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WO2004000757A1 - Procede d'assemblage de materiau a structure d'intercalation de supermolecule anionique - Google Patents

Procede d'assemblage de materiau a structure d'intercalation de supermolecule anionique Download PDF

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Publication number
WO2004000757A1
WO2004000757A1 PCT/CN2002/000754 CN0200754W WO2004000757A1 WO 2004000757 A1 WO2004000757 A1 WO 2004000757A1 CN 0200754 W CN0200754 W CN 0200754W WO 2004000757 A1 WO2004000757 A1 WO 2004000757A1
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Prior art keywords
acid
ldhs
guest
add
interlayer
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Ceased
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PCT/CN2002/000754
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English (en)
Chinese (zh)
Inventor
Xue Duan
Lingling Ren
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Publication of WO2004000757A1 publication Critical patent/WO2004000757A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/049—Pillared clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/145—After-treatment of oxides or hydroxides, e.g. pulverising, drying, decreasing the acidity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C01F7/785—Hydrotalcite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type

Definitions

  • the invention relates to an interlayer assembly method of an anionic supermolecular structure layer pillar material.
  • Bimetal composite hydroxides also known as Layered Double Hydroxides (LDHs for short), have the properties of intercalation assembly, which can be used to obtain a variety of different anionic supramolecular layer materials. Intercalation assembly methods include co-precipitation, ion exchange, and structural restoration.
  • LDHs Layered Double Hydroxides
  • the literature [V.Prevot, C. Forano and JPBesse, Inorg. Chem., 1998, 37,4293-4301] adopted the structure recovery method under the protection of N 2 gas to obtain a layered material with interlayer objects as organic macromolecules.
  • the disadvantage is that the obtained material has a large number of amorphous phases.
  • SUMMARY OF THE INVENTION The purpose of the present invention is: According to the synthesis principle of LDHs layered pillar materials, a new intercalation assembly method is used to insert specific guest molecules between LDHs layers to prepare a single crystal phase. LDHs with uniform interlayer structure and pure interlayer object.
  • the so-called back-mixed precipitation method is to back-mix the synthesized CO 3 -LDHs with an acid to form a salt, and the obtained salt is co-precipitated with an alkali to form intercalated hydrotalcite.
  • the reaction mechanism of the present invention is:
  • M 2+ represents Mg2 + , Ni 2+ , Zn 2+ , Fe 2+ or Cu 2+ divalent metal ions
  • M 3+ represents Co 3+ , Fe 3+ , Ti 3+ , Al 3+ or Ga 3+ trivalent metal ion
  • AHx represents an inorganic or organic acid guest molecule, the guest molecule should have a certain water solubility, and the pH value of the aqueous solution is less than 4
  • A represents Cl S0 4 2 N0 3 ⁇ P0 4 3 -and other inorganic Acid acid ion or tartaric acid, glutamic acid, aspartic acid, citric acid, malic acid, benzoic acid, p-aminobenzoic acid, adipic acid and other organic acid acid ion
  • [M 2+ 6 M 3+ 2 (OH) 16 ] (C0 3 ) .4 0 is the structural formula of interlayer anion is CO /-ion hydrotalcite (C0 3 -LDHs); [
  • the advantage of the intercalation assembly method is that, on the one hand, in the mechanism reaction formula 2, the salt generated by the reaction formula 1 is dripped into NaOH, so that the reaction pH> 9 is easy to control; on the other hand, it is prepared by this method Although the LDHs material of the intercalation structure is not protected by gas, there is no CO 3 2 -ion between the layers, which overcomes the defect of coexistence of CO /-ions and guest ions between the layers.
  • the object is an inorganic or organic acid with certain water solubility and its aqueous solution pH ⁇ 4, such as hydrochloric acid, carbonic acid, nitric acid, phosphoric acid, tartaric acid, glutamic acid, aspartic acid, citric acid, malic acid, benzoic acid, Para-aminobenzoic acid, adipic acid, etc.
  • hydrochloric acid carbonic acid, nitric acid, phosphoric acid, tartaric acid, glutamic acid, aspartic acid, citric acid, malic acid, benzoic acid, Para-aminobenzoic acid, adipic acid, etc.
  • step C Prepare an aqueous NaOH solution with a concentration of 0.01-0.5M and add it to the reactor with condensation and stirring. While stirring, add the clear solution obtained in step B dropwise. Keep the dropping process pH> 9. After the dropwise addition is completed, 7 Reflux for about 6 hours, filter, wash thoroughly with hot water to pH ⁇ 8, dry at about 85 ° C for about 24 hours, and insert and assemble to obtain the pillar pillar material A-LDHso.
  • the layered column material prepared by the dilute hydrochloric acid backmix precipitation method has no air bubbles, indicating that although the intercalation structure LDHs material prepared by this method does not use> 1 2 gas protection, there is no C0 3 2 _ ion between the layers, so This synthesis method overcomes the defect of coexistence of CO 3 2 -ions and guest ions in the layers. Concrete real formula
  • Step A Dissolve 61.5 g (0.24 mol) of solid Mg (N0 3 ) 2 ⁇ 6H 2 0 and 45.0 g (0.12 mol) of solid Al (N0 3 ) 3 ⁇ 9 ⁇ 2 0 in 225 ml of 0; 253g (0.24mol) solid N3 ⁇ 4C0 3 and 23.0g (0.58mol) NaOH dissolved in 225ml of water, alkali solution rapidly at room temperature and a solution of salt nucleating film in the rotary reactor, and the resulting crystal slurry was 100 ° C It was centrifuged for 6 hours, centrifuged, and the obtained sample was washed to a pH of less than 8, 70 ° C and dried for 24 hours to obtain Mg-Al-LDHs, whose Mg ⁇ / A + ⁇ : 1.
  • Step B 4.0 g of LDHs were added to a container containing 100 ml of deionized water, magnetically stirred at room temperature, and an excess of 7.5 g of glutamic acid was added. At this time, the turbid liquid in the container changed to a clear solution.
  • Step C Dissolve 2 g of NaOH in the container with 100 ml of pure water, and then pour into the reactor with condensation and stirring. While stirring, add the clarified solution in step B dropwise. Keep the dropping process pH> 9. Dropping is completed. It was condensed and refluxed for 6 hours, filtered, washed with hot water to pH ⁇ 8, and dried at about 85 ° C for 241 ⁇ m. The interlayer was assembled to obtain LDHs with glutamic acid intercalation structure. o
  • Step B Add 3.0 g of LDHs to a container containing 100 ml of deionized water, magnetically stir at room temperature, and add 6.5 g of excess lactic acid. At this time, the turbid liquid in the container changes to a clear solution.
  • Step C According to the method of Step C in Example 1, a Mg-Al type hydrotalcite pillar material with an interlayer anion of tartaric acid was prepared.
  • IR spectrum shows that the prepared lactic acid intercalation structure LDHs material has a C0 3 2 -peak at 1377cm- 1 and disappears, and carboxylates appear at 1587 and B ⁇ cm- 1 respectively .
  • Asymmetric and symmetrical absorption bands of acid ions are known from the X-ray diffraction pattern.
  • the experiment proves that the lactic acid is assembled into the interlayer of LDHs by the back-mixed precipitation method, and the Mg-Al type hydrotalcite pillar material with interlayer anion as lactic acid molecule is obtained.
  • the layered pillar material prepared by the mixed precipitation method has no air bubbles, indicating that the LDHs layered pillar material prepared by this method Although no gas protection is used, there is no co 3 2 -ion between the layers, so this synthesis method can better overcome the coexistence of co 3 2 -ions and guest ions between the layers.
  • Step A Dissolve 123.1 g (0.48 mol) of solid Mg (N0 3 ) 2 6H 2 0 and 45.0 g (0.12 mol) of solid Al (N0 3 ) 3 * 9H 2 0 in 225 ml of H 2 0; Separately, 50.9g (0.48mol) solid N3 ⁇ 4C0 3 and 38.4g (0.96mol) NaOH dissolved in 225ml water, prepared according to example step a 1 is obtained by Mg-Al-LDHs, which Mg ⁇ / a: 1 .
  • Step B Add 3.0 g of LDHs to a container containing 100 ml of deionized water, magnetically stir at room temperature, and add 6.5 g of excess phosphoric acid. At this time, the turbid liquid in the container becomes a clear solution.
  • Step C According to the method of Step C in Example 1, a Mg-Al type hydrotalcite pillar material with interlayer anions was prepared.
  • the backmixed precipitation method is used to assemble the LDHs into the layer, and the Mg-Al type hydrotalcite pillar material with interlayer anions as molecules is obtained.
  • the pillar prepared by the backmixed precipitation method is diluted with dilute hydrochloric acid. Material, no air bubbles, indicating that although the LDHs layered pillar material prepared by this method does not use N 2 gas protection, there is no C0 3 2 -ion between the layers, so this synthesis method is better than C0 3 2 -Defects in which ions and guest ions coexist between layers.
  • Step B Add 3.0 g of LDHs to a container containing 100 ml of deionized water and stir magnetically at room temperature. An excess of 5.5 g of malic acid was added, and the vessel changed from a turbid liquid to a clear solution.
  • Step C According to the method of Step C in Example 1, a Zn-Al type hydrotalcite pillar material with an interlayer anion of tartaric acid was prepared.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne un procédé d'assemblage de matériau à structure d'intercalation de supermolécule anionique. Selon le principe de la synthèse de matériau à pilier lamellaire de HDL (hydroxyde double lamellaire), les molécules anions invitées sont assemblées entre des hydrotalcites afin d'obtenir le matériau à structure de pilier lamellaire par sélection de molécules spéciales invitées et par l'utilisation d'un procédé d'assemblage d'intercalation à déposition par rétromélange, et par maîtrise de la densité des ions, des types de cations et des types d'invités dans les lamellaires. Ce procédé n'utilise pas d'azote en tant que gaz écran, et il est plus simple à mettre en oeuvre, le cristal obtenu est plus unitaire, la structure est plus concordante et les invités interlamellaires sont purs. Ce procédé évite les problèmes rencontrés dans les précédents procédés d'assemblage d'intercalation à savoir la présence de plusieurs phases amorphes, l'utilisation d'azote en tant que gaz écran et l'obtention d'invités interlamellaires non purs.
PCT/CN2002/000754 2002-06-24 2002-10-25 Procede d'assemblage de materiau a structure d'intercalation de supermolecule anionique Ceased WO2004000757A1 (fr)

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CN02123763 2002-06-24
CN02123763.8 2002-06-24

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100453170C (zh) * 2007-04-27 2009-01-21 北京化工大学 一种高稳定双活性组分钛基复合金属氧化物及其制备方法
CN103638905A (zh) * 2013-11-28 2014-03-19 沈阳化工大学 一种利用酒石酸插层水滑石吸附重金属的方法
CN110624513A (zh) * 2019-10-09 2019-12-31 武汉纺织大学 一种聚天冬氨酸插层水滑石复合材料及其制备方法与应用
WO2020120976A1 (fr) * 2018-12-14 2020-06-18 Bp Exploration Operating Company Limited Matériaux d'hydroxydes doubles lamellaires en tant qu'additifs destinés à prolonger la durée de vie d'un traitement chimique du tarte par esquichage
CN112920458A (zh) * 2021-01-27 2021-06-08 北京化工大学 一种高分子材料用缓释型助剂及其制备方法
CN113564573A (zh) * 2021-07-22 2021-10-29 重庆大学 一种镁合金表面SLIPS/LDHs复合膜层的制备方法及应用
CN116285942A (zh) * 2023-03-20 2023-06-23 云南中烟工业有限责任公司 一种温致可逆变色水性染料、其制备方法及应用

Citations (6)

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CN1056827A (zh) * 1990-05-25 1991-12-11 密歇根州州立大学托管委员会 多酸根嵌入的层状复氢氧化物
JPH08311253A (ja) * 1995-05-18 1996-11-26 Chisso Corp 結晶性ポリオレフィン組成物
CN1171979A (zh) * 1996-07-29 1998-02-04 德国泰克萨科股份公司 制备水滑石及其金属氧化物的方法
CN1288078A (zh) * 1999-09-14 2001-03-21 北京化工大学 均分散超细阴离子层状材料的新合成方法
CN1289307A (zh) * 1998-12-01 2001-03-28 协和化学工业株式会社 水滑石类化合物和其制法以及含该化合物的农用薄膜
CN1358691A (zh) * 2000-12-14 2002-07-17 北京化工大学 全返混液膜反应器及其在制备超细阴离子层状材料中的应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1056827A (zh) * 1990-05-25 1991-12-11 密歇根州州立大学托管委员会 多酸根嵌入的层状复氢氧化物
JPH08311253A (ja) * 1995-05-18 1996-11-26 Chisso Corp 結晶性ポリオレフィン組成物
CN1171979A (zh) * 1996-07-29 1998-02-04 德国泰克萨科股份公司 制备水滑石及其金属氧化物的方法
CN1289307A (zh) * 1998-12-01 2001-03-28 协和化学工业株式会社 水滑石类化合物和其制法以及含该化合物的农用薄膜
CN1288078A (zh) * 1999-09-14 2001-03-21 北京化工大学 均分散超细阴离子层状材料的新合成方法
CN1358691A (zh) * 2000-12-14 2002-07-17 北京化工大学 全返混液膜反应器及其在制备超细阴离子层状材料中的应用

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100453170C (zh) * 2007-04-27 2009-01-21 北京化工大学 一种高稳定双活性组分钛基复合金属氧化物及其制备方法
CN103638905A (zh) * 2013-11-28 2014-03-19 沈阳化工大学 一种利用酒石酸插层水滑石吸附重金属的方法
WO2020120976A1 (fr) * 2018-12-14 2020-06-18 Bp Exploration Operating Company Limited Matériaux d'hydroxydes doubles lamellaires en tant qu'additifs destinés à prolonger la durée de vie d'un traitement chimique du tarte par esquichage
CN110624513A (zh) * 2019-10-09 2019-12-31 武汉纺织大学 一种聚天冬氨酸插层水滑石复合材料及其制备方法与应用
CN112920458A (zh) * 2021-01-27 2021-06-08 北京化工大学 一种高分子材料用缓释型助剂及其制备方法
CN112920458B (zh) * 2021-01-27 2022-05-10 北京化工大学 一种高分子材料用缓释型助剂及其制备方法
CN113564573A (zh) * 2021-07-22 2021-10-29 重庆大学 一种镁合金表面SLIPS/LDHs复合膜层的制备方法及应用
CN116285942A (zh) * 2023-03-20 2023-06-23 云南中烟工业有限责任公司 一种温致可逆变色水性染料、其制备方法及应用

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