CN101503182A - Method for in situ modification by isoelectric point layered composite metal hydroxides - Google Patents
Method for in situ modification by isoelectric point layered composite metal hydroxides Download PDFInfo
- Publication number
- CN101503182A CN101503182A CNA200910080719XA CN200910080719A CN101503182A CN 101503182 A CN101503182 A CN 101503182A CN A200910080719X A CNA200910080719X A CN A200910080719XA CN 200910080719 A CN200910080719 A CN 200910080719A CN 101503182 A CN101503182 A CN 101503182A
- Authority
- CN
- China
- Prior art keywords
- acid
- ldhs
- modification
- iso
- slurries
- 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.)
- Granted
Links
- 238000012986 modification Methods 0.000 title claims abstract description 38
- 230000004048 modification Effects 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 14
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims description 13
- 150000004692 metal hydroxides Chemical class 0.000 title claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 10
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001962 electrophoresis Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000005639 Lauric acid Substances 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 4
- 229940082004 sodium laurate Drugs 0.000 claims description 4
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 4
- -1 zirconium aluminate Chemical class 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 229960002989 glutamic acid Drugs 0.000 claims description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 2
- 229930002839 ionone Natural products 0.000 claims description 2
- 150000002499 ionone derivatives Chemical class 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 claims description 2
- 238000010899 nucleation Methods 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 14
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000010954 inorganic particle Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000003607 modifier Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 238000000386 microscopy Methods 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
Images
Abstract
The invention provides a technology for carrying out surface in situ modification on clad composite metal hydroxid by using isoelectric points. After the clad composite metal hydroxid is prepared for reaction, the system PH value is adjusted to be lower than the isoelectric points of particles before washing, and then modifying agent is directly added for in situ modification so as to lead modifying agent molecules and surface groups of inorganic particles to have physico chemical adsorption and cover on the surface, thus achieving good modification effect. After modification, products can quickly float on the water, so that the process of separation and filtration can be simplified. The method not only effectively avoids ion glomeration, but also greatly simplifies the washing process, thus reducing water consumption when in washing.
Description
Technical field:
The present invention relates to a kind of method of utilizing iso-electric point layered composite metal hydroxides to be carried out the in-situ surface organic modification.
Background technology:
General inorganic powder in use, especially in the time of in add organic systems such as macromolecular material to as the functional agent material, need carry out organic modification of surface to it usually, to increase the consistency of itself and organic matrix, make it reach good dispersion effect, bring into play good action effect.
At present, both at home and abroad the surface modification to inorganic powder generally all adopts the dry method surface treatment, normally inorganic powder is added high-speed mixer, adds organic modifiers under high-speed stirring, heats and fully stirs and finish.There is complex manufacturing in this method, surface treatment is inhomogeneous and problem such as easy generation reunion.Document [silane coupling agent is used for the mechanism of non-metal powder surface modification and uses the problem that should note, Chinese powder industry, 2006 (4): 12-14] has carried out more detailed description to this.
Layered composite metal hydroxides (Layered Double Hydroxides is called for short LDHs) is hydrotalcite again, is a kind of typical anionic type laminated material, and its chemical constitution formula is [M
2+ 1-xM
3+ x(OH)
2] A
N- X/nMH
2O, wherein M
2+, M
3+Represent divalence and trivalent metal cation respectively, A
N-Be interlayer anion, x is M
3+The ionic molar fraction, m is the quantity of crystal water.The kind of the element kind of LDHs main body laminate and proportion of composing, interlayer object and quantity is modulation in relative broad range as required, thereby obtains a series of materials with special construction and performance.The adjustable sex change of LDHs The Nomenclature Composition and Structure of Complexes and the multifunctionality that is caused thus, make it become the type material that a class has research potential and application prospect, be widely used in fields such as fire-retardant, resin treatment, plastic sheeting for farm use as functional agents such as the high smoke-inhibiting flame retardant agent of Halogen, non-toxic heat stabilizer, selective infrared absorbing material and ultraviolet blocking materials.
Provide a kind of among the patent of invention ZL99119386.5 LDHs has been carried out wet-process modified technology, this technology is to add organic modifiers in the LDHs preparation process in the slurries that it washs, under certain temperature, reacted 15～60 minutes, and then filter, drying, reach the purpose of organic modification of surface.Because this method is modification before dry, has overcome the problem that particle is easily reunited in the first dry post-modification process, has realized the integrated of powder preparing and modification, for good product basis has been laid in the application of LDHs.But, because modification is to finish, still need to expend a large amount of bath wateies after washing, especially for the product of difficult washing, the water of productive use amount is huge, and production cost is increased greatly.
Summary of the invention
The purpose of this invention is to provide a kind of technology of utilizing iso-electric point layered composite metal hydroxides to be carried out the surface in situ modification.
Utilize iso-electric point as follows to the concrete operations step that layered composite metal hydroxides carries out the surface in situ modification:
A. be M in molar ratio with solvable divalent metal salt and solvable trivalent metal salt
2+/ M
3+=2～4 are dissolved in and are made into mixing salt solution, wherein [M in the deionized water
2+]=0.1～2.0mol/L; Press n (NaOH)/[n (M
2+)+n (M
3+)]=1.8～2.5 molar ratio, NaOH is dissolved in the alkaline solution that is made into equal volume in the deionized water; Two kinds of solution are added in the full back-mixing liquid film reactor nucleation fast simultaneously,, obtain layered composite metal hydroxides LDHs slurries the slurry reflux crystallization that obtains 5-6 hour; Wherein the quality percentage composition of LDHs is 0.5～20%, and the pH value is greater than 10; Full back-mixing liquid film reactor is seen patent of invention ZL00132145.5
The chemical general formula of described layered composite metal hydroxides LDHs is:
[M
2+ 1-xM
3+ x(OH)
2]
x+(A
n-)
x/2·yH
2O，
Wherein, M
2+Represent divalent metal Mg
2+, Zn
2+, Ca
2+, Cu
2+, Ni
2+, Co
2+, Fe
2+, Mn
2+Or Cd
2+In one or both, preferably Mg
2+, Zn
2+, Ca
2+In one or both;
M
3+Represent trivalent metal cation Al
3+, Ni
3+, Co
3+, Fe
3+, Mn
3+, Cr
3+, V
3+Or Ti
3+In a kind of, preferably Al
3+Or Ni
3+
A
N-Be Cl
-, CO
3 2-, NO
3 -, Bn
2-, F
-, Br
-, I
-, SO
4 2-, ClO
3 -, OH
-, PO
4 3-, H
2PO
4 -, WO
4 2-, in Whitfield's ointment, tartrate, L-glutamic acid, oxysuccinic acid, phenylformic acid, hexanodioic acid or the organic sulfonic acid negatively charged ion one or both, preferably CO
3 2-, NO
3 -, Cl
-, SO
4 2-, PO
4 3-, in the phenylformic acid, Whitfield's ointment one or both; X is M
3+The ionic molar fraction; Y is the quantity of crystal water, and its span is 0≤y≤2.
B. be 0.1～30% acid solution with concentration, slowly be added drop-wise under the agitation condition in the above-mentioned LDHs slurries that the pH value of regulation system makes it be lower than the iso-electric point for the treatment of the modification slurries;
Described acid solution is sulfuric acid, hydrochloric acid or salpeter solution;
Described iso-electric point numerical evaluation method is: the dilute sulphuric acid with 1% is regulated the pH value of modification slurries, and the employing electrophoresis apparatus is measured the zeta-potential under the different pH values, draws ζ-pH curve, and the pH value when zeta-potential is zero is the iso-electric point of this material; Above-mentioned LDHs iso-electric point numerical range is 8.6～10.5.
The principle schematic of isoelectric point determination is seen Fig. 1.As can be seen from the figure, descend with the pH value, the zeta-potential of sample constantly increases, from negative value become on the occasion of, wherein, the pH value of correspondence is called iso-electric point when zeta-potential is zero, i.e. A point among the figure.
C. in system, add properties-correcting agent, the add-on of properties-correcting agent be in the system powder total amount 0.1～15%, be warmed up to more than the properties-correcting agent melting temperature, stirring reaction 5～120min isolates the upper strata solid after the cooling, washing, drying obtain the LDHs powder of modification.
Described properties-correcting agent comprises a kind of in stearic acid, sodium stearate, lauric acid, sodium laurate, oleic acid, sodium oleate, palmitinic acid, Sodium pentadecanecarboxylate, silane coupling agent, titanate coupling agent, aluminate coupling agent or the zirconium aluminate coupling agent, preferably stearic acid, sodium stearate, lauric acid, sodium laurate or titanate coupling agent;
Owing to have excessive raw material alkali in the LDHs slurries that steps A obtains, promptly have a large amount of OH
-, this moment pH value generally all more than 11, and LDHs is with permanent positive charge, surface potential shows electropositivity, the OH in these product slurries
-Ion can become the gegenion preferentially adsorbed in the LDHs surface, makes the LDHs particle be in OH
-Encirclement in.
Common modification all is earlier LDHs to be washed, and to remove these gegenions, again it is carried out modification, need expend a large amount of bath wateies, inefficiency like this.And the present invention is before washing, pH value by regulation system makes it to drop to below the iso-electric point of particle, make particle surface show electropositivity, and the quantity of the anti-electric charge of reduction particle surface, add organic modifiers then, make modifier molecules under electrostatic attraction and intermolecular forces effect, clamp-on Stern (stern) layer, with particle surface group generation physical and chemical adsorption, and along with the increase of modifier molecules adsorptive capacity, the OH of surface adsorption
-Quantity can be fewer and feweri, finally reaches the particle surface degree that agent molecule covers fully that is modified, and plays good modified effect.Particle and water fast hierarchical and float on the upper strata of water after the modification are highly susceptible to separating with the aqueous solution.And because organically-modified agent molecule is coated on the inorganic particulate surface, isolated by product and excessive alkaline solution, only needed the little water washing, washing process is simplified greatly.
The mechanism of iso-electric point in-situ techniques modification is: the inorganic particulate surface generally all has the electric charge of different densities, has surface potential, the electric charge of its surface meeting absorption contrary sign constitutes electrostatic double layer in solution, and wherein the gegenion adsorbed close layer that mortise forms at surperficial volume owing to strong attraction is called Stern (stern) layer.The electric charge of these contrary signs concentration from the near to the remote reduces gradually, and the voltage that produces at electrostatic double layer slipping plane place is called Zeta (ζ) current potential, and its numerical value can calculate by the mensuration of electrophoresis or electric osmose speed.Become under the condition in certain temperature, pressure and media pack, the pH value of medium was called iso-electric point (Isoelectric point) when the zeta current potential was zero.
Purified LDHs surface is positively charged, owing to there are a large amount of excessive raw material alkali in the LDHs slurries system that obtains of steps A, the pH value is greater than iso-electric point, surface adsorption a large amount of OH
-, make the LDHs particle electronegative, with the modifier molecules of being with anionic group the electrostatic repulsion effect has taken place, simultaneously owing to OH in the solution
-Concentration is excessive, a large amount of OH
-Clamp-on the stern layer LDHs particle has been formed fine and close parcel, spatially also play and stop modifier molecules to enter the effect that stern layer and particle surface react, do not reach the purpose of organic modification of surface; Regulate pH value by dilute sulphuric acid, when system pH during, LDHs ion band positive electricity less than iso-electric point, the effect that can inhale mutually with the modifier molecules generation static of being with anionic group, and the OH of surface adsorption
-Ion is less, and is more loose to the parcel of LDHs particle, and this moment, modifier molecules can more easily be clamp-oned the stern layer under electrostatic attraction and intermolecular forces effect, and with particle surface generation physical and chemical adsorption, thereby reach the purpose of organic modification of surface.Along with the increase of modifier molecules adsorptive capacity, the OH quantity of surface adsorption can be fewer and feweri, finally reaches the LDHs surface degree that agent molecule covers fully that is modified.
The LDHs surface presents hydrophobic nature through modify and graft organic molecule rear surface, can float on the upper strata with water stratification very soon, has simplified the separating and filtering process.In addition, because organically-modified agent molecule is direct and the LDHs surface bonding, can when modification, the gritty particle in the LDHs and the aqueous solution be kept apart, simplified washing process greatly, reduce the bath water amount, reduced production costs, can also prevent particle agglomeration well simultaneously.The result shows that the bath water amount has reduced more than 80%, and Na in the product
+Be lower than 0.05% Deng hetero-ion content.
Characteristics of the present invention are before preparation feedback finishes back and washing, regulation system pH value makes the iso-electric point less than particle, directly adding properties-correcting agent then carries out in-situ modified, make modifier molecules can with the surface group generation physical and chemical adsorption effect of inorganic particulate, and be coated on the surface, reach good modified effect.This method has not only effectively been avoided the ion reunion, has also simplified washing process greatly, has reduced the bath water amount.
Description of drawings
Fig. 1 isoelectric point determination principle schematic
Fig. 2 carries out in-situ modified design sketch, wherein a.pH=9.0b.pH=9.5c.pH=10.0d.pH=10.5 under different pH condition among the embodiment 1.
Fig. 3 is the XRD spectra (pH=9.5) of the LDHs that obtains in the following modification of iso-electric point among the embodiment 1.
Fig. 4 is the FT-IR spectrogram (pH=9.0) of the LDHs that obtains in the following modification of iso-electric point among the embodiment 2.
Embodiment:
Embodiment 1
With 102.5g Mg (NO
3) 6H
2O and 75.0gAl (NO
3)
39H
2O is dissolved in and is made into the 500ml mixing salt solution in the deionized water, with 38.4g NaOH and 42.3g Na
2CO
3Be made into the 500ml alkaline solution with water, two kinds of solution are added full back-mixing liquid film reactor simultaneously, the slurries that obtain place under the 2L flask agitation condition and are heated to backflow, and reaction 6h obtains Mg
4Al
2(OH)
12CO
34H
2The O slurries.Slurries are cooled to room temperature, and the pH value of slurries is 10.6 after measured, and slurries are divided into 4 parts, and every part contains the about 5g of product, measures Mg with DXD2II type television microscopy electrophoresis apparatus
4Al
2(OH)
12CO
34H
2The iso-electric point of O is 9.9.Be to be added drop-wise to respectively in above-mentioned 4 parts of slurries under 0.2% the dilute hydrochloric acid solution agitation condition with concentration, make the pH value of 4 parts of slurries be respectively 10.5,10.0,9.5 and 9.Be warming up to 80 ℃, add stearic acid 0.5g respectively, stirring reaction 30min postcooling is to room temperature.Found that the pH value is layering not occur in 10.5 and 10.0 the slurries, the pH value is very fast generation layering in 9.5 and 9.0 slurries, and the white solid product floats on the water surface.Isolate the upper strata solid to stratified system takes place,, obtain the LDHs powder of modification again through washing, drying.
Slurries carry out the modification result as shown in Figure 2 under different pH condition.Can find out very clearly that from figure when system pH was carried out modification greater than iso-electric point, organically-modified agent molecule failed to graft on the LDHs surface, reaction finishes back LDHs and still is dispersed in the water, does not reach modified effect; When system pH during less than iso-electric point, LDHs all floats on the upper strata of water soon, shows that organically-modified agent molecule has grafted on the LDHs surface, has reached good modified effect.
(Cu target K alpha-ray, 5 ° of sweep velocitys/min), the result as shown in Figure 3 to adopt the Japanese Shimadzu XRD-6000 of company type X-ray powder diffraction instrument to measure the crystalline structure of above-mentioned sample.As can be seen from the figure, the characteristic diffraction peak peak shape of sample point is alarmmed, and baseline is low flat, and interpret sample has complete layered crystal structure, and the adding of acid does not produce sample and destroys when regulating the pH value.
Adopt German Bruker Vector22 type FT-IR infrared spectrometer that above-mentioned sample is carried out infrared analysis, the result as shown in Figure 4.Spectrogram is consistent with the standard spectrogram of LDHs, wherein 1384cm
-1The absorption peak at place is CO
3 2-Unsymmetrically υ
3Vibration modes, intensity and go out the peak position and do not change illustrates that preparation process does not exert an influence to product.
Embodiment 2
With 129.4g ZnSO
47H
2O and 50.0gAl
2(SO
4)
318H
2O is dissolved in and is made into the 300ml mixing salt solution in the deionized water, 38.4g NaOH is dissolved in proportionaling alkali-forming solution in the 300ml water, two kinds of solution are added full back-mixing liquid film reactor simultaneously, and the slurries that obtain place under the 2L flask agitation condition and are heated to backflow, and reaction 6h obtains Zn
6Al
2(OH)
12SO
44H
2The O slurries are cooled to room temperature, are divided into 4 parts, and every part contains the about 5g of product, and the pH value of slurries is 10.5 after measured.Measure Zn with DXD2II type television microscopy electrophoresis apparatus
6Al
2(OH)
12SO
44H
2The iso-electric point of O is 9.7.Configuration concentration is 0.2% dilution heat of sulfuric acid, is added drop-wise under the agitation condition in the above-mentioned slurries, and regulation system pH value is 10.5,10.0,9.5 and 9 respectively.Be warming up to 80 ℃, add titanic acid ester 0.25g respectively, stirring reaction 60min postcooling is to room temperature.Found that not layering of system when the pH value is 10.5 and 10.0, the very fast generation layering of system when the pH value is 9.5 and 9.0, the white solid product floats on the water surface.Isolate the upper strata solid to stratified system takes place, washing, drying obtain the LDHs powder of modification.
Adopt the Japanese Shimadzu ICPS-7500 of company type plasma emission spectrum that embodiment 2 samples are carried out elementary composition analysis, the result is as shown in table 1.As can be seen from the table, sample is elementary composition suitable with theoretical value, and hetero-ion content such as Na is very low, illustrates that washing effect is remarkable, and modifying process produces sample and destroys.
The ultimate analysis of table 1 sample
Embodiment 3
With 76.9g Mg (NO
3)
26H
2O and 56.3g Al (NO
3)
39H
2O is dissolved in and is made into the 500ml mixing salt solution in the deionized water, 36.0g NaOH is dissolved in proportionaling alkali-forming solution in the 300ml water, two kinds of solution are added full back-mixing liquid film reactor simultaneously, and the slurries that obtain place under the 2L flask agitation condition and are heated to backflow, and reaction 6h obtains Mg
4Al
2(OH)
12NO
34H
2The O slurries are cooled to room temperature, are divided into 4 parts, and every part contains the about 5g of product, and the pH value of slurries is 10.2 after measured.Measure Mg with DXD2II type television microscopy electrophoresis apparatus
4Al
2(OH)
12NO
34H
2The iso-electric point of O is 9.4.Configuration concentration is 0.1% dilution heat of sulfuric acid, is added drop-wise under the agitation condition in the above-mentioned slurries, and regulation system pH value is 10.5,10.0,9.5 and 9 respectively.Be warming up to 80 ℃, add lauric acid 0.2g respectively, stirring reaction 30min postcooling is to room temperature.Found that not layering of system when the pH value is 10.5,10.0 and 9.5, the very fast generation layering of system when the pH value is 9.0, the white solid product floats on the water surface.Isolate the upper strata solid to stratified system takes place, washing, drying obtain the LDHs powder of modification.
Embodiment 4
With 15.4g Mg (NO
3)
26H
2O and 11.3g Al (NO
3)
39H
2O is dissolved in and is made into the 200ml mixing salt solution in the deionized water, 8.3g Whitfield's ointment and 9.6g NaOH are made into proportionaling alkali-forming solution in the 200ml water, two kinds of solution are added full back-mixing liquid film reactor simultaneously, and the slurries that obtain place under the 1L flask agitation condition and are heated to backflow, and reaction 6h obtains Mg
4Al
2(OH)
12(HOC
6H
4COO) 4H
2The O slurries are cooled to room temperature, are divided into 4 parts, and every part contains the about 2g of product, and the pH value of slurries is 10.1 after measured.Measure Mg with DXD2II type television microscopy electrophoresis apparatus
4Al
2(OH)
12(HOC
6H
4COO) 4H
2The iso-electric point of O is 8.9.Configuration concentration is 0.1% dilution heat of sulfuric acid, is added drop-wise under the agitation condition in the above-mentioned slurries, and regulation system pH value is 10.0,9.5,9.0 and 8.5 respectively.Be warming up to 80 ℃, add silane coupling agent 0.1g respectively, stirring reaction 30min postcooling is to room temperature.Found that not layering of system when the pH value is 10.0,9.5 and 9.0, the very fast generation layering of system when the pH value is 8.5, the white solid product floats on the water surface.Isolate the upper strata solid to stratified system takes place, washing, drying obtain the LDHs powder of modification.
Claims (4)
1. utilize iso-electric point that layered composite metal hydroxides is carried out in-situ modified method, the concrete operations step is as follows:
A. be M in molar ratio with solvable divalent metal salt and solvable trivalent metal salt
2+/ M
3+=2～4 are dissolved in and are made into mixing salt solution, wherein [M in the deionized water
2+]=0.1～2.0mol/L; Press n (NaOH)/[n (M
2+)+n (M
3+)]=1.8～2.5 molar ratio, NaOH is dissolved in the alkaline solution that is made into equal volume in the deionized water; Two kinds of solution are added in the full back-mixing liquid film reactor nucleation fast simultaneously,, obtain layered composite metal hydroxides LDHs slurries the slurry reflux crystallization that obtains 5-6 hour; Wherein the quality percentage composition of LDHs is 0.5～20%, and the pH value is greater than 10;
The chemical general formula of described LDHs is: [M
2+ 1-xM
3+ x(OH)
2]
X+(A
N-)
X/2YH
2O, wherein, M
2+Represent divalent metal Mg
2+, Zn
2+, Ca
2+, Cu
2+, Ni
2+, Co
2+, Fe
2+, Mn
2+Or Cd
2+In one or both; M
3+Represent trivalent metal cation Al
3+, Ni
3+, Co
3+, Fe
3+, Mn
3+, Cr
3+, V
3+Or Ti
3+In a kind of;
A
N-Be Cl
-, CO
3 2-, NO
3 -, B
N2-, F
-, Br
-, I
-, SO
4 2-, ClO
3 -, OH
-, PO
4 3-, H
2PO
4 -, WO
4 2-, in Whitfield's ointment, tartrate, L-glutamic acid, oxysuccinic acid, phenylformic acid, hexanodioic acid or the organic sulfonic acid negatively charged ion one or both, y is the quantity of crystal water, its span is 0≤y≤2;
B. be 0.1～30% acid solution with concentration, slowly be added drop-wise under the agitation condition in the above-mentioned LDHs slurries that the pH value of regulation system makes it be lower than the iso-electric point for the treatment of the modification slurries; Described acid solution is sulfuric acid, hydrochloric acid or salpeter solution;
C. in system, add properties-correcting agent, the add-on of properties-correcting agent be in the system powder total amount 0.1～15%, be warmed up to more than the properties-correcting agent melting temperature, stirring reaction 5～120min isolates the upper strata solid after the cooling, washing, drying obtain the LDHs powder of modification;
Described properties-correcting agent comprises a kind of in stearic acid, sodium stearate, lauric acid, sodium laurate, oleic acid, sodium oleate, palmitinic acid, Sodium pentadecanecarboxylate, silane coupling agent, titanate coupling agent, aluminate coupling agent or the zirconium aluminate coupling agent.
2. the iso-electric point of utilizing according to claim 1 is carried out in-situ modified method to layered composite metal hydroxides, it is characterized in that in the chemical general formula of the described LDHs of steps A M
2+Be Mg
2+, Zn
2+Or Ca
2+In one or both; M
3+Be Al
3+Or Ni
3+A
N-Be CO
3 2-, NO
3 -, Cl
-, SO
4 2-, PO
4 3-, in phenylformic acid or the Whitfield's ointment one or both.
3. the iso-electric point of utilizing according to claim 1 is carried out in-situ modified method to layered composite metal hydroxides, it is characterized in that the described isoelectric point determination method of modification slurries for the treatment of of step B is: the dilute sulphuric acid with 1% is regulated the pH value for the treatment of the modification slurries, the employing electrophoresis apparatus is measured the zeta-potential under the different pH values, draw ζ-pH curve, the pH value when zeta-potential is zero is the iso-electric point of this material.
4. the iso-electric point of utilizing according to claim 1 is carried out in-situ modified method to layered composite metal hydroxides, it is characterized in that the described properties-correcting agent of step C is stearic acid, sodium stearate, lauric acid, sodium laurate or titanate coupling agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910080719XA CN101503182B (en) | 2009-03-27 | 2009-03-27 | Method for in situ modification by isoelectric point layered composite metal hydroxides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910080719XA CN101503182B (en) | 2009-03-27 | 2009-03-27 | Method for in situ modification by isoelectric point layered composite metal hydroxides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101503182A true CN101503182A (en) | 2009-08-12 |
| CN101503182B CN101503182B (en) | 2011-02-16 |
Family
ID=40975572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910080719XA Expired - Fee Related CN101503182B (en) | 2009-03-27 | 2009-03-27 | Method for in situ modification by isoelectric point layered composite metal hydroxides |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101503182B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205981A (en) * | 2011-04-28 | 2011-10-05 | 北京化工大学 | Preparation method of layered compound metal hydroxide for controlling surface defects and surface potentials |
| CN101665233B (en) * | 2009-09-15 | 2012-06-06 | 北京化工大学 | Layered double hydroxide and preparation method thereof |
| CN102616747A (en) * | 2012-03-23 | 2012-08-01 | 中国科学院广州地球化学研究所 | Synthetic method for high length-diameter ratio layered doubled hydroxides grafted by organosilane |
| CN102616750A (en) * | 2012-03-23 | 2012-08-01 | 中国科学院广州地球化学研究所 | In-situ co-precipitation synthesis method for organic silane grafted hydrotalcite with controllable interlayer spacing |
| CN103723748A (en) * | 2013-12-30 | 2014-04-16 | 北京化工大学 | Method for preparing ultraviolet barrier material by taking hydrotalcite as precursor |
| CN108659514A (en) * | 2018-06-02 | 2018-10-16 | 北京化工大学 | A kind of preparation and application of the efficient smoke suppressant of polyurethane |
| CN112055696A (en) * | 2018-05-14 | 2020-12-08 | Scg化学有限公司 | Surface-modified layered double hydroxides |
| CN113072745A (en) * | 2021-03-20 | 2021-07-06 | 合肥工业大学 | Preparation method and device of halogen-free composite flame retardant based on modified LDHs |
| CN113398950A (en) * | 2021-05-19 | 2021-09-17 | 华南理工大学 | Crystal face regulated and controlled supported nano alloy catalyst and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192560A (en) * | 2017-12-06 | 2018-06-22 | 常州市绿意管道有限公司 | A kind of preparation method of flame-retardant high-strength building sealant |
-
2009
- 2009-03-27 CN CN200910080719XA patent/CN101503182B/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665233B (en) * | 2009-09-15 | 2012-06-06 | 北京化工大学 | Layered double hydroxide and preparation method thereof |
| CN102205981A (en) * | 2011-04-28 | 2011-10-05 | 北京化工大学 | Preparation method of layered compound metal hydroxide for controlling surface defects and surface potentials |
| CN102205981B (en) * | 2011-04-28 | 2012-12-12 | 北京化工大学 | Preparation method of layered compound metal hydroxide for controlling surface defects and surface potentials |
| CN102616747A (en) * | 2012-03-23 | 2012-08-01 | 中国科学院广州地球化学研究所 | Synthetic method for high length-diameter ratio layered doubled hydroxides grafted by organosilane |
| CN102616750A (en) * | 2012-03-23 | 2012-08-01 | 中国科学院广州地球化学研究所 | In-situ co-precipitation synthesis method for organic silane grafted hydrotalcite with controllable interlayer spacing |
| CN103723748B (en) * | 2013-12-30 | 2015-07-08 | 北京化工大学 | Method for preparing ultraviolet barrier material by taking hydrotalcite as precursor |
| CN103723748A (en) * | 2013-12-30 | 2014-04-16 | 北京化工大学 | Method for preparing ultraviolet barrier material by taking hydrotalcite as precursor |
| CN112055696A (en) * | 2018-05-14 | 2020-12-08 | Scg化学有限公司 | Surface-modified layered double hydroxides |
| CN108659514A (en) * | 2018-06-02 | 2018-10-16 | 北京化工大学 | A kind of preparation and application of the efficient smoke suppressant of polyurethane |
| CN108659514B (en) * | 2018-06-02 | 2020-11-03 | 北京化工大学 | Preparation and application of polyurethane efficient smoke suppressant |
| CN113072745A (en) * | 2021-03-20 | 2021-07-06 | 合肥工业大学 | Preparation method and device of halogen-free composite flame retardant based on modified LDHs |
| CN113398950A (en) * | 2021-05-19 | 2021-09-17 | 华南理工大学 | Crystal face regulated and controlled supported nano alloy catalyst and preparation method and application thereof |
| CN113398950B (en) * | 2021-05-19 | 2022-05-24 | 华南理工大学 | Crystal face regulated and controlled supported nano alloy catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101503182B (en) | 2011-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101503182B (en) | Method for in situ modification by isoelectric point layered composite metal hydroxides | |
| Zhan et al. | Ultrathin layered double hydroxide nanosheets prepared from a water-in-ionic liquid surfactant-free microemulsion for phosphate removal from aquatic systems | |
| Nassar et al. | Sphere-like Mn2O3 nanoparticles: facile hydrothermal synthesis and adsorption properties | |
| Zou et al. | Superior coagulation of graphene oxides on nanoscale layered double hydroxides and layered double oxides | |
| CN102515252B (en) | Film-coating production technology for nano zinc oxide | |
| Yu et al. | Metal-based adsorbents for lithium recovery from aqueous resources | |
| Nejati et al. | Synthesis of ZnO nanoparticles and investigation of the ionic template effect on their size and shape | |
| Hu et al. | Superior sorption capacities of Ca-Ti and Ca-Al bimetallic oxides for U (VI) from aqueous solutions | |
| Luo et al. | Extraction of lithium from salt lake brines by granulated adsorbents | |
| Lv et al. | In situ synthesis of nanolamellas of hydrophobic magnesium hydroxide | |
| Marthi et al. | Application and limitations of a H2TiO3–Diatomaceous earth composite synthesized from titania slag as a selective lithium adsorbent | |
| JPWO2009072488A1 (en) | Method for producing anion-exchange layered double hydroxide | |
| CN1962453A (en) | Process for producing hydrotalcite-like layered hydroxide | |
| Shang et al. | Preparation and characterization of rose-like NiO nanostructures | |
| CN111559760A (en) | Magnetic hydrotalcite and preparation method and application thereof | |
| Zhuang et al. | Alcohol-assisted self-assembled 3D hierarchical iron (hydr) oxide nanostructures for water treatment | |
| Xaba et al. | SYNTHESIS OF SILVER SULFIDE NANOPARTICLES THROUGH HOMOGENEOUS PRECIPITATION ROUTE AND THE PREPARATION OF THE Ag 2 S-CHITOSAN NANOCOMPOSITES FOR THE REMOVAL OF IRON (II) ION FROM WASTEWATER. | |
| JP3574725B2 (en) | Synthetic charcoal alumite compound and production method thereof | |
| CN105347310B (en) | A kind of method for preparing high-purity calcium based hydrotalcite | |
| CN109415219A (en) | Prepare the method for adsorbent material and the method using the material extraction lithium | |
| CN1537807A (en) | Method of preparing bimetal oxide and hydrotalcite | |
| CN106564962B (en) | A kind of method that protein matter reduction prepares class graphene molybdenum disulfide-ferriferrous oxide composite material | |
| Siahpoosh et al. | Synthesis of γ-Alumina nanoparticles with high-surface-area via Sol-Gel method and their performance for the removal of Nickel from aqueous solution | |
| CN115090254A (en) | Transition metal sulfide/NiCr LDHs composite material and preparation method and application thereof | |
| CN111204820B (en) | Method for rapidly preparing nitrate type hydrotalcite single-layer nanosheet at low temperature |
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 | ||
| ASS | Succession or assignment of patent right |
Owner name: JIANGYIN RUIFA CHEMICAL CO., LTD. Effective date: 20130509 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Lin Yanjun Inventor after: Li Dianqing Inventor after: Duan Xue Inventor after: Chen Hanzhou Inventor after: Jia Xuefei Inventor after: Wen Chenfa Inventor after: Tan Xuchang Inventor before: Lin Yanjun Inventor before: Li Dianqing Inventor before: Duan Xue Inventor before: Chen Hanzhou Inventor before: Jia Xuefei |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: LIN YANJUN LI DIANQING DUAN XUE CHEN HANZHOU JIA XUEFEI TO: LIN YANJUN LI DIANQING DUAN XUE CHEN HANZHOU JIA XUEFEI WEN CHENFA TAN XUCHANG |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130509 Address after: 100029 Beijing, North Third Ring Road, No. 15 East Road, Chaoyang District Patentee after: Beijing University of Chemical Technology Patentee after: JIANGYINSHI RUIFA CHEMICAL CO., LTD. Address before: 100029 Beijing, North Third Ring Road, No. 15 East Road, Chaoyang District Patentee before: Beijing University of Chemical Technology |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110216 Termination date: 20190327 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |