CN100496726C - Hydrotalcite like structural catalyst with mica as matrix and preparation method - Google Patents
Hydrotalcite like structural catalyst with mica as matrix and preparation method Download PDFInfo
- Publication number
- CN100496726C CN100496726C CNB2005101171855A CN200510117185A CN100496726C CN 100496726 C CN100496726 C CN 100496726C CN B2005101171855 A CNB2005101171855 A CN B2005101171855A CN 200510117185 A CN200510117185 A CN 200510117185A CN 100496726 C CN100496726 C CN 100496726C
- Authority
- CN
- China
- Prior art keywords
- ldhs
- mica
- catalyst
- matrix
- hydrotalcite
- 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
Images
Abstract
The invention discloses a hydrotalcite catalyst which uses mica as base and relative preparing method. The invention uses the active component of LDHs to grow on the surface of mica plate, while the loading rate of LDHs is 0.4-2.5%, the LDHs and mica have higher adhesive force, and therefore, they will not drop after the heating process and rehydration treatment. The invention arranges the mica base whose layer is just removed into the solution of carbamide and relative metal salt to control the negative ion via controlling the reaction temperature, time and the decompose speed of carbamide, to make the LDHs form core and grow on the base to attain the LDHS catalyst with the mica base. The invention can solve the problems of former technique which uses the LDHs powder as catalyst that the catalyst loses easily and is hard to separated from reaction material and reaction product. And it also solve the problem that easy drop of after-activating treatment caused by lower adhesive force of LDHs on the base, when depositing the LDHs on the base.
Description
Technical field
The present invention relates to a kind of hydrotalcite-like structuring catalyst and preparation method thereof, be specifically related to a kind of preparation method who is grown in the hydrotalcite-like structuring catalyst on the mica matrix.
Background technology
Houghite is also referred to as layered di-hydroxyl composite metal oxidate (LDHs), is the important inorganic functional material of a class, and its chemical general formula is [M
2+ 1-xM
3+ x(OH)
2]
X+(A
N-)
X/nYH
2O).Because of it has the adjustable sex change of layer structure, laminate element and the interchangeability of interlayer anion, have a wide range of applications.LDHs is applied to have in the reactive organic molecule active high, advantages such as selectivity is good, active component decentralization height, good regeneration repeatability directly or indirectly as the composite oxide catalysts precursor.The LDHs material is mainly used in base catalysis, redox catalysis as catalyst.It is all to have the alkali center in the resulting product of roasting of roasting presoma that LDHs reaches with it, thereby can be used for base catalysis.LDHs mainly is used to two big class reactions as base catalyst: alkylene oxide polymerization and aldol reaction.For example, be applied to isomerisation of olefin, nucleophilic halo, alkylation, alkene epoxidation and Claisen-Schmidt reaction etc.Oxidation reduction catalyst with LDHs for the preparation of roasting presoma has remarkable advantages than the similar component catalyst with the additive method preparation: levels of transition metals height (66%～77%), high stability has high relatively activity as a rule.Usually, the oxidation reduction catalyst from LDHs preparation is mainly used in following reaction: synthesizing methanol, higher alcohol are synthetic, methane reforming, hydrogen peroxide phenol hydroxylation, phenol hydrogenation, water-gas shift and Fischer-Tropsch reaction etc.
LDHs particular structure characteristic, element are formed the adjustable sex change of adjustable sex change in wide region, pore structure and excellent catalytic performance and have been established the basis that this class material might become the industrial catalyst with potential application foreground.LDHs shows good prospects for application in the heterogeneous catalysis research field, but limitation is also arranged: one simultaneously, the particle size of all dispersions mixed oxide (LDO) powder that forms through the LDHs powder calcination is extremely tiny, although the bigger serface that brings thus, help fully contacting of catalyst and reactant substrate, to realize catalytic activity and selectivity efficiently, but, catalyst granules is too tiny, adopts traditional filtration or centrifugation method to be difficult to fast and effeciently realize reclaiming fully; And after the moulding, particle size increases, and reaction contact area reduces, and catalytic activity must descend, and selectivity also is subjected to influence to a certain degree simultaneously; Its two, adopt tank reactor in the current technology, generally do not have agitating device, this has brought difficulty for enforcement of heterogeneous catalysis.
In recent years, the direction that chemical industry just towards safety, cleaning, efficiently, is finally being realized the production process zero-emission develops, to satisfy the requirement of environmental protection and sustainable development.The approach that realizes comprises, at chemical aspect developing catalyst new, that selectivity is higher; New, efficient, pollution processing technology routine are still less sought in the engineering aspect.Aspect catalyst research, not only to consider the active sites of molecule aspect and, also will consider the diffusion of effective heterogeneous contact and reaction mass such as the problem of catalyst engineering aspects such as porosity, catalyst shape, microstructure and composition.Therefore, in recent years aspect catalyst and DESIGN OF REACTOR, proposed to want emphasis to consider scale effect in the design especially to go out to send the novel macro-structured catalyst of development from macro-scale.On catalytic reaction engineering, require to overcome conventional heterophase reactor, the shortcoming as slurry attitude bed, fixed bed (trickle bed) reaction reduces diffusion influence, makes even fluid distribution, so the design of the novel reactor of structural catalyst is a focus of research.At present, the process of these two approach realizations is called process intensification.Their intersection is that catalyst reactor uses with structured way, comprises multi-functional and structurized reactor.Under such background, the imagination of structural catalyst is proposed, it combines Catalyst Design and reactor design, thereby promotes catalytic action better.At present, activity of such catalysts component, structure carrier and reactor three integration thoughts become the most important and received new thinking of catalytic field.
As previously mentioned, because LDHs can be used as multiple catalyst for reaction and has excellent catalytic performance,, can promote the commercial Application of LDHs catalyst undoubtedly if can obtain the LDHs structural catalyst.But, only on supporter with the LDHs immobilization, could obtain LDHs structural catalyst (being also referred to as integer catalyzer), not only can improve its functioning efficiency, prevent that it runs off, and help to realize using the low energy consumption of LDHs class catalyst, the novel catalyzing technology process of zero-emission.Yet for such structural catalyst, relevant development does not also obtain understanding.Although intercalation LDHs is because its highly active catalytic performance has obtained affirmation, because the difficulty of such material immobilized aspect, its commercial Application progress has been subjected to obstruction.
At document Adv.Mater., 2001,13 (16): in 1263, people such as E.Gandner are deposited on the magnalium LDHs film that has obtained the alkoxyl intercalation on glass with the colloidal solution of LDHs; At Langmuir, 2002,18 (5): in 1580, people such as J.X.He will be deposited on mica sheet and obtain the LDHs film from the magnalium carbonate LDHs that the Langmir-Blodgett film obtains; At document Chem.Commun., 2003:2740 and Langmuir, 1998,14 (10): in 2890, people such as J.H.Lee and K.Yao respectively with the LDHs crystal deposition in the aqueous solution on high directed thermal cracking graphite and silicon (100) wafer.All these immobilized LDHs are deposited on the matrix by LDHs colloid that will synthesize or powder to obtain, and all exist with matrix bond not closely, peel off easily when carrying out follow-up activation processing, problem such as practicality is not high.If LDHs is grown in matrix surface by chemical action power, these problems can be readily solved naturally.
In application number was 200410090816.4 patent application, we had introduced the growth of LDHs at polymer surface, have solved problems such as LDHs and basal body binding force are not tight.Since poor-performings such as organic matrix resistance to elevated temperatures and organic solvent-resistant, and LDHs will could embody its catalytic performance better through corresponding activation processing such as high-temperature roastings.Macromolecular material does not obviously meet the requirement as LDHs structural catalyst matrix.
Mica is a kind of important nonmetallic mineral, and it is the hydrous alumino silicates of alkali metal and alkaline-earth metal, belongs to phyllosilicate, and is cheap and easy to get.Aspect thermal property, mica can be high temperature resistant, is the non-conductor of heat; Aspect chemical property, mica is acidproof, alkaline-resisting, organic solvent-resistant, and its water imbibition and hygroscopicity are very little; Aspect machining property, have higher mechanical strength, stripping branchs is good, it is good to shell thin slice, the nerve be divided into as thin as a wafer along cleavage surface, when on the strip off face during no external contamination thing, machinings such as crystal can dash because of the affinity combination again of surface molecular, cuts, glues, volume.If LDHs can be fixed on the mica, can adopt multiple means that immobilized LDHs is handled, and according to the moulding that requires of reactor, thereby the catalytic performance of LDHs is embodied and make it device---promptly make the LDHs structural catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of is the hydrotalcite-like structuring catalyst of matrix with the mica, it is the preparation method of the LDHs structural catalyst of matrix with the mica that another object of the present invention provides a kind of, i.e. the method for immobilization LDHs catalyst on the mica matrix of fresh stripping layer.Preparation has the LDHs structural catalyst of high adhesion force, difficult drop-off, to realize the commercial Application of LDHs catalyst.
LDHs structural catalyst provided by the invention is: be matrix with the mica, active constituent LDHs grows in the mica sheet surface, wherein the load factor of LDHs counts 0.4～2.5% with the quality percentage composition, preferable load factor counts 1.0～2.0% with the quality percentage composition, LDHs and mica adhesive force are big in this structural catalyst, handle equal difficult drop-off through heat treatment and rehydration;
Wherein the chemical general formula of LDHs is: [M
2+ 1-xM
3+ x(OH)
2]
X+(CO
3 2-)
X/2YH
2O,
M
2+Represent bivalent metal ion Mg
2+, Zn
2+, Ni
2+, Fe
2+, Mn
2+In any, that preferable is Mg
2+Or Ni
2+M
3+Represent trivalent metal ion Al
3+, Cr
3+, Fe
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any, that preferable is Al
3+Or Fe
3+M
2+/ M
3+Mol ratio be 1.6～4.5:1; The span of y is 0≤y≤2.
Concrete preparation process of the present invention is as follows:
A: the mica sheet of fresh stripping layer is cut into difformity and big or small sheet as required, and the salpeter solution with 1～10% soaked 2～5 hours, rinsed well standby with deionized water;
B: in reaction vessel, with solubility divalence inorganic salts M
2+Y and solubility trivalent inorganic salts M
3+Y is by 1.6～4.5: 1 mol ratio is mixed with the mixing salt solution that the metal ion total concentration is 0.005mol/L～0.5mol/L, and the ratio of urea in [urea]/[Y]=2～6 added reactor and make it to be dissolved in the mixing salt solution; Wherein the ratio of negative ions should satisfy the requirement of charge balance in solubility divalence inorganic salts and the solubility trivalent inorganic salts;
C: the mixing salt solution that places the good mica sheet of processing of step A step B to be prepared in the ratio of mica/metal ion total amount=50～500g/mol, sealed reaction vessel, isothermal reaction is 1～10 day under 50～180 ℃ of temperature, and preferable reaction condition is isothermal reaction 2～5 days under 70～120 ℃ of temperature; Treat solution cooling back taking-up mica sheet, rinse well with deionized water, oven dry, the LDHs that is synthesized promptly is grown in mica surface, thereby obtains the LDHs structural catalyst.
The described mica material of steps A is muscovite, phlogopite, biotite or lepidolite.
M among the step B
2+Be Mg
2+, Zn
2+, Ni
2+, Fe
2+, Mn
2+In any, that preferable is Mg
2+Or Ni
2+M
3+Be Al
3+, Cr
3+, Fe
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any, that preferable is Al
3+Or Fe
3+, Y is Cl
-, NO
3 -, F
-, Br
-, SO
4 2-In any, that preferable is NO
3 -
Urea is a kind of very weak
Alkali (pK
b=13.8), and very high solubility arranged in water.Urea in the decomposition mechanism in the water shown in following reaction equation:
CO (NH
2)
2→ NH
4CNO: slow
NH
4CNO+2H
2O → (NH
4)
2CO
3: fast
When temperature when 60 ℃ rise to 100 ℃, this reaction rate constants can increase about 200 times.Can provide OH for solution after the ammonium carbonate hydrolysis that produces
-And CO
3 2-, the pH value of solution being near 7-9, thereby can providing suitable pH condition for LDHs synthetic, the present invention controls anion OH by the synthesis temperature of control step C
-And CO
3 2-Rate of release, and then successfully control the nucleation and the growth of LDHs crystal.
Mica is in polar water solution, and is permanent electronegative because of the surface, must cause Electrostatic Absorption solution metal cation.Therefore when slowly decomposing, urea discharges OH
-And CO
3 2-The time, the ion concentration on mica sheet surface can form the LDHs nucleus after reaching supersaturation.Along with the further decomposition of urea, the LDHs nucleus of mica-based surface is grown up gradually, and obtaining at last with the mica is the LDHs structural catalyst of matrix.
Adopt the German Bruker Vector22 of the company type Fourier transformation infrared spectrometer of the attenuate total reflection annex of band U.S. PIKE company that sample is carried out qualitative analysis.By attenuate total reflection Fourier transform spectrum (ATR-FT-IR) spectrogram of embodiment one gained sample as shown in Figure 1,1361cm
-1The strong absworption peak at place can belong to and is magnalium carbonate LDHs interlayer anion CO
3 2-Feature symmetrical stretching vibration absworption peak.
Adopt the pattern of Japanese HITACHI S-3500N type SEM (SEM) and observing samples, energy spectrum analysis (EDS) is analyzed with Britain Oxford Instrument Isis300 type spectroscopy systems in this SEM system.Fig. 2 is the SEM photograph and the constituency EDS spectrogram of the sample of embodiment 1 preparation.As seen from the figure, have some incomplete hexagon flaky substances on smooth mica surface, these tablets all have certain included angle with the mica matrix.By constituency EDS spectrogram A as can be seen, do not have the white space of tablet not have the Mg element, the height at Al element peak is lower than the Si element, and its composition is consistent with mica; And occurred the Mg element among the EDS spectrogram B of tablet, and Al element peak is than Si element height.It is as follows to obtain each atoms of elements content (%) by spectrogram:
With Si is that calculating the Mg/Al mol ratio is 1.83 the Al that deducts in the mica is formed by the A point in the basis from B after.With the tablet of sample surfaces with dilute nitric acid dissolution after (mica does not dissolve), the ratio that adopts day island proper Tianjin ICPS-7500 type plasma emission spectrum (ICP) instrument to record Mg/Al in the tablet is 2.06, these two values are all near the ratio of Mg/Al in the reaction solution.According to ATR-FT-IR, SEM, EDS and ICP test result, the imperfect hexagon tablet that can be fixed on mica surface certainly is magnalium carbonate LDHs.
Generally will be when LDHs is used as catalyst through calcining and rehydration activation processing.Fig. 3 be the sample of embodiment 2 preparation at the SEM image of 500 ℃ of calcinings after 8 hours, Fig. 4 be this calcination sample in removing carbon dioxide water in the SEM image of rehydration under the room temperature after 5 hours.After calcining, the composite oxides LDO that is generated does not come off as can be seen from Figure 3, still attached to mica surface, and has kept the laminated structure of LDHs.Fig. 4 illustrates then that after rehydration the regeneration hydroxyl LDHs that is obtained also still is retained in mica surface, structure in the form of sheets.Fig. 3 and Fig. 4 prove that there are very strong adhesive force (chemical bonding force) in LDHs and mica surface, also are not easy to come off under very strong external force effect.
Adopt acetone to be converted into the catalytic activity of the reaction investigation LDHs structural catalyst of DAA (DAA) from condensation.The activation process of LDHs structural catalyst is: 500 ℃ of calcinings 8 hours, the cooling back was adopted and was gone in the carbon dioxide water under room temperature rehydration 5 hours after sample was warmed up to 500 ℃ with the speed of 10 ℃/min, and these two processing procedures are all at N
2Carry out in the atmosphere, remove excessive water by vacuum drying at last.Catalytic reaction process is as follows:
2mol (116g) is analyzed pure acetone join in the there-necked flask, at N
2Under the atmosphere protection; with ice-water bath stabilising system temperature is 0 ℃; add the activated LDHs structural catalyst of 10g then; under gentle agitation, begin reaction; certain hour is got the reactant liquor of trace at interval; with Shimdzu QP2010 type GC-MS (GCMS) analysis of mixtures, be the output that interior mark is determined DAA with isooctane.In addition, adopt 0.3g to contrast through the LDHs powder catalyst of the same manner activation, this LDHs powder is deposited on the powder of reaction container bottom when being taken from preparation LDHs structural catalyst.
Fig. 5 is that the catalyst that adopts embodiment 1 to be obtained carries out the result of acetone from the condensation catalytic reaction.Fig. 5 curve A shows employing LDHs structural catalyst, behind reaction 460min under 0 ℃, acetone conversion is that the conversion ratio of DAA is 23.01%, very near thermodynamical equilibrium conversion ratio (the document Chem.Eng.Sci. of acetone self-condensation reaction under this temperature, the thermodynamical equilibrium conversion ratio that 1997,52 (17): 2991 reports are calculated is 23.1%).Shown in Fig. 5 curve B, when adopting LDHs powder catalyst, the conversion ratio of acetone just reaches 22.82% behind the reaction 560min but under the same conditions.The load factor of LDHs is 1.7% in the prepared structural catalyst of embodiment 1, thereby participates in the reactive activity component and have only 0.17g, is less than the 0.3g of powder catalyst far away.Document J.Catal., 2001,203:184 and Catal.Today, 2000, adopt LDHs powder catalyst among the 60:297, under similarity condition, do not reach balance as yet behind the reaction 24h.Obviously, the catalytic activity of LDHs structural catalyst is apparently higher than LDHs powder catalyst.This is because LDHs is grown in mica surface, makes it fixing well and be dispersed in mica surface, and the LDHs structural catalyst is in catalytic reaction, and its activated centre can be easy to or combine with acetone molecules very fully, makes reaction speed speed; And the dispersiveness of powder LDHs is well below structural catalyst, makes the minimizing that contacts of powder activity of such catalysts center and reaction solution, so reaction speed is not as the structural catalyst height.This LDHs structural catalyst is used further to the acetone self-condensation reaction after recovery, reuse 20 times, still can make this react on 700min and reach balance; And the yield of LDHs powder catalyst obviously reduces.This shows that the loss of active constituent in the LDHs structure catalyst is considerably less.
Remarkable result of the present invention is the active constituent LDHs in the LDHs structural catalyst that the present invention prepares, is grown in the mica-based surface by chemical force, in conjunction with closely, and difficult drop-off.Adopt method provided by the invention on mica sheet, to obtain the LDHs structural catalyst by fixed L DHs, simple synthetic method, catalytic performance is good.
Description of drawings
Fig. 1 is the ATR-FT-IR spectrogram of embodiment 1 gained LDHs structural catalyst;
Fig. 2 is the SEM photograph and the constituency EDS spectrogram of embodiment 1 gained LDHs structural catalyst;
Fig. 3 is the SEM photographs of embodiment 2 gained LDHs structural catalysts after calcining;
The SEM photograph that Fig. 4 is 2 LDHs structural catalysts of embodiment after calcining/rehydrated;
Fig. 5 is conversion ratio-time diagram that embodiment 1 gained LDHs structural catalyst is used for the acetone self-condensation reaction after activated;
Fig. 6 is the SEM photograph on embodiment 2 gained LDHs structural catalyst surfaces;
Fig. 7 is the SEM photograph on embodiment 3 gained LDHs structural catalyst surfaces.
The specific embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1
Shelled layer nitric acid dousing of also shearing good white clouds master slice employing 10% 3 hours with fresh, standby after rinsing well with deionized water.
In the 1000mL reaction vessel, with 19.23g Mg (NO
3)
26H
2O and 14.07gAl (NO
3)
39H
2O is dissolved in the 750mL deionized water, and being mixed with the Mg/Al mol ratio is 2: 1, and total concentration of metal ions is the mixing salt solution of 0.15mol/L, adds 60.06g urea again and makes it dissolving.
Get the mixed solution that white clouds master slice that 45g handles well places above-mentioned reaction vessel, behind the airtight container,, treat that solution cooling back takes out the mica substrate, rinse 100 ℃ of oven dry in following 24 hours with deionized water well in 70 ℃ of following isothermal reactions 7 days.
The ATR-FT-IR spectrogram of resulting structures catalyst is seen Fig. 1, and SEM photograph and constituency EDS spectrogram are seen Fig. 2, shows that the tablet that mica surface forms is magnalium carbonate LDHs.The Mg/Al mol ratio is 1.97 among the LDHs, and the load factor of LDHs is 0.47% (percetage by weight).
Embodiment 2
Shelled layer nitric acid dousing of also shearing good white clouds master slice employing 5% 4 hours with fresh, standby after rinsing well with deionized water.
In the 1000mL reaction vessel, with 19.23g Mg (NO
3)
26H
2O and 14.07g Al (NO
3)
39H
2O is dissolved in the 750mL deionized water, and being mixed with the Mg/Al mol ratio is 2: 1, and total concentration of metal ions is the solution of 0.15mol/L, adds 75.08g urea and makes it dissolving.
Get the mixed solution that white clouds master slice that 45g handles well places above-mentioned reaction vessel, behind the airtight container, in 90 ℃ of following isothermal reactions 3 days.Treat solution cooling back taking-up mica sheet, rinse well, 100 ℃ of oven dry in following 24 hours with deionized water.
The SEM photo of resulting structures catalyst is seen Fig. 6, and the tablet that mica surface forms is magnalium carbonate LDHs.The Mg/Al mol ratio is 2.06 among the LDHs, and the load factor of LDHs is 1.71% (percetage by weight).
Embodiment 3
Shelled layer nitric acid dousing of also shearing good white clouds master slice employing 7% 3 hours with fresh, standby after rinsing well with deionized water.
In the 1000mL reaction vessel, with 19.23g Mg (NO
3)
26H
2O and 14.07g Al (NO
3)
39H
2O is dissolved in the 750mL deionized water, and being mixed with the Mg/Al mol ratio is 2: 1, and total concentration of metal ions is the solution of 0.15mol/L, adds 63.06g urea and makes it dissolving.
135g is handled well the mixed solution that the white clouds master slice places above-mentioned reaction vessel, behind the airtight container, in 120 ℃ of following isothermal reactions 3 days.Treat solution cooling back taking-up mica sheet, adopt deionized water rinsing clean, 100 ℃ of oven dry in following 24 hours.
The SEM photograph of resulting structures catalyst is seen Fig. 7, and the tablet on mica sheet surface is magnalium carbonate LDHs.The Mg/Al mol ratio is 2.02 among the LDHs, and the load factor of LDHs is 0.97% (percetage by weight).
Embodiment 4
Shelled layer nitric acid dousing of also shearing good phlogopite sheet employing 10% 2 hours with fresh, standby after rinsing well with deionized water.
In the 1000mL reaction vessel, with 19.23g Mg (NO
3)
26H
2O and 14.07g Al (NO
3)
39H
2O is dissolved in the 750mL deionized water, and being mixed with the Mg/Al mol ratio is 2: 1, and total concentration of metal ions is the solution of 0.15mol/L; Add 90.09g urea and make it dissolving.
The phlogopite sheet that 45g is handled well places the mixed solution of above-mentioned reaction vessel, behind the airtight container, in 90 ℃ of following isothermal reactions 3 days.Treat solution cooling back taking-up mica sheet, adopt deionized water rinsing clean, 100 ℃ of oven dry in following 24 hours.
The tablet that mica surface forms is magnalium carbonate LDHs.The Mg/Al mol ratio is 1.96 among the LDHs, and the load factor of LDHs is 1.53% (percetage by weight).
Embodiment 5
Shelled layer nitric acid dousing of also shearing good phlogopite sheet employing 2% 5 hours with fresh, standby after rinsing well with deionized water.
In the 1000mL reaction vessel, with 21.63g Mg (NO
3)
26H
2O and 10.55g Al (NO
3)
39H
2O is dissolved in the 750mL deionized water, and being mixed with the Mg/Al mol ratio is 3:1, and total concentration of metal ions is the solution of 0.15mol/L, adds 63.6g urea and makes it dissolving.
The white clouds master slice that 45g is handled well places the mixed solution of above-mentioned reaction vessel, behind the airtight container, in 90 ℃ of following isothermal reactions 3 days.Treat solution cooling back taking-up mica sheet, adopt deionized water rinsing clean, 100 ℃ of oven dry in following 24 hours.
The tablet that mica surface forms is magnalium carbonate LDHs.The Mg/Al mol ratio is 2.36 among the LDHs, and the load factor of LDHs is 1.48% (percetage by weight).
Embodiment 6
Shelled layer nitric acid dousing of also shearing good black clouds master slice employing 8% 2 hours with fresh, standby after rinsing well with deionized water.
In the 1000mL reaction vessel, with 2.163g Mg (NO
3)
26H
2O and 1.055g Al (NO
3)
39H
2O is dissolved in the 750mL deionized water, and being mixed with the Mg/Al mol ratio is 3:1, and total concentration of metal ions is the solution of 0.015mol/L, adds 5.73g urea and makes it dissolving.
The black clouds master slice that 15g is handled well places the mixed solution of above-mentioned reaction vessel, behind the airtight container, in 70 ℃ of following isothermal reactions 8 days.Treat solution cooling back taking-up mica sheet, adopt deionized water rinsing clean, 100 ℃ of oven dry in following 24 hours.
The tablet that mica surface forms is magnalium carbonate LDHs.The Mg/Al mol ratio is 2.51 among the LDHs, and the load factor of LDHs is 0.68% (percetage by weight).
Embodiment 7
Shelled layer nitric acid dousing of also shearing good white clouds master slice employing 8% 2 hours with fresh, standby after rinsing well with deionized water.
In the 1000mL reaction vessel, with 28.50g MgCl
2With 10.01g AlCl
3Be dissolved in the 750mL deionized water, being mixed with the Mg/Al mol ratio is 4:1, and total concentration of metal ions is the solution of 0.5mol/L, adds 120.12g urea and makes it dissolving.
The white clouds master slice that 90g is handled well places the mixed solution of above-mentioned reaction vessel, behind the airtight container, in 90 ℃ of following isothermal reactions 5 days.Treat solution cooling back taking-up mica sheet, adopt deionized water rinsing clean, 100 ℃ of oven dry in following 24 hours.
The tablet that mica surface forms is magnalium carbonate LDHs.The Mg/Al mol ratio is 3.44 among the LDHs, and the load factor of LDHs is 1.28% (percetage by weight).
Embodiment 8
Shelled layer nitric acid dousing of also shearing good white clouds master slice employing 3% 8 hours with fresh, standby after rinsing well with deionized water.
In the 1000mL reaction vessel, with 21.81g Ni (NO
3)
26H
2O and 14.07g Al (NO
3)
39H
2O is dissolved in the 750mL deionized water, and being mixed with the Ni/Al mol ratio is 2:1, and total concentration of metal ions is the solution of 0.15mol/L, adds 60.06g urea and makes it dissolving.
The white clouds master slice that 90g is handled well places the mixed solution of above-mentioned reaction vessel, behind the airtight container, in 120 ℃ of following isothermal reactions 2 days.Treat solution cooling back taking-up mica sheet, adopt deionized water rinsing clean, 100 ℃ of oven dry in following 24 hours.
The tablet that mica surface forms is nickel aluminium carbonate LDHs.The Ni/Al mol ratio is 2.04 among the LDHs, and the load factor of LDHs is 0.92% (percetage by weight).
Embodiment 9
Shelled layer nitric acid dousing of also shearing good white clouds master slice employing 3% 5 hours with fresh, standby after rinsing well with deionized water.
In the 1000mL reaction vessel, with 21.81g Ni (NO
3)
26H
2O and 14.07g Fe (NO
3)
39H
2O is dissolved in the 750mL deionized water, and being mixed with the Ni/Fe mol ratio is 2:1, and total concentration of metal ions is the solution of 0.15mol/L, adds 45.05g urea and makes it dissolving.
The white clouds master slice that 30g is handled well places the mixed solution of above-mentioned reaction vessel, behind the airtight container, in 100 ℃ of following isothermal reactions 3 days.Treat solution cooling back taking-up mica sheet, adopt deionized water rinsing clean, 100 ℃ of oven dry in following 24 hours.
The tablet that mica surface forms is ferronickel carbonate LDHs.The Ni/Fe mol ratio is 1.98 among the LDHs, and the load factor of LDHs is 0.79% (percetage by weight).
Claims (5)
1. be the hydrotalcite-like structuring catalyst of matrix with the mica, it is characterized in that active constituent LDHs grows in the mica sheet surface, the load factor of LDHs counts 0.4～2.5% with the quality percentage composition;
The chemical general formula of LDHs is: [M
2+ 1-xM
3+ x(OH)
2]
X+(CO
3 2-)
X/2YH
2O
M wherein
2+Represent bivalent metal ion Mg
2+, Zn
2+, Ni
2+, Fe
2+, Mn
2+In any; M
3+Represent trivalent metal ion Al
3+, Cr
3+, Fe
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any; M
2+/ M
3+Mol ratio be 1.6～4.5:1; The span of y is 0≤y≤2.
2. according to claim 1 is the hydrotalcite-like structuring catalyst of matrix with the mica, it is characterized in that the load factor of active constituent LDHs counts 1.0～2.0% with the quality percentage composition.
3. according to claim 1 is the hydrotalcite-like structuring catalyst of matrix with the mica, it is characterized in that in the chemical general formula of LDHs M
2+Be Mg
2+Or Ni
2+, M
3+Be Al
3+Or Fe
3+
4. one kind is the preparation method of the hydrotalcite-like structuring catalyst of matrix with the mica, and concrete preparation process is as follows:
A: the mica sheet of fresh stripping layer is cut into difformity and big or small sheet as required, and the salpeter solution with 1～10% soaked 2～5 hours, rinsed well standby with deionized water;
B: in reaction vessel, with solubility divalence inorganic salts M
2+Y and solubility trivalent inorganic salts M
3+Y is mixed with the mixing salt solution that the metal ion total concentration is 0.005～0.5mol/L by the mol ratio of 1.6～4.5:1, and the ratio of urea in [urea]/[Y]=2～6 added reactor and make it to be dissolved in the mixing salt solution; Wherein the ratio of negative ions should satisfy the requirement of charge balance in solubility divalence inorganic salts and the solubility trivalent inorganic salts;
M wherein
2+Be Mg
2+, Zn
2+, Ni
2+, Fe
2+, Mn
2+In any, M
3+Be Al
3+, Cr
3+, Fe
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any, Y is Cl
-, NO
3 -, F
-, Br
-, SO
4 2-In any;
C: the mixed solution that places the good mica sheet of processing of step A step B to be prepared in the ratio of mica/metal ion total amount=50～500g/mol, sealed reaction vessel, isothermal reaction is 1～10 day under 50～180 ℃ of temperature, treat solution cooling back taking-up mica sheet, rinse well with deionized water, oven dry, the LDHs that is synthesized promptly is grown in mica surface, thereby obtains the LDHs structural catalyst.
5. according to claim 5 is the preparation method of the hydrotalcite-like structuring catalyst of matrix with the mica, it is characterized in that:
The described mica material of steps A is muscovite, phlogopite, biotite or lepidolite;
M among the step B
2+Be Mg
2+Or Ni
2+M
3+Be Al
3+Or Fe
3+, Y is NO
3 -
The reaction of step C is under 70～120 ℃ of temperature, isothermal reaction 2～5 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101171855A CN100496726C (en) | 2005-11-03 | 2005-11-03 | Hydrotalcite like structural catalyst with mica as matrix and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101171855A CN100496726C (en) | 2005-11-03 | 2005-11-03 | Hydrotalcite like structural catalyst with mica as matrix and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1768940A CN1768940A (en) | 2006-05-10 |
| CN100496726C true CN100496726C (en) | 2009-06-10 |
Family
ID=36750624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101171855A Expired - Fee Related CN100496726C (en) | 2005-11-03 | 2005-11-03 | Hydrotalcite like structural catalyst with mica as matrix and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100496726C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101507917B (en) * | 2009-04-02 | 2011-01-19 | 北京化工大学 | Solid base catalyst for synthesizing alkanolamide type compound and preparation method thereof |
| CN102343283B (en) * | 2011-07-21 | 2013-07-17 | 北京化工大学 | Vertically aligned layered double hydroxides (LDHs) film and application thereof in structured catalysis |
| CN103570114B (en) * | 2013-10-24 | 2015-03-25 | 上海大学 | Reduction treatment method for nitrates in water |
| CN104857927A (en) * | 2015-05-14 | 2015-08-26 | 北京化工大学 | Vermiculite surface in-situ growth hydrotalcite material and preparation method thereof |
| CN105597722A (en) * | 2015-10-30 | 2016-05-25 | 广东美的制冷设备有限公司 | Composite material and preparation method thereof |
-
2005
- 2005-11-03 CN CNB2005101171855A patent/CN100496726C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1768940A (en) | 2006-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106693945B (en) | Delamination hydrotalcite nano piece based composite catalyst and preparation method thereof | |
| CN100382890C (en) | Aluminium-based pseudo-hydrotalcite structuralization catalyst, and its prepn. method | |
| Funatsu et al. | Synthesis of monolayer platinum nanosheets | |
| CN109772355B (en) | Preparation method of amorphous iron oxyhydroxide/bismuth vanadate composite photocatalytic material | |
| Pal et al. | Hierarchically order porous lotus shaped nano-structured MnO 2 through MnCO 3: chelate mediated growth and shape dependent improved catalytic activity | |
| CN108002443B (en) | MnO for normal-temperature deep mineralising phenolic waste water2The preparation method and application of catalyst | |
| CN112169799B (en) | Method for synthesizing low-carbon olefin by carbon dioxide hydrogenation by iron-based catalyst | |
| CN105688867B (en) | A kind of six prismatics graphene metal organic frame composite and preparation method thereof | |
| CN100496726C (en) | Hydrotalcite like structural catalyst with mica as matrix and preparation method | |
| Liu et al. | Two-dimensional porous γ-AlOOH and γ-Al 2 O 3 nanosheets: hydrothermal synthesis, formation mechanism and catalytic performance | |
| CN105728019A (en) | Application and preparation method of ZSM-5 molecular sieve with mesopores and micropores | |
| CN103203231B (en) | In situ controllable synthesis method for hydrotalcite-supported Pd nano crystal catalysts with different morphologies and application of hydrotalcite-supported Pd nano crystal catalysts in catalysis of Heck reaction | |
| CN108453265A (en) | A kind of Silica Nanotube confinement nano nickel particles and preparation method thereof | |
| CN108559101B (en) | Method for preparing two-dimensional sheet Cu-MOF material | |
| CN104098106A (en) | One-step synthesizing method for hollow type multilevel-hole Fe-Silicalite-1 | |
| Chen et al. | Pt nanoparticles on Ti 3 C 2 T x-based MXenes as efficient catalysts for the selective hydrogenation of nitroaromatic compounds to amines | |
| CN105921155A (en) | High-dispersion supported ruthenium dioxide catalyst and preparing method thereof | |
| CN114570369B (en) | MOFs derived nano-sheet self-assembled hierarchical double-layer hollow nano-material and preparation method thereof | |
| CN102658132A (en) | Preparation method for gold-containing hydrotalcite composite material | |
| CN107349922B (en) | A kind of copper/zirconium oxide-graphene composite carrier catalyst and preparation method and application | |
| CN109092340A (en) | Graphene-supported bismuth oxychloride-basic carbonate bismuth oxide photocatalyst and its preparation method | |
| CN103212396B (en) | Layered bimetal hydroxide with three-layer structure as well as preparation method and using method of layered bimetal hydroxide | |
| CN101565208A (en) | Method for preparing manganic manganous oxide nano-material | |
| CN104841430B (en) | A kind of low-load amount hydrotalcite catalyst for phenol hydroxylation reaction and preparation method thereof | |
| CN114917932B (en) | For CO 2 Photo-reduction synthesis of CO and H 2 Catalyst, preparation method and application thereof |
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: 20090610 Termination date: 20091203 |