CN100429146C - Method for synthesizing composite material of organic - inorganic bentonite - Google Patents
Method for synthesizing composite material of organic - inorganic bentonite Download PDFInfo
- Publication number
- CN100429146C CN100429146C CNB200610154849XA CN200610154849A CN100429146C CN 100429146 C CN100429146 C CN 100429146C CN B200610154849X A CNB200610154849X A CN B200610154849XA CN 200610154849 A CN200610154849 A CN 200610154849A CN 100429146 C CN100429146 C CN 100429146C
- Authority
- CN
- China
- Prior art keywords
- bentonite
- inorganic
- organic
- pillared
- hours
- 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.)
- Expired - Fee Related
Links
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910000278 bentonite Inorganic materials 0.000 title claims abstract description 90
- 239000000440 bentonite Substances 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 21
- 238000012986 modification Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 18
- RKFMOTBTFHXWCM-UHFFFAOYSA-M [AlH2]O Chemical compound [AlH2]O RKFMOTBTFHXWCM-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229940092782 bentonite Drugs 0.000 claims description 81
- 239000007788 liquid Substances 0.000 claims description 47
- 238000001914 filtration Methods 0.000 claims description 36
- 238000000926 separation method Methods 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 239000012265 solid product Substances 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000002444 silanisation Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 206010016825 Flushing Diseases 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- 238000011010 flushing procedure Methods 0.000 claims description 9
- 229910021647 smectite Inorganic materials 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- -1 amino, methoxy Chemical group 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical group 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 claims description 5
- 229940080314 sodium bentonite Drugs 0.000 claims description 5
- 229910000280 sodium bentonite Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 5
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000006884 silylation reaction Methods 0.000 abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052799 carbon Inorganic materials 0.000 abstract description 16
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 10
- 239000007864 aqueous solution Substances 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000005341 cation exchange Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 239000010815 organic waste Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 19
- 239000004927 clay Substances 0.000 description 11
- 239000013543 active substance Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 229910010271 silicon carbide Inorganic materials 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 229910018540 Si C Inorganic materials 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 241000282326 Felis catus Species 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 239000002734 clay mineral Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002594 sorbent Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 150000001455 metallic ions Chemical class 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000001457 metallic cations Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 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 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
This invention discloses a method for synthesizing organic-inorganic bentonite composite. The method comprises: utilizing bentonite as the main material, performing inorganic modification through cation-exchange reaction by using hydroxyl aluminum aqueous solution, torrefying to obtain hydroxyl-containing aluminum-pillared bentonite with high porosity and high specific surface area, and reacting between the hydroxyls and silylation agent to graft silane groups onto aluminum-pillared bentonite and obtain organic-inorganic bentonite composite. The organic-inorganic bentonite composite has both the advantages of inorganic pillared bentonite such as high porosity and high specific surface area, and those of organic bentonite such as high organic carbon content and high hydrophobicity thus can be used to treat organic waste gases and wastewater with a good effect by surface adsorption as well as distribution.
Description
Technical field
The invention belongs to clay mineral processing and utilization field, be specifically related to a kind of method for synthesizing composite material of organic-inorganic bentonite, particularly successively by inorganic, organically-modified synthetic composite material of organic-inorganic bentonite that can be used for fields such as organic exhaust gas, waste water adsorption treatment and preparation method thereof.
Background technology
Wilkinite is to be 2: 1 type layered clay minerals of typical case that essential mineral is formed with the montmorillonite, is one of non-metallic minerals that is most widely used.Wilkinite has performances such as good water-swelling, cohesiveness, adsorptivity, catalytic activity, thixotropy, suspension, plasticity-, oilness and cationic exchange, thereby can be used as binding agent, absorption agent, sorbent material, weighting agent, catalyzer, thixotropic agent, flocculation agent, washing composition, stablizer and thickening material etc., be widely used in fields such as metallurgy, machinery, chemical industry, oil, weaving, food, water conservancy, traffic, medical papermaking and environmental protection.Wilkinite is used widely as a kind of novel mineral material because of having very high specific surface area, strong surfactivity and characteristics such as cheap and easy to get.
Often wilkinite is carried out modification or activation treatment for satisfying different needs, produce various modified alta-muds, have function, colour change function, antibacterial, catalysis of adsorb organic compound, mineral ion etc.According to the type difference of properties-correcting agent, modified alta-mud can be divided into organobentonite, inorganic bentonite, organic and inorganic composite bentonite etc.Organobentonite is meant the wilkinite that utilizes organic molecule, ion, polymer modification, and using maximum is with the quaternary surfactant modification.Organobentonite organic carbon content height after the modification, the organic phase that forms between bentonite bed because of properties-correcting agent is to organic affinity interaction, generally the organic molecule absorption property is improved greatly, organic energy force rate original soil high tens is to hundred times in the removal water, in the gas, can be used as the organic contamination sorbent material, also can be used as the presoma of composite nano polymer/clay material.The known method that the synthetic aspect of a lot of organobentonites is arranged both at home and abroad, as US4434075, US6036765, US5634969, CN1263132A CN1446845A, CN1807241A etc., but generally adopt tensio-active agent, particularly cats product to carry out modification.Surfactant-modified organobentonite uses as sorbent material and has following problem: the agent molecule that is modified between (1) bentonite bed occupies, specific surface area and pore volume sharply reduce, to the adsorption effect of lower concentration adsorbate relatively poor and when Gas Phase Adsorption during slow, the adsorbed gas of rate of adsorption resistance to mass transfer big; (2) organic modifiers normally loads on the wilkinite with cationic exchange or physisorption, reactive force a little less than, in planar water, easily come off in organism or the regenerative process; In addition, thermostability depends on the decomposition temperature of modified surface promoting agent, and suitable synthetic bentonite tensio-active agent is thermally-stabilised not high, thereby thermostability relatively poor (＜250 ℃), so cause the regeneration difficulty.
Another route of synthesis of bentonite is to adopt organosilane (as chlorosilane, organoalkoxysilane) and surface of clay reactive hydroxyl to carry out Silanization reaction, reach the purpose that changes the clay hydrophobicity, increases organic carbon content thereby silylation is grafted to surface of clay, as patent disclosures such as U.S. Pat 6136994, US6136994 directly react the method that obtains the hydrophobicity clay by organosilane with clay mineral such as wilkinite; Patent US4874728 discloses the method that clays such as quaternary surfactant and the common modified alta-mud of organosilane prepare organic clay.Compare with surfactant-modified organobentonite, the silanization organobentonite has and the similar height indicator face of tensio-active agent hydrophobicity, and because the combining of silylation and surface of clay by covalent bonds, thermostability strengthens greatly, far above the boiling point (＞500 ℃) of the used silanization reality of modification.The problem that the silanization organobentonite exists is that reactive hydroxyl mainly is positioned at outside surface in the bentonitic structure, most hydroxyls are that the aluminium hydroxyl that is wrapped in the silicon-oxy tetrahedron is non-reacted hydroxyl, so directly the result that wilkinite is carried out silanization is that organic carbon content is low, and the silylation multidigit is in the surface, little to the influence in the layer, can not show a candle to the organobentonite of cats product modification.
Polymer/metallic ion pillared modification is the Bentonite Modification Technologies of the other quasi-representative except that organically-modified, its ultimate principle be by the polymer-inorganic metallic cation by with layered clay mineral layers such as wilkinite in the ion exchange insert structure layer of metallic cation, and then roasting and the porous material that forms.The polymerizing cationically that enters interlayer makes basal spacing increase than original metal ion die, by heating, polymerizing cationically dehydration, deshydroxy change the metal oxide cluster of what is called " layer post " into, these layers post makes silicate layer permanently keep certain distance, even under comparatively high temps, the clay silicate layer is also unlikely to cave in, thereby has improved the thermostability of clay.The modified alta-mud that this method obtains is commonly referred to as inorganic pillared bentonite and also is cross-linked bentonite.Known inorganic pillared bentonite preparation method is more, and the polymer/metallic ion that relates to Al, Zr, Ti etc. is pillared, can be used as sorbent material, catalyzer etc., as US4637991, US4176090, US5415850 etc.Compare the important variation of inorganic pillared bentonite with the original soil nature and characteristic and also have specific surface area, original soil since interlayer occupied by metal ion and water molecules, the specific surface area that can measure is very little, but through inorganic pillared after, specific surface area can increase to 200 ~ 400m
2/ g compares with organobentonite, and inorganic pillared bentonite has specific surface area and the bigger advantage of pore volume, but hydrophobicity is not so good as organobentonite, thereby not remarkable to organic adsorption.
Pillared the combining with the cats product modification of polymerization hydroxy metal ion can be synthesized existing good hydrophobicity, can have the organic and inorganic composite bentonite of the bigger advantage of inorganic pillared bentonite specific surface area and pore volume again by the distributional effects adsorb organic compound.Currently known methods such as US4916095, US4845066, CN1751794A etc. have obtained the organic and inorganic composite bentonite by to the inorganic pillared and common modification of cats product.Existing traditional bentonite advantage, overcome its specific surface area again to a certain extent and pore volume is little, to the deficiency a little less than the lower concentration adsorbate adsorptive power.Find also that simultaneously wilkinite is through after the polymer/metallic ion pillared modification, CEC sharply descends, the partial cation tensio-active agent is by physical adsorption but not cationic exchange enters interlayer, thereby the reduction of tensio-active agent charge capacity, come off easily, and still do not solve the low problem of thermostability.
Though conventional inorganic pillared bentonite thermostability is good than organobentonite, but obviously do not possess organobentonite improves loading capacity by high organic carbon content ability, the synthetic problem that has solved organobentonite and the existence of inorganic pillared bentonite to a certain extent of organic and inorganic composite bentonite, but thermostability is compared with organobentonite still and is not improved, and the caducous problem of tensio-active agent also is difficult to overcome.
At the problem of above-mentioned existence, the present invention is by improving bentonite modified approach in the hope of overcoming the problem of above existence.Basic ideas are by the pillared raising wilkinite of polymerization hydroxy metal ion (as hydroxy aluminum) surface-area, enlarge the bentonite bed spacing, form conventional inorganic pillared bentonite, the hydroxy metal of polymerization simultaneously ionic is introduced also for interlayer provides a large amount of reactive hydroxyls, makes the wilkinite surfaces externally and internally all have the ability of reacting with organosilicon; Further inorganic pillared bentonitic surfaces externally and internally is carried out silylation modification by Silanization reaction, thereby synthesize novel inorganic-organobentonite matrix material, so that it is keeping conventional organobentonite and the bentonitic advantage of silanization aspect organic carbon content, the hydrophobicity, possesses the advantage of inorganic pillared bentonite and silanization wilkinite Heat stability is good simultaneously again; In addition, inorganic pillared owing at first passing through, space enlargement in the layer though the introducing of organic group may occupy a part of space, is compared with organobentonite, and resistance to mass transfer should be able to obtain improvement to a certain degree.
It is different to what deserves to be explained is that the said organic and inorganic composite bentonite of the present invention material is commonly referred to composite organic-inorganic materials such as " composite nano polymer/clay materials " (US6562891, US6252020, CN1769191A etc.) with material science, and " organic " of the present invention, " inorganic " are at properties-correcting agent; And latter's what is called " organic " mainly refers to properties-correcting agent, and " inorganic " then refers generally to clay itself.
Summary of the invention
The purpose of this invention is to provide a kind of method for synthesizing composite material of organic-inorganic bentonite.
It is with wilkinite as material of main part, earlier obtain inorganic pillared bentonite, and then carry out organic modification with silylating reagent with the hydroxy aluminum modification, finally obtain organic and inorganic composite bentonite sorbing material; Concrete preparation process is as follows:
1) preparation of pillared liquid: under continuously stirring, 50 ℃～80 ℃ conditions of temperature, in 2～5 hours be 0.1～1.0mol/LAlCl that the alkaline solution of 0.5～2.0mol/L is added drop-wise to 1～3 times of volume with concentration
36H
2In the O solution, make the OH in the mixing solutions
-With Al
3+Concentration ratio is 2.0～3.0, dropwises the back and continues to stir 3～6 hours, stops heating then, places ageing 10～36 hours, obtains solution and is pillared liquid;
2) inorganic pillared bentonitic preparation: pillared liquid is heated to 50 ℃～80 ℃, constant temperature, in wilkinite quality and the long-pending ratio of pillared liquid is the proportioning of 20～80g/L, under agitation condition, 0.5 progressively wilkinite is distributed in the pillared liquid in～1 hour, the back continuation that disperses to finish was stirred 4～5 hours, was cooled to room temperature, placed 12～36 hours; Filtering separation, solid product are used and isopyknic water washing of pillared liquid four times and filtering separation, and the solid product after the filtering separation is following dry 12～36 hours at 90～120 ℃;
3) silanization modification: in organic solvent and inorganic pillared bentonite ratio 3～5L/kg, silylating reagent and inorganic pillared bentonite ratio 0.5～2.0mol/kg, inorganic pillared bentonite is mixed with organic solvent, silylating reagent, reacted 12～36 hours, filtering separation is divided 2～3 flushings with the acetone that adds 5～10 times of organic solvent volumes then, removes unreacted silylating reagent and organic solvent, solid product dried in air, 90～120 ℃ of vacuum-dryings 12～36 hours.
Smectite content in the said wilkinite is 65%～100%.Wilkinite is sodium bentonite or calcium-base bentonite.Alkali aqueous solution is aqueous sodium hydroxide solution or aqueous sodium carbonate.Organic solvent is toluene, benzene, acetone or pyridine.Silylating reagent is that chemical structure of general formula is R
N-Si-X
4-NOrganosilane, wherein, N=1～3, R comprises that carbonatoms is that 1～18 alkyl, phenyl and carbonatoms are the organic group of 1～18 amino, cyano group, sulfydryl or chlorine substituted alkyl, X is the hydrolyzable part that comprises halogen, amino, methoxy or ethoxy.
The advantage of the composite material of organic-inorganic bentonite that the present invention obtains is:
(1) compares with the conventional surfactant organic modified bentonite, hydrophobicity and organic carbon content are suitable, but have relatively bigger porosity and specific surface area, high thermal stability more, have stability preferably in the use under liquid-phase condition, the regenerative process, difficult drop-off.
(2) compare with the organobentonite that direct silanization obtains, organic carbon content is higher, helps organic absorption;
(3) compare with inorganic pillared bentonite, have suitable porosity and specific surface area, but possess high hydrophobicity and high organic carbon content that inorganic pillared bentonite lacks, when being used for organic exhaust gas, waste water adsorption treatment, no matter can be simultaneously distribute two kinds of approach adsorb organic compounds by surface adsorption and organic phase, still be that high concentration organic contaminant has good removal effect to lower concentration.
(4) because of form and the wilkinite surface bonding of organic group by covalent linkage, reactive force is strong, compare with the organic-inorganic bentonite that tensio-active agent, the common modification of inorganic metal ion make, overcome the caducous shortcoming of tensio-active agent in use and regenerative process.
Embodiment
The invention will be further elaborated below by example:
Embodiment 1, under continuously stirring, 50 ℃ of conditions of temperature, in 2 hours is the 0.1mol/L AlCl that the aqueous sodium carbonate of 2mol/L is added drop-wise to 3 times of volumes with concentration
36H
2In the O aqueous solution, dropwise the back and continue to stir 3 hours, stop heating then, place ageing 36 hours, obtain pillared liquid.
Pillared liquid is heated to 50 ℃, constant temperature, according to wilkinite quality and the long-pending ratio of pillared liquid is the proportioning of 80g/L, under agitation condition, progressively be that 100% calcium-base bentonite is distributed in the pillared liquid in 1 hour with smectite content, the back continuation that disperses to finish was stirred 4 hours, was cooled to room temperature, placed 36 hours; Filtering separation, solid product are used and isopyknic water washing of pillared liquid four times and filtering separation, 120 ℃ of dryings of the solid product after the filtering separation 12 hours.
In toluene and inorganic pillared bentonite ratio 5L/kg, octadecyl trichlorosilane [Cl
3Si (CH
2)
17CH
3] and inorganic pillared bentonite ratio 2.0mol/kg, inorganic pillared bentonite is mixed with toluene, octadecyl trichlorosilane, reacted 12 hours, filtering separation is divided 2 flushings with the acetone that adds 5 times of organic solvent volumes then, removes unreacted octadecyl trichlorosilane and toluene, solid product dries in air, 90 ℃ of vacuum-dryings 36 hours, obtain composite material of organic-inorganic bentonite, the BET surface-area is 107m
2/ g, pore volume are 0.065cm
3/ g, mean pore size 2.45nm, organic carbon content are 24.1%, silylation content is 85.6mmol/100g, the FTIR characterization result confirms silylation by Si-C covalent linkage and material of main part surface bonding, the demonstration of TG/DTA analytical results, and high heat stability temperature is 508 ℃.
Embodiment 2, under continuously stirring, 80 ℃ of conditions of temperature, in 5 hours are the 1mol/L MCl that the aqueous sodium carbonate of 0.5mol/L is added drop-wise to 1 times of volume with concentration
36H
2In the O aqueous solution, dropwise the back and continue to stir 6 hours, stop heating then, place ageing 10 hours, obtain pillared liquid.
Pillared liquid is heated to 80 ℃, constant temperature, according to wilkinite quality and the long-pending ratio of pillared liquid is the proportioning of 20g/L, under agitation condition, progressively be that 65% calcium-base bentonite is distributed in the pillared liquid in 0.5 hour with smectite content, the back continuation that disperses to finish was stirred 5 hours, was cooled to room temperature, placed 12 hours; Filtering separation, solid product are used and isopyknic water washing of pillared liquid four times and filtering separation, 90 ℃ of dryings of the solid product after the filtering separation 36 hours.
In benzene and inorganic pillared bentonite ratio 5L/kg, trimethylchlorosilane [Cl
3Si (CH
3)
3] and inorganic pillared bentonite ratio 2.0mol/kg, inorganic pillared bentonite is mixed with benzene, trimethylchlorosilane, reacted 36 hours, filtering separation is divided 3 flushings with the acetone that adds 10 times of organic solvent volumes then, removes unreacted silylating reagent and organic solvent, solid product dries in air, 120 ℃ of vacuum-dryings 12 hours, obtain composite material of organic-inorganic bentonite, the BET surface-area is 180m
2/ g, pore volume are 0.15cm
3/ g, mean pore size 2.30nm, organic carbon content are 7.3%, and silylation content is 99.2mmol/100g, and the FTIR characterization result confirms silylation by Si-C covalent linkage and material of main part surface bonding, the demonstration of TG/DTA analytical results, high heat stability temperature is 214 ℃.
Embodiment 3, under continuously stirring, 60 ℃ of conditions of temperature, in 5 hours are the 1mol/L AlCl that the aqueous sodium carbonate of 0.9mol/L is added drop-wise to 3 times of volumes with concentration
36H
2In the O aqueous solution, dropwise the back and continue to stir 6 hours, stop heating then, place ageing 10 hours, obtain pillared liquid.
Pillared liquid is heated to 60 ℃, constant temperature, according to wilkinite quality and the long-pending ratio of pillared liquid is the proportioning of 20g/L, under agitation condition, progressively be that 65% sodium bentonite is distributed in the pillared liquid in 0.5 hour with smectite content, the back continuation that disperses to finish was stirred 5 hours, was cooled to room temperature, placed 12 hours; Filtering separation, solid product are used and isopyknic water washing of pillared liquid four times and filtering separation, 90 ℃ of dryings of the solid product after the filtering separation 36 hours.
In acetone and inorganic pillared bentonite ratio 5L/kg, 3-aminopropyl-triethoxyl silane [(CH
3CH
2O)
3CH
2SiCH
2CH
2CH
2NH
2] and inorganic pillared bentonite ratio 2.0mol/kg, inorganic pillared bentonite is mixed with acetone, 3-aminopropyl-triethoxyl silane, reacted 36 hours, filtering separation is divided 3 flushings with the acetone that adds 10 times of volume of toluene then, removes unreacted silylating reagent and organic solvent, solid product dries in air, 120 ℃ of vacuum-dryings 12 hours, obtain composite material of organic-inorganic bentonite, the BET surface-area is 160m
2/ g, pore volume are 0.12cm
3/ g, mean pore size 2.35nm, organic carbon content are 9.4%, and silylation content is 90.5mmol/100g, and the FTIR characterization result confirms silylation by Si-C covalent linkage and material of main part surface bonding, the demonstration of TG/DTA analytical results, high heat stability temperature is 412 ℃.
Embodiment 4, under continuously stirring, 60 ℃ of conditions of temperature, in 5 hours are the 1mol/L AlCl that the aqueous sodium carbonate of 0.9mol/L is added drop-wise to 3 times of volumes with concentration
36H
2In the O aqueous solution, dropwise the back and continue to stir 6 hours, stop heating then, place ageing 10 hours, obtain pillared liquid.
Pillared liquid is heated to 60 ℃, constant temperature, according to wilkinite quality and the long-pending ratio of pillared liquid is the proportioning of 20g/L, under agitation condition, progressively be that 100% sodium bentonite is distributed in the pillared liquid in 0.5 hour with smectite content, the back continuation that disperses to finish was stirred 5 hours, was cooled to room temperature, placed 12 hours; Filtering separation, solid product are used and isopyknic water washing of pillared liquid four times and filtering separation, 90 ℃ of dryings of the solid product after the filtering separation 36 hours.
In pyridine and inorganic pillared bentonite ratio 5L/kg, phenyl-triethoxyl silane [(CH
3CH
2O)
3SiC
6H
5] and inorganic pillared bentonite ratio 2.0mol/kg, inorganic pillared bentonite is mixed with pyridine, phenyl-triethoxyl silane, reacted 36 hours, filtering separation is divided 3 flushings with the acetone that adds 10 times of volume of toluene then, removes unreacted silylating reagent and organic solvent, solid product dries in air, 120 ℃ of vacuum-dryings 12 hours, obtain composite material of organic-inorganic bentonite, the BET surface-area is 110m
2/ g, pore volume are 0.087cm
3/ g, mean pore size 2.32nm, organic carbon content are 9.415.3%, silylation content is 89.4mmol/100g, the FTIR characterization result confirms silylation by Si-C covalent linkage and material of main part surface bonding, the demonstration of TG/DTA analytical results, and high heat stability temperature is 380 ℃.
Embodiment 5, under continuously stirring, 80 ℃ of conditions of temperature, in 3 hours are the 1mol/L AlCl that the aqueous sodium carbonate of 0.9mol/L is added drop-wise to 3 times of volumes with concentration
36H
2In the O aqueous solution, dropwise the back and continue to stir 6 hours, stop heating then, place ageing 10 hours, obtain pillared liquid.
Pillared liquid is heated to 80 ℃, constant temperature, according to wilkinite quality and the long-pending ratio of pillared liquid is the proportioning of 20g/L, under agitation condition, progressively be that 90% sodium bentonite is distributed in the pillared liquid in 0.5 hour with smectite content, the back continuation that disperses to finish was stirred 5 hours, was cooled to room temperature, placed 12 hours; Filtering separation, solid product are used and isopyknic water washing of pillared liquid four times and filtering separation, 90 ℃ of dryings of the solid product after the filtering separation 36 hours.
In pyridine and inorganic pillared bentonite ratio 5L/kg, 3-cyanogen propyl group-triethoxyl silane [(CH
3CH
2O)
3SiCH
2CH
2CH
2CN] and inorganic pillared bentonite ratio 1.0mol/kg, inorganic pillared bentonite is mixed with pyridine, 3-cyanogen propyl group-triethoxyl silane, reacted 36 hours, filtering separation is divided 3 flushings with the acetone that adds 10 times of volume of toluene then, removes unreacted silylating reagent and organic solvent, solid product dries in air, 120 ℃ of vacuum-dryings 12 hours, obtain composite material of organic-inorganic bentonite, the BET surface-area is 158m
2/ g, pore volume are 0.11cm
3/ g, mean pore size 2.33nm, organic carbon content are 10.8%, silylation content is 88.5mmol/100g, the FTIR characterization result confirms silylation by Si-C covalent linkage and material of main part surface bonding, the demonstration of TG/DTA analytical results, and high heat stability temperature is 423 ℃.
Embodiment 6, under continuously stirring, 50 ℃ of conditions of temperature, in 3 hours are the 1.5mol/L AlCl that the aqueous sodium carbonate of 0.9mol/L is added drop-wise to 3 times of volumes with concentration
36H
2In the O aqueous solution, dropwise the back and continue to stir 6 hours, stop heating then, place ageing 30 hours, obtain pillared liquid.
Pillared liquid is heated to 60 ℃, constant temperature, according to wilkinite quality and the long-pending ratio of pillared liquid is the proportioning of 70g/L, under agitation condition, progressively be that 90% calcium-base bentonite is distributed in the pillared liquid in 0.5 hour with smectite content, the back continuation that disperses to finish was stirred 5 hours, was cooled to room temperature, placed 12 hours; Filtering separation, solid product are used and isopyknic water washing of pillared liquid four times and filtering separation, 90 ℃ of dryings of the solid product after the filtering separation 36 hours.
In pyridine and inorganic pillared bentonite ratio 5L/kg, 3-mercapto propyl group-triethoxyl silane [(CH
3CH
2O)
3SiCH
2CH
2CH
2SH] and inorganic pillared bentonite ratio 1.0mol/kg, inorganic pillared bentonite is mixed with pyridine, 3-mercapto propyl group-triethoxyl silane, reacted 36 hours, filtering separation is divided 3 flushings with the acetone that adds 10 times of volume of toluene then, removes unreacted silylating reagent and organic solvent, solid product dries in air, 120 ℃ of vacuum-dryings 12 hours, obtain composite material of organic-inorganic bentonite, the BET surface-area is 168m
2/ g, pore volume are 0.13cm
3/ g, mean pore size 2.30nm, organic carbon content are 13.4%, silylation content is 87.8mmol/100g, the FTIR characterization result confirms silylation by Si-C covalent linkage and material of main part surface bonding, the demonstration of TG/DTA analytical results, and high heat stability temperature is 433 ℃.
Embodiment 7, under continuously stirring, 80 ℃ of conditions of temperature, in 3 hours are the 1.5mol/L AlCl that the aqueous sodium carbonate of 1.5mol/L is added drop-wise to 3 times of volumes with concentration
36H
2In the O aqueous solution, dropwise the back and continue to stir 6 hours, stop heating then, place ageing 30 hours, obtain pillared liquid.
Pillared liquid is heated to 60 ℃, constant temperature, according to wilkinite quality and the long-pending ratio of pillared liquid is the proportioning of 70g/L, under agitation condition, progressively be that 90% calcium-base bentonite is distributed in the pillared liquid in 0.5 hour with smectite content, the back continuation that disperses to finish was stirred 5 hours, was cooled to room temperature, placed 12 hours; Filtering separation, solid product are used and isopyknic water washing of pillared liquid four times and filtering separation, 90 ℃ of dryings of the solid product after the filtering separation 36 hours.
In toluene and inorganic pillared bentonite ratio 5L/kg, 3-chloro-triethoxyl silane [(CH
3CH
2O)
3SiCH
2CH
2CH
2Cl] and inorganic pillared bentonite ratio 1.0mol/kg, inorganic pillared bentonite is mixed with toluene, 3-chloro-triethoxyl silane, reacted 36 hours, filtering separation is divided 3 flushings with the acetone that adds 10 times of volume of toluene then, removes unreacted silylating reagent and organic solvent, solid product dries in air, 100 ℃ of vacuum-dryings 30 hours, the composite material of organic-inorganic bentonite that obtains, BET surface-area were 106m
2/ g, pore volume are 0.80cm
3/ g, mean pore size 2.50nm, organic carbon content are 25.0%, and silylation content is 86.3mmol/100g, and the FTIR characterization result confirms silylation by Si-C covalent linkage and material of main part surface bonding, and high heat stability temperature is 508 ℃.
Claims (5)
1, a kind of synthetic method of composite material of organic-inorganic bentonite, it is characterized in that with wilkinite as material of main part, earlier obtain inorganic pillared bentonite, and then carry out organic modification, finally obtain organic and inorganic composite bentonite sorbing material with silylating reagent with the hydroxy aluminum modification; Concrete preparation process is as follows:
1) preparation of pillared liquid: under continuously stirring, 50 ℃～80 ℃ conditions of temperature, in 2～5 hours, be the aqueous sodium hydroxide solution of 0.5～2.0mol/L or 0.1～1.0mol/LAlCl that aqueous sodium carbonate is added drop-wise to 1～3 times of volume with concentration
36H
2In the O solution, make the OH in the mixing solutions
-With A1
3+Concentration ratio is 2.0～3.0, dropwises the back and continues to stir 3～6 hours, stops heating then, places ageing 10～36 hours, obtains solution and is pillared liquid;
2) inorganic pillared bentonitic preparation: pillared liquid is heated to 50 ℃～80 ℃, constant temperature, in wilkinite quality and the long-pending ratio of pillared liquid is the proportioning of 20～80g/L, under agitation condition, 0.5 progressively wilkinite is distributed in the pillared liquid in～1 hour, the back continuation that disperses to finish was stirred 4～5 hours, was cooled to room temperature, placed 12～36 hours; Filtering separation, solid product are used and isopyknic water washing of pillared liquid four times and filtering separation, and the solid product after the filtering separation is following dry 12～36 hours at 90～120 ℃;
3) silanization modification: in organic solvent and inorganic pillared bentonite ratio 3～5L/kg, silylating reagent and inorganic pillared bentonite ratio 0.5～2.0mol/kg, inorganic pillared bentonite is mixed with organic solvent, silylating reagent, reacted 12～36 hours, filtering separation is divided 2～3 flushings with the acetone that adds 5～10 times of organic solvent volumes then, removes unreacted silylating reagent and organic solvent, solid product dried in air, 90～120 ℃ of vacuum-dryings 12～36 hours.
2, the synthetic method of a kind of composite material of organic-inorganic bentonite according to claim 1 is characterized in that the smectite content in the said wilkinite is 65%～100%.
3, the synthetic method of a kind of composite material of organic-inorganic bentonite according to claim 1 is characterized in that said wilkinite is sodium bentonite or calcium-base bentonite.
4, the synthetic method of a kind of composite material of organic-inorganic bentonite according to claim 1 is characterized in that said organic solvent is toluene, benzene, acetone or pyridine.
5, the synthetic method of a kind of composite material of organic-inorganic bentonite according to claim 1 is characterized in that said silylating reagent is that chemical structure of general formula is R
N-Si-X
4-NOrganosilane, wherein, N=1～3, R is that carbonatoms is that 1～1 8 alkyl, phenyl and carbonatoms are 1～1 8 amino, cyano group, sulfydryl or chlorine substituted alkyl, X is halogen, amino, methoxy or ethoxy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610154849XA CN100429146C (en) | 2006-11-27 | 2006-11-27 | Method for synthesizing composite material of organic - inorganic bentonite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610154849XA CN100429146C (en) | 2006-11-27 | 2006-11-27 | Method for synthesizing composite material of organic - inorganic bentonite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101003374A CN101003374A (en) | 2007-07-25 |
| CN100429146C true CN100429146C (en) | 2008-10-29 |
Family
ID=38702811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610154849XA Expired - Fee Related CN100429146C (en) | 2006-11-27 | 2006-11-27 | Method for synthesizing composite material of organic - inorganic bentonite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100429146C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935101A (en) * | 2010-08-25 | 2011-01-05 | 常州大学 | Method for preparing absorptive reducing material |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101653719B (en) * | 2008-10-28 | 2012-01-25 | 王趁义 | Method for in-situ pillared modification of bentonite and algal-removing water purifying agent |
| CN101445250B (en) * | 2008-12-05 | 2011-06-01 | 山东师范大学 | Organic matter/mineral complex and preparation method thereof |
| CN102380346B (en) * | 2011-08-12 | 2013-11-06 | 浙江工业大学 | Organic/inorganic flaky adsorbing material and application thereof in acidic printing and dyeing wastewater |
| CN104056594A (en) * | 2013-12-25 | 2014-09-24 | 南通大学 | Clay mineral absorbing material applied to water treatment and preparation method thereof |
| CN105295936B (en) * | 2014-11-07 | 2018-09-11 | 上海市环境科学研究院 | A kind of heavy-metal composite pollution soil remediation medicament and preparation method thereof based on modified clay |
| CN104971694B (en) * | 2015-07-15 | 2017-06-27 | 中国石油天然气股份有限公司 | A kind of Inorganic whisker bentonite clay material and its preparation method and application |
| CN105289506A (en) * | 2015-11-13 | 2016-02-03 | 兰州交通大学 | Multielement modified bentonite adsorption material and preparation method thereof |
| CN105457592B (en) * | 2016-01-18 | 2017-10-03 | 宁波大红鹰学院 | A kind of method that utilization kerosene shale ash prepares water treatment agent |
| CN106861607A (en) * | 2017-03-17 | 2017-06-20 | 武汉理工大学 | A kind of preparation method of the modified carbon/montmorillonite Composite sorbing material of organic-inorganic |
| CN107029659B (en) * | 2017-05-16 | 2019-10-11 | 中国石油天然气股份有限公司 | A kind of tri compound bentone soil material and its preparation method and application |
| WO2019010433A2 (en) * | 2017-07-06 | 2019-01-10 | W. L. Gore & Associates, Inc. | Contamination resistant regenerable desiccant member comprising a bentonite material |
| CN109110772B (en) * | 2018-02-13 | 2020-12-01 | 应急管理部天津消防研究所 | Preparation method of loaded metal organic montmorillonite |
| CN109334619A (en) * | 2018-08-22 | 2019-02-15 | 冯兴 | Water-saving type automobile rapid cleaning method |
| CN109174027A (en) * | 2018-09-19 | 2019-01-11 | 重庆大学 | The preparation method of the fixed aluminium pillared bentonite adsorbent of sodium alginate and its method for adsorbing phosphate radical |
| CN109261129B (en) * | 2018-11-21 | 2021-10-29 | 河西学院 | Attapulgite synergistic adsorbent and preparation method and application thereof |
| CN109569501B (en) * | 2019-01-19 | 2020-01-10 | 长沙达树环保工程有限公司 | Preparation method of special trapping agent for fluorine-containing wastewater treatment |
| CN112007607A (en) * | 2020-05-15 | 2020-12-01 | 苏州国建慧投矿物新材料有限公司 | Bentonite mineral gel for water treatment and its preparation method |
| CN113929250B (en) * | 2020-06-29 | 2023-07-11 | 宝山钢铁股份有限公司 | Cold rolling reverse osmosis concentrated water zero discharge process and treatment system |
| CN111646535A (en) * | 2020-07-06 | 2020-09-11 | 宁波首创厨余垃圾处理有限公司 | Attapulgite surface modification method and application of modified attapulgite |
| CN111905704B (en) * | 2020-07-16 | 2022-07-01 | 浙江工业大学 | Amino modified bentonite/Fe3O4/SiO2Composite material and preparation method and application thereof |
| CN113184867B (en) * | 2021-04-28 | 2023-01-03 | 西北民族大学 | Method for preparing magnetic super-hydrophobic clay mineral composite material and application |
| CN114560575B (en) * | 2021-12-07 | 2023-02-14 | 中煤科工集团杭州研究院有限公司 | Stainless steel pickling wastewater pretreatment method capable of efficiently removing fluorine and heavy metals |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186088A (en) * | 1996-12-27 | 1998-07-01 | 吉林化学工业公司研究院 | Modified bentonite and applications |
| CN1569660A (en) * | 2004-04-28 | 2005-01-26 | 浙江大学 | Method for preparing waste water processing materials of organic-inorganic composite bentonite |
-
2006
- 2006-11-27 CN CNB200610154849XA patent/CN100429146C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186088A (en) * | 1996-12-27 | 1998-07-01 | 吉林化学工业公司研究院 | Modified bentonite and applications |
| CN1569660A (en) * | 2004-04-28 | 2005-01-26 | 浙江大学 | Method for preparing waste water processing materials of organic-inorganic composite bentonite |
Non-Patent Citations (4)
| Title |
|---|
| 交联蒙脱土研究进展. 孙家寿，杨琼.中国矿业，第12卷第3期. 2003 |
| 交联蒙脱土研究进展. 孙家寿，杨琼.中国矿业，第12卷第3期. 2003 * |
| 有机膨润土的制备方法. 张卫新，单承湘.中外技术情报，第12期. 1995 |
| 有机膨润土的制备方法. 张卫新，单承湘.中外技术情报，第12期. 1995 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935101A (en) * | 2010-08-25 | 2011-01-05 | 常州大学 | Method for preparing absorptive reducing material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101003374A (en) | 2007-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100429146C (en) | Method for synthesizing composite material of organic - inorganic bentonite | |
| CN101066765A (en) | Composite organic-inorganic bentonite material and its synthesis process | |
| Saeed et al. | Synthesis, characterization and applications of silylation based grafted bentonites for the removal of Sudan dyes: Isothermal, kinetic and thermodynamic studies | |
| Alkan et al. | FTIR and zeta potential measurements of sepiolite treated with some organosilanes | |
| Guimarães et al. | Smectite organofunctionalized with thiol groups for adsorption of heavy metal ions | |
| Mureseanu et al. | Modified SBA-15 mesoporous silica for heavy metal ions remediation | |
| Mercier et al. | A functionalized porous clay heterostructure for heavy metal ion (Hg2+) trapping | |
| Kostenko et al. | Bentonites with grafted aminogroups: Synthesis, protolytic properties and assessing Cu (II), Cd (II) and Pb (II) adsorption capacity | |
| Saad et al. | Adsorption of phosphate and nitrate anions on ammonium-functionalized MCM-48: effects of experimental conditions | |
| Brown et al. | One-step synthesis of high capacity mesoporous Hg2+ adsorbents by non-ionic surfactant assembly | |
| Matusik | Arsenate, orthophosphate, sulfate, and nitrate sorption equilibria and kinetics for halloysite and kaolinites with an induced positive charge | |
| Tome et al. | Synthesis, characterization and application of acid and alkaline activated volcanic ash-based geopolymers for adsorptive remotion of cationic and anionic dyes from water | |
| Yang et al. | Alumina nanofibers grafted with functional groups: a new design in efficient sorbents for removal of toxic contaminants from water | |
| CN101239322B (en) | Method for preparing montmorillonite/molecular sieve composite material | |
| Trouvé et al. | Tuning the hydrophobicity of mesoporous silica materials for the adsorption of organic pollutant in aqueous solution | |
| CN113083228B (en) | Carbon-doped sepiolite composite porous adsorption material and preparation method and application thereof | |
| Phothitontimongkol et al. | Preparation and characterization of novel organo-clay minerals for Hg (II) ions adsorption from aqueous solution | |
| US7714156B2 (en) | Synthetic layered silicate nanolayers | |
| Zhu et al. | Silylated pillared clay (SPILC): a novel bentonite-based inorgano–organo composite sorbent synthesized by integration of pillaring and silylation | |
| Halina et al. | Non-hydrothermal synthesis of mesoporous materials using sodium silicate from coal fly ash | |
| da Fonseca et al. | New layered inorganic–organic nanocomposites containing n-propylmercapto copper phyllosilicates | |
| Park et al. | Interlamellar silylation of H-kenyaite with 3-aminopropyltriethoxysilane | |
| Toranzo et al. | Pillaring of saponite with zirconium oligomers | |
| Liu et al. | Advanced mesoporous organosilica material containing microporous β-cyclodextrins for the removal of humic acid from water | |
| Jin et al. | Assembling of tungstovanadogermanic heteropoly acid into mesoporous molecular sieve SBA-15 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081029 Termination date: 20111127 |