CN102642853B - Method for preparing hydrotalcite-like compound with large specific surface area - Google Patents
Method for preparing hydrotalcite-like compound with large specific surface area Download PDFInfo
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- CN102642853B CN102642853B CN 201210120671 CN201210120671A CN102642853B CN 102642853 B CN102642853 B CN 102642853B CN 201210120671 CN201210120671 CN 201210120671 CN 201210120671 A CN201210120671 A CN 201210120671A CN 102642853 B CN102642853 B CN 102642853B
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Abstract
The invention relates to a method for preparing a hydrotalcite-like compound with a large surface area. The method is based on a double-dripping method, the thickness of a laminate is suppressed by means of adding polyethylene glycol, and accordingly the thin platy hydrotalcite-like compound with the large specific surface area and narrow particle size distribution is prepared and is an ideal catalytic precursor material. In addition, the method for preparing the hydrotalcite-like compound is simple in technological process, the hydrotalcite-like compound is prepared under normal pressure, cost is low, and special equipment is omitted.
Description
Technical field
The present invention relates to a kind of preparation method of large specific surface houghite compound, belong to inorganic non-metallic functional materials preparation field.
Background technology
Houghite compound (Hydrotalcite-like Compounds, be called for short HTLs), also claiming complex metal hydroxide (Layered Double Hydroxides is called for short LDHs) or negatively charged ion clay, is by positively charged main body laminate ([M
iI 1-xm
iII x(OH)
2]
x+) and interlayer object hydration negatively charged ion ((A
n-)
x/nyH
2o) class formed has the general name of supramolecular structure anionic compound, and its chemical constitution can be expressed as [M
iI 1-xm
iII x(OH)
2]
x+(A
n-)
x/nyH
2o, be abbreviated as M usually
iIm
iII-A-LDHs, wherein M
iIand M
iIIrepresent respectively divalence and trivalent metal ion, A
n-represent interlayer anion.The adjustable sex change of main body laminate and interlayer object negatively charged ion interchangeability are the principal characters of houghite compound.The kind of the kind by modulation body layer plate metal element and ratio, interlayer object negatively charged ion, can obtain the HTLs with same crystal structure, different physico-chemical properties, form a huge HTLs material family, be widely used in the fields such as catalysis, absorption, ion-exchange and Process Technology of Polymer (functional materialss such as fire retardant, thermo-stabilizer).
HTLs has alkalescence, and in the catalyzed by solid base field, (as catalysis acetone from combined reaction, Claisen-Schmidt condensation reaction etc.) has good application prospect.Solid catalysis reactions all occurs in phase interface, so specific surface area is one of important indicator of catalytic material.HTLs only has outside surface there is no internal surface, causes the BET specific surface area of HTLs less, usually is less than 80 m
2/ g, greatly limited its application.The HTLs overwhelming majority of synthetic is the hexagon flaky powder, and its BET specific surface area is mainly from the upper and lower surface of sheet-like crystallite; Lei etc. (AIChE J 2007, research 53:932) shows, as the active sites of solid base catalyst HTLs be mainly be located thereon, the exposed hydroxyl of lower surface.Prepare the effective means that ultra-thin HTLs improves its specific surface beyond doubt, the thickness reduction of unit mass sheet HTLs crystallite half, its surface-area approximately doubles.
The tradition preparation method, as single droplet method, two methods, nucleation/crystallization isolation method, urea decomposition method, hydrothermal method etc. only can obtain hexagon or the irregular sheet HTL crystallite that thickness is about 20～50 nanometers usually, the BET specific surface area is about 20～80m
2/ g.Wherein, HTLs particle diameter prepared by the nucleation that Zhao etc. (Chem.Mater.2002,14:4286) report for work/crystallization isolation method is less, and thickness is about 20 nanometers, and the BET specific surface area is about 80m
2/ g.He etc. (Coll.Surf.A2004,251:191) employing template has successfully prepared the BET specific surface area and has reached 120m
2the large specific surface fibre-like HTLs that/g is above.This preparation method need to remove template in the preparation later stage, the aftertreatment long flow path, and the process complexity, only limit to experimental study, is unsuitable for industrialization production.Sasaki etc. (Chem.Mater.2005,17:4386) utilize swelling delamination technology to obtain thickness only be about the HTLs thin slice of 0.8 nanometer, for the preparation of the presoma of other inorganic/organic composite material.Due to delamination HTLs thin slice with a large amount of positive charges, therefore can only stable existence in swelling delamination liquid, leaving the buffer action of swelling agent, will be the sheet HTLs crystallite that thickness is about 20～50 nanometers with the balance anion recombine with the HTLs thin slice of a large amount of positive charges.Therefore, can not obtain ultra-thin HTLs powder by swelling delamination technology.At present, the large specific surface HTLs production technology that flow process is short, process is simple, be suitable for suitability for industrialized production there is no report.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of large specific surface sheet houghite compound, take two methods as basis, suppress laminate thickness by adding the auxiliary agent polyoxyethylene glycol, thereby prepare, thin thickness, BET specific surface area are large, the sheet houghite compound of narrow diameter distribution.
The chemical formula general formula of the large specific surface sheet houghite compound HTLs powder that the present invention is prepared is:
[M
II 1-xM
III x(OH)
2]
x+(A
n-)
x/n·yH
2O
Wherein, M
iIrepresent divalent-metal ion in laminate, as Mg
2+, Zn
2+, Ni
2+, Co
2+, Fe
2+, Mn
2+in one or both; M
iIIrepresent trivalent metal ion in laminate, as Al
3+, Ni
3+, Co
3+, Fe
3+, In
3+, Ga
3+in one or both; X is trivalent metal ion M
iIIshared molar fraction in the laminate metal ion, be generally 0.2～0.33 (two, trivalent metal ion mol ratio n (Mg)/n (Al) be 2～4), and the lower laminate electric density of this value is larger; A
n-for interlayer anion, as NO
3 -, CO
3 2-, SO
4 2-in a kind of; The quantity that y is the interlayer crystal water, be generally 0.5～1.5 according to the interlayer anion kind is different with the sample drying condition.
The preparation method of large specific surface houghite compound HTLs provided by the invention comprises following steps successively:
(1) the mixing salt solution A of preparation divalent-metal ion and trivalent metal ion, wherein the metal ion total concn is 0.4mol/L～2.0mol/L, divalence, trivalent metal ion mol ratio n[M
iI]/n[M
iII] be 2～4;
(2) the mixed ammonium/alkali solutions B of preparation negatively charged ion sodium salt and sodium hydroxide, wherein the concentration of sodium hydroxide is 0.64mol/L～3.2mol/L, the mol ratio n[OH of metal ion in sodium hydroxide and mixing salt solution A
-]/(n[M
iI]+n[M
iII]) be 1.2～2.5; Negatively charged ion (A
n-) concentration be 0.075mol/L～3mol/L, the mol ratio n[A of trivalent metal ion in negatively charged ion and mixing salt solution A
n-]/n[M
iII] be 1～2;
(3) the Aqueous Solutions of Polyethylene Glycol C that compound concentration is 2g/L～20g/L, wherein the polymerization degree of polyoxyethylene glycol (PEG) is 600～6000, in the add-on of controlling polyoxyethylene glycol and mixing salt solution A, the ratio of metal ion total mole number is 5g/mol～40g/mol, and preferable range is 10g/mol～20g/mol;
(4) under room temperature, during three kinds of solution that prepared by (1) (2) (3) step under nitrogen envelope and agitation condition synchronously are added drop-wise to deionized water, then be warmed up to 80～140 ℃, crystallization 4～24 hours, be cooled to room temperature, by throw out washing, filtration, drying, obtain the large specific surface houghite compound.
The mixing salt solution A of step (1) is the soluble salt solution of divalent-metal ion and trivalent metal ion, be preferably the mixing salt solution of soluble salt hydrochlorate, nitrate or the vitriol of divalent-metal ion, trivalent metal ion, wherein divalent-metal ion is Mg
2+, Zn
2+, Ni
2+, Co
2+, Fe
2+, Mn
2+in one or both, trivalent metal ion is Al
3+, Ni
3+, Co
3+, Fe
3+, In
3+, Ga
3+in one or both.Divalent-metal ion is preferably Mg
2+, concentration is preferably 0.3mol/L～1.0mol/L, and trivalent metal ion is preferably Al
3+, concentration is preferably 0.075mol/L～0.5mol/L.
In step (2), negatively charged ion is NO
3 -, CO
3 2-, SO
4 2-in a kind of, be preferably CO
3 2-.
Method key of the present invention is to have added the auxiliary agent polyoxyethylene glycol; by hydrogen bond action, with the hydroxyl on the HTLs laminate, combine; form layer protective layer; utilize protective layer restraining effect and its sterically hindered effect in solution to the growth of laminate thickness direction, houghite compound granular size homogeneous, the thickness prepared are less than 15nm, BET specific surface area>140m
2/ g, be a kind of desirable catalyst precursor material, and preparation method's technological process of the present invention is simple, under normal pressure, prepares, and cost is low, and does not require specific installation.
The accompanying drawing explanation:
Fig. 1, Fig. 2 are respectively large BET specific surface area hydrotalcite X-ray diffraction (XRD) figure that embodiment 1,2 makes.
Fig. 3, Fig. 4 are respectively large BET specific surface area HTLs transmission electron microscope (TEM) figure that embodiment 1,2 makes.
Fig. 5 is large BET specific surface area HTLs scanning electron microscope (SEM) figure that embodiment 3 makes.
Embodiment:
Below the mode with embodiment is further described the present invention, but does not form limiting the scope of the invention.
Embodiment 1:
(1) preparation 50mlMgCl
2concentration is 0.3mol/L, AlCl
3the mixing salt solution A that concentration is 0.1mol/L;
(2) preparation 50mlNa
2cO
3concentration is that 0.2mol/L, NaOH concentration are 0.64mol/L mixed ammonium/alkali solutions B;
(3) solution C that preparation 50ml polyoxyethylene glycol (PEG-1000) concentration is 6g/L;
(4) under room temperature, under agitation condition, A, B, C solution synchronously are added drop-wise in the 50ml deionized water, are warming up to 95 ℃ after dropwising, constant temperature was cooled to room temperature after 6 hours, throw out is washed to the pH value and is less than 8, filtration, drying.Obtaining thickness is 12.1 nanometers, and the BET specific surface area is 150.5m
2the HTLs product of/g.
Embodiment 2:
(1) preparation 50mlMgCl
2concentration is 0.3mol/L, AlCl
3the mixing salt solution A that concentration is 0.1mol/L;
(2) preparation 50mlNa
2cO
3concentration is that 0.2mol/L, NaOH concentration are 0.64mol/L mixed ammonium/alkali solutions B;
(3) solution C that preparation 50ml polyoxyethylene glycol (PEG-1000) concentration is 8g/L;
(4) under room temperature, under agitation condition, A, B, C solution synchronously are added drop-wise in the 50ml deionized water, are warming up to 95 ℃ after dropwising, constant temperature was cooled to room temperature after 6 hours, throw out is washed to the pH value and is less than 8, filtration, drying.Obtaining thickness is 10.8 nanometers, the HTLs product that the BET specific surface area is 160.5m2/g.
Embodiment 3:
(1) preparation 50mlMgCl
2concentration is 0.3mol/L, AlCl
3the mixing salt solution A that concentration is 0.1mol/L;
(2) preparation 50mlNa
2cO
3concentration is that 0.2mol/L, NaOH concentration are 0.64mol/L mixed ammonium/alkali solutions B;
(3) solution C that preparation 50ml polyoxyethylene glycol (PEG-4000) concentration is 4g/L;
(4) under room temperature, under agitation condition, A, B, C solution synchronously are added drop-wise in the 50ml deionized water, are warming up to 95 ℃ after dropwising, constant temperature was cooled to room temperature after 6 hours, throw out is washed to the pH value and is less than 8, filtration, drying.Obtaining thickness is 13.9 nanometers, and the BET specific surface area is 145.4m
2the HTLs product of/g.
Embodiment 4:
(1) preparation 200mlMgCl
2concentration is 0.75mol/L, AlCl
3the mixing salt solution A that concentration is 0.25mol/L;
(2) preparation 200mlNa
2cO
3concentration is that 0.5mol/L, NaOH concentration are 1.60mol/L mixed ammonium/alkali solutions B;
(3) solution C that preparation 200ml polyoxyethylene glycol (PEG-2000) concentration is 20g/L;
(4) under room temperature, under agitation condition, A, B, C solution synchronously are added drop-wise in the 200ml deionized water, are warming up to 95 ℃ after dropwising, constant temperature was cooled to room temperature after 6 hours, throw out is washed to the pH value and is less than 8, filtration, drying.Obtaining thickness is 12.5 nanometers, and the BET specific surface area is 154.2m
2the HTLs product of/g.
Embodiment 5:
(1) preparation 50mlMgCl
2concentration is 0.3mol/L, AlCl
3the mixing salt solution A that concentration is 0.075mol/L;
(2) preparation 50mlNa
2cO
3concentration is that 0.2mol/L, NaOH concentration are 0.64mol/L mixed ammonium/alkali solutions B;
(3) solution C that preparation 50ml polyoxyethylene glycol (PEG-1000) concentration is 8g/L;
(4) under room temperature, under agitation condition, A, B, C solution synchronously are added drop-wise in the 50ml deionized water, are warming up to 95 ℃ after dropwising, constant temperature was cooled to room temperature after 6 hours, throw out is washed to the pH value and is less than 8, filtration, drying.Obtaining thickness is 13.6 nanometers, and the BET specific surface area is 148.4m
2the HTLs product of/g.
Embodiment 6:
(1) preparation 50mlMg (NO
3)
2concentration is 0.3mol/L, Al (NO
3)
3the mixing salt solution A that concentration is 0.1mol/L;
(2) the alkaline solution B that preparation 50mlNaOH concentration is 0.64mol/L;
(3) solution C that preparation 50ml polyoxyethylene glycol (PEG-2000) concentration is 8g/L;
(4) room temperature, synchronously be added drop-wise to A, B, C solution in the 50ml deionized water under nitrogen envelope, agitation condition, is warming up to 80 ℃ after dropwising, and constant temperature was cooled to room temperature after 12 hours, throw out is washed to the pH value and is less than 8, filtration, drying.Obtaining thickness is 11.2 nanometers, and the BET specific surface area is 159.2m
2the nitrate radical intercalation HTLs product of/g.
Embodiment 7:
(1) preparation 50mlMgCl
2concentration is 0.25mol/L, ZnCl
2concentration is 0.05mol/L, AlCl
3the mixing salt solution A that concentration is 0.1mol/L;
(2) preparation 50mlNa
2cO
3concentration is that 0.2mol/L, NaOH concentration are 0.64mol/L mixed ammonium/alkali solutions B;
(3) solution C that preparation 50ml polyoxyethylene glycol (PEG-2000) concentration is 8g/L;
(4) under room temperature, under agitation condition, A, B, C solution synchronously are added drop-wise in the 50ml deionized water, are warming up to 110 ℃ after dropwising, constant temperature was cooled to room temperature after 4 hours, throw out is washed to the pH value and is less than 8, filtration, drying.Obtaining thickness is 12.8 nanometers, and the BET specific surface area is 151.7m
2the MgZnAl-HTLs product of/g.
In the embodiment of the present invention, the thickness of product HTLs is according to the X-ray diffraction characterization data, utilizes the Scherrer formula to calculate.Can find out that from sample transmission electron microscope photo (Fig. 3 and Fig. 4) HTLs crystallite thickness is less than 15 nanometers, can see that from the Sample Scan electromicroscopic photograph HTLs crystallite is the hexagon sheet-like morphology, thickness is less than 15 nanometers.
Claims (3)
1. the preparation method of a large specific surface houghite compound comprises following steps successively:
(1) preparation divalent-metal ion Mg
2+with trivalent metal ion Al
3+mixing salt solution A, wherein the metal ion total concn is 0.4mol/L～2.0mol/L, divalence, trivalent metal ion mol ratio are 2～4; Mixing salt solution A is divalent-metal ion Mg
2+with trivalent metal ion Al
3+the mixing solutions of soluble salt hydrochlorate, nitrate or vitriol;
(2) the mixed ammonium/alkali solutions B of preparation sodium carbonate and sodium hydroxide, wherein the concentration of sodium hydroxide is 0.64mol/L～3.2mol/L, in sodium hydroxide and mixing salt solution A, the mol ratio of metal ion is 1.2～2.5; CO
3 2-concentration be 0.075mol/L～3mol/L, CO
3 2-with the mol ratio of trivalent metal ion in mixing salt solution A be 1～2;
(3) the Aqueous Solutions of Polyethylene Glycol C that compound concentration is 2g/L～20g/L, the polymerization degree of polyoxyethylene glycol is 600～6000, in the add-on of controlling polyoxyethylene glycol and mixing salt solution A, the ratio of metal ion total mole number is 5g/mol～40g/mol;
(4) under room temperature, during three kinds of solution that prepared by (1) (2) (3) step under nitrogen envelope and agitation condition synchronously are added drop-wise to deionized water, then be warmed up to 80～140 ℃, crystallization 4～24 hours, be cooled to room temperature, by throw out washing, filtration, drying, obtain the large specific surface houghite compound.
2. the preparation method of large specific surface houghite compound according to claim 1, is characterized in that: divalent-metal ion Mg in the mixing salt solution A of step (1)
2+, concentration is 0.3mol/L～1.0mol/L, trivalent metal ion Al
3+, concentration is 0.075mol/L～0.5mol/L.
3. the preparation method of large specific surface houghite compound according to claim 1 is characterized in that: in step (3) in the add-on of polyoxyethylene glycol and mixing salt solution A the ratio of metal ion total mole number be 10g/mol～20g/mol.
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