CN1883787A - Process for polyvinyl alcohol embedding preparation of spherical bentonite - Google Patents
Process for polyvinyl alcohol embedding preparation of spherical bentonite Download PDFInfo
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- CN1883787A CN1883787A CN 200610050877 CN200610050877A CN1883787A CN 1883787 A CN1883787 A CN 1883787A CN 200610050877 CN200610050877 CN 200610050877 CN 200610050877 A CN200610050877 A CN 200610050877A CN 1883787 A CN1883787 A CN 1883787A
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- bentonite
- polyvinyl alcohol
- organobentonite
- spherical
- water
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 65
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910000278 bentonite Inorganic materials 0.000 title claims description 100
- 239000000440 bentonite Substances 0.000 title claims description 100
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 title claims description 100
- 238000000034 method Methods 0.000 title claims description 17
- 230000008569 process Effects 0.000 title claims description 10
- 238000003756 stirring Methods 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000004132 cross linking Methods 0.000 claims abstract description 31
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 31
- 238000001914 filtration Methods 0.000 claims abstract description 17
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012153 distilled water Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 16
- 239000000661 sodium alginate Substances 0.000 claims abstract description 16
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 16
- 235000012216 bentonite Nutrition 0.000 claims description 110
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 62
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 38
- 238000005341 cation exchange Methods 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 17
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 15
- 238000006136 alcoholysis reaction Methods 0.000 claims description 15
- 239000001110 calcium chloride Substances 0.000 claims description 15
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 15
- 238000011010 flushing procedure Methods 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 230000001105 regulatory effect Effects 0.000 claims description 15
- 229920006395 saturated elastomer Polymers 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 12
- 125000002091 cationic group Chemical group 0.000 claims description 11
- -1 alkyl carbon Chemical compound 0.000 claims description 5
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 claims description 5
- 229960001927 cetylpyridinium chloride Drugs 0.000 claims description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- UMVUVPBFYZELCF-UHFFFAOYSA-N 2-tetradecylpyridine Chemical compound CCCCCCCCCCCCCCC1=CC=CC=N1 UMVUVPBFYZELCF-UHFFFAOYSA-N 0.000 claims description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 3
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- OWQGBDSLJUVLKF-UHFFFAOYSA-N 2-dodecylpyridine Chemical compound CCCCCCCCCCCCC1=CC=CC=N1 OWQGBDSLJUVLKF-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 11
- 239000004094 surface-active agent Substances 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 7
- 238000004062 sedimentation Methods 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 2
- 239000000843 powder Substances 0.000 abstract 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000005201 scrubbing Methods 0.000 abstract 1
- 229940092782 bentonite Drugs 0.000 description 92
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 20
- 238000010521 absorption reaction Methods 0.000 description 20
- 239000007788 liquid Substances 0.000 description 19
- 230000004048 modification Effects 0.000 description 14
- 238000012986 modification Methods 0.000 description 14
- 229950011260 betanaphthol Drugs 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 8
- 229940080314 sodium bentonite Drugs 0.000 description 8
- 229910000280 sodium bentonite Inorganic materials 0.000 description 8
- 239000005416 organic matter Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000004065 wastewater treatment Methods 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 239000003403 water pollutant Substances 0.000 description 6
- 238000003795 desorption Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001767 cationic compounds Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910001411 inorganic cation Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention discloses a preparation method of polyvinyl alcohol embedded spherical alta-mud, which characterized in the steps: (1) dissolving the quaternary ammonium salt cationic surface active agent into water, adding natural alta-mud, stirring, scrubbing, filtering, drying, activating, grinding by 100 mesh sieve and obtaining organobentonite; (2) mixing the said organobentonite and polyvinyl alcohol solution of 10 % containing sodium alginate of 0.02-0.2 % and stirring; (3) dripping the said mixture by separatory funnel with liquid-transfer head to crosslinking agent, after crosslinking reaction, rinsing with distilled water and drying. The excellence of the invention is: not needing filtration, centrifugation or sedimentation after adsorbing contaminant in water; having equivalent effect of removing organics to powder state alta-mud, having better effect of removing heavy metal than powder state alta-mud, capable of realizing simultaneously removing organic contaminant and heavy metal in waste-water, and capable of repetitious using after simple processing.
Description
Technical field
It is synthetic to the present invention relates to new material, relates in particular to a kind of process for polyvinyl alcohol embedding preparation of spherical bentonite.
Background technology
Nearly 50,000,000,000 tons of China's sewage annual emissions, wherein most sewage are unprocessed just directly to enter rivers,lakes and seas, and people's life security in serious threat.Causing the with serious pollution one of the main reasons of water is to lack economy, wastewater treatment practical technique efficiently and new material, and environmental pollution control is one of home and abroad environment scientific and engineering field problem that must solve with repairing, therefore, seek a kind of efficient, economic, simple and direct method of wastewater treatment and seem particularly important.Bentonite be a kind of be the clay rock of main component with montmorillonite (Montmorillonite), very abundant in china natural resources, occupy first place in the world, gross reserves is greater than 7,000,000,000 tons, bentonite ore 23 provinces that spread all over the country, more than 20 of large ore deposits.The raising tens of energy force rate natural earth even the hundred times of organic pollution in the organobentonite removal water of quaternary cationics modification, can effectively contain the migration of organic pollution in environment, in wastewater treatment and contaminated environment reparation, good prospects for application be arranged
[1-3]Therefore, if can be with the material of bentonite as wastewater treatment, that will be very desirable.
For a long time, Chinese scholars has been done a large amount of fruitful work to aspects such as bentonite absorption property, the mechanism of action, influence factor and recyclings.But the problem that still has all many-sides awaits researching and solving, such as: solid-liquid separation difficulty after (1) organobentonite adsorption treatment pollutants in waste water, the biggest obstacle of using in environmental project is exactly to be difficult to behind the bentonite absorption pollutant separate with purifying waste water, make the pollution system transfer mud to, cause to be difficult to behind the bentonite in treatment organic wastewater recycle by sewage.(2) common organobentonite functional structure is single, and is very poor to the removal effect of heavy metal, can not remove organic pollution and heavy metal in the waste water effectively simultaneously.Therefore, solid-liquid separates difficult problem behind the solution organobentonite absorption water pollutant, makes it be beneficial to recycling, repeats repeatedly to use; And make it can remove organic matter and heavy metal in the water simultaneously after suitably handling, this has very important significance to bentonite being applied to the actual waste water processing.At above problem, utilize macromolecule embedded material PVA, adopt PVA-H
3BO
3Investment, under certain condition with powdered form organobentonite immobilization globulate bentonite, solid-liquid separates difficult problem after having solved bentonite absorption water pollutant, improved greatly removal rate of heavy metal in the water, and the clearance of organic pollution almost do not reduced, realized the common removal of organic matter and heavy metal.
[1]Xu，S.；Sheng，G；Boyd?S.A.Use?of?organoclays?in?pollutants?abatement.Advances?inAgronomy，1997.59：25-62.
[2]Smith?J.A.；Jaffe?P.R.Benzene?transport?through?landfill?liners?containing?organophilicbentonite.Environ.Eng.，1994，120(6)：1559-1577.
[3]Park?J-W；Jaffe?P?R.Phenanthrene?removal?from?soil?slurries?with?surfactants?treated?oxides.Environ.Eng.，1995，121(6)：430-437.
Summary of the invention
The purpose of this invention is to provide a kind of process for polyvinyl alcohol embedding preparation of spherical bentonite.Solid-liquid separates difficult problem after having solved organobentonite adsorption treatment water pollutant, when keeping organobentonite that organic matter is had high clearance, improves removal rate of heavy metal.
The step of method is as follows:
(1) quaternary cationics is soluble in water, add natural montmorillonite, the quaternary cationics consumption is 50～200% of a bentonite cation exchange capacity, under 20～30 ℃ of temperature, stir 1.5～4h, washing, filtration, oven dry, under 90～110 ℃ of temperature, activate 30～60min, ground 100 mesh sieves, promptly make organobentonite;
(2) be that 7: 50～9: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.02～0.2% sodium alginate with mass volume ratio, stir 30～90min, it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.3～6.7, drips while stirring, and is clean with distilled water flushing behind cross-linking reaction 1～12h, 50～70 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
The average degree of polymerization of described polyvinyl alcohol is 1750 ± 50 or 1750 ± 70, and alcoholysis degree is 98～100%.
Described quaternary cationics is that the alkyl carbon number is at the long chain type quaternary cationics more than 10.The alkyl carbon number at the long chain type cationic surfactant more than 10 is: chlorination dodecyl pyridine, TPC, cetylpyridinium chloride, bromination myristyl pyridine, brocide, ten alkyl trimethyl ammonium bromides, DTAB, TTAB, softex kw, the octadecyl trimethylammonium bromide, ten alkyl trimethyl ammonium chlorides, DTAC, tetradecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride or OTAC.Natural montmorillonite is that particle diameter is 100～200 purpose sodium base or calcium-base bentonites.
Good effect of the present invention: there is not the solid-liquid separation problem in (1) after removing water pollutant, need not filter, centrifugal or sedimentation, has solved bentonite solid-liquid in wastewater treatment and has separated difficult problem; (2) the organic effect of removal is suitable with the powdered form bentonite, the effect of removing heavy metal is better than the powdered form bentonite, can realize removing simultaneously organic pollution and heavy metal in the waste water, and after simple process, can repeat repeatedly to use, help bentonite really is applied to wastewater treatment.(3) raw material is easy to get, and China's bentonite resource is very abundant, occupies first place in the world, and gross reserves is greater than 7,000,000,000 tons.
Description of drawings
Fig. 1 is spherical bentonite and powdered form organobentonite solid-liquid separation case contrast schematic diagram;
Fig. 2 is the comparison schematic diagram of spherical bentonite and powdered form bentonite absorption betanaphthol;
Fig. 3 is the comparison schematic diagram of spherical bentonite and powdered form bentonite absorption naphthalene;
Fig. 4 is spherical bentonite and powdered form bentonite absorption Cd
2+The comparison schematic diagram;
Fig. 5 is that spherical bentonite is to the multiple adsorb of betanaphthol and the desorption schematic diagram of surfactant.
The specific embodiment
Preparation principle of the present invention is:
The used PVA-H of the present invention
3BO
3The principle of embedding techniques is as follows:
PVA and H
3BO
3Chemical reaction takes place generate gel.The gel that utilizes this method to form, particle mechanical strength height, long service life, and good springiness.
The removal mechanism of pollutants is adsorbed in the present invention:
The bentonite main component is a montmorillonite.Montmorillonite is the layer silicate mineral of 2: 1 types, belongs to monoclinic system, and unit cell is formed by two-layer silicon-oxy tetrahedron folder layer of aluminum (magnesium) oxygen (hydroxyl) is octahedra.Al in the montmorillonite octahedron
3+With the Si in the tetrahedron
4+Often part (or all) is by other non-equivalence cation (Fe
3+, Fe
2+, Zn
2+, Mn
2+, Li
+Deng) replace, form the permanent negative electrical charge of interlayer.In addition, the montmorillonite crystal edge is broken key, and some end face is electronegative in pH＞7, also adsorbable small cations, and therefore, the bentonite original soil can be removed heavy metal ion by ion exchange absorption.But natural montmorillonite makes its surface have the thin moisture film of one deck usually because the surface silicon oxide structure has extremely strong hydrophily and the cationic hydrolysis of a large amount of interchangeabilities of interlayer, can not effectively adsorb hydrophobic organic pollutant.And, can replace the inorganic cation between bentonite bed owing to have hydrophobic effect and strong molecular separating force between the organic ion, make it become hydrophobic organobentonite.Organobentonite with the quaternary cationics modification, because the organic cations aquation is significantly less than inorganic cation, form hydrophobic environment on the organobentonite surface, organic carbon content improves, and therefore removes the raising tens of energy force rate natural earth even the hundred times of hydrophobic organic pollutant from water.
Though organobentonite has good absorption removal effect to organic pollution, but, through surfactant-modified organobentonite since the interchangeability inorganic cation of interlayer replaced by surface active agent ion, and surfactant can not with heavy metal generation surface complexation effect or interlayer mating reaction, therefore, organobentonite counterweight metal ion does not adsorb substantially.And after organobentonite and PVA solution mixes embedding synthesizing spherical organobentonite, PVA enters between bentonite bed, and there are a lot of hydroxyls in the PVA molecule, heavy metal ion can with hydroxyl generation mating reaction, so increased the adsorbance of bentonite to heavy metal, and the increase of adsorbance used surfactant carrying capacity (CEC content) during along with modification and increasing; This is because of the increase along with CEC content, and the amount of surfactant that enters between bentonite bed increases, and interlamellar spacing is increased, and causes the PVA amount that enters between bentonite bed to increase, and removal rate of heavy metal is improved.As seen, the present invention has not only solved the solid-liquid separation problem of bentonite in wastewater treatment, and can remove organic pollution and heavy metal in the water simultaneously.
The used natural montmorillonite sample of the present invention is standby after preliminary treatment such as air dry, fragmentation, screening.The experiment agents useful for same is that analysis is pure substantially, and its mesoboric acid and pyridines cationic surfactant are chemical pure, and institute's water is a deionized water.Test used instrument and mainly contain the THZ-C constant temperature oscillator, LDZ5-2 low speed autobalancing centrifuge, UV-2401 ultraviolet-visible spectrophotometer, AAnalyst 700 type atomic absorption spectrophotometers (Perkin Elmer).
Organic matter and removal rate of heavy metal:
y＝((C
0-C
e)/C
0)×100％
In the formula: y represents clearance; C
0Represent the pollutant initial concentration, C
eRepresent pollutant equilibrium concentration.
Embodiment 1
(1) is that the brocide of bentonite cation exchange capacity 50% is soluble in water with consumption, adds the natural sodium bentonite of 100 orders, under 20 ℃ of temperature, stir 1.5h, washing, filtration, oven dry, under 90 ℃ of temperature, activate 30min, ground 100 mesh sieves, promptly make organobentonite;
(2) be that 8: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.02% sodium alginate with mass volume ratio, the used polyvinyl alcohol degree of polymerization is 1750 ± 50, and alcoholysis degree is 98～99%, stirs 30min, and it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.5, drips while stirring, and is clean with distilled water flushing behind the cross-linking reaction 1h, 50 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
Embodiment 2
(1) is that the bromination myristyl pyridine of bentonite cation exchange capacity 200% is soluble in water with consumption, adds the natural sodium bentonite of 200 orders, under 30 ℃ of temperature, stir 4h, washing, filtration, oven dry, under 110 ℃ of temperature, activate 60min, ground 100 mesh sieves, promptly make organobentonite;
(2) be that 9: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.2% sodium alginate with mass volume ratio, the used polyvinyl alcohol degree of polymerization is 1750 ± 70, and alcoholysis degree is 99～100%, stirs 90min, and it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.7, drips while stirring, and is clean with distilled water flushing behind the cross-linking reaction 12h, 70 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
Embodiment 3
(1) is that the TPC of bentonite cation exchange capacity 60% is soluble in water with consumption, adds the natural sodium bentonite of 100 orders, under 30 ℃ of temperature, stir 2h, washing, filtration, oven dry, under 95 ℃ of temperature, activate 45min, ground 100 mesh sieves, promptly make organobentonite;
(2) be that 7: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.16% sodium alginate with mass volume ratio, the used polyvinyl alcohol degree of polymerization is 1750 ± 50, and alcoholysis degree is 99.8～100%, stirs 60min, and it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.3, drips while stirring, and is clean with distilled water flushing behind the cross-linking reaction 1h, 60 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
Embodiment 4
(1) be that the softex kw of bentonite cation exchange capacity 100% is soluble in water with consumption, add the natural sodium bentonite of 150 orders, under 25 ℃ of temperature, stir 2.5h, washing, filtration, oven dry, under 105 ℃ of temperature, activate 40min, grind 100 mesh sieves, promptly made organobentonite;
(2) be that 8: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.08% sodium alginate with mass volume ratio, the used polyvinyl alcohol degree of polymerization is 1750 ± 70, and alcoholysis degree is 98～99%, stirs 45min, and it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.4, drips while stirring, and is clean with distilled water flushing behind the cross-linking reaction 3h, 60 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
Embodiment 5
(1) be that the octadecyl trimethylammonium bromide of bentonite cation exchange capacity 150% is soluble in water with consumption, add the natural sodium bentonite of 150 orders, under 25 ℃ of temperature, stir 3h, washing, filtration, oven dry, under 105 ℃ of temperature, activate 60min, grind 100 mesh sieves, promptly made organobentonite;
(2) be that 7.5: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.2% sodium alginate with mass volume ratio, the used polyvinyl alcohol degree of polymerization is 1750 ± 50, and alcoholysis degree is 98～99%, stirs 75min, and it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.6, drips while stirring, and is clean with distilled water flushing behind the cross-linking reaction 5h, 55 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
Embodiment 6
(1) be that the TTAB of bentonite cation exchange capacity 80% is soluble in water with consumption, add 200 order natural calcium base bentonites, under 20 ℃ of temperature, stir 2.5h, washing, filtration, oven dry, under 100 ℃ of temperature, activate 50min, grind 100 mesh sieves, promptly made organobentonite;
(2) be that 8.5: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.06% sodium alginate with mass volume ratio, the used polyvinyl alcohol degree of polymerization is 1750 ± 50, and alcoholysis degree is 99.8～100%, stirs 60min, and it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.5, drips while stirring, and is clean with distilled water flushing behind the cross-linking reaction 5h, 60 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
Embodiment 7
(1) be that the DTAB of bentonite cation exchange capacity 180% is soluble in water with consumption, add the natural sodium bentonite of 150 orders, under 25 ℃ of temperature, stir 2h, washing, filtration, oven dry, under 105 ℃ of temperature, activate 60min, grind 100 mesh sieves, promptly made organobentonite;
(2) be that 8.5: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.05% sodium alginate with mass volume ratio, the used polyvinyl alcohol degree of polymerization is 1750 ± 50, and alcoholysis degree is 98～99%, stirs 45min, and it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.3, drips while stirring, and is clean with distilled water flushing behind the cross-linking reaction 6h, 60 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
Embodiment 8
(1) be that the hexadecyltrimethylammonium chloride of bentonite cation exchange capacity 100% is soluble in water with consumption, add 100 order natural calcium base bentonites, under 25 ℃ of temperature, stir 3h, washing, filtration, oven dry, under 100 ℃ of temperature, activate 60min, grind 100 mesh sieves, promptly made organobentonite;
(2) be that 8: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.04% sodium alginate with mass volume ratio, the used polyvinyl alcohol degree of polymerization is 1750 ± 50, and alcoholysis degree is 99.8～100%, stirs 45min, and it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.7, drips while stirring, and is clean with distilled water flushing behind the cross-linking reaction 7h, 70 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
Embodiment 9
(1) be that the OTAC of bentonite cation exchange capacity 120% is soluble in water with consumption, add 150 order natural calcium base bentonites, under 30 ℃ of temperature, stir 1.5h, washing, filtration, oven dry, under 110 ℃ of temperature, activate 30min, grind 100 mesh sieves, promptly made organobentonite;
(2) be that 9: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.15% sodium alginate with mass volume ratio, the used polyvinyl alcohol degree of polymerization is 1750 ± 50, and alcoholysis degree is 99.8～100%, stirs 90min, and it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.5, drips while stirring, and is clean with distilled water flushing behind the cross-linking reaction 9h, 65 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
(1) be that the tetradecyl trimethyl ammonium chloride of bentonite cation exchange capacity 160% is soluble in water with consumption, add the natural sodium bentonite of 100 orders, under 25 ℃ of temperature, stir 2h, washing, filtration, oven dry, under 100 ℃ of temperature, activate 60min, grind 100 mesh sieves, promptly made organobentonite;
(2) be that 7: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.1% sodium alginate with mass volume ratio, the used polyvinyl alcohol degree of polymerization is 1750 ± 70, and alcoholysis degree is 98～99%, stirs 60min, and it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.6, drips while stirring, and is clean with distilled water flushing behind the cross-linking reaction 10h, 60 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
Embodiment 11
(1) be that ten alkyl trimethyl ammonium chlorides of bentonite cation exchange capacity 180% are soluble in water with consumption, add the natural sodium bentonite of 150 orders, under 25 ℃ of temperature, stir 2h, washing, filtration, oven dry, under 100 ℃ of temperature, activate 60min, grind 100 mesh sieves, promptly made organobentonite;
(2) be that 8.5: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.05% sodium alginate with mass volume ratio, the used polyvinyl alcohol degree of polymerization is 1750 ± 50, and alcoholysis degree is 98～99%, stirs 45min, and it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.3, drips while stirring, and is clean with distilled water flushing behind the cross-linking reaction 5h, 60 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
Embodiment 12
(1) it is soluble in water consumption to be respectively the cetylpyridinium chloride of bentonite cation exchange capacity 50%, 80%, 100%, 120%, 150%, 200%, add 100 order natural calcium base bentonites, under 25 ℃ of temperature, stir 2h, washing, filtration, oven dry, under 105 ℃ of temperature, activate 30min, ground 100 mesh sieves, made organobentonite respectively with the modification of different surfaces active dose;
(2) be that 8: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.02% sodium alginate with mass volume ratio, the used polyvinyl alcohol degree of polymerization is 1750 ± 50, and alcoholysis degree is 98～99%, stirs 90min, and it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.5, drips while stirring, and is clean with distilled water flushing behind the cross-linking reaction 2h, 60 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
Embodiment 13
For the bentonitic performance of sphere is characterized, and relatively convenient, prepared the spherical bentonite of low surfactant carrying capacity, as follows:
(1) it is soluble in water consumption to be respectively the cetylpyridinium chloride of bentonite cation exchange capacity 0%, 20%, 30%, add 100 order natural calcium base bentonites, under 25 ℃ of temperature, stir 2h, washing, filtration, oven dry, under 105 ℃ of temperature, activate 30min, ground 100 mesh sieves, made organobentonite respectively with the modification of different surfaces active dose;
(2) be that 8: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.02% sodium alginate with mass volume ratio, the used polyvinyl alcohol degree of polymerization is 1750 ± 50, and alcoholysis degree is 98～99%, stirs 90min, and it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.5, drips while stirring, and is clean with distilled water flushing behind the cross-linking reaction 2h, 60 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
Embodiment 14
With cationic surfactant cetylpyridinium chloride and particle diameter is that spherical bentonite and the powdered form organobentonite that 100 purpose natural calcium base bentonites are prepared from is representative, aspect such as absorption property, Separation of Solid and Liquid from both characterizes performance of the present invention:
(1) comparison of spherical bentonite and Powdered bentonite Separation of Solid and Liquid
Separation of Solid and Liquid situation behind the organobentonite adsorption treatment water pollutant of the present invention and powdered form is relatively referring to Fig. 1, as seen, there is not the Separation of Solid and Liquid problem behind the spherical bentonite adsorption treatment water pollutant, and the separation of powdered form organobentonite solid-liquid needs 20min at least, and there is part to float on the solution top, fine particle is difficult to sedimentation, really realizes very difficulty of Separation of Solid and Liquid.
(2) bentonite is to organic pollutant adsorption
Adopt bentonite a great deal of comparison method, be that bentonite amount among the present invention is suitable with powdered form bentonite amount, with betanaphthol, naphthalene is the organic matter representative, at 25 ℃, hunting speed is under the 150r/min condition, solid-to-liquid ratio is 3: 250 (mass volume ratio), tested the different surfaces activating agent carrying capacity (percentage that is equivalent to the bentonite cation exchange capacity, be CEC content, as be equivalent to 150 of bentonite cation exchange capacity, then be expressed as 1.5CEC or 150%CEC) two kinds of bentonites of modification to they absorption relatively, duration of oscillation is 24h, spherical bentonite is got clear liquid and is directly measured after the adsorption equilibrium, the organobentonite of powdered form is got supernatant and is measured behind centrifugal 30min under the 3000r/min condition, the result is referring to Fig. 2, Fig. 3.As seen from the figure, in CEC content is 50～200% scopes, all more than 85%, CEC content is in 80～200 scopes the time to the clearance of betanaphthol (initial concentration is 500mg/L), naphthalene (initial concentration is 25mg/L) for two kinds of bentonites, and clearance is all more than 90%; CEC content is in 50～200% scopes the time, and both are suitable to organic clearance, and at CEC less than 50 o'clock, spherical bentonite is higher than the organobentonite of powdered form to organic clearance.
(3) bentonite is to the absorption of heavy metal
Under 25 ℃, 150r/min condition, solid-to-liquid ratio is the same, has tested the absorption of two kinds of bentonites of different CEC modifications to heavy metal cadmium in the water, chooses Cd
2+Initial concentration is 10mg/L, and pH is about 6.0 in control, the results are shown in Figure 4.As seen, when 0.5CEC was above, spherical bentonite was to Cd
2+Absorption property be better than the powdered form bentonite, when 1.0CEC was above, spherical bentonite was to Cd
2+Clearance more than 65%, absorption property is significantly better than the powdered form bentonite, and the powdered form bentonite is to Cd
2+Clearance almost nil.
(4) spherical bentonite is to heavy metal and organic removal simultaneously
Choosing betanaphthol is the organic matter representative, Cd
2+Be the heavy metal representative, under 25 ℃, 150r/min condition, solid-to-liquid ratio is the same, has tested spherical bentonite to the betanaphthol of 300mg/L and the Cd of 10mg/L
2+The while removal effect, the bentonite of employing is the bentonite of 1.5CEC modification.The result shows, is 94.6% to the clearance of the betanaphthol of 300mg/L, to Cd
2+Clearance be 85.8%, organic existence has humidification to spherical bentonite absorption heavy metal.
(5) spherical bentonite is to organic multiple adsorb
Under 25 ℃, 150r/min condition, solid-to-liquid ratio is the same, tested the multiple adsorb effect of the spherical bentonite of 1.0CEC and 1.5CEC modification to betanaphthol, the spherical bentonite in each absorption back dries or natural air drying through natural daylight, carry out experiment next time then, the betanaphthol initial concentration is 500mg/L, the results are shown in Figure 5.As seen from the figure, the spherical bentonitic absorption property of 1.5CEC modification is better than the spherical bentonite of 1.0CEC modification, and its 2nd time clearance to betanaphthol is also more than 90%, and the clearance of the 5th is greater than 50%; And the bentonite of 1.0CEC modification, though adsorption effect is slightly poor, its 4th to organic clearance also greater than 40%.Simultaneously, investigated the surfactant of spherical bentonite in multiple adsorb and the desorption situation of PVA of 1.5CEC modification, can get by Fig. 5, CPC is along with the increase desorption rate of absorption number of times increases, but equilibrium concentration is still very low in water, is lower than 35mg/L, and desorption rate is very little; And PVA is in the multiple adsorb of being carried out experiment, and concentration is not all less than 2mg/L (detecting with experimental technique).Therefore, the spherical bentonite of 1.0CEC～1.5CEC modification can effectively carry out the multiple adsorb organic matter, 3 times organic clearance is higher than 70%, and surfactant and PVA desorption are seldom, can not produce secondary pollution.
Claims (5)
1. process for polyvinyl alcohol embedding preparation of spherical bentonite, it is characterized in that: the step of method is as follows:
(1) quaternary cationics is soluble in water, add natural montmorillonite, the quaternary cationics consumption is 50～200% of a bentonite cation exchange capacity, under 20～30 ℃ of temperature, stir 1.5～4h, washing, filtration, oven dry, under 90～110 ℃ of temperature, activate 30～60min, ground 100 mesh sieves, promptly make organobentonite;
(2) be that 7: 50～9: 50 above-mentioned organobentonite mixes with 10% poly-vinyl alcohol solution that contains 0.02～0.2% sodium alginate with mass volume ratio, stir 30～90min, it is mixed;
(3) with the separatory funnel of band liquid-transfering gun head said mixture is added drop-wise to and carries out cross-linking reaction in the crosslinking agent, crosslinking agent is the saturated BAS that contains 2% calcium chloride, and uses Na
2CO
3Solution is regulated pH to 6.3～6.7, drips while stirring, and is clean with distilled water flushing behind cross-linking reaction 1～12h, 50～70 ℃ of oven dry down, makes the spherical bentonite through the PVA embedding.
2. a kind of process for polyvinyl alcohol embedding preparation of spherical bentonite according to claim 1, the average degree of polymerization that it is characterized in that described polyvinyl alcohol is 1750 ± 50 or 1750 ± 70, alcoholysis degree is 98～100%.
3. a kind of process for polyvinyl alcohol embedding preparation of spherical bentonite according to claim 1 is characterized in that described quaternary cationics is that the alkyl carbon number is at the long chain type quaternary cationics more than 10.
4. a kind of process for polyvinyl alcohol embedding preparation of spherical bentonite according to claim 3 is characterized in that described alkyl carbon number at the long chain type cationic surfactant more than 10 is: chlorination dodecyl pyridine, TPC, cetylpyridinium chloride, bromination myristyl pyridine, brocide, ten alkyl trimethyl ammonium bromides, DTAB, TTAB, softex kw, the octadecyl trimethylammonium bromide, ten alkyl trimethyl ammonium chlorides, DTAC, tetradecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride or OTAC.
5. a kind of process for polyvinyl alcohol embedding preparation of spherical bentonite according to claim 1 is characterized in that described natural montmorillonite is that particle diameter is 100～200 purpose sodium base or calcium-base bentonites.
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| CN102059097A (en) * | 2010-11-25 | 2011-05-18 | 中国科学院广州地球化学研究所 | Preparation method of montmorillonite as novel overflowed oil pollution absorbing material |
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| CN106076276A (en) * | 2016-07-05 | 2016-11-09 | 章俊 | A kind of Industrial Wastewater Treatment adsorbent and preparation method thereof |
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| CN113134346A (en) * | 2020-01-20 | 2021-07-20 | 中国地质大学（北京） | Bentonite/polymer adsorption particles with grid structure and preparation method thereof |
| CN113134346B (en) * | 2020-01-20 | 2022-07-15 | 中国地质大学（北京） | Bentonite/polymer adsorption particles with grid structure and preparation method thereof |
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| CN111905698A (en) * | 2020-08-04 | 2020-11-10 | 武汉大学 | Modified bentonite-sodium alginate composite gel ball, preparation method thereof and application of modified bentonite-sodium alginate composite gel ball as adsorption material |
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