CN103480347A - Preparation method of composite flat membrane for adsorbing heavy metal ions and product thereof - Google Patents
Preparation method of composite flat membrane for adsorbing heavy metal ions and product thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a composite flat separation membrane and a product thereof, wherein the composite flat separation membrane has good adsorption ability on heavy metal ions such as nickel, molybdenum, mercury and the like as well as large adsorption capacity and high adsorption efficiency and can be cleaned for recycling. The product provided by the invention is prepared from water-washed and acid-washed attapulgite by modifying attapulgite with tannic acid and compounding with polyvinylidene fluoride. The composite flat membrane provided by the invention has a good adsorption effect on the heavy metal ions such as lead, cadmium, nickel, molybdenum and the like in wastewater, the adsorption rate on nickel ions of the composite membrane in which the mass ratio of polyvinylidene fluoride to modified attapulgite is 1:0.01 is close to 40%, and the adsorption rate on mercury ions is close to 60%. The product provided by the invention integrates the advantages of a polyvinylidene fluoride separation membrane as well as the adsorption performance of attapulgite; the preparation technology is simple and low in cost, does not need special equipment and is easy to implement industrially; the membrane has stable physical performance, and the pure water flux is increased.
Description
Technical field
The present invention relates to the intelligent macromolecule material field, be specifically related to a kind of the heavy metal ion such as mercury, copper, nickel, chromium, lead to be had to compound slab diffusion barrier of good adsorption function and preparation method thereof.This composite membrane, in water, the heavy metal ion adsorbed amounts such as nickel, chromium, lead are large, adsorption efficiency is high, can be applicable to the process field of the sewage such as electroplating industry, chemical industry, and can be through cleaning Reusability.
Background technology
In recent years, the contaminated wastewater that contains the heavy metal ion such as lead, copper, cadmium, chromium, mercury just is being on the rise, heavy metal wastewater thereby pollutes and to have become serious environment and social concern, is the crucial difficult problem of economic development at present in the urgent need to address and Environmental Health, safe drinking water aspect.
Aspect heavy metal ion adsorbed research, inorganic material more and more receives researcher's concern to the absorption property of heavy metal ion, wherein the inorganic mineral material is low and obvious to the absorption property of heavy metal ion because of cost, particularly noticeable aspect heavy metal ion adsorbed, attapulgite is wherein typically a kind of.
Attapulgite is as a kind of natural nonmetallic mineral material, be a kind of have the chain layer structure containing Shuifu County's magnesium silicate clay mineral.The special construction of attapulgite makes it have very large specific area, and physical absorption is very capable.On the other hand, attapulgite is with the aspect negative electrical charge, at interlayer, adsorbed cation with interchangeability so that charge balance, and attapulgite has just had strong ionic adsorption exchange capacity like this.
Attapulgite has good suspension in water, although therefore attapulgite has good adsorption capacity, for water treatment field, pulverous attapulgite can't directly drop in water and use, and need to take certain method to be processed.At present, processing method is to adopt certain immobilized attapulgite of carrier preferably, then drops in water and use.The inventor discloses a kind of preparation method of absorbent-type macromolecule composite aquogel and products thereof [201020595998.1] in early stage invention, utilizes macromolecule hydrogel to make carrier, immobilized attapulgite, thus bring into play well the suction-operated of attapulgite.
At present, in the Industrial Wastewater Treatment field, membrane separation technique because its separative efficiency is high,, non-secondary pollution simple, easy and simple to handle without phase transformation, energy-conserving and environment-protective, equipment, separated product be easy to reclaim, the automaticity advantages of higher, make it in water treatment field, there is sizable technical advantage, become one of indispensable technology in water treatment field.In numerous separation membrane materials, Kynoar (PVDF) is a kind of separation membrane material of high comprehensive performance, its good mechanical performance, have good resistance to impact, wearability and belt cutting-resisting property, also has the properties such as piezoelectricity, dielectricity and pyroelectricity.The inventor discloses a kind of PVDF hydridization flat sheet membrane [ZL201110254106.0] of Adsorption of Heavy Metal Ions in invention in early stage, this invention utilizes the adsorptivity of inorganic mineral attapulgite to heavy metal ion, and preparation has the PVDF-attapulgite hydridization diffusion barrier of adsorption function to heavy metal ion.But the efficiency of this PVDF-attapulgite hydridization diffusion barrier Adsorption of Heavy Metal Ions is low, adsorbance is little.Therefore, how further attapulgite being carried out to modification, is a great problem to improve PVDF-attapulgite hydridization diffusion barrier to the adsorption capacity of heavy metal ion.
Summary of the invention
Be applied to for existing PVDF-attapulgite hydridization diffusion barrier the deficiency that heavy metal ion adsorbed aspect exists, the technical problem that quasi-solution of the present invention is determined is to provide a kind of new modified method of attapulgite, utilizes the attapulgite of the method modification to have the good adsorption ability to heavy metal ion such as mercury, copper, lead, cadmium, nickel, molybdenums and adsorbance is large, adsorption efficiency is high.Utilize the attapulgite clay compounded diffusion barrier of PVDF-of this attapulgite modified preparation to heavy metal ion is large to heavy metal ion adsorbed amounts such as mercury, copper, lead, cadmium, nickel, molybdenums, adsorption efficiency is high, and reuse after capable of washing.Preparation method of the attapulgite clay compounded diffusion barrier of PVDF-that the technology of the present invention provides and products thereof, adopt washing, pickling attapulgite, and then utilize tannic acid modified attapulgite, finally by attapulgite modified, be dispersed in the PVDF casting solution, adopt phase inversion, scrape and make the compound slab diffusion barrier that the counterweight metal ion has adsorption function.
In the compound slab film of described Adsorption of Heavy Metal Ions, contain attapulgite modifiedly, described PVDF and attapulgite modified mass ratio are 1: 0.01～1: 0.1, and described attapulgite modified particle diameter is 300 orders～1000 orders; Available following method obtains:
1. the pretreatment of attapulgite.Take 10g～20g particle diameter 300 orders～1000 purpose attapulgites, with 1L distilled water, wash, get its supernatant liquor after precipitating, get its supernatant liquor after the centrifugal 1min of 500rpm, add a small amount of distilled water in supernatant liquor and mix the centrifugal 1min of rear continuation 500rpm, then get its supernatant liquor, after cyclic washing supernatant liquor like this 3～5 times, finally with 4000rpm, carry out centrifugation, get its precipitation, 90 ℃ of lower vacuum drying 24h, select the sieve of corresponding order number by particle size after grinding, obtain the purifying attapulgite.
The hydrochloric acid solution that configuration concentration is 0.5mol/L～3mol/L, getting 10g～20g purifying attapulgite and 150mL～200mL hydrochloric acid solution joins in small beaker and is uniformly mixed, after 5min, mixture is heated to 70 ℃～80 ℃, stirs 1h～2h, then sonic oscillation 30min～40min, suction filtration, be washed with distilled water to pH and be about 6 left and right, 90 ℃ of lower vacuum drying 24h, select the sieve of corresponding order number after grinding by particle size, obtain sour attapulgite modified.
Get 1g～3g acid attapulgite modified, add the tannic acid solution of 200mL～250mL concentration 2000mg/L, after stirring at room 2h～3h, ethanol is washed till supernatant and FeCl
3solution is without chromogenic reaction, centrifugation, and drying and grinding, select the sieve of corresponding order number by particle size, obtain tannic acid modified attapulgite.
2. the preparation of casting solution.Take PVDF and add in the container that is placed with DMF (DMF), add polyethylene glycol (PEG).Said vesse is placed in to 50 ℃～70 ℃ water-baths, and stirring and dissolving obtains the casting film feed liquid; Add tannic acid modified attapulgite in feed liquid, making PVDF and attapulgite modified mass ratio is 1: 0.01～1: 0.1, fully stirs and sonic oscillation makes the dispersed casting solution that obtains of attapulgite.
3. the preparation of the compound slab film of attached heavy metal ion.Casting solution is inclined to glass plate, by glass bar striking film forming, immerse solidification forming in the coagulating bath Water Tank with Temp.-controlled of 20 ℃～30 ℃, after being shaped from glass plate until film and coming off, place 24h～36h in distilled water, the compound slab film of attached heavy metal ion is cleaned and obtained to distilled water again.
In described step 2, PVDF mass percent in DMF is 15%～20%.
Described PEG molecular weight is 10000;
Described PEG addition is 6%～10% for mass percent in DMF, and PEG is used as pore-foaming agent;
Be distilled water in described coagulating bath water tank, solidify the effect that bath water plays the film coagulating agent.
Beneficial effect of the present invention:
The compound slab film that the present invention solves described attached heavy metal ion is to utilize conventional PVDF separation membrane material and tannic acid modified attapulgite clay compounded preparing.Product of the present invention preparation does not need special installation, industrializing implementation easy, and technique is simple in general, and the cost of film changes little.This flat-plate separation film product has good effect to heavy metal ion such as the lead in the waste water such as free electrolyte, electroplate liquid, cadmium, nickel, molybdenums, the composite membrane that the mass ratio of PVDF and attapulgite is 1: 0.01 approaches 40% to the adsorption rate of nickel ion, the mercury ion adsorption rate is approached to 60%, chromium ion, copper ion etc. is all had to good adsorptivity.Product employing acid washing method of the present invention can Reusability.In addition, prepared by the present invention is the organic and inorganic composite membrane, has concentrated the advantage of PVDF diffusion barrier and the absorption property of attapulgite, the film stable physical property, and pure water flux and hydrophily are improved to some extent.
Tannic acid of the present invention claims again tannic acid, be faint yellow to light brown without the crystalline flour end, belong to the complex compound of multi-phenol, at the occurring in nature rich content, cheap and easy to get.Tannic acid is because it has the structure of phenolic hydroxyl group, so it has very unique physiologically active and chemical characteristic.Two adjacent phenolic hydroxyl groups are arranged in the molecular formula of tannic acid, they can also form the chelate of the five-membered cyclic with stability by the form of negative oxygen ion and the combination of metal ion on every side, although being arranged, individual phenolic hydroxyl group do not participate in complex reaction, but its existence can promote dissociating fast of other two phenolic hydroxyl groups, further can promote to form complex compound and make it there is stability.Therefore, tannic acid can be used for the adsorbing separation of metal ion in water body.
The heavy metal ion adsorbed performance that the tannic acid modified attapulgite of product utilization of the present invention is superior, can effectively adsorb the heavy metal ion such as Pb In Exhausted Water, cadmium, nickel, molybdenum, mercury, and attapulgite consumption in system is few, little on the impact of the key propertys such as the mechanical strength of PVDF flat sheet membrane, permeability.In addition, China Jiangsu, Anhui have the abundant attapulgite resource of reserves, and the attapulgite price is comparatively cheap, and tannic acid consumption of the present invention is very little, and with respect to the PVDF flat sheet membrane, product cost impact of the present invention is little.
The specific embodiment:
The following examples can make the present invention of those skilled in the art comprehend, but do not limit the present invention in any way
Embodiment 1:
(1) pretreatment of attapulgite.Take 10g particle diameter 300 purpose attapulgites, with the washing of 1L distilled water, get its supernatant liquor after precipitating, get its supernatant liquor after the centrifugal 1min of 500rpm, add a small amount of distilled water in supernatant liquor and mix the centrifugal 1min of rear continuation 500rpm, then get its supernatant liquor, so, after cyclic washing supernatant liquor 3 times, finally with 4000rpm, carry out centrifugation, get its precipitation, 90 ℃ of lower vacuum drying 24h, select the sieve of corresponding order number by particle size after grinding, obtain the purifying attapulgite.
The hydrochloric acid solution that configuration concentration is 0.5mol/L, getting 10g purifying attapulgite and 150mL hydrochloric acid solution joins in small beaker and is uniformly mixed, after 5min, mixture is heated to 70 ℃, stirs 1h, then sonic oscillation 30min, suction filtration, be washed with distilled water to pH and be about 6 left and right, 90 ℃ of lower vacuum drying 24h, select the sieve of corresponding order number after grinding by particle size, obtain sour attapulgite modified.
Get 1g acid attapulgite modified, add the tannic acid solution of 200mL concentration 2000mg/L, after stirring at room 2h, ethanol is washed till supernatant and FeCl
3solution is without chromogenic reaction, centrifugation, and drying and grinding, select the sieve of corresponding order number by particle size, obtain tannic acid modified attapulgite.
(2) preparation of casting solution.Take in the beaker that PVDF adds the DMF that fills 500mL, PVDF mass percent in DMF is 18%.Add the pore-foaming agent PEG that molecular weight is 10000, the PEG addition is 8% for mass percent in DMF.Beaker is put in 60 ℃ of water-baths, and under electromagnetic agitation, makes dissolution of solid obtain the casting film feed liquid.Attapulgite modified to adding in feed liquid, the mass ratio that makes PVDF and attapulgite is 1: 0.01, fully stirs and sonic oscillation is uniformly dispersed it to obtain casting solution.
(3) preparation of the compound slab film of attached heavy metal ion.Casting solution is inclined to glass plate, by glass bar striking film forming, immerse solidification forming in the coagulating bath Water Tank with Temp.-controlled of 25 ℃, after being shaped from glass plate until film and coming off, place 24h in distilled water, distilled water is cleaned the PVDF compound slab film that obtains having heavy metal ion adsorbed function again.
Embodiment 2:
(1) pretreatment of attapulgite.Take 10g particle diameter 1000 purpose attapulgites, with the washing of 1L distilled water, precipitation is got its supernatant liquor, after the centrifugal 1min of 500rpm, gets its supernatant liquor, add a small amount of distilled water in supernatant liquor and mix the centrifugal 1min of rear continuation 500rpm, then get its supernatant liquor, so, after cyclic washing supernatant liquor 3 times, finally with 4000rpm, carry out centrifugation, get its precipitation, 90 ℃ of lower vacuum drying 24h, select the sieve of corresponding order number by particle size after grinding, obtain the purifying attapulgite.
The hydrochloric acid solution that configuration concentration is 0.5mol/L, getting 20g purifying attapulgite and 150mL hydrochloric acid solution joins in small beaker and is uniformly mixed, after 5min, mixture is heated to 70 ℃, stirs 1h, then sonic oscillation 30min, suction filtration, be washed with distilled water to pH and be about 6 left and right, 90 ℃ of lower vacuum drying 24h, select the sieve of corresponding order number after grinding by particle size, obtain sour attapulgite modified.
Get 1g acid attapulgite modified, add the tannic acid solution of 250mL concentration 2000mg/L, after stirring at room 2h, ethanol is washed till supernatant and FeCl
3solution is without chromogenic reaction, centrifugation, and drying and grinding, select the sieve of corresponding order number by particle size, obtain tannic acid modified attapulgite.
(2) preparation of casting solution.Take in the beaker that PVDF adds the DMF that fills 500mL, PVDF mass percent in DMF is 16%.Add the pore-foaming agent PEG that molecular weight is 10000, the PEG addition is 8% for mass percent in DMF.Beaker is put in 60 ℃ of water-baths, and under electromagnetic agitation, makes dissolution of solid obtain the casting film feed liquid.A certain amount of attapulgite modified to adding in feed liquid, the mass ratio that makes PVDF and attapulgite is 1: 0.05, fully stirs and sonic oscillation is uniformly dispersed it to obtain casting solution.
(3) preparation of the compound slab film of attached heavy metal ion.Casting solution is inclined to glass plate, by glass bar striking film forming, immerse solidification forming in the coagulating bath Water Tank with Temp.-controlled of 25 ℃, after being shaped from glass plate until film and coming off, place 24h in distilled water, distilled water is cleaned the PVDF compound slab film that obtains having heavy metal ion adsorbed function again.
Embodiment 3:
(1) pretreatment of attapulgite.Take 20g particle diameter 300 purpose attapulgites, with the washing of 1L distilled water, precipitation is got its supernatant liquor, after the centrifugal 1min of 500rpm, gets its supernatant liquor, add a small amount of distilled water in supernatant liquor and mix the centrifugal 1min of rear continuation 500rpm, then get its supernatant liquor, so, after cyclic washing supernatant liquor 5 times, finally with 4000rpm, carry out centrifugation, get its precipitation, 90 ℃ of lower vacuum drying 24h, select the sieve of corresponding order number by particle size after grinding, obtain the purifying attapulgite.
The hydrochloric acid solution that configuration concentration is 3mol/L, getting 10g purifying attapulgite and 150mL hydrochloric acid solution joins in small beaker and is uniformly mixed, after 5min, mixture is heated to 80 ℃, stirs 2h, then sonic oscillation 30min, suction filtration, be washed with distilled water to pH and be about 6 left and right, 90 ℃ of lower vacuum drying 24h, select the sieve of corresponding order number after grinding by particle size, obtain sour attapulgite modified.
Get 1g acid attapulgite modified, add the tannic acid solution of 200mL concentration 2000mg/L, after stirring at room 3h, ethanol is washed till supernatant and FeCl
3solution is without chromogenic reaction, centrifugation, and drying and grinding, select the sieve of corresponding order number by particle size, obtain tannic acid modified attapulgite.
(2) preparation of casting solution.Take in the beaker that PVDF adds the DMF that fills 500mL, PVDF mass percent in DMF is 17%.Add the pore-foaming agent PEG that molecular weight is 10000, the PEG addition is 10% for mass percent in DMF.Beaker is put in 60 ℃ of water-baths, and under electromagnetic agitation, makes dissolution of solid obtain the casting film feed liquid.A certain amount of attapulgite modified to adding in feed liquid, the mass ratio that makes PVDF and attapulgite is 1: 0.05, fully stirs and sonic oscillation is uniformly dispersed it to obtain casting solution.
(3) preparation of the compound slab film of attached heavy metal ion.Casting solution is inclined to glass plate, by glass bar striking film forming, immerse solidification forming in the coagulating bath Water Tank with Temp.-controlled of 30 ℃, after being shaped from glass plate until film and coming off, place 30h in distilled water, distilled water is cleaned the PVDF compound slab film that obtains having heavy metal ion adsorbed function again.
Embodiment 4:
(1) pretreatment of attapulgite.Take 15g particle diameter 500 purpose attapulgites, with the washing of 1L distilled water, precipitation is got its supernatant liquor, after the centrifugal 1min of 500rpm, gets its supernatant liquor, add a small amount of distilled water in supernatant liquor and mix the centrifugal 1min of rear continuation 500rpm, then get its supernatant liquor, so, after cyclic washing supernatant liquor 5 times, finally with 4000rpm, carry out centrifugation, get its precipitation, 90 ℃ of lower vacuum drying 24h, select the sieve of corresponding order number by particle size after grinding, obtain the purifying attapulgite.
The hydrochloric acid solution that configuration concentration is 1mol/L, getting 12g purifying attapulgite and 180mL hydrochloric acid solution joins in small beaker and is uniformly mixed, after 5min, mixture is heated to 70 ℃, stirs 1h, then sonic oscillation 30min, suction filtration, be washed with distilled water to pH and be about 6 left and right, 90 ℃ of lower vacuum drying 24h, select the sieve of corresponding order number after grinding by particle size, obtain sour attapulgite modified.
Get 2g acid attapulgite modified, add the tannic acid solution of 250mL concentration 2000mg/L, after stirring at room 3h, ethanol is washed till supernatant and FeCl
3solution is without chromogenic reaction, centrifugation, and drying and grinding, select the sieve of corresponding order number by particle size, obtain tannic acid modified attapulgite.
(2) preparation of casting solution.Take in the beaker that PVDF adds the DMF that fills 500mL, PVDF mass percent in DMF is 20%.Add the pore-foaming agent PEG that molecular weight is 10000, the PEG addition is 9% for mass percent in DMF.Beaker is put in 60 ℃ of water-baths, and under electromagnetic agitation, makes dissolution of solid obtain the casting film feed liquid.A certain amount of attapulgite modified to adding in feed liquid, the mass ratio that makes PVDF and attapulgite is 1: 0.1, fully stirs and sonic oscillation is uniformly dispersed it to obtain casting solution.
(3) preparation of the compound slab film of attached heavy metal ion.Casting solution is inclined to glass plate, by glass bar striking film forming, immerse solidification forming in the coagulating bath Water Tank with Temp.-controlled of 30 ℃, after being shaped from glass plate until film and coming off, place 24h in distilled water, distilled water is cleaned the PVDF compound slab film that obtains having heavy metal ion adsorbed function again.
Embodiment 5:
(1) pretreatment of attapulgite.Take 16g particle diameter 800 purpose attapulgites, with the washing of 1L distilled water, precipitation is got its supernatant liquor, after the centrifugal 1min of 500rpm, gets its supernatant liquor, add a small amount of distilled water in supernatant liquor and mix the centrifugal 1min of rear continuation 500rpm, then get its supernatant liquor, so, after cyclic washing supernatant liquor 5 times, finally with 4000rpm, carry out centrifugation, get its precipitation, 90 ℃ of lower vacuum drying 24h, select the sieve of corresponding order number by particle size after grinding, obtain the purifying attapulgite.
The hydrochloric acid solution that configuration concentration is 2.5mol/L, getting 18g purifying attapulgite and 160mL hydrochloric acid solution joins in small beaker and is uniformly mixed, after 5min, mixture is heated to 70 ℃, stirs 2h, then sonic oscillation 40min, suction filtration, be washed with distilled water to pH and be about 6 left and right, 90 ℃ of lower vacuum drying 24h, select the sieve of corresponding order number after grinding by particle size, obtain sour attapulgite modified.
Get 2.5g acid attapulgite modified, add the tannic acid solution of 250mL concentration 2000mg/L, after stirring at room 3h, ethanol is washed till supernatant and FeCl
3solution is without chromogenic reaction, centrifugation, and drying and grinding, select the sieve of corresponding order number by particle size, obtain tannic acid modified attapulgite.
(2) preparation of casting solution.Take in the beaker that PVDF adds the DMF that fills 500mL, PVDF mass percent in DMF is 18%.Add the pore-foaming agent PEG that molecular weight is 10000, the PEG addition is 7% for mass percent in DMF.Beaker is put in 60 ℃ of water-baths, and under electromagnetic agitation, makes dissolution of solid obtain the casting film feed liquid.A certain amount of attapulgite modified to adding in feed liquid, the mass ratio that makes PVDF and attapulgite is 1: 0.08, fully stirs and sonic oscillation is uniformly dispersed it to obtain casting solution.
(3) preparation of the compound slab film of attached heavy metal ion.Casting solution is inclined to glass plate, by glass bar striking film forming, immerse solidification forming in the coagulating bath Water Tank with Temp.-controlled of 30 ℃, after being shaped from glass plate until film and coming off, place 36h in distilled water, distilled water is cleaned the PVDF compound slab film that obtains having heavy metal ion adsorbed function again.
Claims (6)
1. the compound slab film of a described Adsorption of Heavy Metal Ions, made by following methods;
(1) pretreatment of attapulgite: the hydrochloric acid solution that configuration concentration is 0.5mol/L～3mol/L, getting 10g～20g purifying attapulgite and 150mL～200mL hydrochloric acid solution joins in small beaker and is uniformly mixed, after 5min, mixture is heated to 70 ℃～80 ℃, stir 1h～2h, then sonic oscillation 30min～40min, suction filtration, be washed with distilled water to pH and be about 6 left and right, 90 ℃ of lower vacuum drying 24h, select the sieve of corresponding order number after grinding by particle size, obtain sour attapulgite modified.Get 1g～3g acid attapulgite modified, add the tannic acid solution of 200mL～250mL concentration 2000mg/L, after stirring at room 2h～3h, ethanol is washed till supernatant and FeCl
3solution is without chromogenic reaction, centrifugation, and drying and grinding, select the sieve of corresponding order number by particle size, obtain tannic acid modified attapulgite;
(2) preparation of casting solution: take PVDF and add in the container that is placed with DMF (DMF), add polyethylene glycol (PEG); Said vesse is placed in to 50 ℃～70 ℃ water-baths, and stirring and dissolving obtains the casting film feed liquid; Attapulgite modified to adding in feed liquid, making PVDF and attapulgite modified mass ratio is 1: 0.01～1: 0.1, fully stirs and sonic oscillation makes the dispersed casting solution that obtains of attapulgite;
(3) preparation of the compound slab film of attached heavy metal ion: casting solution is inclined to glass plate, by glass bar striking film forming, immerse solidification forming in the coagulating bath Water Tank with Temp.-controlled of 20 ℃～30 ℃, after being shaped from glass plate until film and coming off, place 24h～36h in distilled water, the compound slab film of attached heavy metal ion is cleaned and obtained to distilled water again.
2. as weighed the compound slab film of Adsorption of Heavy Metal Ions as described in 1, it is characterized in that described PVDF and attapulgite modified mass ratio are 1: 0.01～1: 0.1.
3. as weighed the compound slab film of Adsorption of Heavy Metal Ions as described in 1, it is characterized in that described attapulgite modified particle diameter is 300 orders～1000 orders.
4. as weighed the compound slab film of Adsorption of Heavy Metal Ions as described in 1, it is characterized in that described attapulgite modified be tannic acid modified attapulgite.
5. one kind as weighed the compound slab film of Adsorption of Heavy Metal Ions as described in 1, it is characterized in that in described step (2), PVDF mass percent in DMF is 15%～20%.
6. as weighed the compound slab film of Adsorption of Heavy Metal Ions as described in 1, it is characterized in that in described step (2), the PEG molecular weight is that 10000, PEG addition is 6%～10% for mass percent in DMF.
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