CN112844338B - 一种黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料 - Google Patents
一种黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料 Download PDFInfo
- Publication number
- CN112844338B CN112844338B CN202011619862.4A CN202011619862A CN112844338B CN 112844338 B CN112844338 B CN 112844338B CN 202011619862 A CN202011619862 A CN 202011619862A CN 112844338 B CN112844338 B CN 112844338B
- Authority
- CN
- China
- Prior art keywords
- black talc
- sodium bicarbonate
- black
- polyvinyl alcohol
- gel composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 27
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 21
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 66
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 43
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 33
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 33
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 32
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003463 adsorbent Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000005187 foaming Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000454 talc Substances 0.000 claims description 25
- 229910052623 talc Inorganic materials 0.000 claims description 25
- 239000000839 emulsion Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 17
- 239000006260 foam Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical group C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 9
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- YYYARFHFWYKNLF-UHFFFAOYSA-N 4-[(2,4-dimethylphenyl)diazenyl]-3-hydroxynaphthalene-2,7-disulfonic acid Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C(S(O)(=O)=O)=CC2=CC(S(O)(=O)=O)=CC=C12 YYYARFHFWYKNLF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000002594 sorbent Substances 0.000 claims 1
- 239000000499 gel Substances 0.000 abstract description 20
- 239000000017 hydrogel Substances 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 3
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 230000009102 absorption Effects 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 230000008961 swelling Effects 0.000 abstract 1
- 235000012222 talc Nutrition 0.000 description 25
- 239000000975 dye Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 3
- WXLFIFHRGFOVCD-UHFFFAOYSA-L azophloxine Chemical compound [Na+].[Na+].OC1=C2C(NC(=O)C)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 WXLFIFHRGFOVCD-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910019092 Mg-O Inorganic materials 0.000 description 2
- 229910019395 Mg—O Inorganic materials 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- QANIADJLTJYOFI-UHFFFAOYSA-K aluminum;magnesium;carbonate;hydroxide;hydrate Chemical compound O.[OH-].[Mg+2].[Al+3].[O-]C([O-])=O QANIADJLTJYOFI-UHFFFAOYSA-K 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- 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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开了一种黑滑石‑聚乙烯醇缩甲醛凝胶复合吸附材料及其制备方法,属于染料吸附制备技术领域。具体为:将聚乙烯醇溶解,随后加入己烷/碳酸氢钠混合液通过搅拌发泡,再加入粒径300nm左右的黑滑石粉末,充分搅拌混合均匀,然后加入甲醛反应交联,制备出水凝胶复合材料,最后在烘箱中固化成型,得到黑滑石‑聚乙烯醇缩甲醛凝胶复合吸附材料。本发明的黑滑石‑聚乙烯醇缩甲醛复合凝胶,不仅能将染料固定/吸附,且具有优异的吸水、溶胀、压缩性能,克服了现有技术中吸附剂难以回收的技术问题;方法简单,易操作,具有广阔的应用前景。
Description
技术领域
本发明属于染料废水治理领域,具体涉及一种黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料及其制备方法与应用。
背景技术
水污染是一个全球关注的重要环境问题。水污染尤其是染料废水的研究引起了广泛的关注因为它会影响水生生物和人类。由于染料有毒,不可生物降解甚至有致癌作用,一旦它们被排放到水中,会对生态环境的平衡造成严重威胁。因此,去除染料废水对防止环境污染至关重要。
黑滑石作为滑石的一种,同样具有滑石的2:1型(T-O-T型)层状结构,两个硅氧四面体片(T)和一个镁氧八面体(O)构成,滑石单层T-O-T层为9.4A,层间厚度约为0.1A,也叫T-O-T型粘土矿物。滑石作为一种不带层电荷的层状硅酸盐矿物,具有优良的化学稳定性,同时滑石表面含有活性官能团,如Mg-O、Si-O、OH、Si-OH等,滑石矿经过破碎后,表面官能团裸露,矿物表面成分和结构失衡,出现粒子缺陷位和表面电荷失衡集中位,即表面活性位点,从而黑滑石粉末具有一定的吸附性。但是,采用这种粉末状吸附剂进行污水处理,固液难分离,而且常常造成流失,回收再利用无法达到理想效果,故近年来将粉体材料成型处理,成为废水处理主要研究方向。
凝胶是一类具有物理或化学交联结构、可吸收自身质量几百或几千倍的水分,但又不溶于水的高分子或聚合物,在水中可保持一定形状和三维空间网络结构并迅速溶胀,也被称为“水材料”。其交联结构含有丰富的功能性基团,通过氢键、静电吸引力、范德华力,离子交换和疏水作用与有机物及金属结合从而减少污染物的浓度。然而,聚乙烯醇缩醛凝胶成型过程中交联度过大导致粘度急剧增加,且化学和机械性能较差,易碎,循环使用效果差。
发明内容
为了克服现有的聚乙烯醇缩醛凝胶化学和机械性能较差、易碎、循环使用效果差的缺陷,本发明提供一种新型黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料及其制备方法与在染料吸附中的应用,本发明方法的目的在于提供一种具有天然矿物材料吸附剂,具有较高的吸附性、易回收、高稳定性的干凝胶吸附剂。
为了解决上述问题,本发明采用以下技术方案:
一种黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料,所述黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料按如下方法制备:
(1)黑滑石-聚乙烯醇反应液的制备:向聚乙烯醇(PVA)加入去离子水,95℃搅拌溶解完全,得8~20wt%(优选10wt%)的聚乙烯醇水溶液;加入粒径为300~400nm的黑滑石粉末,搅拌1h,得黑滑石-聚乙烯醇均相乳液;所述的黑滑石粉末与聚乙烯醇的质量比为1-3:4;
(2)己烷/碳酸氢钠混合泡沫的制备:将己烷与碳酸氢钠混合,加入水A,摇晃均匀起泡,得己烷/碳酸氢钠混合泡沫;所述己烷与碳酸氢钠的质量比为1:10;所述水A与碳酸氢钠的质量比为1~3:1(优选2~3:1);水A就是水,这里用水A来表示只是方便描述,无特殊含义。
(3)待步骤(1)中所得黑滑石-聚乙烯醇均相乳液降温至65~80℃(优选72℃)后,滴加步骤(2)所得己烷/碳酸氢钠混合泡沫,继续搅拌直到混合溶液中碳酸氢钠溶解,(发泡膨胀到原始体积的1.5~2倍体积)降温至25~40℃时(优选40℃)加入甲醛,反应20-60min(20min),将所得反应液倒入模具,60℃固化10-12h(优选12h),水洗至中性(5~10次,去掉未反应的单体),室温干燥(为避免水蒸发时凝胶收缩)得到所述黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料;所述己烷/碳酸氢钠混合泡沫中加入的碳酸氢钠的质量为所述黑滑石-聚乙烯醇均相乳液的质量的3~6%(优选5%);所述甲醛的体积以黑滑石-聚乙烯醇均相乳液中聚乙烯醇的质量计为0.5~1mL/g(优选1mL/g)。
进一步,步骤(1)中所述黑滑石粉末为超细黑滑石粉末,按如下方法制备:(黑滑石来源于江西上饶广丰区)将黑滑石手动破碎、研磨、过50目筛得到黑滑石粉粒,加入乙醇600转/min湿法球磨6-9h,水洗,离心,取沉淀物于60℃干燥24h,即得粒径为300~400nm的黑滑石粉末。
优选地,步骤(1)中所述的黑滑石粉末与聚乙烯醇的质量比为1:2。
优选地,步骤(2)中己烷与碳酸氢钠的质量比为1:10。
本发明还提供一种上述黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料在染料去除中的应用。所述黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料通过吸附染料而达到去除目的。
优选地,所述染料为亚甲基蓝或酸性大红。
与现有技术相比,本发明的优点在于:将超细黑滑石粉末填充到聚合物凝胶溶液中,充分利用了黑滑石表面活性位点的吸附性,并且其表面的官能团与凝胶反应,可稳定气泡,起到骨架支撑作用,避免凝胶在干燥时因巨大的毛细孔压力导致孔隙结构坍塌和严重收缩。此外,这种黑滑石-聚乙烯醇缩甲醛水凝胶粘度低,放入不同形状模具,可根据实际应用各种空间环境,制造成各种形状。
本发明方法制备的复合干凝胶具有丰富的Mg-O、Si-O、-OH,可通过氢键、静电吸引力、范德华力,离子交换和疏水作用与有机物及金属结合从而结合染料,从而达到吸附和去除目的。本发明制备方法简单,反应条件易控制,复合干凝胶具有优异的机械稳定性,抗压缩性,较好的吸附性,具有广阔的应用前景。
附图说明
图1为黑滑石粉末扫描电镜图。
图2为实施例1中制备的黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料实物图。
图3为实施例1中制备的黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料染料吸附效果图。
具体实施方式
下面结合具体实施例,对本发明进行进一步描述,但本发明并不限于下述实施例,在不脱离本发明内容和范围内,变化实施都应包含在本发明的技术范围内。
以下实施例中黑滑石都来源于江西上饶广丰区;对比例中的白滑石来源于广西龙胜华美滑石开发有限公司。
以下实施例中平衡吸附量的测量方法及条件为:
配置浓度分别为10、20、40、60、80、100、150、200ppm的亚甲基蓝和酸性大红溶液各50ml,投入等质量(50mg)吸附剂在室温条件下搅拌反应48h使得吸附达到平衡,取吸附后的溶液离心、,测定其上清液中的亚甲基蓝、酸性大红浓度。最终通过公式q=(Co-Ce)*V/M计算得到吸附剂的平衡吸附量,其中Co为溶液起始浓度,Ce为平衡浓度(ppm),V为初始溶液体积(L),m为吸附剂的质量(g)
以下实施例中黑滑石粉制备方法为:
将80g黑滑石手动破碎、研磨、用50目筛子筛分得到70g 50目的黑滑石粉末,称量50g黑滑石粉置于球磨罐中,加入80ml乙醇,用球磨机600转/min湿法研磨6h,用水洗3次,离心,60℃干燥24h,制备得40g的黑滑石粉末。所制备的黑滑石粉末用扫描电子显微镜观察平均粒径为300nm。
实施例1
(1)将2.0g PVA加入100ml三颈烧瓶中,然后加入18g水,在油浴锅中95℃下搅拌溶解完全,配成10wt%的PVA水溶液。然后加入0.5g黑滑石粉末,搅拌1h,形成黑滑石/PVA均相乳液。降温至72℃。
(2)称取0.1g己烷和1.0g碳酸氢钠在10ml离心管中,加入3ml水摇晃均匀起泡。将起泡液加入降温至72℃的黑滑石/PVA均相乳液搅拌至混合溶液中碳酸氢钠溶解,乳液体积由原始18ml发泡膨胀到36ml。继续搅拌5min后降温至40℃。
(3)当温度降到40℃时加入2ml甲醛,交联反应20min。将水凝胶倒入模具中60℃固化12h,取出,反复泡水,挤压,除去未反应的单体,洗至中性。室温干燥得到复合干凝胶吸附剂3.2g。该干凝胶吸附剂对亚甲基蓝的平衡吸附量为29mg/g,对酸性大红平衡吸附量为18mg/g。
实施例2
(1)将2.0g PVA加入100ml三颈烧瓶中,然后加入18g水,在油浴锅中95℃下搅拌溶解完全,配成10wt%的PVA水溶液。然后加入1.0g黑滑石粉末,搅拌1.5h,形成黑滑石/PVA均相乳液。降温至72℃。
(2)称取0.15g己烷和1.2g碳酸氢钠在10ml离心管中,加入3ml水摇晃均匀起泡。将起泡液加入降温至72℃的黑滑石/PVA均相乳液搅拌至混合溶液中碳酸氢钠溶解,乳液体积由原始22ml发泡膨胀到40ml。继续搅拌5min后降温至室温。
(3)当温度降到室温时加入2ml甲醛反应20min。将水凝胶倒入模具中60℃固化12h,取出,反复泡水,挤压,除去未反应的单体,洗至中性。室温干燥得到复合干凝胶吸附剂3.8g。该干凝胶吸附剂对亚甲基蓝的平衡吸附量为40mg/g,对酸性大红平衡吸附量为31mg/g。
实施例3
(1)将2.0g PVA加入三颈烧瓶中,然后加入18g水,在油浴锅中95℃下搅拌溶解完全,配成10wt%的PVA水溶液。然后加入1.5g黑滑石粉末,搅拌2h,形成黑滑石/PVA均相乳液。降温至72℃。
(2)称取0.15g己烷和1.5g碳酸氢钠在10ml离心管中,加入3ml水摇晃均匀起泡。将起泡液加入降温至72℃的黑滑石/PVA均相乳液搅拌至混合溶液中碳酸氢钠溶解,乳液体积由原始25ml发泡膨胀到55ml。继续搅拌5min后降温至室温
(3)当温度降到室温时加入2ml甲醛反应30min。将水凝胶倒入模具中60℃固化12h,取出,反复泡水,挤压,除去未反应的单体,洗至中性。室温干燥得到复合干凝胶吸附剂4.1g。该干凝胶吸附剂对亚甲基蓝的平衡吸附量为32mg/g,对酸性大红平衡吸附量为22mg/g。
对比例1
(1)将2.0g PVA加入三颈烧瓶中,然后加入18g水,在油浴锅中95℃下搅拌溶解完全,配成10wt%的PVA水溶液。降温至72℃。
(2)称取0.1g己烷和1.0g碳酸氢钠在10ml离心管中,加入3ml水摇晃均匀起泡。将起泡液加入降温至72℃的PVA水溶液,继续搅拌直到混合溶液中碳酸氢钠溶解,乳液体积由原始15ml发泡膨胀到发泡膨胀到30ml。继续搅拌5min后降温至40℃。
(3)当温度降到40℃时加入2ml甲醛反应30min。将水凝胶倒入模具中60℃固化12h,取出,反复泡水,挤压,除去未反应的单体,洗至中性。室温干燥3天得到复合干凝胶吸附剂2.8g。该干凝胶吸附剂对亚甲基蓝的平衡吸附量为1.1mg/g,对酸性大红平衡吸附量为1.5mg/g。
对比例2
(1)将100g白滑石手动破碎、研磨、用50目筛子筛分得到80g 50目的白滑石粉末,称量50g白滑石粉置于球磨罐中,加入80ml乙醇,用球磨机600转/min湿法研磨6h,用水洗3次,离心,60℃干燥24h,制备得40.1g的白滑石粉末。所制备的白滑石粉末用扫描电子显微镜观察平均粒径为240nm。
(2)将2.0g PVA加入三颈烧瓶中,然后加入18g水,在油浴锅中95℃下搅拌溶解完全,配成10wt%的PVA水溶液。然后加入1.0g平均粒径为240nm白滑石粉末,搅拌1.5h,形成白滑石/PVA均相乳液。降温至72℃。
(3)称取0.1g己烷和1.0g碳酸氢钠在10ml离心管中,加入3ml水摇晃均匀起泡。将起泡液加入降温至72℃的白滑石/PVA均相乳液,继续搅拌直到混合溶液中碳酸氢钠溶解,乳液体积由原始20ml发泡膨胀到发泡膨胀到42ml。继续搅拌5min后降温至40℃。
(4)当温度降到40℃时加入2ml甲醛反应20min。将水凝胶倒入模具中60℃固化12h,取出,反复泡水,挤压,除去未反应的单体,洗至中性。室温干燥3天得到复合干凝胶吸附剂3.0g。该干凝胶吸附剂对亚甲基蓝的平衡吸附量为2.83mg/g,对酸性大红平衡吸附量为4.3mg/g。
Claims (10)
1.一种黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料,其特征在于所述黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料按如下方法制备:
(1)黑滑石-聚乙烯醇反应液的制备:向聚乙烯醇加入去离子水,95℃搅拌溶解完全,得8~20wt%的聚乙烯醇水溶液;加入粒径为300~400nm的黑滑石粉末,搅拌1h,得黑滑石-聚乙烯醇均相乳液;所述的黑滑石粉末与聚乙烯醇的质量比为1-3:4;
(2)己烷/碳酸氢钠混合泡沫的制备:将己烷与碳酸氢钠混合,加入水A,摇晃均匀起泡,得己烷/碳酸氢钠混合泡沫;所述己烷与碳酸氢钠的质量比为1~4:10;所述水A与碳酸氢钠的质量比为1~3:1;
(3)待步骤(1)中所得黑滑石-聚乙烯醇均相乳液降温至65~80℃后,滴加步骤(2)所得己烷/碳酸氢钠混合泡沫,继续搅拌直到混合溶液中碳酸氢钠溶解,降温至25~40℃时加入甲醛,反应20-60min,将所得反应液倒入模具,60℃固化10-12h,水洗至中性,室温干燥得到所述黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料;所述己烷/碳酸氢钠混合泡沫中加入的碳酸氢钠的质量为所述黑滑石-聚乙烯醇均相乳液的质量的3~6%;所述甲醛的体积以黑滑石-聚乙烯醇均相乳液中聚乙烯醇的质量计为0.5~1mL/g。
2.如权利要求1所述的黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料,其特征在于:所述聚乙烯醇水溶液浓度为10wt%。
3.如权利要求1所述的黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料,其特征在于:步骤(1)中所述的黑滑石粉末与聚乙烯醇的质量比为1:2。
4.如权利要求1所述的黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料,其特征在于:步骤(2)中己烷与碳酸氢钠的质量比为1:10。
5.如权利要求1所述的黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料,其特征在于:步骤(2)中所述水A与碳酸氢钠的质量比为2~3:1。
6.如权利要求1所述的黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料,其特征在于:步骤(3)中降温至40℃时加入甲醛。
7.如权利要求1所述的黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料,其特征在于:步骤(3)中所述己烷/碳酸氢钠混合泡沫中加入的碳酸氢钠的质量为所述黑滑石-聚乙烯醇均相乳液的质量的5%。
8.如权利要求1所述的黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料,其特征在于:步骤(1)中所述黑滑石粉末为超细黑滑石粉末,按如下方法制备:将黑滑石手动破碎、研磨、过50目筛得到黑滑石粉粒,加入乙醇600转/min湿法球磨6-9h,水洗,离心,取沉淀物于60℃干燥24h,即得粒径为300~400nm的黑滑石粉末。
9.如权利要求1所述的黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料在染料去除中的应用。
10.如权利要求9所述的应用,其特征在于:所述染料为亚甲基蓝或酸性大红。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011619862.4A CN112844338B (zh) | 2020-12-31 | 2020-12-31 | 一种黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011619862.4A CN112844338B (zh) | 2020-12-31 | 2020-12-31 | 一种黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112844338A CN112844338A (zh) | 2021-05-28 |
CN112844338B true CN112844338B (zh) | 2022-05-24 |
Family
ID=75998930
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011619862.4A Active CN112844338B (zh) | 2020-12-31 | 2020-12-31 | 一种黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112844338B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114288985A (zh) * | 2021-12-29 | 2022-04-08 | 浙江工业大学 | 一种黑滑石吸附材料及其制备方法与应用 |
CN115212854A (zh) * | 2022-06-29 | 2022-10-21 | 浙江工业大学 | 一种聚苯胺-黑滑石复合吸附剂及其制备方法与应用 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102430284B (zh) * | 2011-09-19 | 2014-09-10 | 周奇迪 | 去除水中二苯甲酮的过滤介质及其制备方法以及滤芯和净水装置 |
CN105903451A (zh) * | 2016-05-09 | 2016-08-31 | 李迎春 | 一种重金属吸附海绵及其制备方法和应用 |
CN107216479A (zh) * | 2017-07-26 | 2017-09-29 | 河北科技大学 | 一种聚乙烯醇缩甲醛吸水泡沫体的制备方法 |
CN109535619A (zh) * | 2018-09-29 | 2019-03-29 | 浙江工业大学 | 海藻酸钠/聚乙烯醇复合水凝胶及其制备方法与应用 |
CN109173986A (zh) * | 2018-11-08 | 2019-01-11 | 广东顺祥陶瓷有限公司 | 一种可以吸附重金属的陶瓷材料及其制备方法 |
CN111849379A (zh) * | 2020-07-16 | 2020-10-30 | 沈阳天荣电缆材料有限公司 | 一种半导电缓冲胶带及其制备方法、应用和电力电缆 |
-
2020
- 2020-12-31 CN CN202011619862.4A patent/CN112844338B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN112844338A (zh) | 2021-05-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhang et al. | Porous geopolymer composites: A review | |
Li et al. | Shape memory aerogels from nanocellulose and polyethyleneimine as a novel adsorbent for removal of Cu (II) and Pb (II) | |
CN112844338B (zh) | 一种黑滑石-聚乙烯醇缩甲醛凝胶复合吸附材料 | |
CN107973559B (zh) | 多孔地质聚合物微球的制备方法及其应用 | |
JP2620039B2 (ja) | 天然高分子材料の多孔性架橋体 | |
CN111793176B (zh) | 一种具有层次孔结构的木质素基超交联聚合物及其制备方法和吸附应用 | |
CN114100582B (zh) | 水凝胶型复合材料及其制备方法及利用其去除苯系物的方法和应用 | |
CN102824898B (zh) | 一种三维多孔抗压限胀型膨润土吸附材料及其制备方法 | |
Zhao et al. | Preparation of capsules containing 1-nonanol for rapidly removing high concentration phenol from aqueous solution | |
CN103159894A (zh) | 超疏水微孔共轭聚合物和强疏水海绵吸附材料及其制备 | |
CN112063387B (zh) | 一种木质素磺酸盐-酚醛树脂基炭气凝胶微球及其制备方法和应用 | |
CN110694595A (zh) | 一种负载mof的多孔地聚合物气体吸附材料制备方法 | |
CN113385140A (zh) | 用于3d打印的蒙脱石纳米片凝胶墨水及制备方法和基于其的吸附材料和应用 | |
CN114632501A (zh) | 一种凹凸棒石基吸附剂的制备方法及其在染料/重金属离子废水处理中的应用 | |
Xu et al. | Polypropylene fiber grafted calcium alginate with mesoporous silica for adsorption of Bisphenol A and Pb2+ | |
CN110935199A (zh) | 一种具有互穿网络pH响应性的有机硅泡沫 | |
Zhu et al. | Microfluidic synthesis of renewable biosorbent with highly comprehensive adsorption performance for copper (II) | |
CN113231040B (zh) | 一种用于水中放射性铯离子去除的石墨烯吸附材料 | |
Wen et al. | Two‐Dimensional Covalent Organic Frameworks as Tailor‐Made Scaffolds for Water Harvesting | |
JPS6361618B2 (zh) | ||
CN115090269A (zh) | 一种化学稳定性好的超交联聚苯胺在废水处理中的应用 | |
CN114957737A (zh) | 一种利用n-烷基化反应制备超交联聚苯胺的方法 | |
CN110523388B (zh) | 一种明胶/纳米凹凸棒土复合吸附膜及其制备方法 | |
CN100522345C (zh) | 用聚乙烯醇包埋聚间苯二胺吸附剂的方法 | |
CN115232251B (zh) | 一种离子化胺基聚合物微球及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |