CN115430294A - Roll type nanofiltration membrane element capable of efficiently removing trace heavy metals - Google Patents
Roll type nanofiltration membrane element capable of efficiently removing trace heavy metals Download PDFInfo
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- CN115430294A CN115430294A CN202210928143.3A CN202210928143A CN115430294A CN 115430294 A CN115430294 A CN 115430294A CN 202210928143 A CN202210928143 A CN 202210928143A CN 115430294 A CN115430294 A CN 115430294A
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- woven fabric
- acrylic acid
- water
- nanofiltration membrane
- fabric film
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- 239000012528 membrane Substances 0.000 title claims abstract description 88
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 59
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 125
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 68
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 65
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000004744 fabric Substances 0.000 claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 150000001412 amines Chemical class 0.000 claims abstract description 21
- 238000000746 purification Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 36
- 238000007789 sealing Methods 0.000 claims description 17
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- -1 polyethylene terephthalate Polymers 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 230000002285 radioactive effect Effects 0.000 claims description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000005202 decontamination Methods 0.000 claims description 4
- 230000003588 decontaminative effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/06—Tubular membrane modules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/10—Spiral-wound membrane modules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
-
- 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
Abstract
A roll-type nanofiltration membrane element capable of efficiently removing trace heavy metals comprises a central tube and a water purification membrane group wound on the central tube, and is characterized in that the water purification membrane group comprises a water inlet diversion net, a modified water production diversion cloth and a nanofiltration membrane which are folded and combined; the modified water-producing flow guide cloth is obtained by grafting acrylic acid on the surface of a non-woven fabric film and then reacting with organic amine. Through modifying the non-woven fabric, the non-woven fabric is aminated, and the removal rate of trace heavy metals in the water body can reach 99 percent or more.
Description
Technical Field
The invention relates to a fiber membrane element for water body purification, in particular to a nanofiltration membrane element capable of adsorbing heavy metals.
Background
The main of the trace heavy metal that can high-efficiently get rid of in the water of filter membrane component on the existing market adopts reverse osmosis membrane, and general clearance is about 90%, and general nanofiltration membrane is about 83% to the clearance of trace heavy metal generally, and some adopt the composite filter core of receiving filtration, get rid of through adsorption or electrostatic action, if: adding graphene carbon material into the base membrane, grafting and crosslinking on the surface of the membrane to charge the membrane, and removing heavy metal through electrostatic action.
The RO membrane has low removal rate of heavy metals, cannot reach 99 percent removal rate, and has low retention of calcium and magnesium ions in water; the common nanofiltration membrane has low heavy metal removal rate and poor selectivity; the functional adsorption material generally relates to complex chemical reaction, has complicated steps, and some adsorption materials are adsorbed by physical acting force and are easy to desorb, so that secondary pollution is caused.
Disclosure of Invention
The invention aims to solve the technical problem of providing the roll-type nanofiltration membrane element capable of efficiently removing trace heavy metals aiming at the technical current situation.
The first technical solution adopted by the present invention to solve the above technical problems is: a roll-type nanofiltration membrane element capable of efficiently removing trace heavy metals comprises a central tube-level water purification membrane group wound on a central tube, and is characterized in that the water purification membrane group comprises a water inlet flow guide net, a modified water production flow guide cloth and a nanofiltration membrane, wherein the nanofiltration membrane is formed by folding and combining the nanofiltration membrane, the front surface of the nanofiltration membrane faces inwards, the nanofiltration membrane is divided and folded in half to form a water inlet flow channel, a crease end is flush with the central tube, a water production flow channel is formed between the upper surface and the lower surface of two adjacent membranes, and the other three sides of the two adjacent membranes except the side of the central tube are sealed by glue to form a nanofiltration membrane bag; the water inlet flow guide net is laid in the water inlet flow channel; the modified water production flow guide cloth is laid in the water production flow channel;
the modified water-producing flow guide cloth is obtained by grafting acrylic acid on the surface of a non-woven fabric film and then reacting with organic amine.
Preferably, the non-woven fabric film is at least one of polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate.
Preferably, the grafted acrylic acid is prepared by the following steps: placing the non-woven fabric film in an irradiation bottle, adding acrylic acid grafting solution into the irradiation bottle to enable the non-woven fabric film or water-producing flow guide cloth to be completely soaked in the acrylic acid grafting solution, introducing nitrogen for protection for 15-20 min to remove oxygen in the bottle, sealing the irradiation bottle, placing the irradiation bottle in a constant-temperature sleeve container, and circulating water at the constant temperature of 26-28 ℃ in the constant-temperature sleeve to ensure that the temperature in the irradiation bottle is constant at 24-25 ℃. Then the whole set of equipment is placed in 7.4 x 10^14Bg 60 Irradiating in a Co radioactive source, wherein the absorption dose rate is 21.42Gy/min; and after the irradiation is finished, taking the non-woven fabric film out of the acrylic acid solution, cleaning to remove unpolymerized acrylic acid and acrylic acid homopolymer, draining the surface moisture after the cleaning is finished, drying the non-woven fabric film in a vacuum oven at 50-60 ℃ to constant weight, and sealing and storing to obtain the non-woven fabric film grafted with the acrylic acid.
Preferably, the acrylic acid graft solution is disposed as follows: adding ferrous sulfate heptahydrate and deionized water into a container, and stirring the mixture into a transparent solution according to the mass ratio of the ferrous sulfate heptahydrate to the deionized water of 1; and adding acrylic acid into the conical flask according to the mass ratio of the ferrous sulfate heptahydrate to the acrylic acid of 1-35, uniformly stirring, and sealing for later use to obtain the acrylic acid grafting solution.
Preferably, the non-woven fabric film is subjected to decontamination treatment before acrylic acid grafting, and the treatment mode is as follows: placing the non-woven fabric film in an acetone solution, heating to 56 ℃, and refluxing for 1h; taking out, airing, placing in a vacuum oven for drying at normal temperature, sealing and storing to obtain the non-woven fabric film without impurities.
The organic amine reaction conditions are as follows: the non-woven fabric film grafted with the acrylic acid is arranged in 1-10% organic amine solution and reacts for 10-48 h at 40-90 ℃, the non-woven fabric material is completely covered by the modification liquid, and the non-woven fabric film is taken out after the reaction is finished and is naturally dried after being washed for 2-10 h by pure water.
Preferably, the organic amine solution is aqueous solution of diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylenehexamine or polyethyleneimine with the molecular weight of 600-70000.
The second technical solution adopted by the present invention to solve the above technical problems is: the spiral-wound nanofiltration membrane element is characterized in that the water purification membrane group comprises a water inlet flow guide net, a first produced water flow guide cloth, a second produced water flow guide cloth, a nanofiltration membrane and a modified non-woven fabric, wherein the first produced water flow guide cloth is wound on the central pipe, the modified non-woven fabric is wound on the central pipe, and finally the water inlet flow guide net, the second produced water flow guide cloth and the nanofiltration membrane are folded and combined to be wound on the central pipe; the water inlet flow guide net is laid in the water inlet flow channel; the second water production diversion cloth is laid in the water production flow channel;
the modified non-woven fabric is obtained by grafting acrylic acid on the surface of a non-woven fabric film and then reacting with organic amine.
Compared with the prior art, the invention has the advantages that: the non-woven fabric is aminated by modification, the removal rate of trace heavy metals in a water body can reach 99% or more, compared with a common roll-type nanofiltration membrane, the volume of the nanofiltration membrane is not obviously increased, complex modification or various compounding of a nanofiltration membrane is not needed, and the non-woven fabric has the function of efficiently removing trace heavy metal ions; the modified non-woven fabric only needs to be simply soaked, does not have the problem of slow falling or release, has simple process flow and lower cost, is easy to realize industrial production, and can be used in the field of water purification. The inlet non-woven fabric is modified through a low-cost and simple process, so that the common nanofiltration membrane has a function of efficiently removing heavy metals, and compared with the modified nanofiltration membrane on the market, the method for compounding other adsorption materials and the like is simple and efficient.
Drawings
Fig. 1 is a schematic structural diagram of embodiment 1.
Fig. 2 is a schematic structural diagram of embodiment 2.
Detailed Description
The invention is described in further detail below with reference to the following examples of the drawings.
In embodiment 1, as shown in fig. 1, the rolled nanofiltration membrane element capable of efficiently removing trace heavy metals in this embodiment includes a central tube 1 and a water purification membrane group wound on the central tube 1, where the water purification membrane group includes a water inlet flow guide net 2, a modified water production flow guide cloth 4, and a nanofiltration membrane 3, which are folded and combined together, the nanofiltration membrane 3 faces inward, is folded in half to form a water inlet flow channel, a fold end is flush with the central tube 1, a water production flow channel is formed between the upper and lower surfaces of two adjacent membranes, and the remaining three sides of the two adjacent membranes except the central tube side are sealed with glue to form a nanofiltration membrane bag; the water inlet flow guide net 2 is paved in the water inlet flow channel; the modified water producing flow guide cloth 4 is laid in the water producing flow passage; the modified water-producing flow-guiding cloth 4 is obtained by grafting acrylic acid on the surface of a non-woven fabric film and then reacting with organic amine.
The central tube 1 is a hollow but non-communicated central tube, the length of two sections of the inner part is about 1.
The other three sides of one nanofiltration membrane bag are sealed by glue, the sealing time is in the membrane rolling process, the nanofiltration membrane is placed, then glue is dispensed, and then the nanofiltration membrane is rolled into a filter element; the other three surfaces of the water inlet flow channel except the crease are not sealed, and one side of the two sides vertical to the central pipe is a raw water inlet, and the other end of the two sides is a concentrated water outlet; the ratio of the length of the long side of the water inlet flow guide net to the length of the long side of the nanofiltration membrane bag is 1.04-1.2; one water purification membrane group consists of 2 folded nanofiltration membranes. The modified water-producing flow guide cloth is made of polytrimethylene terephthalate.
The water producing flow guide cloth is grafted with acrylic acid by the following steps: and (3) arranging the produced water in an irradiation bottle in a diversion way, adding acrylic acid grafting liquid into the irradiation bottle to enable the produced water diversion cloth to be completely soaked into the acrylic acid grafting liquid, introducing nitrogen for protection for 20min to remove oxygen in the bottle, sealing the irradiation bottle, placing the irradiation bottle in a constant-temperature sleeve container, and circulating water at the constant temperature of 27 ℃ in the constant-temperature sleeve to ensure that the temperature in the irradiation bottle is constant at 24 ℃. Then the whole set of device is placed in a 60Co radioactive source with the radiation intensity of 7.4 x 10 Fa 14Bg for irradiation, wherein the absorption dose rate is 21.42Gy/min; and after the irradiation is finished, taking the water production guide cloth out of the acrylic acid solution, cleaning to remove unpolymerized acrylic acid and acrylic acid homopolymer, draining off surface water after the cleaning is finished, placing the non-woven fabric film in a vacuum oven at 55 ℃ to dry to constant weight, and sealing and storing to obtain the water production guide cloth grafted with the acrylic acid.
The acrylic acid grafting solution was prepared as follows: adding ferrous sulfate heptahydrate and deionized water into a container, and stirring the mixture into a transparent solution according to the mass ratio of the ferrous sulfate heptahydrate to the deionized water of 1; and adding acrylic acid into the conical flask according to the mass ratio of the ferrous sulfate heptahydrate to the acrylic acid of 1.
The water-producing flow guide cloth is subjected to impurity removal treatment before acrylic acid grafting, and the treatment mode is as follows: placing the water-producing diversion cloth in an acetone solution, heating to 56 ℃, and refluxing for 1h; taking out, airing, placing in a vacuum oven for drying at normal temperature, sealing and storing to obtain the water-producing diversion cloth with decontamination.
The organic amine reaction conditions are as follows: and (3) arranging the non-woven fabric film grafted with the acrylic acid in a 10% organic amine solution, reacting for 12 hours at 80 ℃, completely covering the water-producing flow guide cloth with the modified liquid, taking out after the reaction is finished, and naturally drying after pure water is washed for 3 hours. The organic amine solution is an aqueous solution of polyethyleneimine.
In the embodiment, the removal rate of trace heavy metals in the water body can reach 99% or more, and the types of the heavy metals in the embodiment mainly include cadmium ions, chromium ions, copper ions, lead ions, mercury ions, iron ions and manganese ions.
In embodiment 2, as shown in fig. 2, the rolled nanofiltration membrane element capable of efficiently removing trace heavy metals in this embodiment includes a central tube-level water purification membrane group wound around the central tube, the water purification membrane group includes a water inlet flow guide net 2, a first water production flow guide cloth 61, a second water production flow guide cloth 62, a nanofiltration membrane 3 and a modified nonwoven fabric 5, the first water production flow guide cloth 61 is firstly wound on the central tube 1, and the length of the first water production flow guide cloth is 20cm, so that the flux of a filter element can be increased; secondly, winding the modified non-woven fabric 5 on a central pipe, wherein the length of the modified non-woven fabric is 300cm; finally, the water inlet flow guide net 2, the second water production flow guide cloth 62 and the nanofiltration membrane 3 are folded and combined to be wound on the central pipe, the lengths of the water inlet flow guide net 2, the second water production flow guide cloth 62 and the nanofiltration membrane 3 are respectively 50cm, 53cm and 110cm, and the widths of the water inlet flow guide net 2, the second water production flow guide cloth 62 and the nanofiltration membrane 3 are all 26cm; the nanofiltration membrane 3 faces inwards, is divided and folded in half to form a water inlet flow channel, the fold line end is flush with the central pipe, a water production flow channel is formed between the upper surface and the lower surface of two adjacent membranes, the other three sides of the two adjacent membranes except the central pipe side are sealed by glue to form a nanofiltration membrane bag, and the nanofiltration membrane and a second water production diversion cloth which are carried with the water inlet diversion net are repeatedly placed until 3 nanofiltration membrane bags are formed; the water inlet flow guide net 2 is paved in the water inlet flow channel; the second water production flow guide cloth 62 is laid in the water production flow channel; the modified non-woven fabric 5 is obtained by grafting acrylic acid on the surface of a non-woven fabric film and then reacting with organic amine. The modified non-woven fabric material is polybutylene terephthalate.
The non-woven fabric grafting acrylic acid comprises the following steps: non-woven in an irradiation bottle, adding acrylic acid grafting liquid into the irradiation bottle to enable the water-producing diversion cloth to be completely soaked into the acrylic acid grafting liquid, introducing nitrogen for protection for 15min to remove oxygen in the bottle, sealing the irradiation bottle, placing the irradiation bottle in a constant-temperature sleeve container, and circulating water at the constant temperature of 28 ℃ in the constant-temperature sleeve to ensure that the temperature in the irradiation bottle is constant at 25 ℃. Then the whole set of device is placed in 7.4 x 10^14Bg 60 Irradiating in a Co radioactive source, wherein the absorption dose rate is 21.42Gy/min; after the irradiation is finished, taking out the non-woven fabric from the acrylic acid solutionAnd then, cleaning to remove unpolymerized acrylic acid and acrylic acid homopolymer, draining the surface moisture after cleaning, placing the non-woven fabric film in a vacuum oven at 60 ℃ to dry to constant weight, and sealing and storing to obtain the non-woven fabric grafted with acrylic acid.
The acrylic acid grafting solution was prepared as follows: adding ferrous sulfate heptahydrate and deionized water into a container, and stirring the mixture into a transparent solution according to the mass ratio of the ferrous sulfate heptahydrate to the deionized water of 1; and adding acrylic acid into the conical flask according to the mass ratio of the ferrous sulfate heptahydrate to the acrylic acid of 1.
The non-woven fabric is subjected to decontamination treatment before acrylic acid grafting, and the treatment mode is as follows: placing the non-woven fabric in an acetone solution, heating to 56 ℃, and refluxing for 1h; taking out, air drying, placing in a vacuum oven, drying at normal temperature, sealing, and storing to obtain nonwoven fabric with impurity removed.
The organic amine reaction conditions are as follows: and (3) arranging the non-woven fabric film grafted with the acrylic acid in a 1% organic amine solution, reacting for 18h at 90 ℃, completely covering the non-woven fabric with the modification solution, taking out after the reaction is finished, and naturally drying after cleaning for 1h with pure water. The organic amine solution is an aqueous solution of polyethyleneimine.
Claims (10)
1. A roll-type nanofiltration membrane element capable of efficiently removing trace heavy metals comprises a central tube-level water purification membrane group wound on a central tube, and is characterized in that the water purification membrane group comprises a water inlet flow guide net, a modified water production flow guide cloth and a nanofiltration membrane, wherein the nanofiltration membrane is formed by folding and combining the nanofiltration membrane, the front surface of the nanofiltration membrane faces inwards, the nanofiltration membrane is divided and folded in half to form a water inlet flow channel, a crease end is flush with the central tube, a water production flow channel is formed between the upper surface and the lower surface of two adjacent membranes, and the other three sides of the two adjacent membranes except the side of the central tube are sealed by glue to form a nanofiltration membrane bag; the water inlet flow guide net is paved in the water inlet flow channel; the modified water production flow guide cloth is laid in the water production flow channel;
the modified water-producing flow guide cloth is obtained by grafting acrylic acid on the surface of a non-woven fabric film and then reacting with organic amine.
2. The roll-type nanofiltration membrane element capable of efficiently removing trace heavy metals according to claim 1, wherein the non-woven fabric film is at least one of polyethylene terephthalate, polybutylene terephthalate, or polytrimethylene terephthalate.
3. The roll-type nanofiltration membrane element capable of efficiently removing trace heavy metals according to claim 1, wherein the grafting acrylic acid comprises the following steps: placing the non-woven fabric film in an irradiation bottle, adding acrylic acid grafting solution into the irradiation bottle to enable the non-woven fabric film or water-producing flow guide cloth to be completely soaked in the acrylic acid grafting solution, introducing nitrogen for protection for 15-20 min to remove oxygen in the bottle, sealing the irradiation bottle, placing the irradiation bottle in a constant-temperature sleeve container, and circulating water at the constant temperature of 26-28 ℃ in the constant-temperature sleeve to ensure that the temperature in the irradiation bottle is constant at 24-25 ℃. Then the whole set of equipment is placed in 7.4 x 10^14Bg 60 Irradiating in a Co radioactive source, wherein the absorption dose rate is 21.42Gy/min; and after the irradiation is finished, taking the non-woven fabric film out of the acrylic acid solution, cleaning to remove unpolymerized acrylic acid and acrylic acid homopolymer, draining off surface moisture after the cleaning is finished, drying the non-woven fabric film in a vacuum oven at 50-60 ℃ to constant weight, sealing and storing to obtain the non-woven fabric film grafted with the acrylic acid.
4. The rolled nanofiltration membrane element capable of efficiently removing trace heavy metals according to claim 3, wherein the acrylic acid grafting solution is prepared in the following manner: adding ferrous sulfate heptahydrate and deionized water into a container, and stirring the mixture into a transparent solution according to the mass ratio of the ferrous sulfate heptahydrate to the deionized water of 1; and adding acrylic acid into the conical flask according to the mass ratio of the ferrous sulfate heptahydrate to the acrylic acid of 1-35, uniformly stirring, and sealing for later use to obtain the acrylic acid grafting solution.
5. The roll-type nanofiltration membrane element capable of efficiently removing trace heavy metals according to claim 3, wherein the non-woven fabric film is subjected to decontamination treatment before acrylic acid grafting, and the treatment method comprises the following steps: placing the non-woven fabric film in an acetone solution, heating to 56 ℃, and refluxing for 1h; taking out, airing, placing in a vacuum oven for drying at normal temperature, sealing and storing to obtain the non-woven fabric film without impurities.
6. The roll-type nanofiltration membrane element capable of efficiently removing trace heavy metals according to claim 1, wherein the organic amine reaction conditions are as follows:
the non-woven fabric film grafted with the acrylic acid is arranged in 1-10% organic amine solution and reacts for 10-48 h at 40-90 ℃, the non-woven fabric material is completely covered by the modification liquid, and the non-woven fabric film is taken out after the reaction is finished and is naturally dried after being washed for 2-10 h by pure water.
7. The roll-type nanofiltration membrane element capable of efficiently removing trace heavy metals according to claim 6, wherein the organic amine solution is diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine or an aqueous solution of polyethyleneimine with a molecular weight of 600-70000.
8. The spiral-wound nanofiltration membrane element is characterized in that the water purification membrane group comprises a water inlet flow guide net, a first produced water flow guide cloth, a second produced water flow guide cloth, a nanofiltration membrane and a modified non-woven fabric, wherein the first produced water flow guide cloth is wound on the central pipe, the modified non-woven fabric is wound on the central pipe, and finally the water inlet flow guide net, the second produced water flow guide cloth and the nanofiltration membrane are folded and combined to be wound on the central pipe; the water inlet flow guide net is laid in the water inlet flow channel; the second water production diversion cloth is laid in the water production flow channel;
the modified non-woven fabric is obtained by grafting acrylic acid on the surface of a non-woven fabric film and then reacting the non-woven fabric film with organic amine.
9. The rolled nanofiltration membrane element capable of efficiently removing trace heavy metals according to claim 8, wherein the grafting of acrylic acid comprises the following steps: placing a non-woven fabric film in an irradiation bottle, adding acrylic acid grafting solution into the irradiation bottle to completely soak the non-woven fabric film or water-producing diversion cloth into the acrylic acid grafting solution, introducing nitrogen for protection for 15-20 min to remove oxygen in the bottle, sealing the irradiation bottle, placing the bottle in a constant-temperature sleeve container, and circulating water at the constant temperature of 26-28 ℃ in the constant-temperature sleeve to ensure that the temperature in the irradiation bottle is constant at 24-25 ℃. Then the whole set of device is placed in 7.4 x 10^14Bg 60 Irradiating in a Co radioactive source, wherein the absorption dose rate is 21.42Gy/min; and after the irradiation is finished, taking the non-woven fabric film out of the acrylic acid solution, cleaning to remove unpolymerized acrylic acid and acrylic acid homopolymer, draining the surface moisture after the cleaning is finished, drying the non-woven fabric film in a vacuum oven at 50-60 ℃ to constant weight, and sealing and storing to obtain the non-woven fabric film grafted with the acrylic acid.
10. The roll-type nanofiltration membrane element capable of efficiently removing trace heavy metals according to claim 8, wherein the organic amine reaction conditions are as follows:
the non-woven fabric film grafted with the acrylic acid is arranged in 1-10% organic amine solution and reacts for 10-48 h at 40-90 ℃, the non-woven fabric material is completely covered by the modification liquid, and the non-woven fabric film is taken out after the reaction is finished and is naturally dried after being washed for 2-10 h by pure water.
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| CN114082310A (en) * | 2022-01-20 | 2022-02-25 | 湖南叶之能科技有限公司 | Roll type membrane element and preparation method and application thereof |
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