CN205687732U - A kind of processing means of pharmacy waste water - Google Patents

Abstract

This utility model relates to the processing means of a kind of pharmacy waste water, belongs to water-treatment technology field.Including biochemical treatment unit (1) and reverse osmosis membrane (4), described biochemical treatment unit (1) is connected with reverse osmosis membrane (4) by oxidation treatment device (2) and/or ultrafilter membrane (3).This utility model Pharmaceutical Wastewater Treatment can make waste water reach can discharge standard, the rejection of reverse osmosis membrane water outlet simultaneously is high, colour clearance is high, flux stabilized.

Description

A kind of processing means of pharmacy waste water

Technical field

This utility model relates to the processing means of a kind of pharmacy waste water, belongs to water-treatment technology field.

Background technology

Pharmacy waste water mainly include ferment class produce waste water, chemical synthetic drug produce waste water, Chinese traditional medicine wastewater treatment and The big class of plant extract class production process waste water four.The usual complicated component of pharmaceuticals industry waste water, organic pollutant category is many, concentration Height, COD value are high and undulatory property is big, the BOD of waste water₅/ COD value differs greatly, and colourity is deep, and toxicity is big, solid suspension SS concentration High, be China pollute the most seriously, one of the most intractable industrial wastewater.

Pharmacy wastewater treatment main process uses " pretreatment+anaerobic treatment+Aerobic Process for Treatment " at present, in the sewage after process Also remain the heterocycle of a certain amount of difficult for biological degradation, polycyclic aromatic hydrocarbon compounds.Therefore need to increase advanced treatment process to form height Temperature, the reaction condition of high pressure, improve the quantity that free radical is formed simultaneously, and reaching further mineralising Organic substance is carbon dioxide and nothing The purpose of machine ion, thus reach the emission request of national regulation.

Domestic and international many scholars have carried out numerous studies to pharmacy waste water advanced treating, and various physics, chemical method obtain Extensive application, including coagulant sedimentation, absorption method, chemical oxidization method, electrochemical oxidation process, photocatalytic oxidation and membrance separation Deng.There is processing cost height, operation complexity, resistance to overload shock ability, not there is the problems such as broad spectrum activity in current processing method. Patent CN101863535A have employed electrolysis deep treatment of pharmaceutical waste water, and power consumption reaches 40.47 KW h/m³, high power consumption causes Actual motion high cost.Patent CN102807303A discloses a kind of pharmacy waste water advanced treatment process, and this process technique is fitted Poor with broad spectrum activity, to other class pharmacy wastewater treatment poor effect.

When above-mentioned pharmacy wastewater treatment technology is individually used for Sewage advanced treatment or the combination of existing wastewater processing technology, Waste water after process all can not reach emission request, and a combination thereof is also difficult in adapt to complex chemical composition especially heterocyclic compound The pharmacy waste water that thing is big, it is therefore necessary to the process technique for intractable pharmacy waste water makees further research and probe.

Utility model content

The purpose of this utility model is: provide a kind of pharmacy waste water that can solve high COD high chroma processing method and Device.

Technical scheme is:

The processing method of a kind of pharmacy waste water, comprises the steps:

1st step, pharmacy waste water is carried out biochemical treatment；

2nd step, carry out the water outlet of biochemical treatment aoxidizing and/or ultra-filtration filters processes；

3rd step, the product water in the 2nd step is processed with reverse osmosis again.

The COD of described pharmacy waste water is between 200～50000mg/L, and colour is between 8～300.

Described pharmacy waste water contains and includes that fermentation class produces waste water, chemical synthetic drug produces waste water, Chinese medicine produces useless One or several mixture in water or plant extract class production process waste water.

Described biochemical treatment refers to A2O method.

After described biochemical treatment step, carry out solid-liquid separation process to producing water.

Described oxidation step be selected from photochemical oxidation, CWO, sonochemical oxidation, ozone high grade oxidation, One or any several combination in electrochemical oxidation, Fenton oxidation.

The Average Pore Size of UF Membrane used in described ultrafiltration step can be 5nm～50nm, or is molecular cut off It it is the film of 1000～200000Da.

In the step of described ultrafiltration, temperature is between 5～70 DEG C；Pressure is between 0.05～1Mpa；Crossflow velocity exists Between 0.5～10m/s.

In the 2nd described step, refer to first use oxidation processes, then use hyperfiltration treatment.

In the 2nd described step, in producing water, need to add flocculant after the oxidising treat-ment carry out flocculation treatment.

The reverse osmosis concentrated liquid obtained in the 3rd described step returns again to process in the 2nd step, preferably by reverse osmosis concentrated Contracting liquid is sequentially sent to oxidation, flocculation, ultrafiltration step process again after carrying out electrodialysis desalination.

The processing means of a kind of pharmacy waste water, includes biochemical treatment unit and reverse osmosis membrane, described biochemical treatment list Unit is connected with reverse osmosis membrane by oxidation treatment device and/or ultrafilter membrane.

Described biochemical treatment unit passes sequentially through oxidation treatment device and is connected with reverse osmosis membrane with ultrafilter membrane.

Can also be connected on pipeline between oxidation treatment device with ultrafilter membrane and have flocculation tank, all right on flocculation tank The adding apparatus of flocculant is installed.

The structure of biochemical treatment unit includes the anaerobic reation pool-hypoxia response pond-aerobic reaction pond being sequentially connected with.

Oxidation treatment device can use photochemical oxidation reactor, CWO reactor, sonochemical oxidation anti- Answer one or several the group in device, ozone oxidation reaction device, electrochemical oxidation reactions device or Fenton oxidation reactor Close.

The molecular cut off scope of ultrafilter membrane 3 can be can be 5nm in 1000～200000Da or its average pore size ～50nm.

The concentration side of reverse osmosis membrane is connected with the water inlet of oxidation treatment device.Preferably first pass through electrodialysis system, then It is connected with the water inlet of oxidation treatment device.

Beneficial effect

This utility model Pharmaceutical Wastewater Treatment can make waste water reach can discharge standard, retaining of reverse osmosis membrane water outlet simultaneously Rate is high, colour clearance is high, flux stabilized.

Accompanying drawing explanation

Fig. 1 is the installation drawing used in an embodiment of the present utility model.

Wherein, 1, biochemical treatment unit；2, oxidation treatment device；3, ultrafilter membrane；4, reverse osmosis membrane；5, flocculation tank.

Detailed description of the invention

Below by detailed description of the invention, this utility model is described in further detail.But those skilled in the art will Understanding, the following example is merely to illustrate this utility model, and should not be regarded as limiting scope of the present utility model.In embodiment not Indicate concrete technology or condition person, (such as write with reference to Xu Nan equality according to the technology described by the document in this area or condition " inoranic membrane isolation technics and application ", Chemical Industry Press, 2003) or carry out according to product description.Agents useful for same Or instrument unreceipted production firm person, be can by city available from conventional products.

Approximation language used herein can be used for modifying the statement of any quantity in entire disclosure and claims, and it can Permit being changed under conditions of its relevant basic function changes being not resulted in.Therefore, such as term " about " repair The value of decorations is not limited to specified exact value.In at least some cases, approximation language can be with the instrument for measuring this value Precision corresponding.Unless indicated otherwise in context or statement, otherwise range limit can be combined and/or exchange, and And this scope is confirmed as and includes all subranges contained herein.Except operation embodiment in or elsewhere In indicate outside, the numeral of the amount of all expression compositions used in specification and claims, reaction condition etc. or Express the modification that shall be construed as in all cases by word " about ".

The value expressed using range format should be interpreted as in a flexible way not only including clearly listing as scope The numerical value of limit value, but also include containing all single numerical value within the range or subinterval, just as each numerical value and Zi Qu Between be expressly recited out.Such as, the concentration range of " about 0.1% to about 5% " should be understood to not only to include clearly to list The concentration of about 0.1% to about 5%, also includes the single concentration (e.g., 1%, 2%, 3% and 4%) in the range of indication and subinterval (example As, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).

It should be understood that it can be direct with other elements when an element is mentioned and " is connected " with another element It is connected or is indirectly connected to other elements, and between them, being inserted with element.Unless there are the most contrary explanation, otherwise term " include " and " having " is interpreted as stating and comprises listed element, and non-excluded arbitrarily other elements.

Word used herein " includes ", " comprising ", " having " or its any other variant are intended to non-exclusionism Including.Such as, including listing the technique of key element, method, article or standby being not necessarily limited by those key elements, but can be included other It is not expressly set out or belongs to the key element that this technique, method, article or equipment are intrinsic." removal " in this specification, not only Including removing the situation of target substance completely, also include that part removes the situation of (reducing the amount of this material).In this specification " purify ", including removing arbitrary or specific impurity.

Waste water handled by this utility model can be any pharmacy waste water, wherein contains higher COD and colourity, this In the source of pharmacy waste water include but not limited to: fermentation class produces waste water, chemical synthetic drug produces waste water, Chinese traditional medicine wastewater treatment Or one or several the mixture in plant extract class production process waste water.These waste water are generally of high COD and color Spending high feature, such as COD is between 200～50000mg/L, and colour is between 8～1000, and particularly some waste water In containing many difficult for biological degradation, the composition of difficult biochemical treatment, method of the present utility model is more particularly suited for containing at least one Kind of following obstinate COD composition: polycyclic aromatic hydrocarbon, heteroaryl compound, chlorinating aromatic compounds, nitro-aromatics, aromatic amine, Atomatic olefins, aromatic ester, biphenyl and organic cyanide.

For fermentation class produce waste water, its be mainly derived from fermentation, filter, extraction process and subtractive process generation work Skill waste water, flushing water, and high concentrated organic wastewater, ground flushing water and the recirculated water etc. that solvent recovery operation produces.Feature Being that pollutant levels are high, difficult degradation larger molecular organics concentration is high；Salinity is high, and containing biology there being the material of inhibitory action； Nitrogen content is high, mostly is organic nitrogen and ammonia nitrogen；Generally, colourity is higher.

Producing waste water for chemical synthetic drug, it is mainly derived from mother solution class waste water, flushing waste water, recovery residual liquid, auxiliary Help the parts such as process draining and sanitary sewage.Feature is that pollutant levels are high, Residual reactants in waste water, product, solvent, The material concentrations such as catalyst are the highest；Salinity is high, and inorganic salt is generally synthetic the by-product of reaction；Waste component is the most single, Nutritional labeling is not enough, unfavorable growth of microorganism；Effluent part contains some and has virose materials, such as phenols, phenyl amines, with much money The materials such as genus.

Extract class pharmacy waste water to be mainly derived from raw material cleaning waste water, extraction waste water, steam condensate (SC), refined wastewater, set The standby part such as rinse water, ground cleaning water.Feature is that waste component is complicated, mainly includes saccharide, ethanol, glycoside, anthraquinone, wooden The materials such as element, alkaloid；Concentration is the highest.

Chinese medicine class pharmacy waste water derives from leftover bits and pieces waste-liquid cleaning water, extracts workshop section's waste water, equipment cleaning water, assists workshop section Rinse water.Water-quality constituents is more complicated, and the concentration of dissolved matter, colloid and solid matter is the highest；COD, SS concentration High, it is easy to biological treatment；Water yield intermittent discharge, variation water quality is relatively big, and pH value often changes；The temperature of waste discharge is higher, band There are color and Chinese medicine odor.

Former water is processed by the technique in this utility model initially with the mode of biochemical treatment, can get rid of waste water In the composition that can be bacterially decomposed of a part.Here biological treatment is to reduce chemistry by the biologically digesting of antibacterial Oxygen demand (COD) and BOD (BOD) process a kind for the treatment of process of waste water.Generally, its can be divided into anaerobic processes and Aeration process.In most cases, two kinds of processes are all applied.Biological treatment is to carry out in pond or bioreactor.In this reality In novel, biological treatment is used as the pretreatment before other operations, can be decomposed by a part of Organic substance.Preferably Ground, the biological treatment used in this utility model is A2O method (or referred to as A-A/O, anaerobic-anoxic-oxic).

Wherein, as the anaerobe processing means carried out a biological disposal upon of anaerobic waste water ground, as long as have The decomposition efficiency excellence of machine thing, it is possible to use the biological reaction tank of known anaerobe processing mode.Anaerobic is raw Thing processing means can be to carry out acid reaction of formation and 1 slot type of methane reaction of formation in same groove, it is also possible to time in difference 2 slot types of each reaction are carried out in groove.Each reactive tank can be to be the mode of swimming (alr mode), Sludge Bed mode (the heavy side of sludge filtering Formula) etc. any-mode, furthermore it is also possible to be carrier addition type, pelletize mud type.Spy is there is no as anaerobe processing means Not limiting, be preferably provided with acid and generate groove and the reactive tank of UASB (upflow anaerobic sludge blanket process) mode, its reason is can be high Load running.As the oxybiotic organism processing means for anaerobe is carried out a biological disposal upon with processing water aerobism, As long as organic decomposition efficiency excellence, it is possible to use the biological reaction tank of known oxybiotic organism processing mode. It is for instance possible to use in groove, keep the mode of swimming of activated sludge with suspended state, to make activated sludge be attached to carrier enterprising The biomembrane mode etc. that row keeps.It addition, fixed-bed type, fluidized bed type, expansion bed etc. can be used in biomembrane mode Arbitrary microorganism bed mode, and carrier can use activated carbon, various plastic carrier, sponge carrier etc. any one.Carrier Preferably sponge carrier, when being sponge carrier, can maintain microorganism in high concentration.Sponge material is not particularly limited, preferably Ester system polyurethane.The input amount of carrier is also not particularly limited, and the generally carrier with the tankage relative to biological reaction tank is apparent Capacity is calculated as 10～about 50%, particularly preferably 30～about 50%.Decompose as under aerobism state microbes Organic oxybiotic organism reactive tank, it is possible to use be provided with for providing the diffuser of oxygen (air), aerator etc. in groove Oxygen provides the aeration tank of device.Oxybiotic organism reactive tank can be 1 slot type, it is also possible to be multi-groove type, furthermore it is also possible to be 1 slot type, partition walls is set in groove.

After after biochemical treatment, by the way of conventional solid-liquid separation, the solids produced in water can be carried out Removing (filter, sedimentation tank etc.), the most again product water is carried out oxidation processes or hyperfiltration treatment, the effect of oxidation can be decomposed Falling the COD not being bacterially decomposed and the colourity of a part, and a part of COD also can be removed by ultrafiltration, they can realize carrying The effect of the effluent quality of high reverse osmosis flux and raising reverse osmosis.Here oxidation processes selected from photochemical oxidation, be catalyzed wet One or any several group in formula oxidation, sonochemical oxidation, ozone high grade oxidation, electrochemical oxidation, Fenton oxidation Close.Water after oxidation processes is re-fed in ultrafilter membrane filtering.

After biochemical treatment, produce and water also has some antibacterials, undegradable Organic substance, colloid etc., when needs use ultrafiltration When film processes, the phenomenon that antibacterial assembles at ultrafiltration membrane surface, grows can be there is, easily cause asking of microorganism pollution Topic.In one embodiment, being the process simultaneously using oxidation and ultrafiltration, the product water that oxidation processes obtains enters back at ultrafiltration Reason, logical snperoxiaized effect, the activity of antibacterial therein can be destroyed, it is to avoid the untenable problem of Pollution of Ultrafiltration Membrane, flux, In Oxidation, destroy the structure of microbial film with the Oxidation of oxygen atom, to realize bactericidal action.

Hyperfiltration treatment described here, mainly uses ceramic super-filtering film, Average Pore Size of UF Membrane can be 5nm～ 50nm, or be the film of 1000～200000Da for molecular cut off, here, owing to the aperture of ultrafilter membrane is too small and be difficult to electricity consumption Sub-microscopes etc. measure the aperture on film surface, so it is big to replace average pore size to be used as aperture by the value of referred to as molecular cut off Little index.About molecular cut off, as described in the textbook of this area: " will with molecular weight solute as transverse axis, Prevention rate is the longitudinal axis, and the curve drawing data is referred to as molecular cut off curve.And by prevention rate be 90% point Son amount is referred to as the molecular cut off of film ", molecular cut off is as the index of the film properties representing ultrafilter membrane, for people in the art Member is known.Its filter element shape includes, Flat Membrane, tubular film, multi-channel type film, spiral membrane, hollow-fibre membrane etc., all modules Form.As these micro-filtration membrane or the material of ultrafilter membrane, as long as being capable of granule, the suspension removing in above-mentioned alkanolamine solution The composition such as thing, colloid such this utility model purpose, is not particularly limited, can enumerate: cellulose, cellulose esters, Polysulfones, polyether sulfone, polrvinyl chloride, chloropropene, polyolefin, polyvinyl alcohol, polymethyl methacrylate, Kynoar, poly-four The organic materials such as fluorothene, or the inorganic material such as metal or pottery such as rustless steel.This utility model uses ultrafilter membrane pair When raffinate carries out filtering to remove Organic substance therein, " dead-end filtration " pattern can be used, but preferably with " cross-flow Filter " pattern.The fluid separation process of " cross flow filter " form: material liquid is flow at high speed in membrane tube, containing little under pressure-driven The penetrating fluid of molecular components is along direction normal thereto outwards through film, and the muddy pollutant containing macromolecular components are rejected by, from And make fluid reach separation, concentration, the purpose of purification.Can normally continuously run thus it is guaranteed that certain cross-flow amount is film Essential condition；When cross-flow amount is relatively low, the content of the internal impurity of film device can increase sharply, and fouling membrane speed is accelerated, under flux Fall is very fast；When cross-flow amount is higher, energy consumption can increase again, be unfavorable for energy-saving consumption-reducing.

In order to improve reduction COD and the effect of colour further, it is also possible to carried out flocculation treatment before water is produced in ultrafiltration. For flocculant, can enumerate: high polymer coagulant, inorganic flocculating agent.As high polymer coagulant, wad a quilt with cotton as macromolecule Solidifying agent, can list cation system, anion system, both sexes system etc., include, for example out amidine based flocculating agent, acrylamide flocculation Agent, acrylic acid series flocculant etc.；High polymer coagulant addition in waste water preferably 10～1000ppm.As inorganic flocculation Agent, include, for example out the ferrum system flocculant aids such as bodied ferric sulfate (concentration of iron is 5～15%), iron chloride；The aluminum such as aluminum sulfate, PAC It it is flocculant aid etc.；Inorganic flocculating agent addition in waste water preferably 100～5000ppm.Can according to organic kind, Characteristic, treatment situation etc. carry out suitable selection.When being condensed processing, it is added as needed on the nothing that pH regulator will be used Machine flocculating agent adjusts to preferred pH.That is, as pH condition, for example, during ferrum system flocculating agent, it is made to react at below pH5.5 Effectively；During for aluminum system flocculating agent, it is made to adjust after reacting to pH6.0 effective above, the most preferably according to need at below pH5.0 The alkali such as the acid such as hydrochloric acid to be added, sulphuric acid or sodium hydroxide carry out pH adjustment.

After the process of oxidation or ultrafilter membrane, re-use reverse osmosis and carry out advanced treating, wherein remain for removing COD and colour, if directly the product water after oxidation processes is carried out reverse-osmosis treated, find reverse osmosis can not fully by Remaining COD therein and colour are removed, and cause reverse osmosis water outlet water quality bad, and easily occur that reverse osmosis membrane pollutes, leads to The problem that amount declines.After hyperfiltration treatment, a part of COD and colour can be got rid of, additionally can improve reverse osmosis The water quality of water outlet, and solve the problem that reverse osmosis membrane pollutes, flux is low.

As the material of reverse osmosis membrane, generally use cellulose acetate base polymer, polyamide, polyester, polyimides, second The macromolecular materials such as alkenyl polymer.It addition, construct as it, at least side at film is had to have compacted zone, from this compacted zone Internal to film or opposite side surface has the anisotropic membrane of the minute aperture in the aperture slowly becoming big and at this anisotropic membrane Compacted zone on there is the composite membrane etc. of the thinnest active layer formed by other materials.Wherein, as the shape of reverse osmosis membrane Formula, has macaroni yarn, flat film etc..Generally, it is preferred to the thickness of macaroni yarn peace film is 10 μm～1mm, the external diameter of macaroni yarn is 50 μm ～4mm.It addition, as flat film, preferably anisotropic membrane, as composite membrane preferably by substrate support such as fabric, fabric, non-woven fabrics But film., method of the present utility model can not to be used with relying on the material of reverse osmosis membrane, membrane structure or form, The most effective for any one situation.

For the concentrated solution of reverse osmosis, wherein containing more salt, its content of organics is high, and colour is high, can be by it After being back to second pond, then sequentially pass through oxidation and/or hyperfiltration treatment.In one embodiment, the electricity in reverse osmosis concentrated liquid Conductance 10～30ms/cm, COD is between 500～1000；In an other embodiment, electrodialysis system pair can be passed through Reverse osmosis concentrated liquid is re-fed into second pond processing unit after carrying out desalination, can improve the filtration flux of ultrafiltration.

Based on above-mentioned method, the device that this utility model can use is as shown in Figure 1.In going out of biochemical treatment unit 1 The mouth of a river is connected with reverse osmosis membrane 4 by oxidation treatment device 2 and/or ultrafilter membrane 3.The effect of biochemical treatment unit 1 is to useless Water carries out biochemical degradation process, can include the anaerobic reation pool-hypoxia response being sequentially connected with in the structure of biochemical treatment unit 1 Pond-aerobic reaction pond, water inlet and water outlet at reaction tank can also connect the solid-liquid separation such as preliminary sedimentation tank and second pond respectively Device.Biochemical treatment unit 1 can be connected with reverse osmosis membrane 4 with ultrafilter membrane 3 by oxidation treatment device 2 respectively, it is also possible to Pass sequentially through oxidation treatment device 2 to be connected with reverse osmosis membrane 4 again with ultrafilter membrane 4.Oxidation treatment device 2 and ultrafilter membrane 3 all may be used To process the product water of biochemical treatment unit 1 respectively, the effect of reverse osmosis membrane 4 is that the product water to aforementioned means carries out the degree of depth Remove COD and colour processes.

Flocculation tank 5 is had, at flocculation tank it addition, can also be connected on pipeline between oxidation treatment device 2 with ultrafilter membrane 3 The adding apparatus of flocculant it is also equipped with on 5.In another embodiment, can be further by reverse osmosis membrane 4 Concentrated solution side is connected with second pond；Can also be by the concentrated solution side of reverse osmosis membrane 4 by connecting with ultrafilter membrane again after electrodialysis plant Connect.

It addition, oxidation treatment device 2 can use photochemical oxidation reactor, CWO reactor, sonochemistry One in oxidation reactor, ozone oxidation reaction device, electrochemical oxidation reactions device or Fenton oxidation reactor or several The combination planted；And the molecular cut off scope of ultrafilter membrane 3 can be can be in 1000～200000Da or its average pore size 5nm～50nm.

COD is according to China's Industry specification (Chinese Industry Code) HJ/T399-2007 " COD-fast Speed clears up-spectrophotography water-quality determination " measured by COD chromium method.

Colourity is to represent faint yellow to yellow because of dissolve caused by the material being present in or be present in water with colloidal state The degree of brown, utilizes ultraviolet-uisible spectrophotometer (UV-3100) to measure the absorbance near 390nm, by the mark of titer Directrix curve calculates.

Embodiment 1

Handled by the present embodiment is the waste water of synthetic antibiotic workshop generation, and its main component is amide-type chemical combination Thing, diisopropyl ether, chloroform etc., waste water color is orange red, and organic pollutant category is many, and biodegradability is poor, BOD₅/COD_CrValue Little, effluent quality specifically: electrical conductivity 0.33s/cm, pH value 9.27, dissolved oxygen 7.17mg/L, COD_Cr72000mg/L, BOD6.6 mg/L, turbidity 158mg/L.

By waste water after preliminary sedimentation tank processes, then carry out aerobic-anoxia-aerobic biochemical system process.Aerobic biochemical pool exists Following condition is run: inflow temperature 30～32 DEG C, contact-oxidation pool end dissolved oxygen 2.5 mg/L, sludge concentration 3000mg/L, Sludge settling ratio 30%, mixed-liquor return 150%, reaction time 10h；Anaerobic biological pond is run in following condition: water inlet temperature Spend 30～32 DEG C, dissolved oxygen 0.1 mg/L, reaction time 4h.Product water COD after process is 540mg/L, and colourity is 89.

The product water processed, again after second pond solid-liquid separation, is re-fed into oxidation treatment device, uses O₃/H₂O₂Collaborative Oxidation processes.Concrete reaction condition is: pH value former alkaline under the conditions of, O₃And H₂O₂Concentration be respectively 118mg/L and 15mg/L, oxidization time is 30min, reaction temperature 30 DEG C.Product water COD after process is 245mg/L, and colourity is 51.

Oxidation is produced in water entrance ceramic super-filtering film and is carried out filtration treatment, and film average pore size is 50nm, filtration temperature 35 DEG C, across Mould difference 0.4Mpa, crossflow velocity 3m/s, feed liquid concentrates 8 times, and after process 100L feed liquid, the average flux of ultrafilter membrane is 72 L/ m²H, ultrafilter membrane water outlet enters in reverse osmosis membrane and carries out filtration treatment, and reverse osmosis membrane is aromatic polyamide screw type RO Film, feed temperature 35 DEG C, pressure 2.0Mpa, process the average flux of feed liquid reverse osmosis of 100L at 0.5m³/m²About/d, processes After product water COD be 13.3 mg/L, colourity is 2.

Embodiment 2

Handled by the present embodiment is the waste water of synthetic antibiotic workshop generation, and its main component is amide-type chemical combination Thing, diisopropyl ether, chloroform etc., waste water color is orange red, and organic pollutant category is many, and biodegradability is poor, BOD₅/COD_CrValue Little, effluent quality specifically: electrical conductivity 0.33s/cm, pH value 9.27, dissolved oxygen 7.17mg/L, COD_Cr72000mg/L, BOD6.6 mg/L, turbidity 158mg/L.

By waste water after preliminary sedimentation tank processes, then carry out aerobic-anoxia-aerobic biochemical system process.Aerobic biochemical pool exists Following condition is run: inflow temperature 30～32 DEG C, contact-oxidation pool end dissolved oxygen 2.5 mg/L, sludge concentration 3000mg/L, Sludge settling ratio 30%, mixed-liquor return 150%, reaction time 10h；Anaerobic biological pond is run in following condition: water inlet temperature Spend 30～32 DEG C, dissolved oxygen 0.1 mg/L, reaction time 4h.Product water COD after process is 240mg/L, and colourity is 89.

The product water processed, again after second pond solid-liquid separation, is re-fed into oxidation treatment device, uses O₃/H₂O₂Collaborative Oxidation processes.Concrete reaction condition is: pH value former alkaline under the conditions of, O₃And H₂O₂Concentration be respectively 118mg/L and 15mg/L, oxidization time is 30min, reaction temperature 30 DEG C.Product water COD after process is 245mg/L, and colourity is 51.

The liquid caustic soda adding 30 wt% concentration in water water outlet is produced in oxidation, regulates pH to 8.8, and the PAM adding 5 ppm helps solidifying Agent, waste water enters sedimentation tank and starts precipitation.After precipitation a period of time, the supernatant is pumped in ceramic super-filtering film and carry out at filtration Reason, film average pore size is 50nm, filtration temperature 35 DEG C, transmembrane pressure 0.4Mpa, crossflow velocity 3m/s, and feed liquid concentrates 8 times, processes After 100L feed liquid, the average flux of ultrafilter membrane is 87 L/m²H, ultrafilter membrane water outlet enters in reverse osmosis membrane and carries out filtration treatment, Reverse osmosis membrane is aromatic polyamide screw type RO film, feed temperature 35 DEG C, pressure 2.0Mpa, processes the feed liquid reverse osmosis of 100L Saturating average flux is at 0.6m³/m²About/d, the product water COD after process is 7.8 mg/L, and colourity is 1.

After water outlet for oxidation step is flocculated in embodiment 2, improve the flux of ultrafilter membrane, the most further Improve the reverse osmosis rejection for COD.

Embodiment 3

Handled by the present embodiment is the waste water of Chinese patent medicine workshop generation, its waste water brown color, organic contamination Species is many, good biodegradability, BOD₅/COD_CrValue height, effluent quality specifically: SS 450 mg/L, pH value 6.6, COD_Cr 4100mg/L, BOD1500 mg/L, colourity 895.

By waste water after preliminary sedimentation tank processes, then carry out aerobic biochemical system process.Aerobic biochemical pool is transported in following condition OK: inflow temperature 30～32 DEG C, contact-oxidation pool end dissolved oxygen 3 mg/L, sludge concentration 10000mg/L, sludge settling ratio 30%, mixed-liquor return 150%, reaction time 8h；Product water COD after process is 294.1mg/L, and colourity is 100.

The supernatant, again after second pond solid-liquid separation, is pumped in ceramic super-filtering film and carries out at filtration by the product water processed Reason, film average pore size is 20nm, filtration temperature 35 DEG C, transmembrane pressure 0.5Mpa, crossflow velocity 4m/s, and feed liquid concentrates 7 times, processes After 100L feed liquid, the average flux of ultrafilter membrane is 46 L/m²H, ultrafilter membrane water outlet enters in reverse osmosis membrane and carries out filtration treatment, Reverse osmosis membrane is aromatic polyamide screw type RO film, feed temperature 30 DEG C, pressure 2.5Mpa, processes the feed liquid reverse osmosis of 100L Saturating average flux is at 0.5m³/m²About/d, the product water COD after process is 13.7 mg/L, and colourity is 2.

Embodiment 4

Handled by the present embodiment is the waste water of Chinese patent medicine workshop generation, its waste water brown color, organic contamination Species is many, good biodegradability, BOD₅/COD_CrValue height, effluent quality specifically: SS 450 mg/L, pH value 6.6, COD_Cr 4100mg/L, BOD1500 mg/L, colourity 895.

By waste water after preliminary sedimentation tank processes, then carry out aerobic biochemical system process.Aerobic biochemical pool is transported in following condition OK: inflow temperature 30～32 DEG C, contact-oxidation pool end dissolved oxygen 3 mg/L, sludge concentration 10000mg/L, sludge settling ratio 30%, mixed-liquor return 150%, reaction time 8h；Product water COD after process is 294.1mg/L, and colourity is 100.

The product water processed, again after second pond solid-liquid separation, is re-fed into oxidation treatment device, uses O₃/H₂O₂Collaborative Oxidation processes.Concrete reaction condition is: pH value former alkaline under the conditions of, O₃And H₂O₂Concentration be respectively 118mg/L and 15mg/L, oxidization time is 30min, reaction temperature 30 DEG C.Product water COD after process is 115mg/L, and colourity is 41.

The product water processed pumps into and carries out filtration treatment in ceramic super-filtering film, and film average pore size is 20nm, filtration temperature 35 DEG C, Transmembrane pressure 0.5Mpa, crossflow velocity 4m/s, feed liquid concentrates 7 times, and after process 100L feed liquid, the average flux of ultrafilter membrane is 59L/ m²H, ultrafilter membrane water outlet enters in reverse osmosis membrane and carries out filtration treatment, and reverse osmosis membrane is aromatic polyamide screw type RO Film, feed temperature 30 DEG C, pressure 2.5Mpa, process the average flux of feed liquid reverse osmosis of 100L at 0.7m³/m²About/d, processes After product water COD be 8.1mg/L, colourity is 1.

Ultra-filtration process is processed by the way of employing aoxidizes by embodiment 4, antibacterial can be alleviated on film surface Pollute, improve the flux of ultrafiltration, also further increasing the reverse osmosis rejection for COD.

Embodiment 5

Handled by the present embodiment is riboflavin fermentation waste water, has high chroma, high salinity, the feature of high COD, can give birth to The property changed is general, raw wastewater water quality index: pH value: 6.4, COD:26970mg/L, BOD₅: 21830mg/L, NH₃-N:3520mg/L, SS:2787 mg/L.

By waste water after preliminary sedimentation tank processes, then carry out aerobic-anoxia-aerobic biochemical system process.Aerobic biochemical pool exists Following condition is run: inflow temperature 30～32 DEG C, contact-oxidation pool end dissolved oxygen 3.5 mg/L, sludge concentration 3000mg/L, Sludge settling ratio 40%, mixed-liquor return 150%, reaction time 10h；Anaerobic biological pond is run in following condition: water inlet temperature Spend 30～32 DEG C, dissolved oxygen 0.2 mg/L, reaction time 4h.Product water COD after process is 630mg/L, and colourity is 75.

The product water processed, again after second pond solid-liquid separation, is re-fed into oxidation treatment device, uses Fenton reagent Carry out oxidation processes.Concrete reaction condition is: Fe in Fenton reagent²⁺And H₂O₂Concentration is respectively 150mg/L and 35mg/L, System pH is 2, and reaction temperature is 40 DEG C, and the response time is 50min.Product water COD after process is 254mg/L, and colourity is 36。

Oxidation is produced in water entrance ceramic super-filtering film and is carried out filtration treatment, and film average pore size is 50nm, filtration temperature 45 DEG C, across Mould difference 0.5Mpa, carries out filtration treatment under different crossflow velocities, and feed liquid concentrates 8 times, ultrafiltration membrane treatment 100L feed liquid, super Filter membrane water outlet enters in reverse osmosis membrane and carries out filtration treatment, and reverse osmosis membrane is aromatic polyamide screw type RO film, feed liquid temperature Spend 35 DEG C, pressure 2.0Mpa.

Embodiment 6

Handled by the present embodiment is riboflavin fermentation waste water, has high chroma, high salinity, the feature of high COD, can give birth to The property changed is general, raw wastewater water quality index: pH value: 6.4, COD:26970mg/L, BOD₅: 21830mg/L, NH₃-N:3520mg/L, SS:2787 mg/L.

By waste water after preliminary sedimentation tank processes, then carry out aerobic-anoxia-aerobic biochemical system process.Aerobic biochemical pool exists Following condition is run: inflow temperature 30～32 DEG C, contact-oxidation pool end dissolved oxygen 3.5 mg/L, sludge concentration 3000mg/L, Sludge settling ratio 40%, mixed-liquor return 150%, reaction time 10h；Anaerobic biological pond is run in following condition: water inlet temperature Spend 30～32 DEG C, dissolved oxygen 0.2 mg/L, reaction time 4h.Product water COD after process is 630mg/L, and colourity is 75.

The liquid caustic soda adding 30 wt% concentration in water water outlet is produced in oxidation, regulates pH to 8.0, and the PAM adding 20 ppm helps solidifying Agent, waste water enters sedimentation tank and starts precipitation.After precipitation a period of time, the supernatant is pumped in ceramic super-filtering film and carry out at filtration Reason, uses the ultrafilter membrane of different film average pore sizes, filtration temperature 35 DEG C, transmembrane pressure 0.4Mpa, crossflow velocity 3m/s, feed liquid Concentrating 8 times, ultrafilter membrane water outlet enters in reverse osmosis membrane and carries out filtration treatment, and reverse osmosis membrane is aromatic polyamide screw type RO Film, feed temperature 35 DEG C, pressure 2.0Mpa.

Embodiment 7

Handled by the present embodiment is riboflavin fermentation waste water, has high chroma, high salinity, the feature of high COD, can give birth to The property changed is general, raw wastewater water quality index: pH value: 6.4, COD:26970mg/L, BOD₅: 21830mg/L, NH₃-N:3520mg/L, SS:2787 mg/L.

By waste water after preliminary sedimentation tank processes, then carry out aerobic-anoxia-aerobic biochemical system process.Aerobic biochemical pool exists Following condition is run: inflow temperature 30～32 DEG C, contact-oxidation pool end dissolved oxygen 3.5 mg/L, sludge concentration 3000mg/L, Sludge settling ratio 40%, mixed-liquor return 150%, reaction time 10h；Anaerobic biological pond is run in following condition: water inlet temperature Spend 30～32 DEG C, dissolved oxygen 0.2 mg/L, reaction time 4h.Product water COD after process is 630mg/L, and colourity is 75.

The liquid caustic soda adding 30 wt% concentration in water water outlet is produced in oxidation, regulates pH to 8.8, and the PAM adding 5 ppm helps solidifying Agent, waste water enters sedimentation tank and starts precipitation.After precipitation a period of time, the supernatant is pumped in ceramic super-filtering film and carry out at filtration Reason, film average pore size is 50nm, filtration temperature 35 DEG C, transmembrane pressure 0.4Mpa, crossflow velocity 3m/s, and feed liquid concentrates 8 times, processes After 100L feed liquid, the average flux of ultrafilter membrane is 77 L/m²H, ultrafilter membrane water outlet enters in reverse osmosis membrane and carries out filtration treatment, Reverse osmosis membrane is aromatic polyamide screw type RO film, feed temperature 35 DEG C, pressure 2.0Mpa, processes the feed liquid reverse osmosis of 100L Saturating average flux is at 0.6m³/m²About/d, the product water COD after process is 7.4 mg/L, and colourity is 1.

In reverse osmosis concentrated liquid, COD is at about 547mg/L, and electrical conductivity is at 14ms/cm, after returning it in second pond, Re-use same O₃/H₂O₂Synergistic oxidation processes and follow-up helps wadding, hyperfiltration treatment.Ultra-filtration water water quality is COD 32mg/ L, after process 5L feed liquid, the average flux of ultrafilter membrane is 57 L/m²·h。

Embodiment 8

Handled by the present embodiment is riboflavin fermentation waste water, has high chroma, high salinity, the feature of high COD, can give birth to The property changed is general, raw wastewater water quality index: pH value: 6.4, COD:26970mg/L, BOD₅: 21830mg/L, NH₃-N:3520mg/L, SS:2787 mg/L.

By waste water after preliminary sedimentation tank processes, then carry out aerobic-anoxia-aerobic biochemical system process.Aerobic biochemical pool exists Following condition is run: inflow temperature 30～32 DEG C, contact-oxidation pool end dissolved oxygen 3.5 mg/L, sludge concentration 3000mg/L, Sludge settling ratio 40%, mixed-liquor return 150%, reaction time 10h；Anaerobic biological pond is run in following condition: water inlet temperature Spend 30～32 DEG C, dissolved oxygen 0.2 mg/L, reaction time 4h.Product water COD after process is 630mg/L, and colourity is 75.

The liquid caustic soda adding 30 wt% concentration in water water outlet is produced in oxidation, regulates pH to 8.8, and the PAM adding 5 ppm helps solidifying Agent, waste water enters sedimentation tank and starts precipitation.After precipitation a period of time, the supernatant is pumped in ceramic super-filtering film and carry out at filtration Reason, film average pore size is 50nm, filtration temperature 35 DEG C, transmembrane pressure 0.4Mpa, crossflow velocity 3m/s, and feed liquid concentrates 8 times, processes After 100L feed liquid, the average flux of ultrafilter membrane is 77 L/m²H, ultrafilter membrane water outlet enters in reverse osmosis membrane and carries out filtration treatment, Reverse osmosis membrane is aromatic polyamide screw type RO film, feed temperature 35 DEG C, pressure 2.0Mpa, processes the feed liquid reverse osmosis of 100L Saturating average flux is at 0.6m³/m²About/d, the product water COD after process is 7.4 mg/L, and colourity is 1.

In reverse osmosis concentrated liquid, COD is at about 547mg/L, and electrical conductivity, at 14ms/cm, passes it through electrodialysis plant and carries out After being back in second pond after partially desalted, re-use same O₃/H₂O₂Synergistic oxidation processes and follow-up helps wadding, ultrafiltration Process.Ultra-filtration water water quality is COD 27mg/L, and after process 5L feed liquid, the average flux of ultrafilter membrane is 65L/m²·h。

Claims (3)

1. the processing means of a pharmacy waste water, it is characterised in that include biochemical treatment unit (1) and reverse osmosis membrane (4), institute The biochemical treatment unit (1) stated passes sequentially through oxidation treatment device (2) and is connected with reverse osmosis membrane (4) with ultrafilter membrane (3)；Oxidation Processing means (2) is selected from photochemical oxidation reactor, CWO reactor, sonochemical oxidation reactor, ozone oxidation One or several combination in reactor, electrochemical oxidation reactions device or Fenton oxidation reactor；Ultrafilter membrane (3) Molecular cut off scope is 5nm～50nm in 1000～200000Da or its average pore size.

The processing means of pharmacy waste water the most according to claim 1, it is characterised in that: at oxidation treatment device (2) with super It is also associated with flocculation tank (5) on pipeline between filter membrane (3), flocculation tank (5) is also equipped with the adding apparatus of flocculant.

The processing means of pharmacy waste water the most according to claim 1, it is characterised in that: the structure of biochemical treatment unit (1) Include the anaerobic reation pool-hypoxia response pond-aerobic reaction pond being sequentially connected with.