive reaction, catalyst granules loads 10mL, liquid
When air speed SV=1.0h-1, reaction temperature is set as 280 DEG C, reaction pressure 7.2MPa, air mass flow 30mL/min.Continuously go out
Water TOC removal rate, which is stablized, to be stablized in 98% or so, TN removal rate 99% or so.
Claims (6)
1. a kind of method of catalytic wet oxidation processing cephalo-type waste water, it is characterised in that:
Intermittent reaction: cephalo-type waste water is fitted into reaction kettle, and 2~20g of catalyst is added in every liter of waste water, rushes into reaction kettle
Entering pure oxygen to pressure is 1.5~3.5Mpa, and low whipping speed is 300~700r/min, and reaction temperature is permanent at 200~300 DEG C
30~180min of temperature reaction；
Or,
Successive reaction: carrying out successive reaction in the reactor, and reaction pressure is 3.5~8.0Mpa, reaction temperature is 200~300
DEG C, cephalo-type waste water is with 0.5~3.0h of liquid hourly space velocity (LHSV)-1By catalyst bed, oxygen flux control multiplies in wastewater flow and COD
Long-pending 1.2 times or so.
2. the method for catalytic wet oxidation processing cephalo-type waste water according to claim 1, it is characterised in that: cephalo-type waste water
TOC is 3000~10000mg/L, TN is 600~2500mg/L.
3. the method for catalytic wet oxidation processing cephalo-type waste water according to claim 1, it is characterised in that: the catalyst
Preparation method be carrier calcination temperature be 400~1000 DEG C, calcining time is 2~8h；Impregnate active component rear catalyst
Calcination temperature is 400~800 DEG C, and calcination time is 2~8h.
4. the method for catalytic wet oxidation processing cephalo-type waste water according to claim 3, it is characterised in that: the carrier is
One or more of active carbon, titanium dioxide, zirconium dioxide, aluminum oxide, silica, molecular sieve.
5. the method for catalytic wet oxidation processing cephalo-type waste water according to claim 3, it is characterised in that: the active group
It is divided into one or more of ruthenium, rhodium, palladium, silver, platinum, cerium, lanthanum, neodymium, active component weight accounts for catalyst overall weight
1%~5%.
6. the method for catalytic wet oxidation processing cephalo-type waste water according to claim 1, it is characterised in that: in intermittent reaction
Catalyst mesh number is 20~60 mesh；Catalyst particle diameter is 2~5mm in successive reaction, long 2~10mm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087192A (en) * | 2019-12-23 | 2021-07-09 | 南京延长反应技术研究院有限公司 | Treatment system and method for cephalosporin wastewater |
| CN115353189A (en) * | 2022-08-19 | 2022-11-18 | 湘潭大学 | Method for treating ciprofloxacin-containing wastewater by regulating and controlling dissolved oxygen |
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Cited By (4)
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|---|---|---|---|---|
| CN113087192A (en) * | 2019-12-23 | 2021-07-09 | 南京延长反应技术研究院有限公司 | Treatment system and method for cephalosporin wastewater |
| CN113087192B (en) * | 2019-12-23 | 2022-04-01 | 南京延长反应技术研究院有限公司 | Treatment system and method for cephalosporin wastewater |
| CN115353189A (en) * | 2022-08-19 | 2022-11-18 | 湘潭大学 | Method for treating ciprofloxacin-containing wastewater by regulating and controlling dissolved oxygen |
| CN115353189B (en) * | 2022-08-19 | 2024-01-16 | 湘潭大学 | Method for treating ciprofloxacin-containing wastewater by regulating and controlling dissolved oxygen |
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Application publication date: 20190531 |