CN207918627U - A kind of processing unit of animal extraction industrial wastewater - Google Patents
A kind of processing unit of animal extraction industrial wastewater Download PDFInfo
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- CN207918627U CN207918627U CN201721762257.6U CN201721762257U CN207918627U CN 207918627 U CN207918627 U CN 207918627U CN 201721762257 U CN201721762257 U CN 201721762257U CN 207918627 U CN207918627 U CN 207918627U
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Abstract
The utility model is related to the processing units that a kind of animal extracts industrial wastewater, including：NF membrane, for being filtered processing to heparin sodium wastewater；Enzymatic vessel is connected to the concentration side of NF membrane, for carrying out enzymolysis processing to the concentrate obtained in NF membrane；First enrichment facility, is connected to enzymatic vessel, and the enzymolysis liquid for being obtained to enzymolysis carries out concentration；Drying device is connected to the first enrichment facility, and processing is dried in the concentrate for being obtained to the first enrichment facility；Second enrichment facility is connected to the per-meate side of NF membrane, and the brine for being obtained to per-meate side in NF membrane carries out concentration；Third enrichment facility, is connected to the concentrated water side of the second enrichment facility, and the concentrated water for being obtained to the second enrichment facility is concentrated to give recycling salt；Biochemical treatment unit is connected to the dilute side of the second enrichment facility, and biochemical treatment is carried out for the fresh water to the second enrichment facility.
Description
Technical field
It is especially a kind of by ultrafiltration, nanofiltration, electricity the utility model is related to the processing unit that a kind of animal extracts industrial wastewater
The method of dialysis, biochemical process coupling processing heparin sodium high-COD waste water with high salt belongs to animal extraction industrial wastewater and UF membrane skill
Art field.
Background technology
Heparin sodium is a kind of acid mucopolysaccharide, is most effectively anticoagulation medicine in Clinical practice, to arteriovenous thrombus, blood
Plug has unique curative effect.Mainstream production technology is salt solution and enzymatic isolation method, uses pig intestinal mucosa for raw material, under alkaline condition
Crude heparin sodium is obtained by resin adsorption, elution, alcohol precipitation after removing partially protein by salt solution/enzymolysis.Enzymolysis process is given birth to
The waste water formed is produced, major pollutants have chloride, ethyl alcohol, protein, heparin sodium, sugar etc., the spy with high COD with high salt
Point is a kind of animal extraction industrial wastewater difficult to deal with.
Currently, the processing method of heparin sodium high-COD waste water with high salt is mainly equipped with sanitary sewage and is watered into department of biochemistry
System, but system running pressure is big and effluent quality is unstable.There are high concentration albumen to return in heparin sodium high-COD waste water with high salt simultaneously
Receive value, therefore be badly in need of waste water reclaiming with it is innoxious.
It is useless to heparin sodium that Chinese patent CN103936888A discloses a kind of method with centrifugation, drying, membrane filtration coupling
Water is handled, by selecting suitable protein precipitating reagent, be stirred to react the time etc., make in heparin sodium wastewater protein precipitation from
Heart protein feed, centrifugal clear liquid, which carries out nanofiltration membrane discharge, reduces environmental pollution.The method does not provide subsequent nano-filtration and goes out
How water is handled, cannot normal qualified discharge.
Chinese patent CN106830483A discloses a kind of method of heparin sodium wastewater recycling, anti-by ultrafiltration, high pressure
So that waste water COD after infiltration《The method of 120mg/L.The method is high with operation energy consumption, the concentration polarization of high pressure RO films is serious, water quality
Fluctuate the features such as effluent quality is unstable.In addition, the processing that liquid is concentrated by ultrafiltration is not studied.
Utility model content
The purpose of this utility model is to provide a kind of processing unit of animal extraction industrial wastewater, needs to realize that heparin sodium is useless
Recycling of water resource, reduce cost for wastewater treatment, and it is easy to operate, pollution it is small, can realize clean manufacturing, be suitable for large-scale production.
Purifying concentration operation, the particular technique side of use are mainly carried out by ultrafiltration membrane+NF membrane+electrodialysis+biochemistry integrated technology
Case is as follows：
The first aspect of the utility model, provides：
A kind of processing method of animal extraction industrial wastewater, includes the following steps：
1st step, heparin sodium wastewater are sent into NF membrane and are filtered desalination, and permeate and concentrate are obtained；
Protease is added in concentrate and carries out enzyme digestion reaction, obtains enzymolysis liquid, after enzymolysis liquid is concentrated and dried, obtains for 2nd step
To recycling albumen；
3rd step, permeate use concentration, dope to be evaporated concentration, be recycled salt.
In one embodiment, the light liquid of electrodialysis is sent into biochemical reaction processing.
In one embodiment, the heparin sodium wastewater parses to obtain workshop section again after coming from resin adsorption.
In one embodiment, in the heparin sodium wastewater containing COD20000~100000mg/L, TDS1000~
200000mg/L、Cl-Ion 1~4%, NH4 +- N10~1000mg/L, Na+Ion 1~4%.
In one embodiment, the heparin sodium wastewater also passes through ultrafiltration before entering the nanofiltration processing of the 1st step
Filtration treatment；The concentrate of ultrafiltration membrane is sent into the 2nd step and carries out enzymolysis processing.
In one embodiment, 1000~1000000Da of molecular cut off of the ultrafiltration membrane, the material of ultrafiltration membrane
Selected from cellulose, cellulose esters, polysulfones, polyether sulfone, polyvinyl chloride, chloropropene, polyolefin, polyvinyl alcohol, polymethylacrylic acid
One or several kinds of combinations in methyl esters, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), ceramics.
In one embodiment, when ultrafiltration membrane uses ceramic material, the range of average pore size is 50~800nm, cross-film
Pressure differential range is 0.05~0.2MPa, and ultra-filtration filters temperature is preferably 40~70 DEG C, and it is 9~11 times that multiple, which is concentrated by ultrafiltration,.
In one embodiment, the material of the NF membrane is selected from cellulose acetate Type of Collective object, polyamide, gathers
One or several kinds of combinations in ester, polyimides or polyvinyl；Nanofiltration technique preferred parameter is：Operating pressure
For 1.0~2.0 MPa, molecular cut off is 150~1000Da, and cycles of concentration is 8~12 times.
In one embodiment, it is trypsase, chymotrypsin, pepsin, wood to digest the protease used
One or several kinds in the protein decomposition enzymes such as melon protease, kallikrein, cathepsin or thermolysin
Combination；40~70 DEG C of hydrolysis temperature digests pH7~9, enzymolysis time 2~3 hours.
In one embodiment, during enzymolysis liquid is concentrated and dried, concentration preferably uses MVR to concentrate, at drying
Reason is preferably using spray drying.
In one embodiment, the 3rd step permeate uses electrodialysis concentration, electrodialysis desalination preferably to run ginseng
Number is：Electrodialysis operation voltage is 1~20V, and 1~10A of electric current, feed pressure is 0.001~0.05MPa.
In one embodiment, the 3rd step concentration electrodialysis dope preferably uses MVR to concentrate.
In one embodiment, the electrodialytic light liquid of the 3rd step passes through biochemical treatment, and the preferred technique of biochemical treatment is：
UASB+ catalytic oxidations, operating parameter are：UASB loads are 3~5kgCOD/m3D, catalytic oxidation load are 1~2kgCOD/
m3·d。
A kind of processing unit of animal extraction industrial wastewater, including：
NF membrane, for being filtered processing to heparin sodium wastewater；
Enzymatic vessel is connected to the concentration side of NF membrane, for carrying out enzymolysis processing to the concentrate obtained in NF membrane；
First enrichment facility, is connected to enzymatic vessel, and the enzymolysis liquid for being obtained to enzymolysis carries out concentration；
Drying device is connected to the first enrichment facility, and place is dried in the concentrate for being obtained to the first enrichment facility
Reason；
Second enrichment facility is connected to the per-meate side of NF membrane, and the brine for being obtained to per-meate side in NF membrane carries out
Concentration；
Third enrichment facility is connected to the concentrated water side of the second enrichment facility, the concentrated water for being obtained to the second enrichment facility
It is concentrated to give recycling salt；
Biochemical treatment unit is connected to the dilute side of the second enrichment facility, is carried out for the fresh water to the second enrichment facility
Biochemical treatment.
In one embodiment, second enrichment facility is electrodialysis plant.
In one embodiment, first enrichment facility and/or third enrichment facility are MVR inspissators.
In one embodiment, further include ultrafiltration membrane, be connected to the feed inlet of NF membrane, ultrafiltration membrane is used to receive to entering
The heparin sodium wastewater of filter membrane is filtered processing.
In one embodiment, the material of 1000~1000000Da of molecular cut off of ultrafiltration membrane, ultrafiltration membrane are selected from fibre
It ties up element, cellulose esters, polysulfones, polyether sulfone, polyvinyl chloride, chloropropene, polyolefin, polyvinyl alcohol, polymethyl methacrylate, gather
One or several kinds of combinations in vinylidene fluoride, polytetrafluoroethylene (PTFE), ceramics.
In one embodiment, the ultrafiltration membrane uses ceramic material, and the range of average pore size is 50~800nm.
In one embodiment, the material of the NF membrane is selected from cellulose acetate Type of Collective object, polyamide, gathers
One or several kinds of combinations in ester, polyimides or polyvinyl, molecular cut off is 150~1000Da.
In one embodiment, protease throwing device is also associated on enzymatic vessel.
In one embodiment, drying device is spray-drying installation.
Advantageous effect
The utility model is made using most protein and amino acid in ultrafiltration membrane, NF membrane recycling heparin sodium wastewater
Water outlet COD carries out electrodialysis concentration systems after significantly cutting down, water outlet enters the stable operation of biochemical system energy and qualified discharge.Together
When ultrafiltration, nanofiltration system concentrate using protease hydrolyzed processing after enter concentration systems can effectively run and be spray-dried to be formed
Protein feed realizes waste water reclaiming, has good environmental benefit and economic benefit.
Description of the drawings
Fig. 1 is installation drawing provided by the utility model；
Wherein, 1, NF membrane；2, ultrafiltration membrane；3, enzymatic vessel；4, the first enrichment facility；5, drying device；6, the second concentration
Device；7, biochemical treatment unit；8, third enrichment facility.
Specific implementation mode
The utility model is described in further detail below by specific implementation mode.But those skilled in the art will
Understand, the following example is merely to illustrate the utility model, and should not be regarded as limiting the scope of the utility model.In embodiment not
Indicate particular technique or condition person, according to technology or condition described in document in the art or according to product description into
Row.Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.
It should be understood that when an element is mentioned with another element " connection ", it can be direct with other elements
It is connected or is indirectly connected with other elements, and inserted with element between them.Unless there are clearly opposite explanation, otherwise term
It includes listed element that " comprising " and " having ", which is interpreted as statement, and non-excluded arbitrary other elements.
The value expressed using range format should be interpreted as not only in a flexible way including clearly enumerating as range
The numerical value of limit value, but also include all single numbers or the subinterval covered in the range, like each numerical value and sub-district
Between be expressly recited out.For example, the concentration range of " about 0.1% to about 5% " should be understood as including not only clearly enumerating
4%) and subinterval (example the concentration of about 0.1% to about 5% further includes the single concentration in how (e.g., 1%, 2%, 3% and
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).
Word "include", "comprise" used herein, " having " or its any other variant are intended to cover non-exclusionism
Including.E.g., including technique, method, article or the equipment for listing element are not necessarily limited by those elements, but may include it
He is not explicitly listed or belongs to this technique, method, article or the intrinsic element of equipment.
" removal " in this specification includes not only the case where completely removing target substance, further includes that part removal (is reduced
The amount of the substance) the case where." purification " in this specification, including remove arbitrary or specific impurity.
Percentage described in the utility model refers to mass percent in the case of no special instruction.
There are mainly three types of the conventional production methods of the crude product of heparin sodium, such as：Salt solution, enzymatic isolation method, supercritical ultrasonics technology.These
Extracting method is required for after resin adsorption parsing to obtain heparin sodium again, therefore, big point can be mainly contained in resin raffinate
The inorganic salts such as sub- albumen, amino acid and sodium chloride.Especially in current mainstream industry enzyme solution, what resin raffinate was formed is
High-COD waste water with high salt.The utility model waste water to be dealt with is for the resin raffinate obtained after resin adsorption heparin sodium, example
As can be obtained with enzymatic isolation method, in the heparin sodium wastewater mass fraction of albumen be 5~30% (can also be 10%,
15%, 20% it (can also be 1.5%, 2%, 2.3%, 2.6%, 2.9%, 3.5% that, 28%, etc.), the mass fraction of inorganic salts, which is 1~4%,
Deng), pH value of solution=7~9 (can also be 7.5,8,8.5 etc.).The inorganic salts are sodium chloride.
COD20000~100000mg/L, TDS1000~200000mg/L, Cl are typically contained in waste water-Ion 1~4%,
NH4 +- N10~1000mg/L, Na+Ion 1~4%.
The processing method of the utility model is to carry out heparin sodium wastewater after retaining concentrating and desalinating processing by NF membrane,
NaCl therein can be penetrated to NF membrane, while being obtained containing the nanofiltration concentrate compared with polyprotein, macro-molecular protein can
Small molecular protein and polypeptide are obtained in a manner of by enzymolysis, can be applied to during feed etc..Albumen have passed through hydrolysis
Afterwards, enzymolysis protein powder can be obtained by being concentrated by evaporation, being spray-dried.Meanwhile NaCl is mainly contained in the permeate of nanofiltration,
After concentration, evaporative crystallization, drying, the industrial chlorinations sodium salt that is recycled.
In an improved embodiment, heparin sodium wastewater is before entering nanofiltration processing, the filtering also Jing Guo ultrafiltration
Processing；The concentrate of ultrafiltration membrane is sent into enzymolysis processing.Contain more impurity in heparin sodium wastewater due to having, passes through the pre- mistake of ultrafiltration
After filter, a part of high molecular weight protein can be filtered out, while also mitigating the load of NF membrane, and in the concentrate of ultrafiltration
It is that still can be sent into enzymolysis processing containing more albumen.Ultrafiltration membrane is the film that molecular cut off is 1000~1000000,
Referred to as ultrafiltration membrane, UF films etc..Here, being difficult to measure film surface with electron microscope etc. since the aperture of ultrafiltration membrane is too small
Aperture, so replacing average pore size to be used as the index of pore size with the value of referred to as molecular cut off.About retention molecule
Amount, as described in ability domain cookbook：" will be the longitudinal axis by horizontal axis, prevention rate of molecular weight solute, data are drawn and
At curve be known as molecular cut off curve.And the molecular weight that prevention rate is 90% is known as to the molecular cut off of film ", retention
Index of the molecular weight as the film properties for indicating ultrafiltration membrane, is well known to those skilled in the art.Material as these ultrafiltration membranes
Matter, as long as the utility model aim as the above-mentioned high molecular weight protein of concentration and colloid composition can be realized, without special
It limits, can enumerate：Cellulose, polysulfones, polyether sulfone, polyvinyl chloride, chloropropene, polyolefin, polyvinyl alcohol, gathers cellulose esters
The metals such as the organic materials such as methyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene (PTFE) or stainless steel or ceramics etc.
Inorganic material.The material of ultrafiltration membrane from the service life of film consider, the ultrafiltration membrane of preferably ceramic material.It is detached as ceramics are constituted
The material of the perforated membrane of film can suitably be selected from conventionally known ceramic material.It is, for example, possible to use aluminium oxide, oxidation
Zirconium, magnesia, silica, titanium oxide, cerium oxide, yttrium oxide, the oxide materials such as barium titanate；Cordierite, mullite,
The combined oxidations species material such as forsterite, steatite, sialon, zircon, ferrite；Silicon nitride, the nitrogen such as aluminium nitride
Change composition material；The carbon compounds material such as silicon carbide；The hydroxides composition material such as hydroxyapatite；The elements class material such as carbon, silicon；
Or the two or more inorganic composite materials etc. containing them.Natural minerals can also be used（Clay, clay mineral, cry loudly slag,
Silica sand, pottery stone, feldspar, white sand）Or blast-furnace slag, flying dust etc..Wherein, aluminium oxide, zirconium dioxide, titanium oxide, oxygen are preferably selected from
Change one kind or two or more, the pottery more preferably constituted using aluminium oxide, zirconium dioxide or titanium oxide as main body in magnesium, silica
Porcelain powder.Wherein, " as main body " mentioned here indicates the 50 mass % or more of ceramic powders totality（It is preferred that 75 mass % with
Upper, the more preferable 80 mass mass of %~100 %）For aluminium oxide or silica.For example, in the porous material, aluminium oxide is more honest and clean
Valence and operability it is excellent.Further, it is possible to it is readily formed the porous structure with the aperture for being suitable for liquid separation, therefore can
The ceramic separation film with excellent liquid permeability is easily manufactured.Also, in above-mentioned aluminium oxide, α-is particularly preferably used
Aluminium oxide.Alpha-alumina has stable and fusing point and high mechanical strength the characteristic in terms of chemistry.Therefore, by using α-oxygen
Change aluminium, can manufacture can be in broad use（Such as industrial circle）The middle ceramic separation film utilized.The operation of ceramic super-filtering film
In the process, grope by a large number of experiments, the range of the average pore size of ultrafiltration membrane is 50~500nm, because aperture is too big, can be caused
Protein macromolecule penetrates；Aperture is too small, and flux is relatively low, and equipment investment operating cost increases.The material of ceramic super-filtering film is preferably
One kind in aluminium oxide, zirconium oxide, titanium oxide.By groping for a large number of experiments, transmembrane pressure range is preferably 0.05~
0.2MPa, ultra-filtration filters temperature are preferably 40~70 DEG C, and multiple is concentrated by ultrafiltration and is preferably 9~11 times.In one embodiment,
Absorption is carried out to the permeate of ultrafiltration using zeolite and then filtrate is sent into nanofiltration concentration.Due in heparin sodium wastewater
The presence of high molecular weight protein influence whether the adsorption effect of zeolite, keep the adsorption rate of ammonia nitrogen low, therefore by avoiding macromolecular
After absorption of the albumen on zeolite, the influence of Ammonia Nitrogen on Chlorine sodium rejection reduction can be effectively prevented from.Used herein of
Modenite may be used in zeolite.
In one embodiment, high-valence cationic salt is added in the permeate of ultrafiltration, effect mainly has at 3 points：One
Being high-valence cationic salt can be such that albumen is denaturalized, and so that the solubility of albumen is declined, improve nanofiltration to the rejection of albumen, carry
In high yield；Second is that high-valence cationic salt promotes NaCl monovalent salts to penetrate nanofiltration by the road south effect occurred in nanofiltration film surface
Film keeps charge average, improves NF membrane to NaCl transmitances, so that the purity of recycling albumen is improved, and improve the receipts of Nacl
Rate；Third, some high-valence cationics such as Ca2+、Zn2+、Fe3+Deng, be easy retained by NF membrane, they reside in nanofiltration concentrate
When, and with the active effect of enzymolysis protein is promoted, improve the hydrolysis result to protein.These high-valence cationic salt are easy to
It is removed by alkaline precipitation.
NF membrane herein is defined as " preventing the pressure drive membrane less than the particle of 2nm and the macromolecular of dissolving "
Film.The preferably such film of effective NF membrane suitable for the utility model：There is charge in the film surface, thus passes through pore
Separation（Particle size separation）With the electrostatic separation that has benefited from the charge in the film surface in conjunction with and show the separative efficiency improved.
Therefore, it is necessary to using such NF membrane, which can will be used as the alkali metal ion of recycling target different from having
Macromolecule substance is removed while other ions of charge characteristic are detached by charge, by particle size separation.One
In a embodiment, the nanofiltration membrane material be selected from cellulose acetate Type of Collective object, polyamide, polyester, polyimides or
One or several kinds of combinations in polyvinyl etc.；Nanofiltration technique preferred parameter is：Operating pressure is 1.0~2.0
MPa, molecular cut off are 150~1000Da, and cycles of concentration is 8~12 times.The method of the utility model can be independent of receiving
The material of filter membrane or form it is used, it is all effective for any one situation.Nanofiltration membrane component be in order to actually use on
It states NF membrane and is allowed to the substance of shape.In the case that the form of NF membrane is flat membrane, can be incorporated into helical form, tubulose or
It is used in the component of plate and frame, in addition, in the case of macaroni yarn, component can be incorporated on the basis of bundles of into enforcement
With.The utility model can independent of these nanofiltration membrane components the form of the composition be applicable in.
It, can will be big by way of protease hydrolyzed etc. after having obtained ultrafiltration membrane concentrate and NF membrane concentrate
Molecule protein is digested into small molecule amino acid, and it can be trypsase, chymotrypsin, stomach cardia to digest the ferment used
Enzyme, papain, kallikrein, cathepsin either one kind in the protein decomposition enzymes such as thermolysin or
Several combinations；40~70 DEG C of hydrolysis temperature digests pH7~9, enzymolysis time 2~3 hours.
Enzyme digestion reaction liquid drying after concentration is handled；Concentration preferably uses MVR to concentrate, at drying
Reason is preferably using spray drying.
In one embodiment, it have passed through the waste water after nanofiltration desalination, concentration and carry out electrodialysis process, electrodialytic mesh
One side the salinity in waste water can be concentrated, reduce evaporation treatment capacity and cost；On the other hand, electrodialysis mitigates follow-up raw
Change chlorion load, the stabilization of more conducively subsequent biochemical treatment.Electrodialytic operating parameter is：Electrodialysis operation voltage is 1
~20V, 1~10A of electric current, feed pressure are 0.001~0.05MPa.
After having obtained the light liquid of electrodialysis, by biochemical treatment, such as UASB+ catalytic oxidation modes may be used to electricity
The light liquid of dialysis is handled, stable water outlet qualified discharge.Operating parameter is：UASB loads are 3~5kgCOD/m3D contacts oxygen
Change load is 1~2kgCOD/m3·d。
Based on above method, the utility model provides a kind of processing unit of animal extraction industrial wastewater, including：
NF membrane 1, for being filtered processing to heparin sodium wastewater；
Enzymatic vessel 3 is connected to the concentration side of NF membrane 1, for being carried out at enzymolysis to the concentrate obtained in NF membrane 1
Reason；
First enrichment facility 4, is connected to enzymatic vessel 3, and the enzymolysis liquid for being obtained to enzymolysis carries out concentration；
Drying device 5 is connected to the first enrichment facility 4, and the concentrate for being obtained to the first enrichment facility 4 is dried
Processing；
Second enrichment facility 6, is connected to the per-meate side of NF membrane 1, the brine for being obtained to per-meate side in NF membrane 1 into
Row concentration；
Third enrichment facility 8 is connected to the concentrated water side of the second enrichment facility 6, dense for being obtained to the second enrichment facility 6
Water is concentrated to give recycling salt；
Biochemical treatment unit 7 is connected to the dilute side of the second enrichment facility 6, for the fresh water of the second enrichment facility 6 into
Row biochemical treatment.
In one embodiment, second enrichment facility 6 is electrodialysis plant.
In one embodiment, first enrichment facility 4 and/or third enrichment facility 8 are MVR inspissators.
In one embodiment, further include ultrafiltration membrane, be connected to the feed inlet of NF membrane 1, ultrafiltration membrane is used for entering
The heparin sodium wastewater of NF membrane 1 is filtered processing.
In one embodiment, the material of 1000~1000000Da of molecular cut off of ultrafiltration membrane, ultrafiltration membrane are selected from fibre
It ties up element, cellulose esters, polysulfones, polyether sulfone, polyvinyl chloride, chloropropene, polyolefin, polyvinyl alcohol, polymethyl methacrylate, gather
One or several kinds of combinations in vinylidene fluoride, polytetrafluoroethylene (PTFE), ceramics.
In one embodiment, the ultrafiltration membrane uses ceramic material, and the range of average pore size is 50~800nm.
In one embodiment, the material of the NF membrane is selected from cellulose acetate Type of Collective object, polyamide, gathers
One or several kinds of combinations in ester, polyimides or polyvinyl, molecular cut off is 150~1000Da.
In one embodiment, protease throwing device is also associated on enzymatic vessel 3.
In one embodiment, drying device 5 is spray-drying installation.
In the above method, the detection method of content of peptides is in solution：Take 2.5ml sample solutions that 2.5ml10% (W/ are added
V then trichloroacetic acid (TCA) aqueous solution) is centrifuged in uniformly mixed standing 10min on whirlpool mixed instrument at 4000r/min
Supernatant is transferred completely into 50ml volumetric flasks and is settled to scale with 5% TCA by 15min shakes up and then takes 6.0ml above-mentioned molten
Liquid sets addition biuret reagent 4.0ml (sample liquids in another test tube:Biuret reagent=3:It is 2V/V) equal in being mixed on whirlpool mixed instrument
Even standing 10min2000r/min centrifugation 10min takes supernatant to measure OD value reference standard curves under 540nm, and to acquire sample molten
Peptide concentration C (mg/ml) in liquid and then content of peptides in sample can be acquired.
Embodiment 1
Contain COD 650000mg/L, TDS 137000mg/L, Cl in heparin sodium wastewater-Ion 3.2%, NH4 +-N
482mg/L、Na+Ion 2.4% takes waste water 200kg after pre-filtering, is pumped into ultrafiltration membrane system, the average pore size difference of ultrafiltration membrane
It is using 50 nm, 200 nm, 500 nm, material is aluminium oxide, and ultra-filtration process transmembrane pressure 0.2Mpa, 40 DEG C of filtration temperature will
Feed liquid stops after concentrating 10 times.The penetrating fluid of ultrafiltration is sent into NF membrane and is concentrated, operating pressure 1.5MPa, and cycles of concentration is
10 times.It is pumped into enzymatic vessel enzymolysis after ultrafiltration dope and nanofiltration dope are mixed, acid protease, controlled enzymatic hydrolysis are produced using bread mold
PH7.5 reacts 2 hours, 45 DEG C of reaction temperature, and enzymolysis liquid is pumped into evaporation concentration system, stops being spray-dried after 3 times of concentration
Obtain protein feed.NF membrane clear liquid is pumped into electrodialysis system, and electrodialysis operation voltage is 12V, electric current 8A, and feed pressure is
0.01MPa.The light liquid of electrodialysis goes biochemical system biochemical reaction to reduce qualified discharge after COD, ammonia nitrogen, and biochemical system uses UASB+
Catalytic oxidation mode, wherein UASB loads are 4kgCOD/m3D, catalytic oxidation load are 1kgCOD/ m3·d.Electrodialysis dope
Evaporation concentration system is pumped into salt.Test result at different conditions is as follows：
As can be seen that method provided by the utility model preferably can carry out Treatment for Reuse to heparin sodium wastewater.
Embodiment 2
Contain COD 650000mg/L, TDS 137000mg/L, Cl in heparin sodium wastewater-Ion 3.2%, NH4 +-N
482mg/L、Na+Ion 2.4% takes waste water 200kg after pre-filtering, is pumped into ultrafiltration membrane system, and the average pore size of ultrafiltration membrane uses
500 nm, material are aluminium oxide, and 0.1 Mpa, 0.15 Mpa, 0.2Mpa, filtration temperature is respectively adopted in ultra-filtration process transmembrane pressure
40 DEG C, stop after feed liquid is concentrated 10 times.The penetrating fluid of ultrafiltration is sent into NF membrane and is concentrated, operating pressure 2.0MPa, dense
Demagnification number is 10 times.Enzymatic vessel enzymolysis is pumped into after ultrafiltration dope and nanofiltration dope are mixed, controlled enzymatic hydrolysis pH8 reacts 2 hours,
45 DEG C of reaction temperature, enzymolysis liquid are pumped into evaporation concentration system, stop carrying out being spray-dried to obtain protein feed after 3 times of concentration.Nanofiltration
Film clear liquid is pumped into electrodialysis system, and electrodialysis operation voltage is 12V, electric current 8A, feed pressure 0.01MPa.The light liquid of electrodialysis
Biochemical system biochemical reaction is gone to reduce qualified discharge after COD, ammonia nitrogen, biochemical system uses UASB+ catalytic oxidation modes, wherein
UASB loads are 4kgCOD/ m3D, catalytic oxidation load are 1kgCOD/ m3·d.Electrodialysis dope is pumped into evaporation concentration system
At salt.Test result at different conditions is as follows：
As can be seen that method provided by the utility model preferably can carry out Treatment for Reuse to heparin sodium wastewater.
Embodiment 3
Contain COD 450000mg/L, TDS 122000mg/L, Cl in heparin sodium wastewater-Ion 3.5%, NH4 +-N
456mg/L、Na+Ion 2.9% takes waste water 200kg after pre-filtering, is pumped into ultrafiltration membrane system, and the average pore size of ultrafiltration membrane uses
50 nm, material are aluminium oxide, and ultra-filtration process transmembrane pressure uses 0.2Mpa, 40 DEG C of filtration temperature to stop after feed liquid is concentrated 10 times
Only.The penetrating fluid of ultrafiltration is sent into NF membrane and is concentrated, operating pressure is respectively 1.0,1.5,2.0MPa, cycles of concentration is 10
Times.Enzymatic vessel enzymolysis is pumped into after ultrafiltration dope and nanofiltration dope are mixed, controlled enzymatic hydrolysis pH8 reacts 2 hours, reaction temperature 45
DEG C, enzymolysis liquid is pumped into evaporation concentration system, stops carrying out being spray-dried to obtain protein feed after 3.5 times of concentration.NF membrane clear liquid pump
Enter electrodialysis system, electrodialysis operation voltage is 12V, electric current 8A, feed pressure 0.01MPa.The light liquid of electrodialysis removes department of biochemistry
Biochemical reaction of uniting reduces qualified discharge after COD, ammonia nitrogen, and biochemical system is using UASB+ catalytic oxidation modes, wherein UASB loads
4kgCOD/ m3D, catalytic oxidation load are 1kgCOD/ m3·d.Electrodialysis dope is pumped into evaporation concentration system into salt.Not
Test result under the conditions of is as follows：
As can be seen that method provided by the utility model preferably can carry out Treatment for Reuse to heparin sodium wastewater.
Embodiment 4
Contain COD 450000mg/L, TDS 122000mg/L, Cl in heparin sodium wastewater-Ion 3.5%, NH4 +-N
456mg/L、Na+Ion 2.9% takes waste water 200kg after pre-filtering, is pumped into ultrafiltration membrane system, the average pore size difference of ultrafiltration membrane
It is using 50 nm, 200 nm, 500 nm, material is aluminium oxide, and ultra-filtration process transmembrane pressure 0.1Mpa, 40 DEG C of filtration temperature will
Feed liquid stops after concentrating 10 times.The penetrating fluid of ultrafiltration is sent into NF membrane and is concentrated, operating pressure 2.0MPa, and cycles of concentration is
10 times.Enzymatic vessel enzymolysis is pumped into after ultrafiltration dope and nanofiltration dope are mixed, controlled enzymatic hydrolysis pH8.5 reacts 2 hours, reaction temperature
45 DEG C of degree, enzymolysis liquid are pumped into evaporation concentration system, stop carrying out being spray-dried to obtain protein feed after 3.5 times of concentration.NF membrane is clear
Liquid pump enters electrodialysis system, and electrodialysis operation voltage is 12V, electric current 8A, feed pressure 0.01MPa.The light liquid of electrodialysis goes to give birth to
Change system biochemical reaction reduces qualified discharge after COD, ammonia nitrogen, and biochemical system uses UASB+ catalytic oxidation modes, wherein UASB negative
Lotus is 3kgCOD/ m3D, catalytic oxidation load are 1kgCOD/ m3·d.Electrodialysis dope is pumped into evaporation concentration system into salt.
Test result at different conditions is as follows：
As can be seen that method provided by the utility model preferably can carry out Treatment for Reuse to heparin sodium wastewater.
Embodiment 5
Contain COD 450000mg/L, TDS 122000mg/L, Cl in heparin sodium wastewater-Ion 3.5%, NH4 +-N
456mg/L、Na+Ion 2.9% takes waste water 200kg after pre-filtering, is pumped into ultrafiltration membrane system, the average pore size difference of ultrafiltration membrane
It is using 50 nm, 200 nm, 500 nm, material is aluminium oxide, and ultra-filtration process transmembrane pressure 0.1Mpa, 40 DEG C of filtration temperature will
Feed liquid stops after concentrating 10 times.The CaCl of 2wt% is added in the penetrating fluid of ultrafiltration2It is sent into NF membrane to be concentrated, operating pressure is
2.0MPa, cycles of concentration are 10 times.Na is added after ultrafiltration dope and nanofiltration dope are mixed2CO3By Ca2+Precipitation, then pump
Enter enzymatic vessel enzymolysis, controlled enzymatic hydrolysis pH8.5 reacts 2 hours, and 45 DEG C of reaction temperature, enzymolysis liquid is pumped into evaporation concentration system, concentration
Stop carrying out being spray-dried to obtain protein feed after 3.5 times.NF membrane clear liquid is pumped into electrodialysis system, and electrodialysis operation voltage is
12V, electric current 8A, feed pressure 0.01MPa.The light liquid of electrodialysis goes biochemical system biochemical reaction to reduce row up to standard after COD, ammonia nitrogen
It puts, biochemical system uses UASB+ catalytic oxidation modes, and wherein UASB loads are 3kg COD/ m3D, catalytic oxidation load are
1kgCOD/ m3·d.Electrodialysis dope is pumped into evaporation concentration system into salt.Test result at different conditions is as follows：
As can be seen that method provided by the utility model preferably can carry out Treatment for Reuse to heparin sodium wastewater.
Embodiment 6
Contain COD 450000mg/L, TDS 122000mg/L, Cl in heparin sodium wastewater-Ion 3.5%, NH4 +-N
456mg/L、Na+Ion 2.9% takes waste water 200kg after pre-filtering, is pumped into ultrafiltration membrane system, the average pore size difference of ultrafiltration membrane
It is using 50 nm, 200 nm, 500 nm, material is aluminium oxide, and ultra-filtration process transmembrane pressure 0.1Mpa, 40 DEG C of filtration temperature will
Feed liquid stops after concentrating 10 times.1.5wt% modenites are added in the penetrating fluid of ultrafiltration to send after adsorption treatment 30min at 25 DEG C
Enter NF membrane to be concentrated, operating pressure 2.0MPa, cycles of concentration is 10 times.Ultrafiltration dope is passed through into mercerising and nanofiltration dope
Enzymatic vessel enzymolysis is pumped into after mixing, controlled enzymatic hydrolysis pH8.5 reacts 2 hours, and 45 DEG C of reaction temperature, enzymolysis liquid is pumped into evaporation and concentration
System stops carrying out being spray-dried to obtain protein feed after 3.5 times of concentration.NF membrane clear liquid is pumped into electrodialysis system, electrodialysis behaviour
It is 12V, electric current 8A, feed pressure 0.01MPa to make voltage.The light liquid of electrodialysis goes biochemical system biochemical reaction to reduce COD, ammonia nitrogen
Qualified discharge afterwards, biochemical system use UASB+ catalytic oxidation modes, and wherein UASB loads are 3kgCOD/ m3D, catalytic oxidation
Load is 1kgCOD/ m3·d.Electrodialysis dope is pumped into evaporation concentration system into salt.Test result at different conditions is such as
Under：
As can be seen that method provided by the utility model preferably can carry out Treatment for Reuse to heparin sodium wastewater.
Embodiment 7
Contain COD 450000mg/L, TDS 122000mg/L, Cl in heparin sodium wastewater-Ion 3.5%, NH4 +-N
456mg/L、Na+Ion 2.9% takes waste water 200kg that 1.5wt% modenites adsorption treatment at 25 DEG C is added after pre-filtering
30min is pumped into ultrafiltration membrane system, and the average pore size of ultrafiltration membrane is using 50 nm, 200 nm, 500 nm respectively, and material is oxidation
Aluminium, ultra-filtration process transmembrane pressure 0.1Mpa, 40 DEG C of filtration temperature stop after feed liquid is concentrated 10 times.The penetrating fluid of ultrafiltration is sent into
NF membrane is concentrated, operating pressure 2.0MPa, and cycles of concentration is 10 times.It is pumped into after ultrafiltration dope and nanofiltration dope are mixed
Enzymatic vessel digests, controlled enzymatic hydrolysis pH8.5, reacts 2 hours, and 45 DEG C of reaction temperature, enzymolysis liquid is pumped into evaporation concentration system, concentration
Stop carrying out being spray-dried to obtain protein feed after 3.5 times.NF membrane clear liquid is pumped into electrodialysis system, and electrodialysis operation voltage is
12V, electric current 8A, feed pressure 0.01MPa.The light liquid of electrodialysis goes biochemical system biochemical reaction to reduce row up to standard after COD, ammonia nitrogen
It puts, biochemical system uses UASB+ catalytic oxidation modes, and wherein UASB loads are 3kgCOD/ m3D, catalytic oxidation load are
1kgCOD/ m3·d.Electrodialysis dope is pumped into evaporation concentration system into salt.Test result at different conditions is as follows：
As can be seen that method provided by the utility model preferably can carry out Treatment for Reuse to heparin sodium wastewater.
Claims (9)
1. a kind of processing unit of animal extraction industrial wastewater, which is characterized in that including：
NF membrane（1）, for being filtered processing to heparin sodium wastewater；
Enzymatic vessel（3）, it is connected to NF membrane（1）Concentration side, for NF membrane（1）In obtained concentrate carry out at enzymolysis
Reason；
First enrichment facility（4）, it is connected to enzymatic vessel（3）, the enzymolysis liquid progress concentration for being obtained to enzymolysis；
Drying device（5）, it is connected to the first enrichment facility（4）, for the first enrichment facility（4）Obtained concentrate is done
Dry processing；
Second enrichment facility（6）, it is connected to NF membrane（1）Per-meate side, for NF membrane（1）The brine that middle per-meate side obtains
Carry out concentration；
Third enrichment facility（8）, it is connected to the second enrichment facility（6）Concentrated water side, for the second enrichment facility（6）It obtains
Concentrated water is concentrated to give recycling salt；
Biochemical treatment unit（7）, it is connected to the second enrichment facility（6）Dilute side, for the second enrichment facility（6）Fresh water
Carry out biochemical treatment.
2. the processing unit of animal extraction industrial wastewater according to claim 1, which is characterized in that second concentration
Device（6）It is electrodialysis plant.
3. the processing unit of animal extraction industrial wastewater according to claim 1, which is characterized in that first concentration
Device（4）And/or third enrichment facility（8）It is MVR inspissators.
4. the processing unit of animal extraction industrial wastewater according to claim 1, which is characterized in that further include ultrafiltration membrane,
It is connected to NF membrane（1）Feed inlet, ultrafiltration membrane be used for entering NF membrane（1）Heparin sodium wastewater be filtered processing.
5. the processing unit of animal extraction industrial wastewater according to claim 4, which is characterized in that the retention of ultrafiltration membrane point
Son 1000~1000000Da of amount, the material of ultrafiltration membrane are selected from cellulose, cellulose esters, polysulfones, polyether sulfone, polyvinyl chloride, chlorine third
One kind in alkene, polyolefin, polyvinyl alcohol, polymethyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), ceramics.
6. the processing unit of animal extraction industrial wastewater according to claim 4, which is characterized in that the ultrafiltration membrane is adopted
Range with ceramic material, average pore size is 50~800nm.
7. the processing unit of animal extraction industrial wastewater according to claim 1, which is characterized in that the NF membrane
（1）One kind in cellulose acetate Type of Collective object, polyamide, polyester, polyimides or polyvinyl of material,
Molecular cut off is 150~1000Da.
8. the processing unit of animal extraction industrial wastewater according to claim 1, which is characterized in that in enzymatic vessel（3）On
It is also associated with protease throwing device.
9. the processing unit of animal extraction industrial wastewater according to claim 1, which is characterized in that drying device（5）It is
Spray-drying installation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114906963A (en) * | 2021-02-08 | 2022-08-16 | 重庆望业药物研究有限公司 | Comprehensive utilization process of animal viscera extraction wastewater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114906963A (en) * | 2021-02-08 | 2022-08-16 | 重庆望业药物研究有限公司 | Comprehensive utilization process of animal viscera extraction wastewater |
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