CN208151153U - A kind of processing unit of glufosinate-ammonium waste water - Google Patents
A kind of processing unit of glufosinate-ammonium waste water Download PDFInfo
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- CN208151153U CN208151153U CN201721606848.4U CN201721606848U CN208151153U CN 208151153 U CN208151153 U CN 208151153U CN 201721606848 U CN201721606848 U CN 201721606848U CN 208151153 U CN208151153 U CN 208151153U
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Abstract
The utility model relates to a kind of processing units of glufosinate-ammonium waste water.Including：Flocculation tank, for carrying out flocculation reaction processing to waste water；Flocculant concentration tank, is connected to flocculation tank, for adding flocculant into flocculation tank；Equipment for separating liquid from solid is connected to flocculation tank, for the waste water solid separating treatment after flocculation reaction；Ultrafiltration membrane is connected to the per-meate side of equipment for separating liquid from solid, for carrying out hyperfiltration treatment to the waste water after separation of solid and liquid；Nanofiltration membrane is connected to the per-meate side of ultrafiltration membrane, carries out nanofiltration processing for the permeate to ultrafiltration membrane；Precipitation tank is connected to the retention side of nanofiltration membrane, carries out dephosphorization precipitation reaction for the concentrate to nanofiltration membrane；Dephosphorization agent adds tank, is connected to precipitation tank, for adding dephosphorization agent into precipitation tank；Biochemical treatment system is connected to precipitation tank, for carrying out biochemical treatment to the clear liquid after precipitation reaction.
Description
Technical field
It is especially a kind of by flocculation, ultrafiltration, nano filtering process coupling the utility model relates to a kind of processing unit of glufosinate-ammonium waste water
The device for closing processing glufosinate-ammonium phosphorus-containing wastewater, belongs to pesticide industrial wastewater and technical field of membrane separation.
Background technique
Glufosinate-ammonium is a kind of non-selective contact weedicide of phosphonic acid, has the characteristics that efficient, low toxicity, wide spectrum.Mainstream is raw
Production. art is that triethyl phosphite is acidified by grignard reaction, addition reaction, hydrochloric acid, ammonium hydroxide ammonification obtains glufosinate-ammonium.The technique
The phosphorus-containing wastewater complicated component of production, major pollutants have methanol, ethyl alcohol, tetrahydrofuran, sodium chloride, ammonium chloride, phosphate, cyanogen
Compound etc. has the characteristics that high COD, high phosphorus, is a kind of pesticide industrial wastewater difficult to deal with.
Currently, the processing method of glufosinate-ammonium phosphorus-containing wastewater mainly includes biochemical method, incineration method and embrane method etc., wherein with biochemistry
Based on method.Incineration method needs enrichment, while energy consumption is huge, and serious secondary pollution can be brought in burning process, and feasibility is lower.
Chinese patent CN106115974A disclose it is a kind of with complexing, centrifugation coupling method to glufosinate-ammonium phosphorus-containing wastewater into
Row pretreatment makes suspended matter shape in glufosinate-ammonium phosphorus-containing wastewater by selecting suitable complexing agent component, reaction temperature and centrifugal rotational speed
At waste residue, centrifugate carries out subsequent biochemical processing.The method does not provide subsequent biochemical treatment effect, while the toxicity of agricultural chemicals waste water
Cause waste water cannot normal qualified discharge to biochemical inhibited.
Patent CN103964622A discloses a kind of method of organic phosphorus devil liquor recovery, by wet oxidation, evaporation and concentration,
The method of solid phosphate is obtained after high temperature drying.The method has the characteristics that operation energy consumption is high, product phosphate is impure, leads to solid waste
Generation.In addition, used condensing mode is to be concentrated by evaporation, the separation of energy consumption height and the variety classes salt in product is not ground
Study carefully.
In consideration of it, the utility model uses water energy factory using most total phosphorus and COD in nanofiltration membrane removal phosphorus-containing wastewater
Area's reuse, while nanofiltration system concentrate can effectively be run using after dephosphorization agent processing into biochemical system, form circulation production
Operation process has good environmental benefit and economic benefit.
Utility model content
The purpose of the utility model is to provide a kind of processing units of glufosinate-ammonium waste water, need to reduce glufosinate-ammonium bio-chemical effluent
Pollutant load is simultaneously allowed to reuse, reduce cost for wastewater treatment, and it is easy to operate, pollution it is small, be able to achieve clean manufacturing, be suitable for
Large-scale production.Purifying concentration operation, the specific skill of use are mainly carried out by Hollow Fiber Ultrafiltration+nanofiltration membrane integrating technique
Art scheme is as follows：
A kind of processing method of glufosinate-ammonium waste water, includes the following steps：
Flocculant progress flocculation reaction is added in step 1 in glufosinate-ammonium waste water；
Step 2, flocculation reaction liquid are handled by equipment for separating liquid from solid；
Clear liquid is handled by ultrafiltration membrane after step 3, separation of solid and liquid；
Step 4, the permeate of ultrafiltration membrane are using nanofiltration membrane concentration；
Step 5, nanofiltration membrane dope are by entering biochemical system after dephosphorization agent dephosphorization.
In one embodiment, the phosphorus-containing wastewater is discharged after biochemical treatment selected from glufosinate-ammonium production waste water.
Contain COD100~50000mg/L, 20~10000mg/L of total phosphorus, Cl in the glufosinate-ammonium waste water-Ion 0.5
~10%, NH4 +- N10~2000mg/L, Na+Ion 0.5~10%.
In one embodiment, in the step 1, the flocculant that flocculation reaction uses is bodied ferric sulfate, sulfuric acid Asia
The combination of the one or several kinds such as iron, polyacrylamide；20~40 DEG C of flocculation reaction temperature, flocculation reaction pH8.5~10, flocculation
Reaction time 0.5~2 hour, 2~10h of flocculation reaction residence time, 1~50ppm of flocculation reaction flocculant dosage.
In one embodiment, in the step 2, the mode of separation of solid and liquid is selected from centrifuge separation mode, dissolved air flotation
Mode, sedimentation separation mode one of are separated by filtration or several combinations；It is preferred that first using coarse filtration again using sedimentation separation
Device is separated.
In one embodiment, in the step 3,1000~500000Da of molecular cut off of the ultrafiltration membrane,
The material of ultrafiltration membrane be selected from cellulose, cellulose esters, polysulfones, polyether sulfone, polyvinyl chloride, chloropropene, polyolefin, polyvinyl alcohol,
One of polymethyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), ceramics or several combinations.
In one embodiment, in the step 3, the ultrafiltration membrane is polytetrafluoroethylhollow hollow fiber ultrafiltration membrane,
The range of average pore size is 50~200nm, and transmembrane pressure range is 0.05~0.2MPa, and ultra-filtration filters temperature is preferably 25~40
DEG C, it is 9~11 times that multiple, which is concentrated by ultrafiltration,.
In one embodiment, in the step 4, the material of nanofiltration membrane is selected from cellulose acetate quasi polymer, polyamides
One of amine, polyester, polyimides or polyvinyl or several combinations；Nanofiltration technique preferred parameter is：Behaviour
Making pressure is 1.0~2.0 MPa, and molecular cut off is 150~300Da, and cycles of concentration is 8~10 times.
In one embodiment, in the step 5, dephosphorization agent is dephosphorization with ferric salt agent, aluminium salt dephosphorization agent, calcium salt dephosphorization
One of agent, secondary phosphorous dephosphorization agent or several combinations, it is preferred to use secondary phosphorous dephosphorization agent.
In one embodiment, in the step 3, clear liquid is surpassed again after electric flocculation is handled after separation of solid and liquid
Filter；The operating parameter of electric flocculation is：Electrode plate is aluminium sheet, 200~300A/m of current density2, 40~100min of residence time.
In one embodiment, the dephosphorization agent in the step 5 is placed on the electric flocculation in step 3 treated waste water
Middle addition, the nanofiltration dope of step 5 enter biochemical system, and the additional amount of dephosphorization agent is 0.5~10g/L.
A kind of processing unit of Glufosinate waste water, including：
Flocculation tank, for carrying out flocculation reaction processing to waste water；
Flocculant concentration tank, is connected to flocculation tank, for adding flocculant into flocculation tank；
Equipment for separating liquid from solid is connected to flocculation tank, for the waste water solid separating treatment after flocculation reaction；
Ultrafiltration membrane is connected to the per-meate side of equipment for separating liquid from solid, for carrying out hyperfiltration treatment to the waste water after separation of solid and liquid；
Nanofiltration membrane is connected to the per-meate side of ultrafiltration membrane, carries out nanofiltration processing for the permeate to ultrafiltration membrane；
Precipitation tank is connected to the retention side of nanofiltration membrane, carries out dephosphorization precipitation reaction for the concentrate to nanofiltration membrane；
Dephosphorization agent adds tank, is connected to precipitation tank, for adding dephosphorization agent into precipitation tank；
Biochemical treatment system is connected to precipitation tank, for carrying out biochemical treatment to the clear liquid after precipitation reaction.
Beneficial effect
The utility model provides a kind of method of membrane separation technique processing glufosinate-ammonium phosphorus-containing wastewater, using flocculation-sedimentation
It is easy to operate, low energy consumption, realizes clean manufacturing, reduces occupied area with ultrafiltration+nanofiltration coupling, it is biochemical to reduce glufosinate-ammonium
It is discharged pollutant load, solves the problems, such as that phosphorus-containing wastewater is unable to qualified discharge and is allowed to reuse, is suitable for industrial production.
Detailed description of the invention
Fig. 1 is processing unit figure provided by the utility model.
Wherein, 1, flocculation tank；2, flocculant concentration tank；3, equipment for separating liquid from solid；4, ultrafiltration membrane；5, nanofiltration membrane；6, it precipitates
Slot；7, dephosphorization agent adds tank；8, biochemical treatment system.
Specific embodiment
The utility model is described in further detail below by specific embodiment.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 the literature in the art described technology or conditions 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 it can be direct with other elements when an element is mentioned with another element " connection "
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 any other elements.
The value expressed using range format should be interpreted as not only including clearly enumerating as range in a flexible way
The numerical value of limit value, but also including covering all single numbers or subinterval 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 not only including 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, not only includes 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.
The production method of glufosinate-ammonium is more, such as：Drop cloth riel (Gabriel)-diethyl malonate, A Buzuo
Husband (Arbuzov) synthetic method, using methyl ethylene phosphinic acid methyl ester and acetamide as the high-pressure catalytic synthetic method of raw material, Bu He
The synthesis of Le-Bei Gesi (Bucherer-Bergs) method, interior rich (Neber) rearrangement method synthesis, the synthesis of Si Chuike (Strecker) method
Deng.The final step of these synthetic methods is usually to carry out ammonium using ammonia is added by glufosinate-ammonium hydrochloride is prepared
It is prepared after change, therefore, the inorganic salts such as glufosinate-ammonium, sodium chloride and the ammonium chloride generated can be mainly contained in reaction solution.
The utility model reaction solution to be dealt with is the solution obtained after ammoniumization reaction for glufosinate-ammonium hydrochloride,
Such as can be and obtained as starting material, at the end of aminating reaction using phosphorus trichloride or phosphite ester, the glufosinate-ammonium
The mass fraction of glufosinate-ammonium is 15~40% (being also possible to 18%, 22%, 25%, 28%, 32%, 35%, 38% etc.), inorganic salts in solution
Mass fraction be 3~25% (being also possible to 4%, 7%, 10%, 12%, 14%, 18%, 22% etc.), pH value of solution=3~7 (are also possible to
4,5,6 etc.).The inorganic salts are ammonium chloride, sodium chloride or potassium chloride.
Waste water can first pass through biochemical treatment, and biochemical treatment step here may include that anaerobism, aerobic, anoxic etc. are conventional
Step.
COD100~50000mg/L, 20~10000mg/L of total phosphorus, Cl are typically contained in waste water after biochemical treatment-From
Sub 0.5~10%, NH4 +- N10~2000mg/L, Na+Ion 0.5~10%.
The extracting method first step of the utility model is to be acted on by flocculated by mycelia remaining in phosphorous biochemical waste water
The packages such as body, colloid increase, and are detached from it more from water and settle down, in addition, by adjusting pH controlling potential in flocculation process
So that colloid and disperse system is taken off steady and is assembled, improves subsequent sedimentation separating effect, the utility model, which passes through, carries out solid-liquid to reaction solution
The process that initial gross separation, ultrafiltration precision separate removes impurity, then is concentrated by nanofiltration by its reuse.The parameter packet of flocculation process
Type, reaction pH, reaction temperature, added amount of chemical, the reaction time etc. of flocculant are included, the difference of flocculation process influences whether
The sedimentation separation degree of phosphorus-containing wastewater, the technological parameter of ultrafiltration, yield of system etc..If flocculation reaction dosage is more, meeting
Cause to take off after colloid aggregation steady and is discharged COD, turbidity etc. and increases；On the contrary, will lead to glue if flocculation reaction dosage is inadequate
Body and disperse system aggregation not enough generate pollution to ultrafiltration membrane.More preferably flocculation parameter is：Flocculant be bodied ferric sulfate,
The combination of the one or several kinds such as ferrous sulfate, polyacrylamide, 20~40 DEG C of flocculation reaction temperature, flocculation reaction pH8.5~
10, the flocculation reaction time 0.5~2 hour, 2 ~ 10h of flocculation reaction residence time, 1 ~ 50ppm of flocculation reaction flocculant dosage.
After having obtained reaction solution, biggish solids therein can be gone by way of separation of solid and liquid
It removes, the mode of separation of solid and liquid here is not particularly limited.As the method for specific solid-liquid separation treatment, centrifugation can be enumerated
Separate mode, dissolved air flotation mode, sedimentation separation mode.As centrifuge separation mode, horizontal continuous centrifugal separation may be exemplified
Machine (processing of spiral decanter), the board-like centrifugal separator of separation, disc-stack centrifuge filter can be with as dissolved air flotation mode
Dissolved air floatation device is illustrated, as sedimentation separation mode, may be exemplified agglutination sedimentation separation machine, rapid sedimentation separation machine
Deng, but it is not particularly limited in above-mentioned any one.However secondary filter can be reduced by above-mentioned any one or combinations thereof
To the load of film when device and/or ultrafiltration membrane treatment.More preferably mode is to first pass through sedimentation separation to go out solids, then use coarse filtration
Device is re-fed into subsequent ultrafiltration membrane after filtering and is filtered removal of impurities, can mitigate the pollution of ultrafiltration membrane, coarse filter can
To be conventional cloth bag etc..
Ultrafiltration membrane used in the utility model is 1000~500000 film, referred to as ultrafiltration for molecular cut off
Film, UF film etc..Here, being difficult to measure the aperture of film surface with electron microscope etc. since the aperture of ultrafiltration membrane is too small, institute
To replace average pore size as the index of pore size with the value of referred to as molecular cut off.About molecular cut off, such as at this
Described in the handbook of field：" it will be the longitudinal axis by horizontal axis, prevention rate of molecular weight solute, curve made of being drawn to data
Referred to as molecular cut off curve.And the molecular weight that prevention rate is 90% is known as to the molecular cut off of film ", molecular cut off is made
For the index of the film properties of expression ultrafiltration membrane, it is well known to those skilled in the art.
As the material of these ultrafiltration membranes, removed as above-mentioned water soluble polymer and colloid composition as long as can be realized
The utility model aim is not particularly limited, and can enumerate：Cellulose, cellulose esters, polysulfones, polyether sulfone, polychlorostyrene second
The organic materials such as alkene, chloropropene, polyolefin, polyvinyl alcohol, polymethyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene (PTFE),
Or the inorganic material such as the metals such as stainless steel or ceramics.The material of ultrafiltration membrane can be considered waste water index or operation at
Original appropriate selection from the operating cost of film and is used in combination the service life and considers that the doughnut of preferably polytetrafluoroethylene material is super
Filter membrane.
In the operating process of hollow fiber ultrafiltration membrane, grope by a large number of experiments, the range of the average pore size of ultrafiltration membrane is
50~200nm, because aperture is too big, the turbidity that will lead to waste water is increased, and is formed and is polluted to subsequent nano-filtration system；Aperture is too small,
The rate of recovery can also reduce while flux is lower.In ultra-filtration process, the average pore size of the selection of transmembrane pressure and ultrafiltration membrane,
Filtration flux, water outlet quality suffer from interactional relationship, if transmembrane pressure is excessive, after will lead to a part of colloid compression
It is tightly adhered on hollow-fibre membrane and is difficult to clean, even pass through fenestra and reach per-meate side, influence to be discharged quality, if across
Membrane pressure difference is too small, then it is too small to will lead to filtration flux, increased costs.By groping for a large number of experiments, preferred transmembrane pressure model
Enclosing is 0.05~0.2MPa.Filtration temperature is preferably 20~40 DEG C, and cocnentration factor is preferably material and is concentrated 9~11 times.
After obtaining the permeate of ultrafiltration, feed liquid can be handled by way of concentration, so as to total phosphorus and have
Machine object is concentrated, and the mode being preferably concentrated here is concentrated using nanofiltration.
As the material of nanofiltration membrane, cellulose acetate quasi polymer, polyamide, polyester, polyimides, ethylene are generally used
The high molecular materials such as based polyalcohol.The method of the utility model can be subject to benefit independent of the material of nanofiltration membrane or form
With all effective for any one situation.As representative nanofiltration membrane, such as cellulose acetate class or polyamide can be enumerated
Class anisotropic membrane, with polyamide-based, composite membrane of polyureas active layer etc..Nanofiltration membrane component is to actually use above-mentioned receive
Filter membrane and the substance for being allowed to shape.In the case that the form of nanofiltration membrane is flat membrane, can be incorporated into helical form, tubulose or plate with
Carried out in the component of frame using, in addition, in the case where macaroni yarn, can be incorporated on the basis of bundles of component carry out using.
The utility model can independent of these nanofiltration membrane components the form of the composition be applicable in.Nanofiltration technique preferred parameter is：Operation
Pressure is 1.0~2.0 MPa, and cycles of concentration is 8~10 times.Nanofiltration membrane concentration can be substantially reduced material liquid volume, improve reuse
Water yield.Grope by many experiments, nanofiltration retaining molecular weight selects 150Da~300Da, because containing methanol, phosphorus in feed liquid
The substances such as acid esters, molecular cut off, which crosses conference, makes the reduction of phosphate rejection effect；Molecular cut off is too small so that energy consumption is increased.
After having obtained nanofiltration concentrate, phosphate etc. can be removed in such a way that others are except phosphorus reaction, such as
Nanofiltration concentrate can be handled using dephosphorization agent mode is added, the operating time is short, and dephosphorization water outlet enters biochemical system shape
At circular flow technique.Dephosphorization agent is one of dephosphorization with ferric salt agent, aluminium salt dephosphorization agent, calcium salt dephosphorization agent, secondary phosphorous dephosphorization agent
Or several combination, it is preferred to use secondary phosphorous dephosphorization agent.The additional amount of dephosphorization agent is 0.5~10g/L.
In one embodiment, it have passed through the waste water after being separated by solid-liquid separation and carry out electric flocculation processing, the purpose one of electric flocculation
Aspect can remove the ammonia nitrogen in removal waste water, decline the N/P ratio into nanofiltration membrane, improve nanofiltration membrane to the rejection of phosphorus；
On the other hand, the pollution that electric flocculation mitigates ultrafiltration membrane improves ultrafiltration membrane flux；And it can be by secondary phosphorous salt during electric flocculation
It is converted into phosphate, the precipitation process of more conducively subsequent dephosphorization agent, such as dephosphorization with ferric salt agent, aluminium salt dephosphorization can be directly used
The removal such as agent, calcium salt dephosphorization agent.In another embodiment, the addition step of dephosphorization agent can be placed on electric flocculation and handles it
Afterwards, the organic impurities in waste water can be adsorbed by the precipitating that dephosphorization agent generates, the pollution for mitigating ultrafiltration membrane improves ultrafiltration membrane and leads to
Amount.The operating parameter of electric flocculation is：Electrode plate is aluminium sheet, 200~300A/m of current density2, 40~100min of residence time.
A kind of processing unit of Glufosinate waste water, including：
Flocculation tank 1, for carrying out flocculation reaction processing to waste water；
Flocculant concentration tank 2 is connected to flocculation tank 1, for adding flocculant into flocculation tank 1；
Equipment for separating liquid from solid 3 is connected to flocculation tank 1, for the waste water solid separating treatment after flocculation reaction；
Ultrafiltration membrane 4 is connected to the per-meate side of equipment for separating liquid from solid 3, for carrying out at ultrafiltration to the waste water after separation of solid and liquid
Reason；
Nanofiltration membrane 5 is connected to the per-meate side of ultrafiltration membrane 4, carries out nanofiltration processing for the permeate to ultrafiltration membrane 4；
Precipitation tank 6 is connected to the retention side of nanofiltration membrane 5, carries out dephosphorization precipitation reaction for the concentrate to nanofiltration membrane 5；
Dephosphorization agent adds tank 7, is connected to precipitation tank 6, for adding dephosphorization agent into precipitation tank 6；
Biochemical treatment system 8 is connected to precipitation tank 6, for carrying out biochemical treatment to the clear liquid after precipitation reaction.
Production water of the waste water of following embodiment processing from Glufosinate waste water after biochemical treatment, water quality are：
COD3560mg/L, total phosphorus 423mg/L, Cl-Ion 2.1%, NH4 +-N 321mg/L、Na+Ion 1.8%.
Embodiment 1
The phosphorus-containing wastewater 200kg obtained after taking glufosinate-ammonium factory biochemical is pumped into flocculation tank, and polymerization ferrous sulfate 5g is added and carries out
Flocculation reaction, control pH be 9.2, react 0.5h, 25 DEG C of reaction temperature.Reaction solution feeding settling tank is settled, when stop
Between 2h.Settling tank supernatant enters hollow fiber ultrafiltration membrane after being sent into Bag filter, and the average pore size of ultrafiltration membrane is to adopt respectively
With 50 nm, 100 nm, 200 nm, material is polytetrafluoroethylene (PTFE), and ultra-filtration process transmembrane pressure 0.1Mpa 30 DEG C of filtration temperature, will
Feed liquid stops after being concentrated 10 times.Ultrafiltration dope is returned into biochemical system and continues biochemical reaction, the penetrating fluid of ultrafiltration is sent into nanofiltration membrane
Be concentrated, operating pressure 1.5MPa, cycles of concentration is 8 times, in nanofiltration concentrate be added 1.5g/L by Ca (OH) 2 and time
Phosphorous dephosphorization agent presses 1：1 mixed composite dephosphorization phosphorus agent, obtains low-phosphorous low COD recycle-water, send to biochemical treatment.In different condition
Under test result it is as follows：
| Hollow fiber ultrafiltration membrane average pore size | 50nm | 100nm | 200nm |
| COD /ppm | 14.2 | 15.3 | 16.1 |
| TP /ppm | 5.4 | 5.9 | 6 |
| Ammonia nitrogen/ppm | 8.4 | 7.9 | 8.8 |
| Suspended matter/ppm | 0 | 0 | 0 |
| Nanofiltration membrane TP rejection/% | 97.5 | 96.9 | 96.8 |
| Coloration/times | 0.5 | 1 | 1 |
| Ultrafiltration membrane average flux m3/h | 14.6 | 15.6 | 17.5 |
Low-phosphorous low COD recycle-water is sent again to biochemical treatment.
Embodiment 2
The phosphorus-containing wastewater 200kg obtained after taking glufosinate-ammonium factory biochemical is pumped into flocculation tank, and polymerization ferrous sulfate 4g is added and carries out
Flocculation reaction, control pH be 8.5, react 1h, 30 DEG C of reaction temperature.Reaction solution feeding settling tank is settled, the residence time
3h.Settling tank supernatant enters hollow fiber ultrafiltration membrane after being sent into Bag filter, and the average pore size of ultrafiltration membrane is 50 nm, material
It is polytetrafluoroethylene (PTFE), ultra-filtration process transmembrane pressure is 0.05,0.1,0.15,0.2Mpa respectively, 25 DEG C of filtration temperature, feed liquid is dense
Stop after 10 times of contracting.Ultrafiltration dope is returned into biochemical system and continues biochemical reaction, it is dense that the penetrating fluid of ultrafiltration is sent into nanofiltration membrane progress
Contracting, operating pressure 1MPa, cycles of concentration is 8 times, be added in nanofiltration concentrate 1.5g/L by Ca (OH) 2 and the dephosphorization of time phosphorous
Agent presses 1：1 mixed composite dephosphorization phosphorus agent, obtains low-phosphorous low COD recycle-water, send to biochemical treatment.Test at different conditions
As a result as follows：
| Hollow fiber ultrafiltration membrane transmembrane pressure MPa | 0.05 | 0.1 | 0.15 | 0.2 |
| COD /ppm | 14.1 | 14.3 | 14.5 | 15.2 |
| TP /ppm | 5.2 | 5.3 | 5.6 | 5.3 |
| Nanofiltration membrane TP rejection/% | 97.4 | 97.5 | 96.9 | 96.7 |
| Nanofiltration membrane COD rejection/% | 97.9 | 98.4 | 98.1 | 98 |
| Suspended matter/ppm | 0 | 0 | 0 | 0 |
| Coloration/times | 0.5 | 0.5 | 1 | 1 |
| Ultrafiltration membrane average flux m3/h | 12.4 | 14.2 | 15.6 | 18.7 |
Low-phosphorous low COD recycle-water is sent again to biochemical treatment.
Embodiment 3
The phosphorus-containing wastewater 200kg obtained after taking glufosinate-ammonium factory biochemical is pumped into flocculation tank, and polymerization ferrous sulfate 6g is added and carries out
Flocculation reaction, control pH be 9, react 1.5h, 35 DEG C of reaction temperature.Reaction solution feeding settling tank is settled, the residence time
4h.Settling tank supernatant enters hollow fiber ultrafiltration membrane after being sent into Bag filter, and the average pore size of ultrafiltration membrane is 50 nm, material
It is polytetrafluoroethylene (PTFE), ultra-filtration process transmembrane pressure is 0.1Mpa respectively, 25 DEG C of filtration temperature, is stopped after feed liquid is concentrated 10 times.
Ultrafiltration dope is returned into biochemical system and continues biochemical reaction, the penetrating fluid of ultrafiltration is sent into nanofiltration membrane and is concentrated, operating pressure point
Not Wei 1.0,1.5,2.0MPa, cycles of concentration is 10 times, and being removed by Ca (OH) 2 and time phosphorous for 1.5g/L is added in nanofiltration concentrate
Phosphorus agent presses 1：1 mixed composite dephosphorization phosphorus agent, obtains low-phosphorous low COD recycle-water, send to biochemical treatment.Examination at different conditions
It is as follows to test result：
| Nanofiltration membrane operations MPa | 1.0 | 1.5 | 2.0 |
| COD /ppm | 14.3 | 14.2 | 15.1 |
| TP /ppm | 5.3 | 5.1 | 5.4 |
| Nanofiltration membrane TP rejection/% | 97.5 | 97.6 | 97.1 |
| Nanofiltration membrane COD rejection/% | 98.4 | 98.5 | 98 |
| Suspended matter/ppm | 0 | 0 | 0 |
| Coloration/times | 0.5 | 1 | 1 |
Low-phosphorous low COD recycle-water is sent again to biochemical treatment.
Embodiment 4
The phosphorus-containing wastewater 200kg obtained after taking glufosinate-ammonium factory biochemical is pumped into flocculation tank, and polymerization ferrous sulfate 2g is added and carries out
Flocculation reaction, control pH be 9.5, react 2h, 30 DEG C of reaction temperature.Reaction solution feeding settling tank is settled, the residence time
5h.Settling tank supernatant enters hollow fiber ultrafiltration membrane after being sent into Bag filter, and the average pore size of ultrafiltration membrane is using 50 respectively
Nm, 100 nm, 200 nm, material are polytetrafluoroethylene (PTFE), ultra-filtration process transmembrane pressure 0.1Mpa, 35 DEG C of filtration temperature, by feed liquid
Stop after 10 times of concentration.Ultrafiltration dope is returned into biochemical system and continues biochemical reaction, the penetrating fluid of ultrafiltration is sent into nanofiltration membrane and is carried out
Concentration, operating pressure 1MPa, cycles of concentration is 9 times, and being removed by Ca (OH) 2 and time phosphorous for 1.5g/L is added in nanofiltration concentrate
Phosphorus agent presses 1：1 mixed composite dephosphorization phosphorus agent, obtains low-phosphorous low COD recycle-water, send to biochemical treatment.Examination at different conditions
It is as follows to test result：
| Hollow fiber ultrafiltration membrane average pore size | 50nm | 100nm | 200nm |
| COD /ppm | 14.2 | 15.1 | 16.0 |
| TP /ppm | 5.4 | 5.8 | 6 |
| Ammonia nitrogen/ppm | 8.4 | 7.9 | 8.7 |
| Suspended matter/ppm | 0 | 0 | 0 |
| Nanofiltration membrane TP rejection/% | 94.5 | 95.0 | 94.8 |
| Coloration/times | 0.5 | 0.05 | 1 |
| Ultrafiltration membrane average flux m3/h | 12.4 | 14.8 | 18.5 |
Low-phosphorous low COD recycle-water is sent again to biochemical treatment.
Embodiment 5
The phosphorus-containing wastewater 200kg obtained after taking glufosinate-ammonium factory biochemical is pumped into flocculation tank, and polymerization ferrous sulfate 2g is added and carries out
Flocculation reaction, control pH be 9.5, react 2h, 30 DEG C of reaction temperature.Reaction solution feeding settling tank is settled, the residence time
5h.Settling tank supernatant carries out electric flocculation processing after being sent into Bag filter, and electrode plate is aluminium sheet, and current density 110A/m2 is stopped
Time 60min enters hollow fiber ultrafiltration membrane, and the average pore size of ultrafiltration membrane is using 50 nm, 100 nm, 200 nm, material respectively
Matter is polytetrafluoroethylene (PTFE), and ultra-filtration process transmembrane pressure 0.1Mpa, stops after feed liquid is concentrated 10 times by 35 DEG C of filtration temperature.It will surpass
It filters dope and returns to biochemical system continuation biochemical reaction, the penetrating fluid of ultrafiltration is sent into nanofiltration membrane and is concentrated, operating pressure 1MPa,
Cycles of concentration is 9 times, and 1.5g/L is added in nanofiltration concentrate presses 1 by Ca (OH) 2 and time phosphorous dephosphorization agent：1 mixing it is compound
Dephosphorization phosphorus agent obtains low-phosphorous low COD recycle-water, send to biochemical treatment.Test result at different conditions is as follows：
| Hollow fiber ultrafiltration membrane average pore size | 50nm | 100nm | 200nm |
| COD /ppm | 10.1 | 11.2 | 11.8 |
| TP /ppm | 4.4 | 4.1 | 4.5 |
| Ammonia nitrogen/ppm | 4.4 | 4.9 | 4.7 |
| Suspended matter/ppm | 0 | 0 | 0 |
| Nanofiltration membrane TP rejection/% | 98.5 | 98.9 | 99.1 |
| Coloration/times | 0.5 | 0.05 | 1 |
| Ultrafiltration membrane average flux m3/h | 15.6 | 16.8 | 22.1 |
Low-phosphorous low COD recycle-water is sent again to biochemical treatment.
Embodiment 6
The phosphorus-containing wastewater 200kg obtained after taking glufosinate-ammonium factory biochemical is pumped into flocculation tank, and polymerization ferrous sulfate 2g is added and carries out
Flocculation reaction, control pH be 9.5, react 2h, 30 DEG C of reaction temperature.Reaction solution feeding settling tank is settled, the residence time
5h.Settling tank supernatant carries out electric flocculation processing after being sent into Bag filter, and electrode plate is aluminium sheet, and current density 110A/m2 is stopped
Time 60min, add 1.5g/L by Ca (OH) 2 and time phosphorous dephosphorization agent by 1：1 mixed composite dephosphorization phosphorus agent, precipitating are removed
After phosphorus, into hollow fiber ultrafiltration membrane, the average pore size of ultrafiltration membrane is using 50 nm, 100 nm, 200 nm, material respectively
It is polytetrafluoroethylene (PTFE), ultra-filtration process transmembrane pressure 0.1Mpa, stops after feed liquid is concentrated 10 times by 35 DEG C of filtration temperature.By ultrafiltration
Dope returns to biochemical system and continues biochemical reaction, and the penetrating fluid of ultrafiltration is sent into nanofiltration membrane and is concentrated, operating pressure 1MPa, dense
Demagnification number is 9 times, obtains low-phosphorous low COD recycle-water.Test result at different conditions is as follows：
| Hollow fiber ultrafiltration membrane average pore size | 50nm | 100nm | 200nm |
| COD /ppm | 10.1 | 11.2 | 11.8 |
| TP /ppm | 4.4 | 4.1 | 4.5 |
| Ammonia nitrogen/ppm | 4.4 | 4.9 | 4.7 |
| Suspended matter/ppm | 0 | 0 | 0 |
| Coloration/times | 0.5 | 0.05 | 1 |
| Ultrafiltration membrane average flux m3/h | 16.5 | 18.6 | 24.5 |
Low-phosphorous low COD recycle-water is sent again to biochemical treatment.
Claims (3)
1. a kind of processing unit of glufosinate-ammonium waste water, which is characterized in that including：
Flocculation tank（1）, for carrying out flocculation reaction processing to waste water；
Flocculant concentration tank（2）, it is connected to flocculation tank（1）, it is used for flocculation tank（1）In add flocculant；
Equipment for separating liquid from solid（3）, it is connected to flocculation tank（1）, for the waste water solid separating treatment after flocculation reaction；
Ultrafiltration membrane（4）, it is connected to equipment for separating liquid from solid（3）Per-meate side, for after separation of solid and liquid waste water carry out ultrafiltration at
Reason；
Nanofiltration membrane（5）, it is connected to ultrafiltration membrane（4）Per-meate side, for ultrafiltration membrane（4）Permeate carry out nanofiltration processing；
Precipitation tank（6）, it is connected to nanofiltration membrane（5）Retention side, for nanofiltration membrane（5）Concentrate to carry out dephosphorization precipitating anti-
It answers；
Dephosphorization agent adds tank（7）, it is connected to precipitation tank（6）, it is used for precipitation tank（6）In add dephosphorization agent；
Biochemical treatment system（8）, it is connected to precipitation tank（6）, for carrying out biochemical treatment to the clear liquid after precipitation reaction.
2. the processing unit of glufosinate-ammonium waste water according to claim 1, which is characterized in that the retention of the ultrafiltration membrane point
Son 1000~500000Da of amount, the material of ultrafiltration membrane are selected from cellulose, cellulose esters, polysulfones, polyether sulfone, polyvinyl chloride, chlorine third
One of alkene, polyolefin, polyvinyl alcohol, polymethyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), ceramics.
3. the processing unit of glufosinate-ammonium waste water according to claim 1, which is characterized in that the material of nanofiltration membrane is selected from acetic acid
One of cellulosic polymer, polyamide, polyester, polyimides or polyvinyl, molecular cut off is 150~
300Da。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658364A (en) * | 2017-11-27 | 2018-10-16 | 江苏久吾高科技股份有限公司 | A kind of processing method and processing device of glufosinate-ammonium waste water |
| CN113058433A (en) * | 2021-03-19 | 2021-07-02 | 苏州晶洲装备科技有限公司 | Useless developer solution filtration system |
| CN113332859A (en) * | 2021-06-09 | 2021-09-03 | 中国科学院上海高等研究院 | High-permeability-selectivity acid-resistant nanofiltration membrane material, and preparation method and application thereof |
-
2017
- 2017-11-27 CN CN201721606848.4U patent/CN208151153U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658364A (en) * | 2017-11-27 | 2018-10-16 | 江苏久吾高科技股份有限公司 | A kind of processing method and processing device of glufosinate-ammonium waste water |
| CN113058433A (en) * | 2021-03-19 | 2021-07-02 | 苏州晶洲装备科技有限公司 | Useless developer solution filtration system |
| CN113332859A (en) * | 2021-06-09 | 2021-09-03 | 中国科学院上海高等研究院 | High-permeability-selectivity acid-resistant nanofiltration membrane material, and preparation method and application thereof |
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