CN105858928A - Treatment method and system for phosphorus-containing feed solution - Google Patents
Treatment method and system for phosphorus-containing feed solution Download PDFInfo
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- CN105858928A CN105858928A CN201510031885.6A CN201510031885A CN105858928A CN 105858928 A CN105858928 A CN 105858928A CN 201510031885 A CN201510031885 A CN 201510031885A CN 105858928 A CN105858928 A CN 105858928A
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Abstract
An embodiment of the invention discloses a treatment method and system for a phosphorus-containing feed solution. The treatment method and system can separate chloride ions from the phosphorus-containing feed solution, and increase the enrichment rate of phosphorus and effectively utilize phosphorus. A method in the embodiment comprises: first allowing phosphorus-containing feed solution to stand and settle to obtain a supernatant and a base solution; filtering the supernatant to obtain a filtrate and filter residue; treating the filtrate by a first-stage membrane treatment apparatus to obtain first-stage fresh water and a first-stage concentrated water; recovering the first-stage fresh water, and extracting inorganic salt; treating the first-stage concentrated water by a second-stage membrane treatment apparatus to obtain the second-stage concentrated water and second-stage fresh water; recycling the second-stage concentrated water, and extracting a phosphorus-containing compound; treating the second-stage fresh water by a third-stage membrane treatment apparatus to obtain third-stage fresh water and third-stage concentrated water; and returning the third-stage fresh water to the a first-stage membrane treatment apparatus, recycling the third-stage concentrated water and extracting inorganic salts. The embodiment of the invention can separate chloride ions from the phosphorus-containing feed solution, so as to increase the enrichment rate of phosphorus and effectively utilize phosphorus.
Description
Technical field
The present invention relates to chemical field, particularly relate to processing method and the system of a kind of phosphorous feed liquid.
Background technology
Phosphor resource is the non-renewable resources of a kind of preciousness, utilizes phosphor resource the most scientifically and rationally,
The utilization rate improving phosphor resource is always the tireless pursuit of domestic and international expert.Series of phosphate product is
One of product that phosphorus chemical industry is important, various phosphorus chemical products and the production of people, live closely bound up.
In phosphatic commercial process, often have substantial amounts of high-content phosphorus hydrochlorate feed liquid and produce, this
Because with the presence of a large amount of chloride ion impurities in a little feed liquids, limit the use of this portion phosphate feed liquid, from
And produce substantial amounts of high P content waste water, not only cause the serious waste of phosphor resource, and return environment and make
Become the biggest pressure.
China is pesticide producing big country, and pesticide yield occupies the biggest proportion in world pesticide yield, and
Phosphorous pesticide is again a big class of pesticide, in the production process of phosphorous pesticide, can produce substantial amounts of height
Content phosphorus-containing wastewater.Prior art waste material phosphorous for pesticide producing has certain research, main by oxidation
Concentration method, obtains solid phosphorus-containing compound.
But, due to the equivalent characteristics of inorganic matter, existing oxidation concentration method is difficult to phosphorous pesticide and gives up
The efficiently separating of the acid ion of phosphorus and chloride ion in water, is unfavorable for improving the utilization rate of phosphor resource.
Summary of the invention
In view of this, the invention provides processing method and the system of a kind of phosphorous feed liquid, it is possible to by chlorine from
Son separates from phosphorous feed liquid, improves accumulation rate and the effective rate of utilization of phosphorus.
The present invention provides the processing method of a kind of phosphorous feed liquid, it may include:
By phosphorous feed liquid elder generation standing sedimentation, obtain supernatant and end liquid；
Supernatant liquid filtering, obtains filtrate and filtering residue；
Filtrate, through one-level membrane treatment appts, obtains one-level fresh water and the dense water of one-level；
One-level fresh water is reclaimed, extracts inorganic salt；
The dense water of one-level, through secondary membrane processing means, obtains two grades of dense water and two grades of fresh water；
By two grades of dense Water Sproading, extract phosphorus-containing compound；
Two grades of fresh water obtain three grades of fresh water and three grades of dense water through three grades of membrane treatment appts；
Three grades of fresh water return one-level membrane treatment appts, three grades of dense Water Sproading, extract inorganic salt.
Preferably, the film that firsts and seconds membrane treatment appts is used is NF membrane.
Preferably, the film that three grades of membrane treatment appts are used is reverse osmosis membrane.
Preferably, during NF membrane is polyamide-based film, polysulfones film, cellulose acetate class film and inoranic membrane
Any one.
Preferably, reverse osmosis membrane is polyamide-based film or cellulose acetate class film.
Preferably, the operation temperature of firsts and seconds membrane treatment appts independently be 0～80 DEG C, operates pressure
Independently be 1～5MPa.
Preferably, the operation temperature of three grades of membrane treatment appts is 20～60 DEG C, and operation pressure is 2～4MPa.
Preferably, filter and use film pretreatment unit to carry out, the film that described film pretreatment unit is used
Retaining precision is 0.02 micron.
Preferably, before carrying out standing sedimentation, also include: to described phosphorous feed adjustment pH value.
The present invention also provides for the processing system of a kind of phosphorous feed liquid, including:
It is provided with import and the flocculate sedimentation device of supernatant outlet, comprises the acid ion of phosphorus for sedimentation
Phosphorous feed liquid with chloride ion；
The defecator communicated is exported with described flocculate sedimentation device supernatant；
One-level, two grades and the three grades of membrane treatment appts being sequentially communicated with described defecator；
Described secondary membrane processing means is provided with process water out；Described three grades of membrane treatment appts are provided with fresh water and go out
Mouthful, and it communicates with described one-level membrane treatment appts；
The film that described one-level, two grades and three grades of membrane treatment appts are used is independently selected from NF membrane or reverse osmosis
Permeable membrane.
As can be seen from the above technical solutions, the phosphorous feed liquid that the embodiment of the present invention provides enters flocculate and sinks
Falling unit carries out standing sedimentation；Sedimentation device supernatant enters defecator and filters, and removes phosphorous material
The impurity such as float, colloid in liquid, filtrate then enters one-level membrane treatment appts；One-level membrane treatment appts goes out
Moisture two strands, fresh water is sodium chloride solution, and dense water is the mixture of phosphate and sodium chloride, one-level fresh water
Sodium chloride can be entered and reclaim liquid bath, and the dense water of one-level enters secondary membrane processing means；Secondary membrane processing means
Going out two strands: two grades of dense water of moisture is to reach the phosphorous feed liquid after purifying the process required, is that the application needs
Final products, can enter phosphorous feed liquid accumulator tank, and two grades of fresh water is the mixing of phosphate and sodium chloride
Thing, phosphate content is the lowest, mainly sodium chloride composition, enters three grades of membrane treatment appts；At three grades of films
Reason device goes out moisture two strands, and three grades of fresh water are the sodium chloride solutions containing lower content, return at one-level film
Reason device, three grades of dense water are the mixture of phosphate and sodium chloride, and phosphate content is the lowest, mainly chlorine
Change sodium composition, sodium chloride can be entered and reclaim liquid bath.The implementation process of the present invention completes under liquid environment,
Processed by one, two, three film, it is possible to achieve phosphate radical in phosphate feed liquid, orthophosphite ions and
Efficiently separating of chloride ion, improves accumulation rate and the effective rate of utilization of phosphorus, the nothing in the most phosphorous feed liquid
Machine salt is recycled.Additionally, present invention reduces energy resource consumption, reduce toxic and harmful and produce.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the processing method of phosphorous feed liquid in the embodiment of the present invention.
Detailed description of the invention
Embodiments provide the processing method of phosphorous feed liquid, be used for chloride ion from phosphorous feed liquid
Separate, improve accumulation rate and the effective rate of utilization of phosphorus.Below it is described in detail.
The invention provides the processing method of a kind of phosphorous feed liquid, including:
Phosphorous feed liquid, described phosphorous feed liquid is provided to comprise acid ion and the chloride ion of phosphorus；
By described phosphorous feed liquid standing sedimentation, obtain supernatant；
Described supernatant, through filtering, obtains filtrate；
Described filtrate, through one-level membrane treatment appts, obtains the dense water of one-level；
The dense water of described one-level is through secondary membrane processing means, the phosphorous feed liquid after being processed and two grades of fresh water；
Described two grades of fresh water, through three grades of membrane treatment appts, obtain three grades of fresh water；Described three grades of fresh water return described
One-level membrane treatment appts；
The film that described one-level, two grades and three grades of membrane treatment appts are used is independently selected from NF membrane or reverse osmosis
Permeable membrane.
Phosphorous feed liquid after being processed by present invention process, it is possible to achieve phosphate radical, Asia in phosphate feed liquid
Efficiently separating of phosphate anion and chloride ion, according to real needs, by controlling different technic indexs
Different separation purities can be reached, it is achieved the recovery of phosphorous material purifies.
Seeing Fig. 1, Fig. 1 is the schematic flow sheet of the processing method of phosphorous feed liquid in the embodiment of the present invention.
The embodiment of the present invention takes phosphorous feed liquid and processes, described phosphorous feed liquid comprise phosphorus acid ion and
Chloride ion.
Phosphorous feed liquid of the present invention can be phosphate waste, phosphate therein such as sodium ascorbyl phosphate, phosphorus
Acid ammonium salt, potassium phosphate etc.；Can also be different phosphorous agricultural chemicals waste waters.Described phosphate can be one
Valency, bivalence, trivalent, tetravalence, pentavalent salt, say, that the acid ion of phosphorus has phosphate radical and phosphorous
Acid group etc..In an embodiment of the present invention, phosphate radical and the gross mass of orthophosphite in described phosphorous feed liquid
Concentration is 0.1～20%, preferably 0.1～10%, more preferably 2～7%.In described phosphorous feed liquid, chloride ion contains
Amount can be 0.1～15%, preferably 2～10%.Additionally, can be containing small-molecular-weight in described phosphorous feed liquid
Organic substance or do not have Organic substance, this Organic substance does not affect film and processes separating effect.
As preferably, the phosphorous feed liquid of the embodiment of the present application is introduced into pH regulator groove, regulates pH value.At this
In invention, the phosphorous material liquid pH value of scalable to 2～13, preferably 7～13.Described regulation pH value is ability
Technological means known to field technique personnel, can use NaOH and H2SO4Or HCl etc. is adjusted.
Then, regulate the phosphorous feed liquid of pH value and can enter flocculate subsider and carry out standing sedimentation, obtain
Supernatant and end liquid.Described standing sedimentation is not particularly limited by the present invention；The time stood is preferably 1～6
Hour, more preferably 2～4 hours.
The supernatant obtained through subsider preferably enters film pretreatment unit and filters, and removes phosphorous material
The impurity such as float, colloid in liquid, obtains filtrate, i.e. pretreatment feed liquid.Being preferable to carry out in the present invention
In example, the film that film pretreatment unit is used can be ultrafilter membrane, retains precision and is preferably 0.02 micron；
Described ultrafilter membrane can be organic membrane, such as polysulfones film, TPO film and fluorinated film etc., it is also possible to
It is inoranic membrane, such as ceramic membrane, glass-film and metal film.Wherein, described organic membrane is preferably TPO
Film, acid and alkali-resistance and various organic solvent, and mechanical strength and chemical-resistance good；Described inoranic membrane is preferred
For metal film.Additionally, other conditions of described filtration are not particularly limited by the present invention.
In one embodiment of the invention, film pretreatment unit produces discharge 1t/h.The pretreatment material obtained
A liquid part can return to flocculate subsider, proceeds circular treatment subsequently into film pretreatment unit,
Dilute the concentration of former phosphorous feed liquid；Another part then enters one-level membrane treatment appts, the available dense water of one-level
With one-level fresh water.In one embodiment of the invention, the pre-place that flocculate subsider is circulated is returned to
The ratio of reason feed liquid is 20～90%.
In the present invention, the film of one-level membrane treatment appts uses NF membrane or reverse osmosis membrane, preferably nanofiltration
Film, mainly realizes the separation of chloride ion in phosphate feed liquid.If use NF membrane, then can use polyamide-based
Film, polysulfones film, cellulose acetate class film or inoranic membrane, be preferably used polyamide-based film；According to instead
Permeable membrane, then can use polyamide-based film or cellulose acetate class film, preferably use polyamide-based film.One-level film
The operation temperature of processing means arbitrarily can be chosen between 0～80 DEG C, preferably 20 DEG C～50 DEG C；Operation
Pressure arbitrarily can be chosen between 1～5MPa, preferably 2～4MPa.
One-level membrane treatment appts goes out moisture two strands, and fresh water (one-level fresh water) is sodium chloride solution, dense water (one
The dense water of level) it is the mixture of phosphate and sodium chloride；One-level fresh water enters sodium chloride and reclaims liquid bath, can lead to
Cross concentration method and reclaim sodium chloride.And the dense water of one-level obtained enters secondary membrane processing means, after being processed
Phosphorous feed liquid and two grades of fresh water.
In the present invention, the film of secondary membrane processing means uses NF membrane or reverse osmosis membrane, preferably NF membrane,
Mainly realize the separation of chloride ion in phosphate feed liquid further.If use NF membrane, then can use polyamides
Amine film, polysulfones film, cellulose acetate class film or inoranic membrane, be preferably used polyamide-based film；If adopting
With reverse osmosis membrane, then can use polyamide-based film or cellulose acetate class film, preferably use polyamide-based film.Two
The operation temperature of level membrane treatment appts arbitrarily can be chosen between 0～80 DEG C, preferably 20 DEG C～50 DEG C；
Operation pressure arbitrarily can be chosen between 1～5MPa, preferably 2～4MPa.
It is to reach to purify the phosphorous feed liquid required that secondary membrane processing means goes out two strands: two grades of dense water of moisture, is
The final products that we need, enter phosphorous feed liquid accumulator tank, reclaim and store, changing concentration as required；
Two grades of fresh water are the mixture of phosphate and sodium chloride, and phosphate content is the lowest, mainly sodium chloride composition,
Enter three grades of membrane treatment appts.
The film of three grades of membrane treatment appts uses NF membrane or reverse osmosis membrane, it is preferred to use reverse osmosis membrane, mainly
Realize the enrichment concentration etc. of chloride ion.If use NF membrane, then can use polyamide-based film, polysulfones film,
Cellulose acetate class film or inoranic membrane, be preferably used polyamide-based film；According to reverse osmosis membrane, then can use
Polyamide-based film or cellulose acetate class film, preferably use polyamide-based film.The operation of three grades of membrane treatment appts
Temperature arbitrarily can be chosen between 20～60 DEG C, preferably 30 DEG C～50 DEG C；Operation pressure can be 2～4MPa
Between arbitrarily choose.
Three grades of membrane treatment appts go out moisture two strands, and three grades of (salt) fresh water are that the sodium chloride containing lower content is molten
Liquid, returns to one-level membrane treatment appts, and three grades of (salt) dense water are the mixture of phosphate and sodium chloride,
Phosphate content is the lowest, mainly sodium chloride composition, enters sodium chloride and reclaims liquid bath, can pass through concentration method
Reclaim sodium chloride.In embodiments of the present invention, the ratio of three grades of fresh water of one-level membrane treatment appts is returned to
It is 20～50%.
In the present invention, the course of conveying of described feed liquid can use booster pump to complete.The work of described booster pump
It is preferably 0～5MPa, more preferably 0.8MPa～2MPa as pressure.The film of membrane treatment appts at different levels uses
Commercial membrane product commonly used in the art；Control the operation temperature of membrane treatment appts at different levels primarily to
Ensure the functional of film used, typically select room temperature.
Described phosphorous feed liquid through present invention process process after, phosphate radical, the response rate of orthophosphite > 98%；
In the most phosphorous feed liquid of the chloride ion response rate, chloride ion clearance can reach 50%～95%.It addition, this
Bright membrane separation technique also has low cost, can be continuously produced and the advantages such as side-product salt quality better.
Present invention also offers the processing system of a kind of phosphorous feed liquid, including:
It is provided with import and the flocculate sedimentation device of supernatant outlet, comprises the acid ion of phosphorus for sedimentation
Phosphorous feed liquid with chloride ion；
The defecator communicated is exported with described flocculate sedimentation device supernatant；
One-level, two grades and the three grades of membrane treatment appts being sequentially communicated with described defecator；
Described secondary membrane processing means is provided with process water out；Described three grades of membrane treatment appts are provided with fresh water and go out
Mouthful, and it communicates with described one-level membrane treatment appts；
The film that described one-level, two grades and three grades of membrane treatment appts are used is independently selected from NF membrane or reverse osmosis
Permeable membrane.
Processing system of the present invention the most also includes pH regulator groove, available NaOH and H2SO4Or HCl
Regulate the pH value of phosphorous feed liquid to 2～13, preferably 7～13.
Processing system of the present invention includes being connected with pH regulator groove, is provided with import and the wadding of supernatant outlet
Condensate sedimentation device, comprises the acid ion of phosphorus and the phosphorous feed liquid of chloride ion for sedimentation.The present invention couple
Flocculate sedimentation device is not particularly limited, such as available flocculate subsider well known to those skilled in the art.
Processing system of the present invention includes exporting, with described flocculate sedimentation device supernatant, the filtration communicated
Device, is used for removing the impurity such as float, colloid in phosphorous feed liquid.In a preferred embodiment of the invention,
Defecator is film pretreatment unit；The precision that retains of the film used is preferably 0.02 micron.
Processing system of the present invention includes one-level, two grades and three grades being sequentially communicated with described defecator
Membrane treatment appts, the film that described one-level, two grades and three grades of membrane treatment appts are used is independently selected from nanofiltration
Film or reverse osmosis membrane；The content of the film of membrane treatment appts is consistent with content mentioned above, the most superfluous at this
State.
Described secondary membrane processing means is provided with process water out；Described three grades of membrane treatment appts are provided with fresh water and go out
Mouthful, and it communicates with described one-level membrane treatment appts.The concrete process of the embodiment of the present application membrane treatment appts
Flow process is as follows:
One-level membrane treatment appts is used for initial gross separation sodium chloride solution and phosphate, goes out moisture two strands, fresh water
Being sodium chloride solution, dense water is the mixture of phosphate and sodium chloride；
Dense water enters secondary membrane processing means through interface channel；
The further Isolating chlorinated sodium solution of secondary membrane processing means and phosphate, go out moisture two strands: two grades dense
Water is to reach to purify the phosphorous feed liquid required, is our final products of needing, enters phosphorous feed liquid and reclaim
Groove, reclaims and stores, changing concentration as required；Two grades of fresh water are the mixture of phosphate and sodium chloride,
Phosphate content is the lowest, mainly sodium chloride composition；
Two grades of fresh water enter three grades of membrane treatment appts through interface channel；
Three grades of further Isolating chlorinated sodium solutions of membrane treatment appts and phosphate, three grades of membrane treatment appts water outlets
Dividing two strands, three grades of salt fresh water are the sodium chloride solutions containing lower content, return to one-level membrane treatment appts,
Three grades of dense water of salt are the mixture of phosphate and sodium chloride, and phosphate content is the lowest, and mainly sodium chloride becomes
Point, entering sodium chloride and reclaim liquid bath, concentration method reclaims sodium chloride.
Embodiment 1
Table 1 is the former water of phosphorous feed liquid and process testing result in the embodiment of the present invention 1.
Operation temperature chooses 26 DEG C, takes tertiary sodium phosphate feed liquid or the waste liquid 1000kg regulating PH ≈ 10, enters
Enter flocculate subsider standing sedimentation, stand 4h, obtain supernatant.
Film pretreatment unit squeezed into by gained supernatant booster pump, obtains filtrate；Inlet pressure 0.25MPa,
Discharge 1t/h is produced in film pretreatment, and retaining precision is 0.02 micron.
The film of one-level membrane treatment appts uses polyamide-based NF membrane, the water inlet of one-level membrane treatment appts to have two strands:
Water 1t/h, three grades of salt fresh water return flow 0.25t/h, one-level film inlet pressure 1.6MPa are produced in film pretreatment；
One-level membrane treatment appts goes out moisture two strands: one-level fresh-water flow 0.5t/h, enters sodium chloride and reclaims liquid bath, and one
Level concentrated stream amount 0.75t/h, dense water enters secondary membrane processing means.
The film of secondary membrane processing means uses polysulfones NF membrane, and secondary membrane processes out moisture two strands: two grades
Dense water is the phosphorous feed liquid after purification, and flow is 0.375t/h, two grades of fresh-water flow 0.375t/h, enters
Three grades of membrane treatment appts.
The film of three grades of membrane treatment appts uses cellulose acetate class reverse osmosis membrane, three grades of membrane treatment appts water outlets
Dividing two strands: three grades of membrane treatment appts concentrated stream amounts 0.125t/h, enter sodium chloride and reclaim liquid bath, three grades of salt are light
Water 0.25t/h returns one-level membrane treatment appts, for being diluted into the phosphorous feed liquid of one-level membrane treatment appts.
The course of conveying of described feed liquid uses booster pump to complete, and the operating pressure of described booster pump is
0～5MPa.
Detecting the phosphorous feed liquid after purifying and sodium chloride recovered liquid, result sees table 1.
The former water of phosphorous feed liquid and process testing result in table 1 embodiment of the present invention 1
| Name of material | Weight | Cl-Content | PO4 3-Content |
| Former water | 1000kg | 4.44% | 2.48% |
| NaCl recovered liquid | 625kg | 5.83% | 0.06% |
| Feed liquid after purification | 375kg | 2.12% | 6.51% |
As shown in Table 1, the response rate of the present embodiment phosphate radical is 98.5%, and the sodium chloride response rate is 82.07%.
Embodiment 2
Table 2 is the former water of phosphorous feed liquid and process testing result in the embodiment of the present invention 2.
Operation temperature chooses 26 DEG C, takes sodium dihydrogen phosphate feed liquid 1000kg regulating PH ≈ 4, enters wadding
Condensate subsider standing sedimentation, stands 2h, obtains supernatant.
Film pretreatment unit squeezed into by gained supernatant booster pump, obtains filtrate；Inlet pressure 0.25MPa,
Discharge 1t/h is produced in film pretreatment, and retaining precision is 0.02 micron.
The film of one-level membrane treatment appts uses polyamide-based NF membrane, the water inlet of one-level membrane treatment appts to have two strands:
Water 1t/h, three grades of salt fresh water return flow 0.3t/h, one-level film inlet pressure 1.4MPa are produced in film pretreatment；One
Level membrane treatment appts goes out moisture two strands: one-level fresh-water flow 0.5t/h, entrance sodium chloride reclaims liquid bath, one-level
Concentrated stream amount 0.8t/h, dense water enters secondary membrane processing means.
The film of secondary membrane processing means uses polyamide-based NF membrane, and secondary membrane processes out moisture two strands: two
The dense water of level is the phosphorous feed liquid after purification, and flow is 0.4t/h, two grades of fresh-water flow 0.4t/h, enters three
Level membrane treatment appts.
The film of three grades of membrane treatment appts uses polyamide-based reverse osmosis membrane, and three grades of membrane treatment appts go out moisture two
Stock: three grades of membrane treatment appts concentrated stream amounts 0.1t/h, enters sodium chloride and reclaims liquid bath, three grades of salt fresh water 0.3t/h
Return one-level membrane treatment appts, for being diluted into the phosphorous feed liquid of one-level membrane treatment appts.
The course of conveying of described feed liquid uses booster pump to complete, and the operating pressure of described booster pump is
0～5MPa.
The former water of phosphorous feed liquid and process testing result in table 2 embodiment of the present invention 2
| Name of material | Weight | Cl-Content | PO4 3-Content |
| Former water | 1000kg | 5.20% | 5.62% |
| NaCl recovered liquid | 600kg | 5.23% | 0.094% |
| Feed liquid after purification | 400kg | 5.16% | 13.91% |
As shown in Table 2, the response rate of the present embodiment phosphate radical is 99%, and the sodium chloride response rate is 60.35%.
Embodiment 3
Table 3 is the former water of phosphorous feed liquid and process testing result in the embodiment of the present invention 3.
Operation temperature chooses 26 DEG C, takes potassium phosphate feed liquid 1000kg regulating PH ≈ 11, enters flocculate
Subsider standing sedimentation, stands 5h, obtains supernatant.
Film pretreatment unit squeezed into by gained supernatant booster pump, obtains filtrate；It is 0.02 micro-for retaining precision
Rice, inlet pressure 0.3MPa, discharge 1t/h is produced in film pretreatment.
The film of one-level membrane treatment appts uses cellulose acetate class NF membrane, the water inlet of one-level membrane treatment appts to have
Two strands: water 1t/h, three grades of salt fresh water return flow 0.25t/h, one-level film inlet pressure are produced in film pretreatment
1.8MPa；One-level membrane treatment appts goes out moisture two strands: one-level fresh-water flow 0.5t/h, entrance potassium chloride reclaims
Liquid bath, one-level concentrated stream amount 0.75t/h, dense water enters secondary membrane processing means.
The film of secondary membrane processing means uses polysulfones NF membrane, and secondary membrane processes out moisture two strands: two grades
Dense water is the phosphorous feed liquid after purification, and flow is 0.375t/h, two grades of fresh-water flow 0.375t/h, enters
Three grades of membrane treatment appts.
The film of three grades of membrane treatment appts uses inorganic reverse osmosis membrane, and three grades of membrane treatment appts go out moisture two strands:
Three grades of membrane treatment appts concentrated stream amounts 0.125t/h, enter potassium chloride and reclaim liquid bath, three grades of salt fresh water 0.25t/h
Return one-level membrane treatment appts, for being diluted into the phosphorous feed liquid of one-level membrane treatment appts.
The course of conveying of described feed liquid uses booster pump to complete, and the operating pressure of described booster pump is
0～5MPa.
The former water of phosphorous feed liquid and process testing result in table 3 embodiment of the present invention 3
| Name of material | Weight | Cl-Content | PO4 3-Content |
| Former water | 1000kg | 6.73% | 7.68% |
| KCl recovered liquid | 625kg | 9.71% | 0.12% |
| Feed liquid after purification | 375kg | 1.76% | 20.27% |
As shown in Table 3, the response rate of the present embodiment phosphate radical is 99%, and the potassium chloride response rate is 90.17%.
Embodiment 4
Table 4 is the former water of phosphorous feed liquid and process testing result in the embodiment of the present invention 4.
Operation temperature chooses 26 DEG C, takes Diammonium phosphate (DAP) feed liquid 1000kg regulating PH ≈ 8, enters flocculation
Thing subsider standing sedimentation, stands 4h, obtains supernatant.
Film pretreatment unit squeezed into by gained supernatant booster pump, obtains filtrate；It is 0.02 micro-for retaining precision
Rice, inlet pressure 0.40MPa, discharge 1t/h is produced in film pretreatment.
The film of one-level membrane treatment appts uses Inorganic Nanofiltration Membranes, the water inlet of one-level membrane treatment appts to have two strands: film
Water 1t/h, three grades of salt fresh water return flow 0.2t/h, one-level film inlet pressure 1.6MPa are produced in pretreatment；One-level
Membrane treatment appts goes out moisture two strands: one-level fresh-water flow 0.25t/h, enters ammonia nitrogen recovery liquid bath, one-level
Concentrated stream amount 0.95t/h, dense water enters secondary membrane processing means,
The film of secondary membrane processing means uses Inorganic Nanofiltration Membranes, and it is dense that secondary membrane processes out moisture two strands: two grades
Water is the phosphorous feed liquid after purification, and flow is 0.6t/h, two grades of fresh-water flow 0.35t/h, enters three grades of films
Processing means.
The film of three grades of membrane treatment appts uses polysulfones reverse osmosis membrane, and three grades of membrane treatment appts go out moisture two strands:
Three grades of membrane treatment appts concentrated stream amounts 0.15t/h, enter ammonia nitrogen recovery liquid bath, three grades of salt fresh water 0.2t/h
Return one-level membrane treatment appts, for being diluted into the phosphorous feed liquid of one-level membrane treatment appts.
The course of conveying of described feed liquid uses booster pump to complete, and the operating pressure of described booster pump is
0～5MPa.
The former water of phosphorous feed liquid and process testing result in table 4 embodiment of the present invention 4
| Name of material | Weight | Cl-Content | PO4 3-Content |
| Former water | 1000kg | 8.46% | 12.3% |
| NH4Cl recovered liquid | 400kg | 15.74% | 0.198% |
| Feed liquid after purification | 600kg | 3.61% | 20.37% |
As shown in Table 4, the response rate of the present embodiment phosphate radical is 99%, and ammonia nitrogen recovery rate is 74.4%.
Embodiment 5
Table 5 is the former water of phosphorous feed liquid and process testing result in the embodiment of the present invention 5.
Operation temperature chooses 26 DEG C, the glyphosate mother solution 1000kg after deep oxidation of learning from else's experience process, and will
PH is adjusted to about 2, enters flocculate subsider standing sedimentation, stands 9h, obtains supernatant.
Film pretreatment unit squeezed into by gained supernatant booster pump, obtains filtrate；It is 0.02 micro-for retaining precision
Rice, inlet pressure 0.4MPa, discharge 1t/h is produced in film pretreatment.
The film of one-level membrane treatment appts uses polyamide-based NF membrane, the water inlet of one-level membrane treatment appts to have two strands:
Water 1t/h, three grades of salt fresh water return flow 0.5t/h, one-level film inlet pressure 1.9MPa are produced in film pretreatment；One
Level membrane treatment appts goes out moisture two strands: one-level fresh-water flow 0.5t/h, entrance sodium chloride reclaims liquid bath, one-level
Concentrated stream amount 1.0t/h, dense water enters secondary membrane processing means.
The film of secondary membrane processing means uses cellulose acetate class NF membrane, and secondary membrane processes out moisture two strands:
Two grades of dense water are the phosphorous feed liquid after purification, and flow is 0.3t/h, two grades of fresh-water flow 0.7t/h, enter
Three grades of membrane treatment appts.
The film of three grades of membrane treatment appts uses polyamide-based reverse osmosis membrane, and three grades of membrane treatment appts go out moisture two
Stock: three grades of membrane treatment appts concentrated stream amounts 0.2t/h, enters sodium chloride and reclaims liquid bath, three grades of salt fresh water 0.5t/h
Return one-level membrane treatment appts, for being diluted into the phosphorous feed liquid of one-level membrane treatment appts.
The course of conveying of described feed liquid uses booster pump to complete, and the operating pressure of described booster pump is
0～5MPa.
The former water of phosphorous feed liquid and process testing result in table 5 embodiment of the present invention 5
| Name of material | Weight | Cl-Content | PO4 3-Content |
| Former water | 1000kg | 9.0% | 7.0% |
| NaCl recovered liquid | 700kg | 12.34% | 0.12% |
| Feed liquid after purification | 300kg | 1.20% | 23.05% |
As shown in Table 5, the response rate of the present embodiment phosphate radical is 98%, and the sodium chloride response rate is 95.98%.
Embodiment 6
Table 6 is the former water of phosphorous feed liquid and process testing result in the embodiment of the present invention 6.
Operation temperature chooses 26 DEG C, takes disodium hydrogen phosphate feed liquid 1000kg regulating PH ≈ 9, enters wadding
Condensate subsider standing sedimentation, stands 3h, obtains supernatant.
Film pretreatment unit squeezed into by gained supernatant booster pump, obtains filtrate；It is 0.02 micro-for retaining precision
Rice, inlet pressure 0.25MPa, discharge 1t/h is produced in film pretreatment.
The film of one-level membrane treatment appts uses cellulose acetate class NF membrane, the water inlet of one-level membrane treatment appts to have
Two strands: water 1t/h, three grades of salt fresh water return flow 0.2t/h, one-level film inlet pressure 1.2MPa are produced in film pretreatment；
One-level membrane treatment appts goes out moisture two strands: one-level fresh-water flow 0.4t/h, enters sodium chloride and reclaims liquid bath, and one
Level concentrated stream amount 0.8t/h, dense water enters secondary membrane processing means.
The film of secondary membrane processing means uses polyamide-based NF membrane, and secondary membrane processes out moisture two strands: two
The dense water of level is the phosphorous feed liquid after purification, and flow is 0.5t/h, two grades of fresh-water flow 0.3t/h, enters three
Level membrane treatment appts.
The film of three grades of membrane treatment appts uses Inorganic Nanofiltration Membranes, and three grades of membrane treatment appts go out moisture two strands: three
Level membrane treatment appts concentrated stream amount 0.1t/h, enters sodium chloride and reclaims liquid bath, and three grades of salt fresh water 0.2t/h return
One-level membrane treatment appts, for being diluted into the phosphorous feed liquid of one-level membrane treatment appts.
The course of conveying of described feed liquid uses booster pump to complete, and the operating pressure of described booster pump is
0～5MPa.
The former water of phosphorous feed liquid and process testing result in table 6 embodiment of the present invention 6
| Name of material | Weight | Cl-Content | PO4 3-Content |
| Former water | 1000kg | 5.21% | 7.53% |
| NaCl recovered liquid | 500kg | 6.65% | 0.15% |
| Feed liquid after purification | 500kg | 3.77% | 14.91% |
As shown in Table 6, the response rate of the present embodiment phosphate radical is 99%, and the sodium chloride response rate is 63.82%.
As seen from the above embodiment, phosphorous feed liquid entrance flocculate sedimentation device carries out standing sedimentation；Sedimentation
Device supernatant enters defecator and filters, and removes the impurity such as float, colloid in phosphorous feed liquid,
Filtrate then enters one-level membrane treatment appts；One-level membrane treatment appts goes out moisture two strands, and fresh water is that sodium chloride is molten
Liquid, dense water is the mixture of phosphate and sodium chloride, and one-level fresh water can enter sodium chloride and reclaim liquid bath, and
The dense water of one-level enters secondary membrane processing means；It is to reach that secondary membrane processing means goes out two strands: two grades of dense water of moisture
To purifying the phosphorous feed liquid after the process required, it is the final products that need of the application, phosphorous material can be entered
Liquid accumulator tank, and two grades of fresh water is the mixture of phosphate and sodium chloride, phosphate content is the lowest, mainly
It is sodium chloride composition, enters three grades of membrane treatment appts；Three grades of membrane treatment appts go out moisture two strands, and three grades light
Water is the sodium chloride solution containing lower content, returns to one-level membrane treatment appts, and three grades of dense water are phosphate
With the mixture of sodium chloride, phosphate content is the lowest, mainly sodium chloride composition, can enter sodium chloride and return
Liquidceiver.
The implementation process of the present invention completes under liquid environment, is processed by one, two, three film, permissible
Realize efficiently separating of phosphate radical, orthophosphite ions and chloride ion in phosphate feed liquid, improve phosphorus
Accumulation rate and effective rate of utilization, the inorganic salt in the most phosphorous feed liquid is recycled.Wherein phosphate radical
The response rate can reach more than 98%, the response rate of sodium chloride is also more than 60%.
Additionally, present invention reduces energy resource consumption, reduce toxic and harmful and produce.
Claims (10)
1. a processing method for phosphorous feed liquid, including:
Phosphorous feed liquid, described phosphorous feed liquid is provided to comprise acid ion and the chloride ion of phosphorus；
By described phosphorous feed liquid standing sedimentation, obtain supernatant；
Described supernatant, through filtering, obtains filtrate；
Described filtrate, through one-level membrane treatment appts, obtains the dense water of one-level；
The dense water of described one-level is through secondary membrane processing means, the phosphorous feed liquid after being processed and two grades of fresh water；
Described two grades of fresh water, through three grades of membrane treatment appts, obtain three grades of fresh water；Described three grades of fresh water return described
One-level membrane treatment appts；
The film that described one-level, two grades and three grades of membrane treatment appts are used is independently selected from NF membrane or reverse osmosis
Permeable membrane.
Processing method the most according to claim 1, it is characterised in that at described firsts and seconds film
The film that reason device is used is NF membrane.
Processing method the most according to claim 1, it is characterised in that described three grades of membrane treatment appts
The film used is reverse osmosis membrane.
4. according to the processing method according to any one of claims 1 to 3, it is characterised in that described nanofiltration
Film is any one in polyamide-based film, polysulfones film, cellulose acetate class film and inoranic membrane.
5. according to the processing method according to any one of claims 1 to 3, it is characterised in that described reverse osmosis
Permeable membrane is polyamide-based film or cellulose acetate class film.
Processing method the most according to claim 1, it is characterised in that at described firsts and seconds film
The operation temperature of reason device independently be 0～80 DEG C, and operation pressure independently be 1～5MPa.
Processing method the most according to claim 1, it is characterised in that described three grades of membrane treatment appts
Operation temperature be 20～60 DEG C, operation pressure be 2～4MPa.
Processing method the most according to claim 1, it is characterised in that described filtration uses film to locate in advance
Reason device is carried out, and the precision that retains of the film that described film pretreatment unit is used is 0.02 micron.
Processing method the most according to claim 1, it is characterised in that before carrying out standing sedimentation,
Also include: to described phosphorous feed adjustment pH value.
10. a processing system for phosphorous feed liquid, including:
It is provided with import and the flocculate sedimentation device of supernatant outlet, comprises the acid ion of phosphorus for sedimentation
Phosphorous feed liquid with chloride ion；
The defecator communicated is exported with described flocculate sedimentation device supernatant；
One-level, two grades and the three grades of membrane treatment appts being sequentially communicated with described defecator；
Described secondary membrane processing means is provided with process water out；Described three grades of membrane treatment appts are provided with fresh water and go out
Mouthful, and it communicates with described one-level membrane treatment appts；
The film that described one-level, two grades and three grades of membrane treatment appts are used is independently selected from NF membrane or reverse osmosis
Permeable membrane.
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| CN106939589A (en) * | 2017-05-05 | 2017-07-11 | 暨南大学 | Water hyacinth is salvaged and handling process |
| CN108314269A (en) * | 2018-04-04 | 2018-07-24 | 湖北君集水处理有限公司 | A kind of system and method for macropore denitrogenation acid-basic regenerated waste liquids in water processing and reuse |
| CN111646546A (en) * | 2020-06-16 | 2020-09-11 | 包头稀土研究院 | Treatment method and application of mixed rare earth alkaline wastewater |
| CN113321269A (en) * | 2021-06-01 | 2021-08-31 | 中国科学院过程工程研究所 | Method for effectively separating organic matters in high-salinity wastewater |
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