CN105858928B - A kind of processing method and system of phosphorous feed liquid - Google Patents
A kind of processing method and system of phosphorous feed liquid Download PDFInfo
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- CN105858928B CN105858928B CN201510031885.6A CN201510031885A CN105858928B CN 105858928 B CN105858928 B CN 105858928B CN 201510031885 A CN201510031885 A CN 201510031885A CN 105858928 B CN105858928 B CN 105858928B
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Abstract
The embodiment of the invention discloses the processing methods and system of a kind of phosphorous feed liquid, chloride ion can be separated from phosphorous feed liquid, improve the accumulation rate and effective rate of utilization of phosphorus.The method comprise the steps that phosphorous feed liquid elder generation standing sedimentation is obtained supernatant and bottom liquid；Supernatant liquid filtering obtains filtrate and filter residue；Filtrate passes through level-one membrane treatment appts, obtains level-one fresh water and level-one concentrated water；Level-one fresh water is recycled, inorganic salts are extracted；Level-one concentrated water passes through second level membrane treatment appts, obtains second level concentrated water and second level fresh water；Second level concentrated water is recycled, phosphorus-containing compound is extracted；Second level fresh water obtains three-level fresh water and three-level concentrated water by three-level membrane treatment appts；Three-level fresh water returns to level-one membrane treatment appts, and inorganic salts are extracted in the recycling of three-level concentrated water.The embodiment of the present invention can separate chloride ion from phosphorous feed liquid, improve the accumulation rate and effective rate of utilization of phosphorus.
Description
Technical field
The present invention relates to chemical field more particularly to a kind of processing methods and system of phosphorous feed liquid.
Background technique
Phosphor resource is a kind of non-renewable resources of preciousness, how more scientifically and rationally to utilize phosphor resource, improves phosphorus money
The utilization rate in source is always the tireless pursuit of domestic and international expert.Series of phosphate product is the important product of phosphorus chemical industry
One of, production, the life of various phosphorus chemical products and people are closely bound up.In phosphatic commercial process, often
It has a large amount of high-content phosphorus hydrochlorate feed liquid to generate, in these feed liquids because with the presence of a large amount of chloride ion impurities, limits this portion
The use of phosphate feed liquid is divided not only to cause the serious waste of phosphor resource to generate a large amount of high P content waste water, but also
Very big pressure is caused to environment.
China is pesticide producing big country, and pesticide yield occupies very big specific gravity in world pesticide yield, and phosphorous pesticide
It is a major class of pesticide, in the production process of phosphorous pesticide, a large amount of high-content phosphorus-containing wastewater can be generated.The prior art for
The phosphorous waste material of 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 realize phosphorus in phosphorous agricultural chemicals waste water
Acid ion and chloride ion efficiently separate, and are unfavorable for improving the utilization rate of phosphor resource.
Summary of the invention
It, can be by chloride ion from phosphorous in view of this, the present invention provides the processing method and system of a kind of phosphorous feed liquid
It is separated in feed liquid, improves the accumulation rate and effective rate of utilization of phosphorus.
The present invention provides a kind of processing method of phosphorous feed liquid, it may include:
By phosphorous feed liquid elder generation standing sedimentation, supernatant and bottom liquid are obtained；
Supernatant liquid filtering obtains filtrate and filter residue；
Filtrate passes through level-one membrane treatment appts, obtains level-one fresh water and level-one concentrated water；
Level-one fresh water is recycled, inorganic salts are extracted；
Level-one concentrated water passes through second level membrane treatment appts, obtains second level concentrated water and second level fresh water；
Second level concentrated water is recycled, phosphorus-containing compound is extracted；
Second level fresh water obtains three-level fresh water and three-level concentrated water by three-level membrane treatment appts；
Three-level fresh water returns to level-one membrane treatment appts, and inorganic salts are extracted in the recycling of three-level concentrated water.
Preferably, film used in firsts and seconds membrane treatment appts is nanofiltration membrane.
Preferably, film used in three-level membrane treatment appts is reverse osmosis membrane.
Preferably, nanofiltration membrane is any one in polyamide-based film, polysulfones film, cellulose acetate class film and inoranic membrane
Kind.
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 is 0~80 DEG C, and operating pressure independently is
1~5MPa.
Preferably, the operation temperature of three-level membrane treatment appts is 20~60 DEG C, and operating pressure is 2~4MPa.
Preferably, filtering is carried out using film pretreatment unit, the retention precision of film used in the film pretreatment unit
It is 0.02 micron.
Preferably, before carrying out standing sedimentation, further includes: adjust pH value to the phosphorous feed liquid.
The present invention also provides a kind of processing systems of phosphorous feed liquid, comprising:
Flocculate sedimentation device equipped with import and supernatant outlet, for settling acid ion and chloride ion comprising phosphorus
Phosphorous feed liquid；
The filter device communicated with the flocculate sedimentation device supernatant outlet；
Level-one, second level and the three-level membrane treatment appts being sequentially communicated with the filter device；
The second level membrane treatment appts are equipped with processing water out；The three-level membrane treatment appts are equipped with water outlet, and its
It is communicated with the level-one membrane treatment appts；
Film used in the level-one, second level and three-level membrane treatment appts is independently selected from nanofiltration membrane or reverse osmosis membrane.
As can be seen from the above technical solutions, phosphorous feed liquid provided in an embodiment of the present invention enter flocculate sedimentation device into
Row standing sedimentation；Sedimentation device supernatant enters filter device and is filtered, and it is miscellaneous to remove suspended matter, colloid etc. in phosphorous feed liquid
Matter, filtrate then enter level-one membrane treatment appts；Level-one membrane treatment appts go out two strands of moisture, and fresh water is sodium chloride solution, and concentrated water is
The mixture of phosphate and sodium chloride, level-one fresh water can enter sodium chloride and recycle liquid bath, and level-one concentrated water enters second level film process
Device；The water outlet of second level membrane treatment appts be divided to two strands: second level concentrated water is to reach purification requirement treated phosphorous feed liquid, is this Shen
The final products that please be needed can enter phosphorous feed liquid accumulator tank, and second level fresh water is the mixture of phosphate and sodium chloride, phosphoric acid
Salt content is very low, mainly sodium chloride composition, into three-level membrane treatment appts；Three-level membrane treatment appts go out two strands of moisture, three-level
Fresh water is the sodium chloride solution containing lower content, returns to level-one membrane treatment appts, three-level concentrated water is phosphate and sodium chloride
Mixture, phosphate content is very low, mainly sodium chloride composition, can enter sodium chloride and recycle liquid bath.Implementation process of the invention
It is completed under liquid environment, by one, two, three film process, phosphate radical, orthophosphite ions in phosphate feed liquid may be implemented
With efficiently separating for chloride ion, the accumulation rate and effective rate of utilization of phosphorus are improved, while the inorganic salts in phosphorous feed liquid are returned
It receives and utilizes.In addition, reducing toxic and harmful gas present invention reduces energy consumption and generating.
Detailed description of the invention
Fig. 1 is the flow diagram of the processing method of phosphorous feed liquid in the embodiment of the present invention.
Specific embodiment
The embodiment of the invention provides the processing methods of phosphorous feed liquid to mention for separating chloride ion from phosphorous feed liquid
The accumulation rate and effective rate of utilization of high phosphorus.It is described in detail below.
The present invention provides a kind of processing methods of phosphorous feed liquid, comprising:
Phosphorous feed liquid is provided, the phosphorous feed liquid includes the acid ion and chloride ion of phosphorus；
By the phosphorous feed liquid standing sedimentation, supernatant is obtained；
The supernatant is filtered, and filtrate is obtained；
The filtrate passes through level-one membrane treatment appts, obtains level-one concentrated water；
The level-one concentrated water passes through second level membrane treatment appts, obtain that treated phosphorous feed liquid and second level fresh water；Described two
Grade fresh water passes through three-level membrane treatment appts, obtains three-level fresh water；The three-level fresh water returns to the level-one membrane treatment appts；
Film used in the level-one, second level and three-level membrane treatment appts is independently selected from nanofiltration membrane or reverse osmosis membrane.
Phosphorous feed liquid after process through the invention, may be implemented phosphate radical in phosphate feed liquid, orthophosphite from
Son is efficiently separated with chloride ion, and according to specific requirements, it is pure to can achieve different separation by the different technic index of control
Degree realizes the recycling purification of phosphorous material.
Referring to Fig. 1, Fig. 1 is the flow diagram 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 to be handled, and the phosphorous feed liquid includes the acid ion and chloride ion of phosphorus.
Phosphorous feed liquid of the present invention can be phosphate waste, phosphate therein such as sodium ascorbyl phosphate, ammonium phosphate salt, phosphorus
Acid potassium salt etc.；It is also possible to different phosphorous agricultural chemicals waste waters.The phosphate can be monovalence, divalent, trivalent, tetravalence, pentavalent
Salt, that is to say, that the acid ion of phosphorus has phosphate radical and orthophosphite etc..In an embodiment of the present invention, the phosphorous feed liquid
The total mass concentration of middle phosphate radical and orthophosphite is 0.1~20%, preferably 0.1~10%, more preferable 2~7%.It is described phosphorous
Chloride ion content can be 0.1~15%, preferably 2~10% in feed liquid.In addition, containing small-molecular-weight in the phosphorous feed liquid
Organic substance or no organic matter, the organic matter do not influence film process separating effect.
Preferably, the phosphorous feed liquid of the embodiment of the present application is introduced into pH regulating tank, pH value is adjusted.In the present invention, adjustable
Phosphorous material liquid pH value is saved to 2~13, preferably 7~13.The adjusting pH value is technological means well known to those skilled in the art, can
With with NaOH and H2SO4Or HCl etc. is adjusted.
Then, regulate pH value phosphorous feed liquid can enter flocculate subsider carry out standing sedimentation, obtain supernatant and
Bottom liquid.The present invention is not particularly limited the standing sedimentation；The time of standing is preferably 1~6 hour, and more preferably 2~4 is small
When.
Film pretreatment unit is preferably entered by the supernatant that subsider obtains to be filtered, and is removed and is suspended in phosphorous feed liquid
The impurity such as object, colloid obtain filtrate, i.e. pretreatment feed liquid.In a preferred embodiment of the invention, film pretreatment unit is used
Film can be ultrafiltration membrane, retention precision is preferably 0.02 micron；The ultrafiltration membrane can be organic film, and such as polysulfones film gathers
Olefines film and fluorinated film etc., are also possible to inoranic membrane, such as ceramic membrane, glass-film and metal film.Wherein, the organic film is excellent
It is selected as polyolefins film, acid and alkali-resistance and various organic solvents, and mechanical strength and chemical-resistance are good；The inoranic membrane is preferably
Metal film.In addition, the present invention is not particularly limited the other conditions of the filtering.
In one embodiment of the invention, film pretreatment unit produces water flow 1t/h.Obtained pretreatment feed liquid one
Dividing can return to flocculate subsider, continue circular treatment subsequently into film pretreatment unit, dilute the dense of former phosphorous feed liquid
Degree；Another part then enters level-one membrane treatment appts, and level-one concentrated water and level-one fresh water can be obtained.In one embodiment of the present of invention
In, the ratio for returning to the pretreatment feed liquid that flocculate subsider is recycled is 20~90%.
In the present invention, the film of level-one membrane treatment appts uses nanofiltration membrane or reverse osmosis membrane, preferably nanofiltration membrane, main real
The separation of chloride ion in existing phosphate feed liquid.If polyamide-based film, polysulfones film, cellulose acetate can be used using nanofiltration membrane
Class film or inoranic membrane are, it is preferable to use polyamide-based film；According to reverse osmosis membrane, then polyamide-based film or cellulose acetate class can be used
Film, preferably with polyamide-based film.The operation temperature of level-one membrane treatment appts can arbitrarily be chosen between 0~80 DEG C, preferably
20 DEG C~50 DEG C；Operating pressure can arbitrarily be chosen between 1~5MPa, preferably 2~4MPa.
Level-one membrane treatment appts go out two strands of moisture, and fresh water (level-one fresh water) is sodium chloride solution, and concentrated water (level-one concentrated water) is
The mixture of phosphate and sodium chloride；Level-one fresh water enters sodium chloride recycling liquid bath, can recycle sodium chloride by concentration method.And it obtains
To level-one concentrated water enter second level membrane treatment appts, obtain that treated phosphorous feed liquid and second level fresh water.
In the present invention, the film of second level membrane treatment appts uses nanofiltration membrane or reverse osmosis membrane, preferred nanofiltration membrane, mainly into
One step realizes the separation of chloride ion in phosphate feed liquid.If polyamide-based film, polysulfones film, acetic acid can be used using nanofiltration membrane
Cellulose family film or inoranic membrane are, it is preferable to use polyamide-based film；According to reverse osmosis membrane, then it can be used polyamide-based film or acetic acid fine
Plain class film is tieed up, preferably with polyamide-based film.The operation temperature of second level membrane treatment appts can arbitrarily be chosen between 0~80 DEG C,
Preferably 20 DEG C~50 DEG C；Operating pressure can arbitrarily be chosen between 1~5MPa, preferably 2~4MPa.
The water outlet of second level membrane treatment appts be divided to two strands: second level concentrated water is to reach the phosphorous feed liquid of purification requirement, is our needs
Final products, into phosphorous feed liquid accumulator tank, recycling storage, changing concentration as needed；Second level fresh water is phosphate and chlorine
Change the mixture of sodium, phosphate content is very low, mainly sodium chloride composition, into three-level membrane treatment appts.
The film of three-level membrane treatment appts uses nanofiltration membrane or reverse osmosis membrane, it is preferred to use reverse osmosis membrane, it is main realize chlorine from
Enrichment concentration of son etc..If polyamide-based film, polysulfones film, cellulose acetate class film or inoranic membrane can be used using nanofiltration membrane,
It is preferable to use polyamide-based films；According to reverse osmosis membrane, then polyamide-based film or cellulose acetate class film can be used, preferably use polyamides
Amine film.The operation temperature of three-level membrane treatment appts can arbitrarily be chosen between 20~60 DEG C, and preferably 30 DEG C~50 DEG C；Behaviour
Making pressure can arbitrarily choose between 2~4MPa.
Three-level membrane treatment appts go out two strands of moisture, and three-level (salt) fresh water is the sodium chloride solution containing lower content, return to
Level-one membrane treatment appts, three-level (salt) concentrated water are the mixtures of phosphate and sodium chloride, and phosphate content is very low, mainly chlorination
Sodium ingredient recycles liquid bath into sodium chloride, can recycle sodium chloride by concentration method.In embodiments of the present invention, level-one is returned to
The ratio of the three-level fresh water of membrane treatment appts is 20~50%.
In the present invention, booster pump completion can be used in the transmission process of the feed liquid.The operating pressure of the booster pump is excellent
It is selected as 0~5MPa, more preferably 0.8MPa~2MPa.The film of membrane treatment appts at different levels uses commercial membrane product commonly used in the art
?；The operation temperature of membrane treatment appts at different levels is controlled primarily to guaranteeing the functional of film used, generally selects room temperature.
The phosphorous feed liquid is after present invention process is handled, the rate of recovery > 98% of phosphate radical, orthophosphite；Chloride ion returns
Chloride ion removal rate can achieve 50%~95% in yield, that is, phosphorous feed liquid.In addition, inventive film isolation technics also has into
Sheet is low, can be continuously produced the advantages that good with byproduct salt quality.
The present invention also provides a kind of processing systems of phosphorous feed liquid, comprising:
Flocculate sedimentation device equipped with import and supernatant outlet, for settling acid ion and chloride ion comprising phosphorus
Phosphorous feed liquid；
The filter device communicated with the flocculate sedimentation device supernatant outlet；
Level-one, second level and the three-level membrane treatment appts being sequentially communicated with the filter device；
The second level membrane treatment appts are equipped with processing water out；The three-level membrane treatment appts are equipped with water outlet, and its
It is communicated with the level-one membrane treatment appts；
Film used in the level-one, second level and three-level membrane treatment appts is independently selected from nanofiltration membrane or reverse osmosis membrane.
It is also preferable to include pH regulating tanks for processing system of the present invention, can use NaOH and H2SO4Or HCl adjusts phosphorous feed liquid
PH value to 2~13, preferably 7~13.
Processing system of the present invention includes being connected with pH regulating tank, is settled equipped with the flocculate of import and supernatant outlet
Device includes the acid ion of phosphorus and the phosphorous feed liquid of chloride ion for settling.The present invention is to flocculate sedimentation device without spy
Different limitation, such as can be used flocculate subsider well known to those skilled in the art.
Processing system of the present invention includes the filter device communicated with the flocculate sedimentation device supernatant outlet, is used
The impurity such as suspended matter, colloid in the phosphorous feed liquid of removal.In a preferred embodiment of the invention, filter device is film pretreatment dress
It sets；The retention precision of used film is preferably 0.02 micron.
Processing system of the present invention includes the level-one being sequentially communicated with the filter device, second level and three-level film process dress
It sets, film used in the level-one, second level and three-level membrane treatment appts is independently selected from nanofiltration membrane or reverse osmosis membrane；Film process dress
The content for the film set is consistent with content described above, and details are not described herein.
The second level membrane treatment appts are equipped with processing water out；The three-level membrane treatment appts are equipped with water outlet, and its
It is communicated with the level-one membrane treatment appts.The specific process flow of the embodiment of the present application membrane treatment appts is as follows:
Level-one membrane treatment appts are used for initial gross separation sodium chloride solution and phosphate, and two strands of moisture, fresh water are sodium chloride out
Solution, concentrated water are the mixtures of phosphate and sodium chloride；
Concentrated water enters second level membrane treatment appts through interface channel；
Second level membrane treatment appts further Isolating chlorinated sodium solution and phosphate, two strands of moisture out: second level concentrated water is to reach
Desired phosphorous feed liquid is purified, is the final products that we need, into phosphorous feed liquid accumulator tank, recycling is stored, as needed
Changing concentration；Second level fresh water is the mixture of phosphate and sodium chloride, and phosphate content is very low, mainly sodium chloride composition；
Second level fresh water enters three-level membrane treatment appts through interface channel；
Further Isolating chlorinated sodium solution and phosphate, three-level membrane treatment appts go out two strands of moisture to three-level membrane treatment appts,
Three-level salt fresh water is the sodium chloride solution containing lower content, return to level-one membrane treatment appts, three-level salt concentrated water be phosphate and
The mixture of sodium chloride, phosphate content is very low, mainly sodium chloride composition, recycles liquid bath, concentration method recycling into sodium chloride
Sodium chloride.
Embodiment 1
Table 1 is phosphorous feed liquid raw water and processing detection result in the embodiment of the present invention 1.
Operation temperature chooses 26 DEG C, the tertiary sodium phosphate feed liquid or waste liquid 1000kg for regulating PH ≈ 10 is taken, into flocculate
Subsider standing sedimentation stands 4h, obtains supernatant.
Gained supernatant squeezes into film pretreatment unit with booster pump, obtains filtrate；Inlet pressure 0.25MPa, film pretreatment
Water flow 1t/h is produced, retention precision is 0.02 micron.
The film of level-one membrane treatment appts uses polyamide-based nanofiltration membrane, and the water inlet of level-one membrane treatment appts has two strands: film is located in advance
Reason produces water 1t/h, three-level salt fresh water return flow 0.25t/h, level-one film inlet pressure 1.6MPa；The water outlet of level-one membrane treatment appts
It is divided to two strands: level-one fresh-water flow 0.5t/h, recycles liquid bath, level-one concentrated water flow 0.75t/h into sodium chloride, concentrated water enters second level
Membrane treatment appts.
The film of second level membrane treatment appts uses polysulfones nanofiltration membrane, and the water outlet of second level film process is divided to two strands: second level concentrated water is
Phosphorous feed liquid after purification, flow 0.375t/h, second level fresh-water flow 0.375t/h, into three-level membrane treatment appts.
The film of three-level membrane treatment appts uses cellulose acetate class reverse osmosis membrane, and three-level membrane treatment appts go out two strands of moisture:
Three-level membrane treatment appts concentrated water flow 0.125t/h recycles liquid bath into sodium chloride, and three-level salt fresh water 0.25t/h returns to level-one film
Processing unit, for being diluted into the phosphorous feed liquid of level-one membrane treatment appts.
The transmission process of the feed liquid is completed using booster pump, and the operating pressure of the booster pump is 0~5MPa.
To after purification phosphorous feed liquid and sodium chloride recovered liquid detect, as a result referring to table 1.
Phosphorous feed liquid raw water and processing detection result in 1 embodiment of the present invention 1 of table
| Name of material | Weight | Cl-Content | PO4 3-Content |
| Raw 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 rate of recovery of the present embodiment phosphate radical is 98.5%, and the sodium chloride rate of recovery is 82.07%.
Embodiment 2
Table 2 is phosphorous feed liquid raw water and processing detection result in the embodiment of the present invention 2.
Operation temperature chooses 26 DEG C, the sodium dihydrogen phosphate feed liquid 1000kg for regulating PH ≈ 4 is taken, into flocculate subsider
Standing sedimentation stands 2h, obtains supernatant.
Gained supernatant squeezes into film pretreatment unit with booster pump, obtains filtrate；Inlet pressure 0.25MPa, film pretreatment
Water flow 1t/h is produced, retention precision is 0.02 micron.
The film of level-one membrane treatment appts uses polyamide-based nanofiltration membrane, and the water inlet of level-one membrane treatment appts has two strands: film is located in advance
Reason produces water 1t/h, three-level salt fresh water return flow 0.3t/h, level-one film inlet pressure 1.4MPa；Level-one membrane treatment appts go out moisture
Two strands: level-one fresh-water flow 0.5t/h, liquid bath, level-one concentrated water flow 0.8t/h are recycled into sodium chloride, concentrated water enters secondary membrane
Processing unit.
The film of second level membrane treatment appts uses polyamide-based nanofiltration membrane, and the water outlet of second level film process is divided to two strands: second level concentrated water is i.e.
For the phosphorous feed liquid after purification, flow 0.4t/h, second level fresh-water flow 0.4t/h, into three-level membrane treatment appts.
The film of three-level membrane treatment appts uses polyamide-based reverse osmosis membrane, and three-level membrane treatment appts go out two strands of moisture: three-level
Membrane treatment appts concentrated water flow 0.1t/h recycles liquid bath into sodium chloride, and three-level salt fresh water 0.3t/h returns to level-one film process dress
It sets, for being diluted into the phosphorous feed liquid of level-one membrane treatment appts.
The transmission process of the feed liquid is completed using booster pump, and the operating pressure of the booster pump is 0~5MPa.
Phosphorous feed liquid raw water and processing detection result in 2 embodiment of the present invention 2 of table
| Name of material | Weight | Cl-Content | PO4 3-Content |
| Raw 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 rate of recovery of the present embodiment phosphate radical is 99%, and the sodium chloride rate of recovery is 60.35%.
Embodiment 3
Table 3 is phosphorous feed liquid raw water and processing detection result in the embodiment of the present invention 3.
Operation temperature chooses 26 DEG C, takes the potassium phosphate feed liquid 1000kg for regulating PH ≈ 11, quiet into flocculate subsider
Sedimentation is set, 5h is stood, obtains supernatant.
Gained supernatant squeezes into film pretreatment unit with booster pump, obtains filtrate；Retaining precision is 0.02 micron, inlet-pressure
Power 0.3MPa, film pretreatment produce water flow 1t/h.
The film of level-one membrane treatment appts uses cellulose acetate class nanofiltration membrane, and level-one membrane treatment appts, which are intake, two strands: film
Pretreatment produces water 1t/h, three-level salt fresh water return flow 0.25t/h, level-one film inlet pressure 1.8MPa；Level-one membrane treatment appts
Two strands of moisture out: level-one fresh-water flow 0.5t/h recycles liquid bath, level-one concentrated water flow 0.75t/h into potassium chloride, and concentrated water enters
Second level membrane treatment appts.
The film of second level membrane treatment appts uses polysulfones nanofiltration membrane, and the water outlet of second level film process is divided to two strands: second level concentrated water is
Phosphorous feed liquid after purification, flow 0.375t/h, second level fresh-water flow 0.375t/h, into three-level membrane treatment appts.
The film of three-level membrane treatment appts uses inorganic reverse osmosis membrane, and three-level membrane treatment appts go out two strands of moisture: at three-level film
Device concentrated water flow 0.125t/h is managed, recycles liquid bath into potassium chloride, three-level salt fresh water 0.25t/h returns to level-one film process dress
It sets, for being diluted into the phosphorous feed liquid of level-one membrane treatment appts.
The transmission process of the feed liquid is completed using booster pump, and the operating pressure of the booster pump is 0~5MPa.
Phosphorous feed liquid raw water and processing detection result in 3 embodiment of the present invention 3 of table
| Name of material | Weight | Cl-Content | PO4 3-Content |
| Raw 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 rate of recovery of the present embodiment phosphate radical is 99%, and the potassium chloride rate of recovery is 90.17%.
Embodiment 4
Table 4 is phosphorous feed liquid raw water and processing detection result in the embodiment of the present invention 4.
Operation temperature chooses 26 DEG C, takes the Diammonium phosphate (DAP) feed liquid 1000kg for regulating PH ≈ 8, quiet into flocculate subsider
Sedimentation is set, 4h is stood, obtains supernatant.
Gained supernatant squeezes into film pretreatment unit with booster pump, obtains filtrate；Retaining precision is 0.02 micron, inlet-pressure
Power 0.40MPa, film pretreatment produce water flow 1t/h.
The film of level-one membrane treatment appts uses Inorganic Nanofiltration Membranes, and the water inlet of level-one membrane treatment appts has two strands: film pretreatment produces
Water 1t/h, three-level salt fresh water return flow 0.2t/h, level-one film inlet pressure 1.6MPa；Level-one membrane treatment appts go out moisture two
Stock: level-one fresh-water flow 0.25t/h, into ammonia nitrogen recovery liquid bath, level-one concentrated water flow 0.95t/h, concentrated water enters secondary membrane
Processing unit,
The film of second level membrane treatment appts uses Inorganic Nanofiltration Membranes, and the water outlet of second level film process is divided to two strands: second level concentrated water is to mention
Phosphorous feed liquid after pure, flow 0.6t/h, second level fresh-water flow 0.35t/h, into three-level membrane treatment appts.
The film of three-level membrane treatment appts uses polysulfones reverse osmosis membrane, and three-level membrane treatment appts go out two strands of moisture: three-level film
Processing unit concentrated water flow 0.15t/h, into ammonia nitrogen recovery liquid bath, three-level salt fresh water 0.2t/h returns to level-one film process dress
It sets, for being diluted into the phosphorous feed liquid of level-one membrane treatment appts.
The transmission process of the feed liquid is completed using booster pump, and the operating pressure of the booster pump is 0~5MPa.
Phosphorous feed liquid raw water and processing detection result in 4 embodiment of the present invention 4 of table
| Name of material | Weight | Cl-Content | PO4 3-Content |
| Raw 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 rate of recovery of the present embodiment phosphate radical is 99%, and ammonia nitrogen recovery rate is 74.4%.
Embodiment 5
Table 5 is phosphorous feed liquid raw water and processing detection result in the embodiment of the present invention 5.
Operation temperature chooses 26 DEG C, takes the glyphosate mother solution 1000kg after depth oxidation processes, and PH is adjusted to 2
Left and right stands 9h, obtains supernatant into flocculate subsider standing sedimentation.
Gained supernatant squeezes into film pretreatment unit with booster pump, obtains filtrate；Retaining precision is 0.02 micron, inlet-pressure
Power 0.4MPa, film pretreatment produce water flow 1t/h.
The film of level-one membrane treatment appts uses polyamide-based nanofiltration membrane, and the water inlet of level-one membrane treatment appts has two strands: film is located in advance
Reason produces water 1t/h, three-level salt fresh water return flow 0.5t/h, level-one film inlet pressure 1.9MPa；Level-one membrane treatment appts go out moisture
Two strands: level-one fresh-water flow 0.5t/h, liquid bath, level-one concentrated water flow 1.0t/h are recycled into sodium chloride, concentrated water enters secondary membrane
Processing unit.
The film of second level membrane treatment appts uses cellulose acetate class nanofiltration membrane, and the water outlet of second level film process is divided to two strands: second level is dense
Water is the phosphorous feed liquid after purifying, flow 0.3t/h, second level fresh-water flow 0.7t/h, into three-level membrane treatment appts.
The film of three-level membrane treatment appts uses polyamide-based reverse osmosis membrane, and three-level membrane treatment appts go out two strands of moisture: three-level
Membrane treatment appts concentrated water flow 0.2t/h recycles liquid bath into sodium chloride, and three-level salt fresh water 0.5t/h returns to level-one film process dress
It sets, for being diluted into the phosphorous feed liquid of level-one membrane treatment appts.
The transmission process of the feed liquid is completed using booster pump, and the operating pressure of the booster pump is 0~5MPa.
Phosphorous feed liquid raw water and processing detection result in 5 embodiment of the present invention 5 of table
| Name of material | Weight | Cl-Content | PO4 3-Content |
| Raw 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 rate of recovery of the present embodiment phosphate radical is 98%, and the sodium chloride rate of recovery is 95.98%.
Embodiment 6
Table 6 is phosphorous feed liquid raw water and processing detection result in the embodiment of the present invention 6.
Operation temperature chooses 26 DEG C, the disodium hydrogen phosphate feed liquid 1000kg for regulating PH ≈ 9 is taken, into flocculate subsider
Standing sedimentation stands 3h, obtains supernatant.
Gained supernatant squeezes into film pretreatment unit with booster pump, obtains filtrate；Retaining precision is 0.02 micron, inlet-pressure
Power 0.25MPa, film pretreatment produce water flow 1t/h.
The film of level-one membrane treatment appts uses cellulose acetate class nanofiltration membrane, and level-one membrane treatment appts, which are intake, two strands: film
Pretreatment produces water 1t/h, three-level salt fresh water return flow 0.2t/h, level-one film inlet pressure 1.2MPa；Level-one membrane treatment appts go out
Two strands of moisture: level-one fresh-water flow 0.4t/h, liquid bath, level-one concentrated water flow 0.8t/h are recycled into sodium chloride, concentrated water enters two
Grade membrane treatment appts.
The film of second level membrane treatment appts uses polyamide-based nanofiltration membrane, and the water outlet of second level film process is divided to two strands: second level concentrated water is i.e.
For the phosphorous feed liquid after purification, flow 0.5t/h, second level fresh-water flow 0.3t/h, into three-level membrane treatment appts.
The film of three-level membrane treatment appts uses Inorganic Nanofiltration Membranes, and three-level membrane treatment appts go out two strands of moisture: three-level film process
Device concentrated water flow 0.1t/h recycles liquid bath into sodium chloride, and three-level salt fresh water 0.2t/h returns to level-one membrane treatment appts, is used for
It is diluted into the phosphorous feed liquid of level-one membrane treatment appts.
The transmission process of the feed liquid is completed using booster pump, and the operating pressure of the booster pump is 0~5MPa.
Phosphorous feed liquid raw water and processing detection result in 6 embodiment of the present invention 6 of table
| Name of material | Weight | Cl-Content | PO4 3-Content |
| Raw 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 rate of recovery of the present embodiment phosphate radical is 99%, and the sodium chloride rate of recovery is 63.82%.
As seen from the above embodiment, phosphorous feed liquid enters flocculate sedimentation device progress standing sedimentation；Sedimentation device supernatant
Liquid enters filter device and is filtered, and removes the impurity such as suspended matter, colloid in phosphorous feed liquid, and filtrate then enters level-one film process dress
It sets；Level-one membrane treatment appts go out two strands of moisture, and fresh water is sodium chloride solution, and concentrated water is the mixture of phosphate and sodium chloride, and one
Grade fresh water can enter sodium chloride and recycle liquid bath, and level-one concentrated water enters second level membrane treatment appts；The water outlet point of second level membrane treatment appts
Two strands: second level concentrated water is to reach purification to require treated phosphorous feed liquid, is the final products that the application needs, can enter and contain
Phosphorus feed liquid accumulator tank, and second level fresh water is the mixture of phosphate and sodium chloride, phosphate content is very low, mainly sodium chloride at
Point, into three-level membrane treatment appts；Three-level membrane treatment appts go out two strands of moisture, and three-level fresh water is that the sodium chloride containing lower content is molten
Liquid returns to level-one membrane treatment appts, and three-level concentrated water is the mixture of phosphate and sodium chloride, and phosphate content is very low, mainly
It is sodium chloride composition, sodium chloride can be entered and recycle liquid bath.
Implementation process of the invention is completed under liquid environment, and by one, two, three film process, phosphate may be implemented
Phosphate radical in feed liquid, orthophosphite ions and chloride ion efficiently separate, and improve the accumulation rate and effective rate of utilization of phosphorus, simultaneously
Inorganic salts in phosphorous feed liquid are recycled.Wherein the rate of recovery of phosphate radical can achieve 98% or more, and sodium chloride returns
Yield is also 60% or more.
In addition, reducing toxic and harmful gas present invention reduces energy consumption and generating.
Claims (3)
1. a kind of processing method of phosphorous feed liquid, comprising:
Phosphorous feed liquid is provided, the phosphorous feed liquid includes the acid ion and chloride ion of phosphorus；Chloride ion contains in the phosphorous feed liquid
Amount is 4.44~15%；
By the phosphorous feed liquid standing sedimentation, supernatant is obtained；Before carrying out standing sedimentation, further includes: to the phosphorous material
Liquid adjusts pH value；
The supernatant is filtered, and filtrate is obtained；The filtering is carried out using film pretreatment unit, the film pretreatment unit institute
The retention precision of the film used is 0.02 micron；The film pretreatment unit produces water flow 1t/h；
The filtrate passes through level-one membrane treatment appts, obtains level-one concentrated water；
The level-one concentrated water passes through second level membrane treatment appts, obtain that treated phosphorous feed liquid and second level fresh water；The second level is light
Water passes through three-level membrane treatment appts, obtains three-level fresh water；The three-level fresh water returns to the level-one membrane treatment appts；Back to one
The ratio of the three-level fresh water of grade membrane treatment appts is 20~50%；
Film used in the firsts and seconds membrane treatment appts is nanofiltration membrane, film used in the three-level membrane treatment appts
For reverse osmosis membrane；
The operation temperature of the firsts and seconds membrane treatment appts independently is 0~80 DEG C, and operating pressure independently is 1~
5MPa；The operation temperature of the three-level membrane treatment appts is 20~60 DEG C, and operating pressure is 2~4MPa.
2. processing method according to claim 1, which is characterized in that the nanofiltration membrane be polyamide-based film, polysulfones film,
Any one in cellulose acetate class film and inoranic membrane.
3. processing method according to claim 1, which is characterized in that the reverse osmosis membrane is that polyamide-based film or acetic acid are fine
Tie up plain class film.
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| CN106939589B (en) * | 2017-05-05 | 2019-10-22 | 暨南大学 | Water hyacinth is salvaged and treatment 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 |
| CN111646546B (en) * | 2020-06-16 | 2023-01-10 | 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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| CN101648971A (en) * | 2009-08-20 | 2010-02-17 | 南通江山农药化工股份有限公司 | Method for concentrating and separating glyphosate in glyphosate mother liquor by film process |
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