CN105293744B - A kind of processing method of fluorine-containing phosphorus-containing wastewater - Google Patents
A kind of processing method of fluorine-containing phosphorus-containing wastewater Download PDFInfo
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Abstract
The invention discloses a kind of processing method of fluorine-containing phosphorus-containing wastewater, it is characterised in that the fluorine-containing phosphorus-containing wastewater contains F‑、PO4 3‑、SO4 2‑And Al3+, the processing method of the fluorine-containing phosphorus-containing wastewater includes：1) under conditions of pH value is 59, by F in fluorine-containing phosphorus-containing wastewater and precipitable waste water‑And PO4 3‑Aluminum contained compound contact, obtain water-containing sludge；2) by step 1) in obtained water-containing sludge carry out sludge dewatering treatment, obtain dewatered sludge and liquid phase；3) by step 2) in obtained liquid phase mix progress coagulating kinetics with other waste water, water outlet after handle, wherein, other described waste water are the not fluorine-containing waste water with phosphorus.Method of the invention is particularly suitable for SO4 2‑The processing of the higher fluorine-containing phosphorus-containing wastewater of content.
Description
Technical field
The present invention relates to a kind of processing method of fluorine-containing phosphorus-containing wastewater, in particular it relates in a kind of process of producing molecular sieve
The processing method of effective fluorine removal dephosphorization of the fluorine-containing phosphorus-containing wastewater produced.
Background technology
Phosphorous skeletal silicon-rich ultra-steady Y molecular sieve (i.e. PSRY molecular sieves) is NaY molecular sieve by hydrothermal calcine and is combined
The skeletal silicon-rich novel molecular sieve that sour dealumination complement silicon is prepared, due to the stream prepared using PSRY molecular sieves as main active component
Fluidized catalytic cracking (FCC) catalyst has that coke selectivity is good, octane number is high, heavy oil pyrolysis ability is strong, diesel yield is high
The features such as, from after successfully carrying out THE INDUSTRIAL TRIAL, the FCC catalyst using PSRY molecular sieves as main active component is complete
Used on many heavy oil catalytically cracking equipments of state, achieve good economic benefit and social benefit.
Due to a certain amount of fluosilicic acid and phosphoric acid must be used in process of production, what PSRY process of producing molecular sieve was produced
There is significant difference in waste water, with conventional molecular sieve production waste water wherein most outstanding feature is F in waste water-、PO4 3-And SO4 2-Content
Height (F-Content is often beyond 2000mg/L, PO4 3-Content is more than 100mg/L, SO4 2-Content is more than 20000mg/L), while PSRY
Silicon, aluminium and the ammonia-nitrogen content that molecular sieve production waste water possesses conventional molecular sieve production waste water are high, the characteristics of pH value is low.Common molecular
The main purpose of sieve production wastewater treatment is aluminium, silicon and the ammonia nitrogen contained in removing water, and this kind of wastewater processing technology has passed through
Development is improved for many years, process route is increasingly rationalized, actual processing effect disclosure satisfy that molecular sieve production and environment protection emission requirement.Mesh
Before, molecular sieve and Catalyst Production producer are only that PSRY molecular sieves are produced waste water with other kinds of molecular sieve production waste water
Handled together after mixing, actual processing effect shows, this processing mode can not reach Oil repellent and phosphorus content in waste water
Environmental emission standard.
Excessive P elements can cause the eutrophication of water body in water, therefore phosphorus is the main pollution row that country strictly controls
Put one of index.Excessive fluorine can cause to seriously endanger to environment, not only human body fluorine poisoning can be caused (to show as invading tooth
Systemic chronic lesion based on tooth and bone), and fluoride pollution can make animal and plant be poisoned, influence agricultural and animal husbandry production,
Therefore, discharge of the national wastewater discharge standard to fluorine has strict demand.Therefore, it is the normal production of guarantee PSRY molecular sieves, must
It must solve the problems, such as that PSRY molecular sieves produce the fluorine and phosphorus content discharge beyond standards of waste water.
In the prior art on the Patents of FLUORIDE REMOVAL IN WASTEWATER dephosphorization and being described below for periodical literature：
It is acid that CN102070267A (a kind of method of the phosphorous fluoride waste of processing high-concentration acidic wastewater) discloses a kind of processing
The method of phosphorous fluoride waste.This method comprises the steps：1) calcium hydroxide is added in first oxytropism phosphor fluorine containing waste water, and controlled
The pH value of system processed obtains the reaction system containing precipitation between 12-14, is designated as reaction system 1；2) reaction system is removed
Precipitation in 1, and sulphur acid for adjusting pH value is added between 9-11 into remaining liq, it is subsequently added into aluminum sulfate and adjusts pH value in 6-
Between 7, the reaction system 2 containing precipitation is obtained；3) reaction system 2 is precipitated, removes sediment therein, obtain everywhere
Waste water after reason.Waste water Oil repellent after being handled through the inventive method is less than 10mg/L, and phosphorus content is less than 0.5mg/L, and pH value is 6
Between~7, Phosphate Fertilizer Industry pollution discharge standard (GB15580-95) is reached.
CN1351968A (treating method for high fluorice acid waste water) proposes high fluorine-containing, high suspended matter in a kind of phophatic fertilizer production process
Process for treating acidic waste water, it is adaptable to containing solid suspension, high fluoric acid wastewater treatment.This method is using calcium carbonate as main fluorine removal
Agent, defluorinating agent supplemented by calcium oxide, and fraction solids sediment is returned be used as aggregation crystal seed.Its control condition is to be sequentially added into master
Defluorinating agent, aggregation crystal seed, auxiliary defluorinating agent, adjust pH value 6-9, sedimentation separation solid and processing water, part sediment are returned into raw water
In, the comprehensive utilization of part sediment.There is this method medicament to originate, and wide, price is low, treatment time of water is short, technique is simple and water process
The low advantage of cost.
CN102267768A (a kind of method of lime-flyash Combined Treatment high-concentration fluorine-containing waste water) discloses a kind of stone
The method of ash-flyash Combined Treatment high-concentration fluorine-containing waste water, comprises the following steps：The lime one-level precipitation process stage：Temperature
For 10 DEG C, 0.1~0.2g of lime adding amount per 50mL fluoride wastes, adsorption time be that 30~60min, pH are 5.0~8.0；Powder
Coal ash secondary absorption processing stage：Temperature is 15 DEG C~45 DEG C, 5.0~15.0g of flyash addition often 50mL fluoride wastes, suctions
The attached time is that 60~120min, pH are 5.0~7.0, and the flyash first passes through acid solution modification in advance.Flyash modified place
It is used for Industrial Wastewater Treatment after reason, improves utilization of fly ash rates and utilizing status, and flyash belongs to regrown material, passes through pickling
It can be recycled etc. technique.
In the design and operation (Treatment of Industrial Water, the 2nd phase of volume 25 in 2005) text of fluorine-containing treatment of Phosphorus Containing Waste Water technique
Shao Zhiguo, Wang Qichao, Quan Yulian handle the acid waste water of fluorine-containing, phosphorous acid group using the method for lime neutralization precipitation, and control is useless
The reaction pH of water is respectively 8.5 and 11.0, and adds excessive strong electrolyte calcium chloride, distinguishes fluorine ion and phosphate anion
Precipitation.Sediment is separated with waste water again, reach the purpose of the fluorine ion and phosphate anion that remove in acid-bearing wastewater.Finally adopt
Neutralized with watery hydrochloric acid so that fluorine-containing, phosphate anion waste water qualified discharge after treatment.The technological process is simple, equipment effect
Rate is high, easy to operate, with good environmental benefit.
Various methods of the prior art are with Ca above2+As the main reactant of fluorine removal, pass through Ca2+With F-Reaction life
The purpose for removing most of fluorine and phosphorus in waste water is reached into water insoluble calcium precipitation.But, any of the above method is difficult
To be efficiently applied to F in molecular sieve manufacturing enterprise-、PO4 3-、SO4 2-And Al3+The fluorine removal dephosphorization of the higher fluorine-containing phosphorus-containing wastewater of content
Processing.
The content of the invention
The purpose of the present invention is to overcome the processing in the prior art to FLUORIDE REMOVAL IN WASTEWATER dephosphorization not to be suitable for SO4 2-Content compared with
The fluorine removal dephosphorization processing of high fluorine-containing phosphorus-containing wastewater, i.e., Oil repellent and/or phosphorus content do not reach discharge standard in processed waste water
Defect, and provide and a kind of be applied to SO4 2-The method of effective fluorine removal dephosphorization of the higher fluorine-containing phosphorus-containing wastewater of content, particularly
Produce effective fluorine removal phosphorus removing method of the fluorine-containing phosphorus-containing wastewater of Catalyst Production enterprise of PSRY molecular sieves so that described fluorine-containing phosphorous
The Oil repellent and phosphorus content qualified discharge of waste water.
It was found by the inventors of the present invention that the waste water handled by use fluorine removal dephosphorization treatment method of the prior art does not have
There is the characteristics of sulfate radical content is high.For PSRY molecular sieves production waste water, wherein containing substantial amounts of SO4 2-Ion, such as
Fruit routine defluorinating agent Ca2+Handled, CaSO can be generated4, and CaSO4Generation can severe jamming CaF2Formation efficiency and
Sedimentation function, and have a strong impact on the fluorine removal phosphor-removing effect of waste water.And the silicon of high content can be tight in PSRY molecular sieves production waste water
Ghost image rings adsorbent (referring to the flyash in absorption method, such as CN102267768A) and recycles efficiency.Based on above-mentioned discovery, this hair
Bright inventor completes the present invention.
To achieve these goals, the present invention provides a kind of processing method of fluorine-containing phosphorus-containing wastewater, wherein, it is described fluorine-containing to contain
Phosphorus waste water contains F-、PO4 3-、SO4 2-And Al3+, the processing method of the fluorine-containing phosphorus-containing wastewater includes：
1) under conditions of pH value is 5-9, by F in fluorine-containing phosphorus-containing wastewater and precipitable waste water-And PO4 3-Containing calorize close
Thing is contacted, and obtains water-containing sludge；
2) by step 1) in obtained water-containing sludge carry out sludge dewatering treatment, obtain dewatered sludge and liquid phase；
3) by step 2) in obtained liquid phase mix progress coagulating kinetics with other waste water, water outlet after being handled,
Wherein, other described waste water are the not fluorine-containing waste water with phosphorus.
The actual conditions for the method combined catalyst manufacturing enterprise that the present invention is provided, are making full use of fluorine-containing phosphorus-containing wastewater,
The Al contained in the fluorine-containing phosphorus-containing wastewater particularly produced in catalyst production process3+On the basis of fluorine removal reactant, knot
Conjunction can precipitate F in waste water-And PO4 3-Aluminum contained compound, and can by the coagulating kinetics of other catalyst production waste waters
So that the F in waste water-And PO4 3-The supplement process for being used as fluorine removal dephosphorization for being converted into sediment carries out further fluorine removal
Dephosphorization, so as to reach the purpose that effective fluorine removal dephosphorization is carried out to waste water.
Therefore, the present invention possesses advantage following prominent：
A, the present invention are without using Ca2+As defluorinating agent but utilize Al3+It is used as the precipitation cation of fluorine removal dephosphorization, it is to avoid
The SO that molecular sieve production waste water largely contains4 2-Influence to fluorine removal dephosphorization process.
B, the present invention fully effectively utilize fluorine-containing phosphorus-containing wastewater contained Al in itself3+As fluorine removal dephosphorization reactant, fill again
Point by the use of molecular sieve and Catalyst Production enterprise other waste water coagulating kinetics as the supplement process of fluorine removal dephosphorization, that is, carry
High fluorine removal dephosphorization efficiency, reduces the consumption of additional fluorine removal dephosphorization agent, has reached the purpose of resource recycling again.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
According to the processing method of fluorine-containing phosphorus-containing wastewater provided by the present invention, wherein, the fluorine-containing phosphorus-containing wastewater contains F-、
PO4 3-、SO4 2-And Al3+, the processing method of the fluorine-containing phosphorus-containing wastewater includes：
1) under conditions of pH value is 5-9, by F in fluorine-containing phosphorus-containing wastewater and precipitable waste water-And PO4 3-Containing calorize close
Thing is contacted, and obtains water-containing sludge；
2) by step 1) in obtained water-containing sludge carry out sludge dewatering treatment, obtain dewatered sludge and liquid phase；
3) by step 2) in obtained liquid phase mix progress coagulating kinetics with other waste water, water outlet after being handled,
Wherein, other described waste water are the not fluorine-containing waste water with phosphorus.
According to the present invention, the process step of the fluorine-containing phosphorus-containing wastewater corresponds mainly to three below process：Namely 1) one
Level fluorine removal dephosphorization process (below sometimes also abbreviation process 1)), 2) sludge dewatering process (below sometimes also abbreviation process 2)), 3)
Two grades of fluorine removal dephosphorization processes (below sometimes also abbreviation process 3)).
Three processes to the present invention are described in detail below.
1) one-level fluorine removal dephosphorization process
One-level fluorine removal dephosphorization process is：Under conditions of pH value is 5-9, by F in fluorine-containing phosphorus-containing wastewater and precipitable waste water-
And PO4 3-Aluminum contained compound contact, obtain water-containing sludge.
In the present invention, by making one-level fluorine removal dephosphorization process be carried out under conditions of pH value is 5-9, it can make in waste water
Original Al3+And the aluminum contained compound and F of addition-And PO4 3-Reaction fully carry out, make the portion dissolved in fluorine-containing phosphorus-containing wastewater
Fluorine and phosphorus is divided to be converted into solid insoluble, i.e., fluorine-containing or phosphorous suspension reaches part F in removing waste water-And PO4 3-Purpose.
Major part F in waste water can be removed by the process-And PO4 3-。
According to the present invention, in order to further promote the F in fluorine-containing phosphorus-containing wastewater-And PO4 3-Solid insoluble is converted into, it is excellent
The process is selected to be carried out under conditions of pH value is 6.5-8.
The pH value of usual fluorine-containing phosphorus-containing wastewater is in the range of 1-5, in order that one-level fluorine removal dephosphorization process can be above-mentioned
Carry out, can be adjusted by alkaline pH adjuster known in the field under pH value condition.The alkaline ph values regulation
Agent is preferably inorganic base.Can be sodium hydroxide and/or potassium hydroxide, preferably sodium hydroxide as such inorganic base.
According to the present invention, in order to ensure Al3+With F-And PO4 3-The abundant progress of reaction, process 1) in, the bar of the contact
Part includes：The time of contact is no less than 10 minutes, preferably 15-60 minutes, more preferably 20-30 minutes；The temperature of contact is led to
It is often the actual temperature of water, for example, can is 5-40 DEG C, preferably 10-30 DEG C.
, according to the invention it is preferred in the case of, F in the precipitable waste water-And PO4 3-Aluminum contained compound be aluminium salt.Make
It is preferably the one or more in aluminum sulfate, aluminium chloride, aluminium polychloride and polyaluminium sulfate for such aluminium salt；More preferably
Aluminium chloride and/or aluminium polychloride.Pass through the Al of above-mentioned aluminium salt3+F in waste water can further be made-And PO4 3-It is converted into solid not
Molten thing, part F in water is further removed so as to reach-And PO4 3-Purpose
In addition, in order to ensure the F in waste water-And PO4 3-Fully reacted and precipitated, in process 1) in, in terms of aluminium element,
F in the precipitable waste water-And PO4 3-The consumption of aluminum contained compound be preferably 5-5000mg/L waste water；More preferably 200-
2000mg/L waste water；More preferably 50-1000mg/L waste water；More preferably 100-900mg/L waste water；Further
Preferably 150-600mg/L waste water；Still more preferably it is 300-550mg/L waste water.
2) sludge dewatering process
Sludge dewatering process is：By step 1) in obtained water-containing sludge carry out sludge dewatering treatment, obtain dewatered sludge
And liquid phase.
In order to increase the dewatering of fluorine-containing suspension and phosphorous suspension in water, fluorine-containing hang is efficiently separated to reach
The purpose of float and phosphorous suspension.It is preferred that the method for the present invention also includes：By step 1) in obtained water-containing sludge carry out
Before sludge dewatering treatment, by step 1) in obtained water-containing sludge contacted with filter aid.
According to the present invention, the filter aid is that can improve the material of suspension aggregation extent and dewatering in waste water,
Its specific species is known to those skilled in the art, under preferable case, the filter aid be aluminium chloride, aluminium polychloride,
One or more in iron chloride, poly-ferric chloride and polyacrylamide；More preferably described filter aid is polyacrylamide
(PAM).As long as the addition of the filter aid can improve the dewatering of the fluorine-containing suspension and phosphorous suspension in waste water,
So as to beneficial to follow-up sludge dewatering treatment, therefore, according to the species of selected filter aid, the optional model of its consumption
Enclose wider, under preferable case, the consumption of the filter aid is 0.5-200mg/L waste water；More preferably 1-50mg/L waste water；It is more excellent
Elect 1.5-25mg/L waste water as；More preferably 1.5-10mg/L waste water；More preferably 1.5-4mg/L waste water, most preferably 2-
3mg/L waste water.
According to the present invention, by step 1) in the mode that is contacted with filter aid of obtained water-containing sludge be preferably to mix,
As long as the time of mixing ensures that the two is fully mixed, such as no less than 2 minutes.
According to the present invention, the dewatered sludge obtained after sludge dewatering treatment is as fixed-end forces, due to still containing in liquid phase
There is F-And PO4 3-Ion and a large amount of suspensions, coagulating kinetics are carried out by obtained liquid phase and other waste water (not fluorine-containing and phosphorus)
After finally give processing after water outlet.
3) two grades of fluorine removal dephosphorization processes
Two grades of fluorine removal dephosphorization processes are：By step 2) in obtained liquid phase carry out coagulating kinetics with other waste water, obtain
Water outlet after to processing.
According to the present invention, in process 3) in, other described waste water for not fluorine-containing and phosphorus waste water, by using not fluorine-containing and
The waste water of phosphorus, can prevent the extra increase F in the fluorine-containing phosphorus-containing wastewater of the present invention-And PO4 3-The content of ion.In addition, passing through
The coagulating kinetics of other waste water can further fluorine removal dephosphorization, so as to reach the mesh that effective fluorine removal dephosphorization is carried out to waste water
's.The waste water of the not fluorine-containing and phosphorus produced in molecular sieve and/or catalyst production process can be used as such waste water.
, will be in process 2 according to the present invention) in water outlet (i.e. described liquid phase) carried out with other described waste water at coagulating sedimentation
Reason, the method and condition of the coagulating kinetics can be with methods and condition commonly used in the art.For example, the coagulation is heavy
The condition handled of forming sediment includes：PH value is 6-9, preferably 6.5-8.0；The temperature of coagulating kinetics is usually the actual temperature of water
Degree, preferably for example, 5-40 DEG C, 10-30 DEG C；The time of coagulating sedimentation is no less than 10 minutes, preferably 60-120 minutes.
In addition, process 3) in, there is no particular limitation for the consumption of other waste water, as long as can make the liquid phase (i.e.
The liquid phase obtained in (step 2)) in F-And PO4 3-Sediment is further converted to, it can be used for the conventional of this area
Amount.Can also be to the F in the liquid phase in view of other waste water-And PO4 3-With diluting effect, institute is preferably largely used
State other waste water.In addition, the F from the liquid phase is made-And PO4 3-Further it is fully converted into sediment to consider, relative to step
It is rapid 2) in obtained liquid phase 1L, the consumption of other waste water is more than 1L；More preferably more than 5L；More preferably 8L with
On.
According to the present invention, process 3) in after obtained processing water outlet be supernatant after coagulating kinetics, the supernatant
In phosphorus content and Oil repellent then reached emission request, can carry out follow-up conventional other pollutant removals processing or
Can directly it discharge.
According to the present invention, above-mentioned operation 2) in the method for involved sludge dewatering can use those skilled in the art institute
Known various methods, as long as ensure that being sufficiently separated for solid suspension and liquid phase, for example, can enter to stand
The conventional solid-liquid separation method of row gravitational settling, centrifugation and press filtration (such as plate-frame filtering).In the present invention, it is preferred to will
Sludge is transported to progress press filtration processing in sludge dehydration device.
According to the present invention, F in the fluorine-containing phosphorus-containing wastewater-Content be 100-5000mg/L, PO4 3-- P content is 10-
500mg/L, SO4 2-Content be less than 50000mg/L, Al3+Content be 100-5000mg/L；Preferably, it is described fluorine-containing phosphorous useless
F in water-Content be 1400-2300mg/L, PO4 3-- P content is 75-110mg/L, SO4 2-Content be 16000-
25000mg/L, Al3+Content be 3000-4500mg/L.The pH value of the fluorine-containing phosphorus-containing wastewater of before processing is usually 1-5.
The method of wastewater treatment of the present invention is suitably applied the various fluorine-containing phosphorus-containing wastewaters for meeting above-mentioned ion concentration, especially
The processing of the fluorine-containing phosphorus-containing wastewater produced suitable for production PSRY molecular sieves.
The present invention will be described in detail by way of examples below.
In following examples, it is the fluorine-containing phosphorous useless of PSRY molecular sieves generation that the molecular sieve, which produces fluorine-containing phosphorus-containing wastewater,
Water.F in the fluorine-containing phosphorus-containing wastewater-Content, PO4 3-- P content, SO4 2-Content, Al3+The method of testing of content is respectively fluorine reagent
Spectra photometric method (GB/T57505-2006), molybdenum-antimony anti-spectrophotometric method (GB11893-89), EDTA titrations, inductive etc. from
Sub- emission spectrometry (ICP).The assay method of silicone content is national standard method in fluorine-containing phosphorus-containing wastewater：GB/T12149-2007.
In following examples, SO in the waste water of described not fluorine-containing and phosphorus4 2-Content, Al3+The method of testing of content is respectively
EDTA titrations and inductive coupling plasma emission spectrum method (ICP).The measure of silicone content in the waste water of described not fluorine-containing and phosphorus
Method is national standard method：GB/T12149-2007.
The number-average molecular weight of polyacrylamide (PAM) is 8,000,000, purchased from Beijing Xitao Development Tech Co., Ltd..Polymerization
Aluminium chloride (PAC) is purchased from Hong Yuan water-purifying materials factory of Gongyi City.
Embodiment 1
The present embodiment is used for the processing method for illustrating the fluorine-containing phosphorus-containing wastewater that the present invention is provided.
PSRY molecular sieves produce fluorine-containing phosphorus-containing wastewater：F-Content：1441mg/L；PO4 3-- P content：77.3mg/L；SO4 2-Contain
Amount：16704mg/L；Al3+Content：3001mg/L；SiO2Content：107mg/L；pH：3.37.
Not fluorine-containing and phosphorus the waste water of molecular sieve production：SO4 2-Content：1350mg/L；Al3+Content：1056mg/L；SiO2Contain
Amount：225mg/L；pH：4.49.
Take 1000mL PSRY molecular sieves to produce fluorine-containing phosphorus-containing wastewater, add the aluminium chloride of 2500mg/L waste water (with aluminium member
Element is calculated as 500mg/L waste water), pH value is adjusted to 6.7, stirring reaction 20min using NaOH after being well mixed；
Then the PAM of 2mg/L waste water is added, well mixed progress helps solidifying reaction 2min, filtering means dehydration is carried out afterwards, is obtained
Filtrate；
The filtrate 500mL obtained is produced after not fluorine-containing and phosphorus waste water is mixed with 2000mL molecular sieves and is carried out coagulating sedimentation
Processing, the pH value of coagulating sedimentation is 7.0, and the time of coagulating sedimentation is 90min, and the supernatant finally obtained is final outflow water, most
Whole water outlet F-Content is 6.1mg/L, PO4 3-Content is less than 0.1mg/L.
Embodiment 2
The present embodiment is used for the processing method for illustrating the fluorine-containing phosphorus-containing wastewater that the present invention is provided.
PSRY molecular sieves produce fluorine-containing phosphorus-containing wastewater：F-Content：2223mg/L；PO4 3-- P content：107.9mg/L；SO4 2-
Content：24700mg/L；Al3+Content：4441mg/L；SiO2Content：386mg/L；pH：2.96.
Not fluorine-containing and phosphorus the waste water of molecular sieve production：SO4 2-Content：1050mg/L；Al3+Content：855mg/L；SiO2Contain
Amount：195mg/L；pH：4.05.
Take 1000mL PSRY molecular sieves to produce fluorine-containing phosphorus-containing wastewater, add 2000mg/L waste water aluminium polychloride (with
Aluminium element is calculated as 310mg/L waste water), pH value is adjusted to 6.9, stirring reaction 15min using NaOH after being well mixed；
Then the PAM of 3mg/L waste water is added, well mixed progress helps solidifying reaction 2min, filtering means dehydration is carried out afterwards, is obtained
Filtrate；
The filtrate 500mL obtained is produced after not fluorine-containing and phosphorus waste water is mixed with 3000mL molecular sieves and is carried out coagulating sedimentation
Processing, the pH value of coagulating sedimentation is 7.5, and the time of coagulating sedimentation is 90min, and the supernatant finally obtained is final outflow water, most
Whole water outlet F-Content is 8.8mg/L, PO4 3-- P content is less than 0.1mg/L.
Embodiment 3
The present embodiment is used for the processing method for illustrating the fluorine-containing phosphorus-containing wastewater that the present invention is provided.
PSRY molecular sieves produce fluorine-containing phosphorus-containing wastewater：F-Content：2036mg/L；PO4 3-- P content：93.2mg/L；SO4 2-Contain
Amount：22200mg/L；Al3+Content：4075mg/L；SiO2Content：432mg/L；pH：3.28.
Not fluorine-containing and phosphorus the waste water of molecular sieve production：SO4 2-Content：950mg/L；Al3+Content：655mg/L；SiO2Content：
135mg/L；pH：4.05.
Take 1000mL PSRY molecular sieves to produce fluorine-containing phosphorus-containing wastewater, add 3000mg/L waste water aluminium polychloride (with
Aluminium element is calculated as 465mg/L waste water), pH value is adjusted to 6.9, stirring reaction 20min using NaOH；
Then the PAM of 2mg/L waste water is added, well mixed progress helps solidifying reaction 2min, filtering means dehydration is carried out afterwards, is obtained
Filtrate；
The filtrate 500mL obtained is produced after not fluorine-containing and phosphorus waste water is mixed with 5000mL molecular sieves and is carried out coagulating sedimentation
Processing, the pH value of coagulating sedimentation is 7.5, and the time of coagulating sedimentation is 90min, obtains supernatant for final outflow water, finally obtains
Final outflow water F-Content is 5.7mg/L, PO4 3-- P content is less than 0.1mg/L.
By above-described embodiment, by method of the invention, it is possible to effectively to SO4 2-Higher fluorine-containing of content contains
Phosphorus waste water is handled so that the Oil repellent of the fluorine-containing phosphorus-containing wastewater reaches below 8.8mg/L, and phosphorus content reaches 0.1mg/L
Below.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (8)
1. a kind of processing method of fluorine-containing phosphorus-containing wastewater, it is characterised in that the fluorine-containing phosphorus-containing wastewater contains F-、PO4 3-、SO4 2-With
Al3+, the fluorine-containing phosphorus-containing wastewater that the fluorine-containing phosphorus-containing wastewater produces for production PSRY molecular sieves, the processing of the fluorine-containing phosphorus-containing wastewater
Method includes：
1) under conditions of pH value is 5-9, by F in fluorine-containing phosphorus-containing wastewater and precipitable waste water-And PO4 3-Aluminum contained compound connect
Touch, obtain F in water-containing sludge, the precipitable waste water-And PO4 3-Aluminum contained compound be aluminium salt, the aluminium salt be aluminum sulfate,
One or more in aluminium chloride, aluminium polychloride and polyaluminium sulfate；
2) by step 1) in obtained water-containing sludge carry out sludge dewatering treatment, obtain dewatered sludge and liquid phase；
3) by step 2) in obtained liquid phase mix progress coagulating kinetics with other waste water, water outlet after being handled, wherein,
Other described waste water are the waste water of the not fluorine-containing and phosphorus produced in molecular sieve and/or catalyst production process.
2. according to the method described in claim 1, wherein, in step 1) in, F in fluorine-containing phosphorus-containing wastewater and precipitable waste water-With
PO4 3-The contact of aluminum contained compound carry out under agitation, the condition of the contact includes：The temperature of contact is 5-40 DEG C；Contact
Time be no less than 10 minutes.
3. method according to claim 2, wherein, the time of contact is 15~60min.
4. according to the method described in claim 1, wherein, in step 1) in, the pH value be 6.5-8.
5. according to the method described in claim 1, wherein, in step 1) in, in terms of aluminium element, F in the precipitable waste water-With
PO4 3-Aluminum contained compound consumption be 5-5000mg/L waste water.
6. according to the method described in claim 1, wherein, this method also includes：By step 1) in obtained water-containing sludge enter
Before row sludge dewatering, by step 1) in obtained water-containing sludge contacted with filter aid；The filter aid is that can improve waste water
The material of middle suspension aggregation extent and dewatering.
7. method according to claim 6, wherein, the filter aid is aluminium chloride, aluminium polychloride, iron chloride, polymerization
One or more in iron chloride and polyacrylamide.
8. according to the method described in claim 1, wherein, F in the fluorine-containing phosphorus-containing wastewater-Content be 100-5000mg/L,
PO4 3-- P content is 10-500mg/L, SO4 2-Content be less than 50000mg/L, Al3+Content be 100-5000mg/L, processing
The pH value of preceding fluorine-containing phosphorus-containing wastewater is 1-5.
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| JPH0753276B2 (en) * | 1989-10-03 | 1995-06-07 | 栗田工業株式会社 | Fluoride-containing water treatment method |
| JP2842384B2 (en) * | 1996-06-25 | 1999-01-06 | 日本電気株式会社 | Treatment method for wastewater containing phosphoric acid and fluorine |
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