CN109354086A - A kind of method of complexing agent enhancing nanofiltration membrane catching heavy metal ion - Google Patents
A kind of method of complexing agent enhancing nanofiltration membrane catching heavy metal ion Download PDFInfo
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- CN109354086A CN109354086A CN201811548694.7A CN201811548694A CN109354086A CN 109354086 A CN109354086 A CN 109354086A CN 201811548694 A CN201811548694 A CN 201811548694A CN 109354086 A CN109354086 A CN 109354086A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/04—Feed pretreatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
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Abstract
The present invention relates to a kind of methods of complexing agent enhancing nanofiltration membrane catching heavy metal ion, and described method includes following steps: compound complex agent is added in the industrial wastewater containing heavy metal ion, after mixing by nanofiltration membrane；The compound complex agent is made of EDTA, sodium oxalate and citric acid.This method of the present invention in industrial wastewater by adding compound complex agent, contents of many kinds of heavy metal ion and compound complex agent in industrial wastewater is complexed, and then to the rejection of heavy metal ion to 85% or more when improving nanofiltration membrane to the Industrial Wastewater Treatment, in the process parameters range of the method provided by the present invention, the permeation flux of nanofiltration membrane is in 39.98-50.49L/ (hm2) in variation.This method simple process can effectively remove the contents of many kinds of heavy metal ion in industrial wastewater, industrial applicability is preferable convenient for operation.
Description
Technical field
The invention belongs to field of environmental improvement, are related to a kind of minimizing technology more particularly to one of heavy metal ions in wastewater
The method of kind complexing agent enhancing nanofiltration membrane catching heavy metal ion.
Background technique
Contain a large amount of Pb in industrial wastewater2+、Cd2+、Mn2+、Zn2+With Cu2+Etc. heavy metal ion, due in industrial wastewater
Heavy metal ion it is varied, single method is unable to reach the effect for being effectively removed heavy metal ion.
Currently, the minimizing technology of the heavy metal ion in industrial wastewater mainly has chemical method, physical-chemical process and biology
Chemical method.Wherein, chemical method includes chemical precipitation method, oxidation-reduction method and electrochemistry exchange entry, but chemical precipitation method is removing
Other hetero atoms can be introduced when heavy metal ion, and need the pH value of strict control industrial wastewater, operating condition is more stringent, and
The heavy metal removing rate of oxidation-reduction method is lower, and electrochemical reducing needs to consume a large amount of computer.
Physical-chemical process includes solvent extraction, absorption method, ion-exchange, hyperfiltration and electroosmose process.Wherein, molten
Agent extraction needs to consume a large amount of solvent, and also with the loss of this solvent in extraction process, economy is lower；Absorption method
Then using the heavy metal ion in adsorbent material absorption waste water, but single adsorption material only to specific heavy metal ion have compared with
High adsorption rate, when the heavy metal ion complicated component in waste water, adsorption effect is bad；Ion-exchange is to be inhaled using waste water
The method of attached heavy metal ions in wastewater, but equipment scale needed for this method is larger, and exists to the processing flow of industrial wastewater
Strict requirements；Hyperfiltration is to be retained to the heavy metal ion in waste water by reverse osmosis membrane, but reverse osmosis membrane
Aperture is smaller, is easily blocked by heavy metal ion；Electroosmose process is only suitable for handling the lesser waste water of concentration of heavy metal ion.
Biochemical process includes bio-flocculation process, biosorption process and phytoremediation method, but the processing of biochemical process is all
Phase is longer.In order to effectively and quickly remove containing the various heavy in heavy metal wastewater thereby, people expand relevant grind to this
Study carefully.
102432123 A of CN discloses a kind of application method of renewable heavy metal complexing agent, and this method is to copper-containing wastewater
In copper ion effectively removed, this method joined certain complexing agent in waste water, so that complexing agent and copper ion
Luo He, to make the rejection of copper reach 90% or more, but this method is only applicable to the waste water containing heavy metal copper ion.
106044951 A of CN discloses the recoverying and utilizing method and device of a kind of industrial acidic wastewater, which utilizes more
Grade nanofiltration membrane recycles industrial acidic wastewater with method associated with multi-stage reverse osmosis film, while can also remove in waste water
Contained heavy metal ion.But this method needs multistage membrane stack, and equipment investment is higher, less economical, and the connection of multistage membrane stack
With causing the anti-fluctuation ability of system poor, it is unfavorable for industrial applications.
CN 103374659A discloses valuable, rare metal refinement recovery method in a kind of waste, and this method is selected
Different nanofiltration membranes separates heavy metal ion different in waste water, although being convenient for the enrichment respectively of heavy metal ion,
It needs that different nanofiltration membranes is arranged according to the concrete condition of waste water, not only equipment investment is larger, is also unfavorable for industrial applications.
Therefore, it develops one kind and simply and effectively removes the method containing heavy metal in heavy metal wastewater thereby with important meaning
Justice.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of complexing agent enhancing nanofiltration membrane retention weight
The method of metal ion, this method make the various heavy in industrial wastewater by adding compound complex agent in industrial wastewater
Ion and compound complex agent are complexed, and then to the rejection of heavy metal ion when improving nanofiltration membrane to the Industrial Wastewater Treatment, and
Influence of this method to nanofiltration membrane permeation flux is smaller.This method simple process can effectively remove industrial wastewater convenient for operation
In contents of many kinds of heavy metal ion, industrial applicability is preferable.
To achieve this purpose, the present invention adopts the following technical scheme:
The present invention provides a kind of methods of complexing agent enhancing nanofiltration membrane catching heavy metal ion, and the method includes as follows
Step: compound complex agent is added in the industrial wastewater containing heavy metal ion, after mixing by nanofiltration membrane.
The compound complex agent is made of EDTA, sodium oxalate and citric acid, EDTA, sodium oxalate and lemon in compound complex agent
The molar ratio of lemon acid is (3-5): (1-3): (1-2), such as can be 2:1:1,3:1:1,3:2:2,4:1:2,4:3:1,5:2:1
Or 5:1:2, preferably 2:1:1.
The present invention makes heavy metal ion and compound network in industrial wastewater by adding compound complex agent in industrial wastewater
Mixture is complexed, and improves ionic radius, to improve nanofiltration membrane to the rejection of heavy metal ion, and the present invention is added
Influence of the compound complex agent added to the permeation flux of nanofiltration membrane is smaller.
Preferably, the heavy metal ion includes Pb2+、Cu2+、Cd2+、Zn2+Or Mn2+In any one or at least two
Combination, such as can be Pb2+With Cu2+Composition, Cu2+、Cd2+With Zn2+Composition, Pb2+、Cd2+、Zn2+With Mn2+Combination
Or Pb2+、Cu2+、Cd2+、Zn2+With Mn2+Combination, preferably Pb2+、Cu2+、Cd2+、Zn2+And Mn2+。
Preferably, the total mol concentration of the heavy metals in industrial wastewater ion is 100-150mmol/L, such as be can be
100mmol/L, 110mmol/L, 120mmol/L, 130mmol/L, 140mmol/L or 150mmol/L, preferably 110-
140mmol/L。
Preferably, the Pb2+Molar concentration be 10-15mmol/L, such as can be 10mmol/L, 11mmol/L,
12mmol/L, 13mmol/L, 14mmol/L or 15mmol/L, preferably 12-14mmol/L.
Preferably, the Cu2+Molar concentration be 30-50mmol/L, such as can be 30mmol/L, 35mmol/L,
40mmol/L, 45mmol/L or 50mmol/L, preferably 40-45mmol/L.
Preferably, the Cd2+Molar concentration be 5-10mmol/L, such as can be 5mmol/L, 6mmol/L, 7mmol/
L, 8mmol/L, 9mmol/L or 10mmol/L, preferably 6-8mmol/L.
Preferably, the Zn2+Molar concentration be 25-35mmol/L, such as can be 25mmol/L, 26mmol/L,
27mmol/L, 28mmol/L, 29mmol/L, 30mmol/L, 31mmol/L, 32mmol/L, 33mmol/L, 34mmol/L or
35mmol/L, preferably 28-32mmol/L.
Preferably, the Mn2+Molar concentration be 30-40mmol/L, such as can be 30mmol/L, 31mmol/L,
32mmol/L, 33mmol/L, 34mmol/L, 35mmol/L, 36mmol/L, 37mmol/L, 38mmol/L, 39mmol/L or
40mmol/L, preferably 35-38mmol/L.
Preferably, the pH value of the industrial wastewater is 2-6, such as can be 2,3,4,5 or 6, preferably 3-5.
Preferably, the ratio between the integral molar quantity of the heavy metals in industrial wastewater ion and the mole of compound complex agent are
(2-5): 1, such as can be 2:1,3:1,4:1 or 5:1, preferably (3-4): 1.The mole of compound complex agent of the present invention
For the integral molar quantity of EDTA, sodium oxalate and citric acid in compound complex agent.
Preferably, transmembrane pressure when passing through nanofiltration membrane is 1.5-2.5MPa, for example, can be 1.5MPa,
1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa, 2MPa, 2.1MPa, 2.2MPa, 2.3MPa, 2.4MPa or 2.5MPa, preferably
1.8-2.2MPa。
Preferably, the aperture of the nanofiltration membrane be 1-2nm, such as can be 1nm, 1.1nm, 1.2nm, 1.3nm, 1.4nm,
1.5nm, 1.6nm, 1.7nm, 1.8nm, 1.9nm or 2nm, preferably 1.2-1.8nm.
As the optimal technical scheme of first aspect present invention the method, described method includes following steps:
(1) contain Pb2+、Cu2+、Cd2+、Zn2+With Mn2+Heavy metal ion, pH be 2-6 industrial wastewater in addition by
The compound complex agent of EDTA, sodium oxalate and citric acid composition, EDTA in the compound complex agent, sodium oxalate and citric acid rub
, than being (3-5): (1-3): (1-2), the total mol concentration of heavy metals in industrial wastewater ion is 100-150mmol/L, described for you
Pb2+Molar concentration be 10-15mmol/L, the Cu2+Molar concentration be 30-50mmol/L, the Cd2+Molar concentration
For 5-10mmol/L, the Zn2+Molar concentration be 25-35mmol/L, the Mn2+Molar concentration be 30-40mmol/L,
The ratio between the integral molar quantity of the heavy metals in industrial wastewater ion and the mole of compound complex agent are (2-5): 1；
(2) nanofiltration membrane that compound complex agent and industrial wastewater are after mixing 1-2nm by aperture, when filtering across
Membrane pressure difference is 1.5-2.5MPa.
Numberical range of the present invention not only includes enumerated point value, further includes the above-mentioned numerical value not included
Arbitrary point value between range, as space is limited and for concise consideration, range described in the present invention no longer exclusive list includes
Specific point value.
Compared with prior art, the invention has the benefit that
This method of the present invention by adding compound complex agent in industrial wastewater, make various heavy in industrial wastewater from
Son is complexed with compound complex agent, and then to the rejection of heavy metal ion, Pb when improving nanofiltration membrane to the Industrial Wastewater Treatment2+、
Cu2+、Cd2+、Zn2+And Mn2+Rejection can reach 85% or more, and influence of this method to nanofiltration membrane permeation flux compared with
Small, in the process parameters range of the method provided by the present invention, the permeation flux of nanofiltration membrane is in 39.98-50.49L/ (hm2) in
Variation.This method simple process can effectively remove the contents of many kinds of heavy metal ion in industrial wastewater, industrial application convenient for operation
Property is preferable.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Embodiment 1
A kind of method for present embodiments providing complexing agent enhancing nanofiltration membrane catching heavy metal ion, the method includes such as
Lower step:
(1) contain 13mmol/LPb2+、42mmol/LCu2+、7mmol/LCd2+、30mmol/LZn2+With 36mmol/LMn2+
Heavy metal ion, pH are described multiple to add the compound complex agent being made of EDTA, sodium oxalate and citric acid in 4 industrial wastewater
The molar ratio for closing EDTA, sodium oxalate and citric acid in complexing agent is 2:1:1, and the heavy metals in industrial wastewater ion always rubs
The ratio between that amount and the integral molar quantity of each complexing agent in compound complex agent are 3:1；
(2) nanofiltration membrane that compound complex agent and industrial wastewater are after mixing 1.5nm by aperture, when filtering across
Membrane pressure difference is 2MPa.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 0.76mmol/LPb2 +、2.31mmol/LCu2+、0.24mmol/LCd2+、1.47mmol/LZn2+With 2.63mmol/LMn2+, wherein Pb2+Rejection
For 94.1%, Cu2+Rejection be 94.5%, Cd2+Rejection be 96.5%, Zn2+Rejection be 95.1%, Mn2+Cut
Staying rate is 92.7%；In nanofiltration process, the permeation flux of nanofiltration membrane is 45.98L/ (hm2)。
Embodiment 2
A kind of method for present embodiments providing complexing agent enhancing nanofiltration membrane catching heavy metal ion, the method includes such as
Lower step:
(1) contain 12mmol/LPb2+、40mmol/LCu2+、6mmol/LCd2+、28mmol/LZn2+With 35mmol/LMn2+
Heavy metal ion, pH are described multiple to add the compound complex agent being made of EDTA, sodium oxalate and citric acid in 3 industrial wastewater
The molar ratio for closing EDTA, sodium oxalate and citric acid in complexing agent is 3:3:1, and the heavy metals in industrial wastewater ion always rubs
The ratio between that amount and the integral molar quantity of each complexing agent in compound complex agent are 3:1；
(2) nanofiltration membrane that compound complex agent and industrial wastewater are after mixing 1nm by aperture, cross-film when filtering
Pressure difference is 2MPa.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 0.73mmol/LPb2 +、3.04mmol/LCu2+、0.42mmol/LCd2+、1.72mmol/LZn2+With 3.32mmol/LMn2+, wherein Pb2+Rejection
For 93.9%, Cu2+Rejection be 92.4%, Cd2+Rejection be 93%, Zn2+Rejection be 93.8%, Mn2+Retention
Rate is 90.5%；In nanofiltration process, the permeation flux of nanofiltration membrane is 46.23L/ (hm2)。
Embodiment 3
A kind of method for present embodiments providing complexing agent enhancing nanofiltration membrane catching heavy metal ion, the method includes such as
Lower step:
(1) contain 14mmol/LPb2+、45mmol/LCu2+、8mmol/LCd2+、32mmol/LZn2+With 38mmol/LMn2+
Heavy metal ion, pH are described multiple to add the compound complex agent being made of EDTA, sodium oxalate and citric acid in 5 industrial wastewater
The molar ratio for closing EDTA, sodium oxalate and citric acid in complexing agent is 5:2:2, and the heavy metals in industrial wastewater ion always rubs
The ratio between that amount and the integral molar quantity of each complexing agent in compound complex agent are 4:1；
(2) nanofiltration membrane that compound complex agent and industrial wastewater are after mixing 1nm by aperture, cross-film when filtering
Pressure difference is 2MPa.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 1.15mmol/LPb2 +、4.13mmol/LCu2+、0.7mmol/LCd2+、3.08mmol/LZn2+With 4.33mmol/LMn2+, wherein Pb2+Rejection be
91.8%, Cu2+Rejection be 90.8%, Cd2+Rejection be 91.2%, Zn2+Rejection be 90.4%, Mn2+Retention
Rate is 88.6%；In nanofiltration process, the permeation flux of nanofiltration membrane is 48.76L/ (hm2)。
Embodiment 4
A kind of method for present embodiments providing complexing agent enhancing nanofiltration membrane catching heavy metal ion, the method includes such as
Lower step:
(1) contain 10mmol/LPb2+、30mmol/LCu2+、5mmol/LCd2+、25mmol/LZn2+With 30mmol/LMn2+
Heavy metal ion, pH are described multiple to add the compound complex agent being made of EDTA, sodium oxalate and citric acid in 2 industrial wastewater
The molar ratio for closing EDTA, sodium oxalate and citric acid in complexing agent is 4:1:2, and the heavy metals in industrial wastewater ion always rubs
The ratio between that amount and the integral molar quantity of each complexing agent in compound complex agent are 2:1；
(2) nanofiltration membrane that compound complex agent and industrial wastewater are after mixing 1.5nm by aperture, when filtering across
Membrane pressure difference is 2MPa.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 0.79mmol/LPb2 +、2.67mmol/LCu2+、0.41mmol/LCd2+、2.17mmol/LZn2+With 3.25mmol/LMn2+, wherein Pb2+Rejection
For 92.1%, Cu2+Rejection be 91.1%, Cd2+Rejection be 91.8%, Zn2+Rejection be 91.3%, Mn2+Cut
Staying rate is 89.2%；In nanofiltration process, the permeation flux of nanofiltration membrane is 41.81L/ (hm2)。
Embodiment 5
A kind of method for present embodiments providing complexing agent enhancing nanofiltration membrane catching heavy metal ion, the method includes such as
Lower step:
(1) contain 15mmol/LPb2+、50mmol/LCu2+、10mmol/LCd2+、35mmol/LZn2+With 40mmol/LMn2+
Heavy metal ion, pH are described multiple to add the compound complex agent being made of EDTA, sodium oxalate and citric acid in 6 industrial wastewater
The molar ratio for closing EDTA, sodium oxalate and citric acid in complexing agent is 5:3:2, and the heavy metals in industrial wastewater ion always rubs
The ratio between that amount and the integral molar quantity of each complexing agent in compound complex agent are 5:1；
(2) nanofiltration membrane that compound complex agent and industrial wastewater are after mixing 1.5nm by aperture, when filtering across
Membrane pressure difference is 2MPa.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 1.73mmol/LPb2 +、6.76mmol/LCu2+、1.41mmol/LCd2+、4.64mmol/LZn2+With 5.96mmol/LMn2+, wherein Pb2+Rejection
For 88.5%, Cu2+Rejection be 86.5%, Cd2+Rejection be 85.9%, Zn2+Rejection be 86.7%, Mn2+Cut
Staying rate is 85.1%；In nanofiltration process, the permeation flux of nanofiltration membrane is 50.49L/ (hm2)。
Embodiment 6
A kind of method for present embodiments providing complexing agent enhancing nanofiltration membrane catching heavy metal ion, removes and receives in step (2)
Filter sizes are 1.8nm, and transmembrane pressure is outside 1.8MPa, remaining is same as Example 1.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 0.81mmol/LPb2 +、2.48mmol/LCu2+、0.41mmol/LCd2+、1.71mmol/LZn2+With 2.96mmol/LMn2+, wherein Pb2+Rejection
For 93.8%, Cu2+Rejection be 94.1%, Cd2+Rejection be 94.1%, Zn2+Rejection be 94.3%, Mn2+Cut
Staying rate is 91.8%；In nanofiltration process, the permeation flux of nanofiltration membrane is 45.14L/ (hm2)。
Embodiment 7
A kind of method for present embodiments providing complexing agent enhancing nanofiltration membrane catching heavy metal ion, removes and receives in step (2)
Filter sizes are 1.2nm, and transmembrane pressure is outside 2.2MPa, remaining is same as Example 1.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 0.74mmol/LPb2 +、2.23mmol/LCu2+、0.21mmol/LCd2+、1.35mmol/LZn2+With 2.58mmol/LMn2+, wherein Pb2+Rejection
For 94.3%, Cu2+Rejection be 94.7%, Cd2+Rejection be 97%, Zn2+Rejection be 95.5%, Mn2+Retention
Rate is 92.8%；In nanofiltration process, the permeation flux of nanofiltration membrane is 43.31L/ (hm2)。
Embodiment 8
A kind of method for present embodiments providing complexing agent enhancing nanofiltration membrane catching heavy metal ion, removes and receives in step (2)
Filter sizes are 1nm, and transmembrane pressure is outside 2.5MPa, remaining is same as Example 1.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 0.71mmol/LPb2 +、2.19mmol/LCu2+、0.2mmol/LCd2+、1.31mmol/LZn2+With 2.47mmol/LMn2+, wherein Pb2+Rejection be
94.5%, Cu2+Rejection be 94.8%, Cd2+Rejection be 97.1%, Zn2+Rejection be 95.6%, Mn2+Retention
Rate is 93.1%；In nanofiltration process, the permeation flux of nanofiltration membrane is 39.98L/ (hm2)。
Embodiment 9
A kind of method for present embodiments providing complexing agent enhancing nanofiltration membrane catching heavy metal ion, removes and receives in step (2)
Filter sizes are 2nm, and transmembrane pressure is outside 1.5MPa, remaining is same as Example 1.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 0.81mmol/LPb2 +、2.52mmol/LCu2+、0.28mmol/LCd2+、1.71mmol/LZn2+With 2.87mmol/LMn2+, wherein Pb2+Rejection
For 93.8%, Cu2+Rejection be 94%, Cd2+Rejection be 96%, Zn2+Rejection be 94.3%, Mn2+Rejection
It is 92%；In nanofiltration process, the permeation flux of nanofiltration membrane is 47.11L/ (hm2)。
Embodiment 10
A kind of method for present embodiments providing complexing agent enhancing nanofiltration membrane catching heavy metal ion, except work described in step 1
In the integral molar quantity and compound complex agent of industry heavy metal ions in wastewater the ratio between integral molar quantity of each complexing agent be 5.5:1 outside,
Yu Jun is same as Example 1.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 1.73mmol/LPb2 +、4.68mmol/LCu2+、0.59mmol/LCd2+、2.93mmol/LZn2+With 5.35mmol/LMn2+, wherein Pb2+Rejection
For 86.7%, Cu2+Rejection be 88.8%, Cd2+Rejection be 91.6%, Zn2+Rejection be 90.2%, Mn2+Cut
Staying rate is 85.1%；In nanofiltration process, the permeation flux of nanofiltration membrane is 51.31L/ (hm2)。
Embodiment 11
A kind of method for present embodiments providing complexing agent enhancing nanofiltration membrane catching heavy metal ion, except work described in step 1
In the integral molar quantity and compound complex agent of industry heavy metal ions in wastewater the ratio between integral molar quantity of each complexing agent be 1.5:1 outside,
Yu Jun is same as Example 1.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 0.72mmol/LPb2 +、2.18mmol/LCu2+、0.22mmol/LCd2+、1.36mmol/LZn2+With 2.57mmol/LMn2+, wherein Pb2+Rejection
For 94.5%, Cu2+Rejection be 94.8%, Cd2+Rejection be 96.8%, Zn2+Rejection be 95.5%, Mn2+Cut
Staying rate is 92.8%；In nanofiltration process, the permeation flux of nanofiltration membrane is 36.31L/ (hm2)。
Comparative example 1
This comparative example provides a kind of method of nanofiltration membrane catching heavy metal ion, and described method includes following steps: containing
There is 13mmol/LPb2+、42mmol/LCu2+、7mmol/LCd2+、30mmol/LZn2+With 36mmol/LMn2+Heavy metal ion, pH
The nanofiltration membrane that industrial wastewater for 4 is 1.5nm by aperture, transmembrane pressure when filtering are 2MPa.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 3.76mmol/LPb2 +、10.33mmol/LCu2+、3.13mmol/LCd2+、8.76mmol/LZn2+With 8.32mmol/LMn2+, wherein Pb2+Rejection
For 71.1%, Cu2+Rejection be 75.4%, Cd2+Rejection be 55.3%, Zn2+Rejection be 70.8%, Mn2+Cut
Staying rate is 76.9%；In nanofiltration process, the permeation flux of nanofiltration membrane is 52.69L/ (hm2)。
Comparative example 2
This comparative example provides a kind of method of nanofiltration membrane catching heavy metal ion, and the method is except answering in step (1)
It closes complexing agent to be made of EDTA and sodium oxalate, the molar ratio of EDTA and sodium oxalate is 2:1, industrial wastewater in the compound complex agent
In the integral molar quantity and compound complex agent of middle heavy metal ion the ratio between integral molar quantity of each complexing agent be 3:1 outside, remaining with reality
It is identical to apply example 1.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 1.62mmol/LPb2 +、5.63mmol/LCu2+、0.38mmol/LCd2+、5.34mmol/LZn2+With 4.06mmol/LMn2+, wherein Pb2+Rejection
For 87.5%, Cu2+Rejection be 86.6%, Cd2+Rejection be 94.5%, Zn2+Rejection be 82.2%, Mn2+Cut
Staying rate is 88.7%；In nanofiltration process, the permeation flux of nanofiltration membrane is 45.43L/ (hm2)。
Comparative example 3
This comparative example provides a kind of method of nanofiltration membrane catching heavy metal ion, and the method is except answering in step (1)
It closes complexing agent to be made of EDTA and citric acid, the molar ratio of EDTA and citric acid is 2:1, industrial wastewater in the compound complex agent
In the integral molar quantity and compound complex agent of middle heavy metal ion the ratio between integral molar quantity of each complexing agent be 3:1 outside, remaining with reality
It is identical to apply example 1.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 4.07mmol/LPb2 +、6.97mmol/LCu2+、0.46mmol/LCd2+、6.99mmol/LZn2+With 3.744mmol/LMn2+, wherein Pb2+Rejection
For 68.7%, Cu2+Rejection be 83.4%, Cd2+Rejection be 93.5%, Zn2+Rejection be 76.7%, Mn2+Cut
Staying rate is 89.6%；In nanofiltration process, the permeation flux of nanofiltration membrane is 45.67L/ (hm2)。
Comparative example 4
This comparative example provides a kind of method of nanofiltration membrane catching heavy metal ion, and the method is except answering in step (1)
It closes complexing agent to be made of sodium oxalate and citric acid, the molar ratio of the compound complex agent mesoxalic acid sodium and citric acid is 1:1, industry
The ratio between integral molar quantity of each complexing agent is outside 3:1 in the integral molar quantity and compound complex agent of heavy metal ions in wastewater, remaining is
It is same as Example 1.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 2.98mmol/LPb2 +、7.81mmol/LCu2+、2.3mmol/LCd2+、7.98mmol/LZn2+With 6.52mmol/LMn2+, wherein Pb2+Rejection be
77.1%, Cu2+Rejection be 81.4%, Cd2+Rejection be 67.1%, Zn2+Rejection be 73.4%, Mn2+Retention
Rate is 81.9%；In nanofiltration process, the permeation flux of nanofiltration membrane is 46.07L/ (hm2)。
Comparative example 5
This comparative example provides a kind of method of complexing agent enhancing nanofiltration membrane catching heavy metal ion, except described in step 1
The molar ratio of EDTA, sodium oxalate and citric acid are outside 1:1:1 in compound complex agent, remaining is same as Example 1.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 1.52mmol/LPb2 +、3.77mmol/LCu2+、0.41mmol/LCd2+、3.29mmol/LZn2+With 3.11mmol/LMn2+, wherein Pb2+Rejection
For 88.3%, Cu2+Rejection be 91%, Cd2+Rejection be 94.1%, Zn2+Rejection be 89%, Mn2+Rejection
It is 91.4%；In nanofiltration process, the permeation flux of nanofiltration membrane is 47.61L/ (hm2)。
Comparative example 6
This comparative example provides a kind of method of complexing agent enhancing nanofiltration membrane catching heavy metal ion, except described in step 1
The molar ratio of EDTA, sodium oxalate and citric acid are outside 2:2:1 in compound complex agent, remaining is same as Example 1.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 0.97mmol/LPb2 +、2.59mmol/LCu2+、0.47mmol/LCd2+、1.74mmol/LZn2+With 5.17mmol/LMn2+, wherein Pb2+Rejection
For 92.5%, Cu2+Rejection be 93.8%, Cd2+Rejection be 93.3%, Zn2+Rejection be 94.2%, Mn2+Cut
Staying rate is 85.6%；In nanofiltration process, the permeation flux of nanofiltration membrane is 46.53L/ (hm2)。
Comparative example 7
This comparative example provides a kind of method of complexing agent enhancing nanofiltration membrane catching heavy metal ion, except described in step 1
The molar ratio of EDTA, sodium oxalate and citric acid are outside 2:1:2 in compound complex agent, remaining is same as Example 1.
Measure the concentration through the postindustrial heavy metal ions in wastewater of nanofiltration membrane treatment, measurement result are as follows: 1.51mmol/LPb2 +、4.12mmol/LCu2+、0.53mmol/LCd2+、2.29mmol/LZn2+With 2.88mmol/LMn2+, wherein Pb2+Rejection
For 88.5%, Cu2+Rejection be 90.2%, Cd2+Rejection be 92.4%, Zn2+Rejection be 92.3%, Mn2+Cut
Staying rate is 92%；In nanofiltration process, the permeation flux of nanofiltration membrane is 46.37L/ (hm2)。
In embodiment 1-11 and comparative example 1-7 provided by the invention, Pb2+、Cu2+、Cd2+、Zn2+With Mn2+Five kinds of huge sum of moneys
The permeation flux of the rejection and nanofiltration membrane that belong to ion is as shown in table 1.
Table 1
As shown in Table 1, in embodiment 1-9 provided by the invention, Pb2+Rejection be 88.5-94.5%, Cu2+Retention
Rate is 86.5-94.8%, Cd2+Rejection be 85.9-97.1%, Zn2+Rejection be 86.7-95.6%, Mn2+Retention
Rate is 85.1-93.1%, and the rejection of five heavy metal species ions is 85% or more, and the permeation flux of nanofiltration membrane is 39.98-
50.49L/(h·m2), the treating capacity of nanofiltration membrane is larger.
It is each in the integral molar quantity and compound complex agent of heavy metals in industrial wastewater ion in embodiment 10 provided by the invention
The ratio between integral molar quantity of complexing agent is 5.5:1, and compared with Example 1, the compound complex agent being added in embodiment 10 is less, although
The permeation flux of nanofiltration membrane is by 45.98L/ (hm2) rise to 51.31L/ (hm2), but Pb2+Rejection by 94.1% drop
Down to 86.7%, Cu2+Rejection be reduced to 88.8%, Cd by 94.5%2+Rejection be reduced to 91.6% by 96.5%,
Zn2+Rejection be reduced to 90.2%, Mn by 95.1%2+Rejection be reduced to 85.1% by 92.7%.
It is each in the integral molar quantity and compound complex agent of heavy metals in industrial wastewater ion in embodiment 11 provided by the invention
The ratio between integral molar quantity of complexing agent is 1.5:1, and compared with Example 1, the compound complex agent being added in embodiment 11 is more, Pb2+
Rejection rise to 94.5%, Cu by 94.1%2+Rejection rise to 94.8%, Cd by 94.5%2+Rejection by
96.5% rises to 96.8%, Zn2+Rejection rise to 95.5%, Mn by 95.1%2+Rejection risen to by 92.7%
92.8%, but the permeation flux of nanofiltration membrane is by 45.98L/ (hm2) it is reduced to 36.13L/ (hm2)。
Comparative example 1 provided by the invention is compared with Example 1, no in the industrial wastewater of comparative example 1 that compound complexing is added
Agent.Although the permeation flux of nanofiltration membrane is by 45.98L/ (hm2) it is increased to 52.69L/ (hm2), but Pb2+Rejection by
94.1% is reduced to 71.1%, Cu2+Rejection be reduced to 75.4%, Cd by 94.5%2+Rejection be reduced to by 96.5%
55.3%, Zn2+Rejection be reduced to 70.8%, Mn by 95.1%2+Rejection be reduced to 76.9% by 92.7%.
Compared with Example 1, the compound complex agent in comparative example 2 is by EDTA and sodium oxalate for comparative example 2 provided by the invention
It forms, the molar ratio of EDTA and sodium oxalate is 2:1 in the compound complex agent.The permeation flux of nanofiltration membrane is by 45.98L/ (h
m2) become 47.43L/ (hm2), Pb2+Rejection be reduced to 87.5%, Cu by 94.1%2+Rejection by 94.5% reduce
To 86.6%, Cd2+Rejection be reduced to 94.5%, Zn by 96.5%2+Rejection be reduced to 82.2%, Mn by 95.1%2+
Rejection be reduced to 88.7% by 92.7%.
Compared with Example 1, the compound complex agent in comparative example 3 is by EDTA and citric acid for comparative example 3 provided by the invention
It forms, the molar ratio of EDTA and citric acid is 2:1 in the compound complex agent.The permeation flux of nanofiltration membrane is by 45.98L/ (h
m2) become 48.67L/ (hm2), Pb2+Rejection be reduced to 68.7%, Cu by 94.1%2+Rejection by 94.5% reduce
To 83.4%, Cd2+Rejection be reduced to 93.5%, Zn by 96.5%2+Rejection be reduced to 76.7%, Mn by 95.1%2+
Rejection be reduced to 89.6% by 92.7%.
Compared with Example 1, the compound complex agent in comparative example 4 is by sodium oxalate and lemon for comparative example 4 provided by the invention
The molar ratio of acid composition, the compound complex agent mesoxalic acid sodium and citric acid is 1:1.The permeation flux of nanofiltration membrane is by 45.98L/
(h·m2) become 50.07L/ (hm2), Pb2+Rejection be reduced to 77.1%, Cu by 94.1%2+Rejection by 94.5%
It is reduced to 81.4%, Cd2+Rejection be reduced to 67.1%, Zn by 96.5%2+Rejection be reduced to by 95.1%
73.4%, Mn2+Rejection be reduced to 81.9% by 92.7%.
In comparative example 5 provided by the invention compared with Example 1, EDTA, sodium oxalate and citric acid in compound complex agent
Molar ratio be 1:1:1, comparative example 5 be added compound complex agent in EDTA content it is less.Although the permeation flux of nanofiltration membrane
By 45.98L/ (hm2) it is increased to 47.61L/ (hm2), but Pb2+Rejection be reduced to 88.3%, Cu by 94.1%2+'s
Rejection is reduced to 91%, Cd by 94.5%2+Rejection be reduced to 94.1%, Zn by 96.5%2+Rejection by 95.1%
It is reduced to 89%, Mn2+Rejection be reduced to 91.4% by 92.7%.
In comparative example 6 provided by the invention compared with Example 1, EDTA, sodium oxalate and citric acid in compound complex agent
Molar ratio be 2:2:1, comparative example 6 be added compound complex agent mesoxalic acid sodium content it is more.Although the infiltration of nanofiltration membrane is logical
Amount is by 45.98L/ (hm2) it is increased to 46.53L/ (hm2), but Pb2+Rejection be reduced to 92.5%, Cu by 94.1%2+
Rejection be reduced to 93.8%, Cd by 94.5%2+Rejection be reduced to 93.3%, Zn by 96.5%2+Rejection by
95.1% is reduced to 94.2%, Mn2+Rejection be reduced to 85.6% by 92.7%, wherein Mn2+Rejection decline it is more.
In comparative example 7 provided by the invention compared with Example 1, EDTA, sodium oxalate and citric acid in compound complex agent
Molar ratio be 2:1:2, comparative example 7 be added compound complex agent mesoxalic acid sodium content it is more.Although the infiltration of nanofiltration membrane is logical
Amount is by 45.98L/ (hm2) it is increased to 46.37L/ (hm2), but Pb2+Rejection be reduced to 88.5%, Cu by 94.1%2+
Rejection be reduced to 90.2%, Cd by 94.5%2+Rejection be reduced to 92.4%, Zn by 96.5%2+Rejection by
95.1% is reduced to 92.3%, Mn2+Rejection be reduced to 92% by 92.7%.
In conclusion this method of the present invention is made more in industrial wastewater by adding compound complex agent in industrial wastewater
Heavy metal species ion and compound complex agent are complexed, and then while improving nanofiltration membrane to the Industrial Wastewater Treatment cuts heavy metal ion
Stay rate, Pb2+、Cu2+、Cd2+、Zn2+And Mn2+Rejection can reach 85% or more, and this method nanofiltration membrane is permeated it is logical
The influence of amount is smaller, and in the process parameters range of the method provided by the present invention, the permeation flux of nanofiltration membrane is in 39.98-50.49L/
(h·m2) in variation.This method simple process can effectively remove the contents of many kinds of heavy metal ion in industrial wastewater convenient for operation,
Industrial applicability is preferable.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of method of complexing agent enhancing nanofiltration membrane catching heavy metal ion, which is characterized in that the method includes walking as follows
It is rapid: compound complex agent to be added in the industrial wastewater containing heavy metal ion, after mixing by nanofiltration membrane；
The compound complex agent is made of EDTA, sodium oxalate and citric acid, and the molar ratio of EDTA, sodium oxalate and citric acid are
(3-5):(1-3):(1-2)。
2. the method according to claim 1, wherein EDTA, sodium oxalate and lemon in the compound complex agent
The molar ratio of acid is 2:1:1.
3. method according to claim 1 or 2, which is characterized in that the heavy metal ion includes Pb2+、Cu2+、Cd2+、Zn2 +Or Mn2+In any one or at least two combination, preferably Pb2+、Cu2+、Cd2+、Zn2+And Mn2+。
4. method according to claim 1-3, which is characterized in that the heavy metals in industrial wastewater ion it is total
Molar concentration is 100-150mmol/L, preferably 110-140mmol/L.
5. method according to claim 1-4, which is characterized in that Pb in the industrial wastewater2+Molar concentration
For 10-15mmol/L, preferably 12-14mmol/L；
Preferably, the Cu2+Molar concentration be 30-50mmol/L, preferably 40-45mmol/L；
Preferably, the Cd2+Molar concentration be 5-10mmol/L, preferably 6-8mmol/L；
Preferably, the Zn2+Molar concentration be 25-35mmol/L, preferably 28-32mmol/L；
Preferably, the Mn2+Molar concentration be 30-40mmol/L, preferably 35-38mmol/L.
6. method according to claim 1-5, which is characterized in that the pH value of the industrial wastewater is 2-6, preferably
For 3-5.
7. method according to claim 1-6, which is characterized in that the heavy metals in industrial wastewater ion it is total
The ratio between mole and the mole of compound complex agent are (2-5): 1, preferably (3-4): 1.
8. method according to claim 1-7, which is characterized in that transmembrane pressure when passing through nanofiltration membrane is
1.5-2.5MPa preferably 1.8-2.2MPa.
9. method according to claim 1-8, which is characterized in that the aperture of the nanofiltration membrane is 1-2nm, preferably
For 1.2-1.8nm.
10. -9 described in any item methods according to claim 1, which is characterized in that described method includes following steps:
(1) contain Pb2+、Cu2+、Cd2+、Zn2+With Mn2+Heavy metal ion, pH are to add in the industrial wastewater of 2-6 by EDTA, oxalic acid
The compound complex agent of sodium and citric acid composition, the molar ratio of EDTA, sodium oxalate and citric acid are (3- in the compound complex agent
5): (1-3): (1-2), the total mol concentration of heavy metals in industrial wastewater ion are 100-150mmol/L, the Pb2+Mole
Concentration is 10-15mmol/L, the Cu2+Molar concentration be 30-50mmol/L, the Cd2+Molar concentration be 5-
10mmol/L, the Zn2+Molar concentration be 25-35mmol/L, the Mn2+Molar concentration be 30-40mmol/L, it is described
The ratio between the integral molar quantity of heavy metals in industrial wastewater ion and the mole of compound complex agent are (2-5): 1；
(2) nanofiltration membrane that compound complex agent and industrial wastewater are after mixing 1-2nm by aperture, transmembrane pressure when filtering
Difference is 1.5-2.5MPa.
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