CN106000356A - Attapulgite/polyacrylic acid compound heavy metal absorbent and preparation method thereof - Google Patents

Attapulgite/polyacrylic acid compound heavy metal absorbent and preparation method thereof Download PDF

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Publication number
CN106000356A
CN106000356A CN201610430624.6A CN201610430624A CN106000356A CN 106000356 A CN106000356 A CN 106000356A CN 201610430624 A CN201610430624 A CN 201610430624A CN 106000356 A CN106000356 A CN 106000356A
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attapulgite
heavy metal
metal absorbent
preparation
compound heavy
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万怀新
彭勇刚
蔡沐芳
郑先进
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JIANGSU MAI GE ADSORBENT Co Ltd
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JIANGSU MAI GE ADSORBENT Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention belongs to the technical field of heavy metal pollution control, and relates to an attapulgite/polyacrylic acid compound heavy metal absorbent and a preparation method thereof. The preparation method includes the steps that firstly, attapulgite and a silane coupling agent containing carbon-carbon double bonds are subjected to a silanization reaction, and modified attapulgite is obtained; then, the modified attapulgite is added into ethyl alcohol, an initiator is added, low-temperature stirring is carried out for a reaction, standing is carried out, and initiator-loaded attapulgite is obtained; finally, acrylic monomers are added, stirring is carried out for a reaction under nitrogen protection, filtering, washing and drying are carried out after the reaction is finished, and the attapulgite compound heavy metal absorbent grafted with polyacrylic acid is obtained.

Description

A kind of compound heavy metal absorbent of attapulgite clay/polyacrylic acid and preparation method thereof
Technical field
The invention belongs to Heavy Metal Pollution technical field, relate to a kind of compound heavy metal of attapulgite clay/polyacrylic acid and inhale Attached dose and preparation method thereof.
Background technology
Attapulgite also known as Paligorskite, be a kind of have special chain layer structure containing Shuifu County's zeopan class clay Mineral, its theoretical chemistry formula is Si8Mg5O20(OH)2(H2O)4·4H2O, its natural nano passage and nanocrystal are allowed to have Flourishing interior external surface area, is often used for grease-decolor, the absorption of pet excrement as natural low-cost sorbent.
For widening the application of attapulgite, someone uses it for the absorption of industrial wastewater, but due to attapulgite basis The mineralogical limitation of body, is directly used in Industrial Wastewater Treatment and be there is the problem that absorption property is not good enough.To this end, much study Person uses he acid-heat activation, organic cation surfactant-modified, silane coupler modified and the mode such as surface grafting changes The absorption property of kind attapulgite.Wherein, causing the carbon-carbon double bond polymerization on attapulgite clay surface is also a kind of common attapulgite clay surface Graft modification mode.
But, in the presence of an initiator, more of a kind of self-discovery of the polyreaction of carbon-carbon double bond as, this just leads Caused the monomer having part carbon-carbon double bonds in reactor non-grafted to attapulgite clay surface time, have occurred that polymerization each other Become macromole, reduce the activity of monomer, thus have impact on grafting efficiency.
Summary of the invention
The technical problem to be solved is: promote the monomer of carbon-carbon double bonds to be grafted to attapulgite clay table as far as possible Face, improves the efficiency of graft modification, saves monomer consumption.
For solving this technical problem, the technical solution used in the present invention is: provide a kind of attapulgite clay/polyacrylic acid compound Heavy metal absorbent and preparation method thereof,
Above-mentioned compound heavy metal absorbent, with attapulgite clay as carrier, has polyacrylic acid at attapulgite clay surface grafting；
The preparation method of above-mentioned compound heavy metal absorbent is:
(1) with the attapulgite of purified, acid activation as raw material, silicon is carried out by the silane coupler with carbon-carbon double bonds Alkylation reaction, introduces carbon-carbon double bond, obtains attapulgite modified on attapulgite surface,
Wherein, purify, the concretely comprising the following steps of acid activation,
By the pulverizing of raw ore attapulgite, ball milling, sieve, obtain powdery attapulgite soil, take powdery attapulgite soil and add solute matter Amount mark is that in the sodium hexametaphosphate solution of 3%～5%, attapulgite is 1:20～1:30 with the mass ratio of aqueous solution, stirs After mixing 12～36h, naturally stand, take upper strata suspension and filter, dry, grind, prepare and purify attapulgite,
Add in the hydrochloric acid solution that concentration is 1～6mol//L by purifying attapulgite, attapulgite and the matter of hydrochloric acid solution Amount volume ratio is calculated as 1:10～1:15 with g/ml, is stirred at room temperature 0.5～2h, and centrifugation, precipitate with deionized water washing is to using 0.1mol/L silver nitrate solution detects without chloride ion post-drying, obtains the attapulgite of acid activation,
The silane coupler of above-mentioned carbon-carbon double bonds is γ-propyl methacrylate base trimethoxy silane (MPS),
Concretely comprising the following steps of Silanization reaction: 12g is purified, acid activation attapulgite joins the toluene of 100ml In, it is warming up to 60 DEG C, and adds 10ml γ-propyl methacrylate base trimethoxy silane when being stirred vigorously, protect Temperature also continues stirring reaction 4 hours, and product uses toluene, dehydrated alcohol and deionized water wash after being separated by filtration successively, And be dried at 80 DEG C, obtain attapulgite modified；
(2) attapulgite modified join in ethanol, under low temperature when being stirred vigorously by what step (1) obtained Adding initiator, keep low temperature continue stirring reaction and stand, product, after natural drying, obtains changing of initiator load Property attapulgite, low-temperature dark preserve,
Wherein, initiator is azodiisobutyronitrile,
The concrete operations of step (2) are:
The attapulgite modified 10g obtained in step (1) is joined in 16g ethanol, acutely under 2 to 5 DEG C of low temperature Add azodiisobutyronitrile 4.5g under the state of stirring, keep low temperature continue stirring 15 minutes and stand 4 hours, by reacted Attapulgite natural filtration and at 10 DEG C natural drying, obtain azodiisobutyronitrile load attapulgite modified, 10 DEG C with Under keep in Dark Place,
This step loads initiator at low temperatures and preserves, partly in order to avoid temperature too high and cause azo two Isopropyl cyanide self decomposes, and on the other hand promotes azodiisobutyronitrile initiation to be carried on recessed also for avoiding temperature too high The double bond of the silane coupler on soil and produce addition polymerization,
Do not carry out deionized water or washing with alcohol after filtration, be in order to the initiator in proof load as far as possible to attapulgite clay not by Rinse out；
(3) the attapulgite modified of the initiator obtained in step (2) load is joined in toluene, add acrylic acid Monomer, is stirred reaction under nitrogen protection, filters after having reacted, and product is successively with toluene, dehydrated alcohol and deionization Water washs, and is dried, must be grafted with polyacrylic attapulgite,
Concrete operations are: the attapulgite modified 2g that the initiator obtained in step (2) loads joins the first of 80ml In benzene, adding acrylic monomers, acrylic monomers is 5:1～8:1 with the attapulgite modified mass ratio of initiator load, Being warming up to 70 DEG C under nitrogen protection and be stirred reaction simultaneously, filtering after react 16 hours, product uses toluene, anhydrous successively Ethanol and deionized water wash remove unnecessary acrylic acid, and are dried at 80 DEG C, must be grafted with polyacrylic attapulgite Soil.
The present invention utilizes the structural advantage of attapulgite clay self, first by initiator physical load on attapulgite clay, so rear of continuing rising Temperature, under stirring operation, initiator gradually transits to attapulgite clay surface so that initiator can first initiation grafting on attapulgite clay surface Silane coupler on double bond open, and with acrylic monomers generation polyaddition reaction nearby, avoid trip as far as possible Invalid polymerization between the acrylic monomers of shape and the surface of attapulgite clay cannot be grafted to；Secondly as attapulgite clay itself has good Good dispersibility, enables load initiator thereon to be uniformly distributed, adds subsequent propylene acid monomers and be grafted on attapulgite clay Uniformity coefficient, improves absorption property；And owing to initiator is that gradually from attapulgite clay, transition out, promotes polyreaction Sustainable carry out, it is to avoid most of monomer is initiated simultaneously and causes generating heat in a large number, thus affects stablizing of reaction.
Detailed description of the invention
In following embodiment, comparative example, the purification of attapulgite, acid activation technique are:
By the pulverizing of raw ore attapulgite, ball milling, sieve, obtain powdery attapulgite soil, take powdery attapulgite soil and add solute matter Amount mark is that in the sodium hexametaphosphate solution of 5%, attapulgite is 1:25 with the mass ratio of aqueous solution, after stirring 20h, natural Stand, take upper strata suspension and filter, dry, grind, prepare and purify attapulgite,
Add in the hydrochloric acid solution that concentration is 2mol//L by purifying attapulgite, attapulgite and the quality of hydrochloric acid solution Volume ratio is calculated as 1:15 with g/ml, and 2h, centrifugation are stirred at room temperature, and precipitate with deionized water washing is to using 0.1mol/L silver nitrate Solution detects without chloride ion post-drying, obtains the attapulgite of acid activation.
Embodiment 1
(1), during 12g is purified, acid activation attapulgite joins the toluene of 100ml, it is warming up to 60 DEG C, and in play Add 10ml γ-propyl methacrylate base trimethoxy silane under the state of strong stirring, be incubated and to continue stirring reaction 4 little Time, product is used toluene, dehydrated alcohol and deionized water wash successively after being separated by filtration, and is dried at 80 DEG C, to obtain final product Attapulgite modified；
(2) the attapulgite modified 10g obtained in step (1) is joined in 16g ethanol, be stirred vigorously at 4 DEG C State under add azodiisobutyronitrile 4.5g, keeps 4 DEG C to continue to stir 15 minutes and stand 4 hours, by reacted concavo-convex Rod soil natural filtration and at 10 DEG C natural drying, obtain azodiisobutyronitrile load attapulgite modified, at 5 DEG C lucifuge protect Deposit；
(3) the attapulgite modified 2g that the azodiisobutyronitrile obtained in step (2) loads is joined the toluene of 80ml In, adding acrylic monomers, acrylic monomers is 6:1 with the attapulgite modified mass ratio of azodiisobutyronitrile load, Being warming up to 70 DEG C under nitrogen protection and be stirred reaction simultaneously, filtering after react 16 hours, product uses toluene, anhydrous successively Ethanol and deionized water wash, and be dried at 80 DEG C, polyacrylic attapulgite clay compounded type heavy metal must be grafted with and inhale Attached dose.
Embodiment 2
(1), during 12g is purified, acid activation attapulgite joins the toluene of 100ml, it is warming up to 60 DEG C, and in play Add 10ml γ-propyl methacrylate base trimethoxy silane under the state of strong stirring, be incubated and to continue stirring reaction 4 little Time, product is used toluene, dehydrated alcohol and deionized water wash successively after being separated by filtration, and is dried at 80 DEG C, to obtain final product Attapulgite modified；
(2) the attapulgite modified 10g obtained in step (1) is joined in 16g ethanol, be stirred vigorously at 5 DEG C State under add azodiisobutyronitrile 4.5g, keeps 4 DEG C to continue to stir 15 minutes and stand 4 hours, by reacted concavo-convex Rod soil natural filtration and at 10 DEG C natural drying, obtain azodiisobutyronitrile load attapulgite modified, at 7 DEG C lucifuge protect Deposit；
(3) the attapulgite modified 2g that the azodiisobutyronitrile obtained in step (2) loads is joined the toluene of 80ml In, adding acrylic monomers, acrylic monomers is 7:1 with the attapulgite modified mass ratio of azodiisobutyronitrile load, Being warming up to 70 DEG C under nitrogen protection and be stirred reaction simultaneously, filtering after react 16 hours, product uses toluene, anhydrous successively Ethanol and deionized water wash, and be dried at 80 DEG C, polyacrylic attapulgite clay compounded type heavy metal must be grafted with and inhale Attached dose.
Comparative example 1
Initiator is not loaded on attapulgite clay by this comparative example, but initiator is added in the lump with acrylic monomers Entering, remaining operation, with embodiment 1, specifically comprises the following steps that
(1), during 12g is purified, acid activation attapulgite joins the toluene of 100ml, it is warming up to 60 DEG C, and in play Add 10ml γ-propyl methacrylate base trimethoxy silane under the state of strong stirring, be incubated and to continue stirring reaction 4 little Time, product is used toluene, dehydrated alcohol and deionized water wash successively after being separated by filtration, and is dried at 80 DEG C, to obtain final product Attapulgite modified；
(2) the attapulgite modified 2g obtained in step (1) is joined in the toluene of 80ml, add 4.5g azo two Isopropyl cyanide and acrylic monomers, acrylic monomers and attapulgite modified mass ratio are 6:1, are warming up to 70 under nitrogen protection DEG C and be stirred reaction simultaneously, filter after react 16 hours, product uses toluene, dehydrated alcohol and deionized water wash successively, And be dried at 80 DEG C, polyacrylic attapulgite clay compounded type heavy metal absorbent must be grafted with.
Adsorption experiment method: weigh the compound heavy metal absorbent in 40mg various embodiments above, comparative example, point Do not add the Pb of 20mL0.002mol/L2+In solution, 25 DEG C of constant temperature stand 20h, filter, and measure the Pb of residual in solution2+Dense Degree, according to the change of concentration of metal ions before and after absorption, is calculated as follows adsorbance (result is as shown in table 1):
q e = ( C 0 - C e ) × V m
In formula: C0Concentration (the mg L of metal ion before absorption-1)；Concentration (the mg L of metal ion after Ce absorption-1)；The volume (L) of V solution；The dosage (g) of m adsorbent.
Table 1
Embodiment 1 Embodiment 2 Comparative example 1
Adsorbance (mg g-1) 75 71 42

Claims (9)

1. the compound heavy metal absorbent of attapulgite clay/polyacrylic acid, it is characterised in that: described compound heavy metal absorbent With attapulgite clay as carrier, there is polyacrylic acid at attapulgite clay surface grafting.
The preparation method of compound heavy metal absorbent the most as claimed in claim 1, it is characterised in that: described preparation method For,
(1) with the attapulgite of purified, acid activation as raw material, silanization is carried out by the silane coupler with carbon-carbon double bonds Reaction, introduces carbon-carbon double bond, obtains attapulgite modified on attapulgite surface；
(2) attapulgite modified join in ethanol by what step (1) obtained, add when being stirred vigorously under low temperature Initiator, keeps low temperature continue stirring reaction and stand, and product is after natural drying, and the modification obtaining initiator load is recessed Convex rod soil, low-temperature dark preserves；
(3) the attapulgite modified of the initiator obtained in step (2) load is joined in toluene, add acrylic acid list Body, is stirred reaction under nitrogen protection, filters after having reacted, and product is successively with toluene, dehydrated alcohol and deionized water Washing, is dried, must be grafted with polyacrylic attapulgite clay compounded type heavy metal absorbent.
The preparation method of compound heavy metal absorbent the most as claimed in claim 2, it is characterised in that: step (1) purifies, Concretely comprising the following steps of acid activation,
By the pulverizing of raw ore attapulgite, ball milling, sieve, obtain powdery attapulgite soil, take powdery attapulgite soil addition Solute mass and divide Number is in the sodium hexametaphosphate solution of 3%～5%, and attapulgite is 1:20～1:30 with the mass ratio of aqueous solution, stirs 12 ～after 36h, naturally stand, take upper strata suspension and filter, dry, grind, prepare and purify attapulgite,
Add in the hydrochloric acid solution that concentration is 1～6mol//L by purifying attapulgite, attapulgite and the mass body of hydrochloric acid solution Long-pending ratio is calculated as 1:10～1:15 with g/ml, is stirred at room temperature 0.5～2h, and centrifugation, precipitate with deionized water washing is to using 0.1mol/L silver nitrate solution detects without chloride ion post-drying, obtains the attapulgite of acid activation.
The preparation method of compound heavy metal absorbent the most as claimed in claim 2, it is characterised in that: described in step (1) The silane coupler of carbon-carbon double bonds be γ-propyl methacrylate base trimethoxy silane.
The preparation method of compound heavy metal absorbent the most as claimed in claim 4, it is characterised in that: described in step (1) Concretely comprising the following steps of Silanization reaction, 12g is purified, acid activation attapulgite joins in the toluene of 100ml, is warming up to 60 DEG C, and 10ml γ-propyl methacrylate base trimethoxy silane is added when being stirred vigorously, it is incubated and continues to stir Mixing reaction 4 hours, product uses toluene, dehydrated alcohol and deionized water wash after being separated by filtration successively, and at 80 DEG C It is dried, obtains attapulgite modified.
The preparation method of compound heavy metal absorbent the most as claimed in claim 2, it is characterised in that: described in step (2) Initiator be azodiisobutyronitrile.
The preparation method of compound heavy metal absorbent the most as claimed in claim 6, it is characterised in that: step (2) concrete Operation is,
The attapulgite modified 10g obtained in step (1) is joined in 16g ethanol, is being stirred vigorously under 2 to 5 DEG C of low temperature State under add azodiisobutyronitrile 4.5g, keep low temperature to continue stirring and also stand 4 hours, by reacted concavo-convex in 15 minutes Rod soil natural filtration and at 10 DEG C natural drying, obtain azodiisobutyronitrile load attapulgite modified, keep away for less than 10 DEG C Light preserves.
The preparation method of compound heavy metal absorbent the most as claimed in claim 2, it is characterised in that: step (3) concrete Operation is,
The attapulgite modified 2g that the initiator obtained in step (2) loads is joined in the toluene of 80ml, add propylene Acid monomers, is warming up to 70 DEG C under nitrogen protection and is stirred reaction simultaneously, filtering after reacting 16 hours, and product uses first successively Benzene, dehydrated alcohol and deionized water wash remove unnecessary acrylic acid, and are dried at 80 DEG C, must be grafted with polyacrylic Attapulgite clay compounded type heavy metal absorbent.
The preparation method of compound heavy metal absorbent the most as claimed in claim 8, it is characterised in that: in step (3), propylene Acid monomers is 5:1～8:1 with the attapulgite modified mass ratio of initiator load.
CN201610430624.6A 2016-06-16 2016-06-16 Attapulgite/polyacrylic acid compound heavy metal absorbent and preparation method thereof Pending CN106000356A (en)

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CN106512924A (en) * 2016-12-14 2017-03-22 严帝 Attapulgite adsorbent with large adsorption capacity and preparation method thereof
CN106582583A (en) * 2016-12-14 2017-04-26 严帝 Polymethyl methacrylate modified attapulgite adsorbent and preparation method thereof
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CN106832340A (en) * 2016-11-10 2017-06-13 安徽博硕科技有限公司 A kind of magnetic attapulgite/polyacrylic acid nano plural gel and preparation method thereof
CN106669619A (en) * 2016-12-14 2017-05-17 严帝 Lignin modified attapulgite clay adsorbent and preparation method thereof
CN106693902A (en) * 2016-12-14 2017-05-24 严帝 Quaternary ammonium salt modified attapulgite adsorbent and preparation method thereof
CN106693901A (en) * 2016-12-14 2017-05-24 严帝 Stable attapulgite adsorbent and preparation method thereof
CN106732397A (en) * 2016-12-14 2017-05-31 严帝 A kind of attapulgite clay adsorbent that can be sterilized and preparation method thereof
CN106732455A (en) * 2016-12-14 2017-05-31 严帝 Modified attapulgite clay adsorbent of a kind of ceramic fibre and preparation method thereof
CN106732395A (en) * 2016-12-14 2017-05-31 严帝 Modified attapulgite clay adsorbent of a kind of alkyl guanidine and preparation method thereof
CN106582583A (en) * 2016-12-14 2017-04-26 严帝 Polymethyl methacrylate modified attapulgite adsorbent and preparation method thereof
CN106512924A (en) * 2016-12-14 2017-03-22 严帝 Attapulgite adsorbent with large adsorption capacity and preparation method thereof
CN106582306A (en) * 2016-12-31 2017-04-26 天津汉晴环保科技有限公司 Heavy-metal-ion-adsorbing type hybrid flat sheet separation film and preparation method thereof
CN107285474B (en) * 2017-08-11 2020-07-24 盛世生态环境股份有限公司 Artificial wetland device for removing heavy metal/PPCPs (pentatricopeptide repeats) composite pollutants in sewage
CN107285474A (en) * 2017-08-11 2017-10-24 盛世园林集团股份有限公司 One kind removes the constructed wetland device of heavy metal/PPCPs combined pollutants in sewage
CN107694532A (en) * 2017-12-11 2018-02-16 河南永泽环境科技有限公司 A kind of soil heavy mental adsorbent and preparation method thereof
CN108285507A (en) * 2018-01-26 2018-07-17 常州大学 A kind of preparation method of attapulgite/polyacrylic complex thickener
CN108285507B (en) * 2018-01-26 2020-05-26 常州大学 Preparation method of attapulgite/polyacrylic acid composite thickening agent
CN108499517A (en) * 2018-04-17 2018-09-07 湖南师范大学 Fiber glass waste modification prepares the method for metal-chelator and the application of metal-chelator
CN109824426A (en) * 2019-01-25 2019-05-31 兰州大学 A kind of slow release fertilizer improving heavy metal pollution of soil
CN109824427A (en) * 2019-01-25 2019-05-31 兰州大学 A kind of Slow-release organic fertilizer improving heavy metal pollution of soil
CN110389117A (en) * 2019-06-21 2019-10-29 淮阴工学院 Recessed soil-thiocoumarin function hybrid material and its preparation method and application
CN110389117B (en) * 2019-06-21 2020-10-27 淮阴工学院 Attapulgite-thiocoumarin functional hybrid material and preparation method and application thereof
CN110642598A (en) * 2019-10-30 2020-01-03 湖北工业大学 Preparation method of ion selective adsorption ceramsite
CN110642598B (en) * 2019-10-30 2021-10-29 湖北工业大学 Preparation method of ion selective adsorption ceramsite
WO2021143584A1 (en) * 2020-01-17 2021-07-22 中山大学附属口腔医院 Long-acting renewable antibacterial coating for surface of titanium implant
CN113104959A (en) * 2021-03-23 2021-07-13 温州市工业科学研究院 Magnetic filler for sewage treatment and preparation method thereof
CN113135744A (en) * 2021-04-02 2021-07-20 浙江凯色丽科技发展有限公司 Attapulgite/mica/carbon composite material and preparation method thereof
CN113135744B (en) * 2021-04-02 2022-04-01 浙江凯色丽科技发展有限公司 Attapulgite/mica/carbon composite material and preparation method thereof

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