CN103212396A - Layered bimetal hydroxide with three-layer structure as well as preparation method and using method of layered bimetal hydroxide - Google Patents
Layered bimetal hydroxide with three-layer structure as well as preparation method and using method of layered bimetal hydroxide Download PDFInfo
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- CN103212396A CN103212396A CN2013101065102A CN201310106510A CN103212396A CN 103212396 A CN103212396 A CN 103212396A CN 2013101065102 A CN2013101065102 A CN 2013101065102A CN 201310106510 A CN201310106510 A CN 201310106510A CN 103212396 A CN103212396 A CN 103212396A
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Abstract
The invention discloses a layered bimetal hydroxide with a three-layer structure as well as a preparation method and a using method of the layered bimetal hydroxide. Rose-shaped micro-particles with secondary structures, which are assembled by LDHs (Lactate Dehydrogenase) sheets with primary structures, are prepared and obtained by utilizing hexamethylene tetramine as precipitators under the guide of sodium stearate; and roasting-hydration restoring treatment is carried out onto the rose-shaped micro-particles and nano-sheets with secondary structures are generated on the LDHs sheets by utilizing memory effect characteristics of the LDHs structures to obtain magnesium-aluminum or calcium-aluminum Mal (Methylacrolein)-LDHs with a tertiary structure, wherein M is Mg or Ca. The staggered and alternated multi-level structure of the material can be used for exposing more interlayer alkali activity centers, so that the material has higher alkali density. The layered bimetal hydroxide with the three-layer structure is used as a solid alkali catalyst for preparing methyl butyrate while being applied to catalyzing ester exchange reaction of tributyrin and carbinol, so that excellent alkali catalytic activity is reflected.
Description
Technical field
The invention belongs to the solid base catalyst technical field, a kind of have tertiary structure layered double hydroxide and preparation thereof, using method particularly are provided, and this material prepares methyl butyrate as the ester exchange reaction that solid base catalyst is used for catalysis tributyrin and methyl alcohol.
Background technology
The structure diversity of inorganic material is all being brought into play important effect at aspects such as the function diversification of material and potential applications.In the synthetic field of material, in order to obtain material more promising and application potential, the controlledly synthesis with inorganic material of specific morphology and high-sequential structure is one and is full of challenging work.Layered double hydroxide (Layered Double Hydroxides is abbreviated as LDHs) is a kind of anionic type laminated material, because of special construction and the composition of LDHs, makes it have many-sided critical nature.In recent years, LDHs class material all is widely used in various aspects such as catalyst, catalyst carrier, polymer composites stabilizing agent, medical material and sewage disposal adsorbents.Therefore, the structure control of LDHs research has caused the deepest concern of increasing researcher.
At present, the LDHs for preparing is mainly primary structure and secondary structure form.Generally, LDHs is the primary structure of hexagonal flake, but we change size and the pattern that the preparation method can control LDHs effectively by the series reaction conditioned disjunction in the modulation LDHs building-up process.At insulating materials .2006,39 (6): among the 28-30, Yan Yan etc. have changed the primary structure feature of LDHs crystal by the modulation to the conditions such as pH value of the character of the charging sequence in the LDHs building-up process, coprecipitation mode, reagent and concentration, nucleation temperature, system, and introduce the influence of different preparation methods to the LDHs shape characteristic.The multilevel hierarchy of considering LDHs can make the character of material itself and application performance be improved, and the LDHs of secondary structure becomes the focus of people's research.At Applied Clay Science, among the 2007 37:23 – 31, Kentaro Okamoto etc. are under hydrothermal synthesizing condition, investigate different metal salt (chlorate and nitrate) and precipitating reagent (urea and hexamethylenetetramine) to the influence of LDHs pattern, prepared to Success in Experiment rose-shaped secondary structure MgAl-LDHs.On this basis, people have also studied the influence of the introducing of additive to the LDHs architectural feature, and what usually add has various large biological molecules, surfactant, a big molecule organic additive etc.In Ind. Eng. Chem. Res. 2010 49:2759-2767, Hui Wang etc. are in sodium alginate aqueous solution, modulation by to synthetic parameters such as hydrothermal crystallizing time, concentration of salt solution and reaction temperatures has successfully prepared bobbles shape, marigold shape and coralloid secondary structure NiAl-LDHs.At Materials Research Bulletin, among 2011 46:1922-1927, Lingna Sun etc. have prepared rose-shaped respectively and the secondary structure MgAl-LDHs chrysanthemum shape by solvent thermal method in softex kw (CTAB) aqueous solution.
Summary of the invention
The purpose of this invention is to provide a kind of have tertiary structure layered double hydroxide and preparation thereof, using method, up to the present, the report of tertiary structure LDHs preparation is not arranged also.The staggered multilevel hierarchy that interts of this material is exposed more interlayer basic active center and makes the LDHs material have higher basic sites density.It is prepared methyl butyrate as the ester exchange reaction that solid base catalyst is applied to catalysis tributyrin and methyl alcohol, show good base catalysis activity.The tertiary structure LDHs material that utilizes the present invention to prepare is compared with the secondary structure material with one-level in the past, not only at catalytic field, also will show more excellent performance at other fields such as separation, absorption.
The present invention utilizes hexamethylenetetramine to be precipitating reagent, under the odium stearate guiding, prepare the rose-shaped micron particles of secondary structure that is assembled into by primary structure LDHs sheet, again it is carried out roasting-hydration and restore processing, utilize the structure memory effect characteristic of LDHs self, on the LDHs sheet, generate the nanometer sheet of aggregated(particle) structure, obtain having the magnalium of tertiary structure or calcium aluminium MAl-LDHs (M=Mg, Ca).
Wherein, primary structure LDHs chip size is distributed as 0.5-1 μ m, and the secondary particle particle diameter of being assembled by primary structure is distributed as 1-5 μ m, and the nanometer sheet Size Distribution of aggregated(particle) structure is 50-100nm on the LDHs sheet, and the specific area of MAl-LDHs is 70-150 m
2/ g, the alkali bit density is 0.1-0.5 mmol/g.
Above-mentioned tertiary structure LDHs preparation methods is as follows:
(1) odium stearate is dissolved in compound concentration is 0.01～0.1mol/L solution A in the deionized water;
(2) obtain M (NO with the deionized water preparation
3)
2And Al (NO
3)
3Mixing salt solution, wherein divalent metal M represents a kind of among Mg and the Ca, M
2+Concentration be 0.01～0.5mol/L, M
2+With Al
3+Molar concentration rate is 1～10; Again solution A is joined in this solution to stir and obtain mixed solution B, and make M in the mixed solution
2+With the molar concentration rate of odium stearate be 1～50:1;
(3) hexamethylenetetramine is added in the solution B, make that hexamethylenetetramine concentration is 0.1～1mol/L in the solution, stir it is fully dissolved;
(4) above-mentioned mixed solution is transferred in the autoclave, 80～180 ℃ of following crystallization 1～48 hour, preferable crystallization condition is 120～160 ℃ of following crystallization 4～12 hours, after reaction finishes, naturally cool to room temperature, centrifugation goes out solid product, centrifuge washing is to upper strata clear liquid pH value=7～8, use ethanol, the residual odium stearate of acetone soln flush away again, filter cake is placed baking oven, 60～120 ℃ of dryings 8～24 hours, obtain secondary structure layered double hydroxide MAl-LDHs.
(5) the secondary structure layered double hydroxide LDHs that previous step is obtained places high temperature resistance furnace (Muffle furnace), under air atmosphere, slowly is warmed up to 400-700 ℃ and roasting insulation 3-12h with the heating rate of 1-10 ℃/min.To be cooled to room temperature, obtain product of roasting.
(6) take by weighing the 1g product of roasting and join in the 250ml four-hole boiling flask, in bottle, add 100ml again and remove CO
2Deionized water, at N
2Protection is fully stirred 3-12h with the rotating speed of 1200rpm down.After reaction finished, cool to room temperature with the products therefrom centrifugation, took off layer precipitation and places the 40-120 ℃ of dry 3-12h of baking oven, obtains tertiary structure layered double hydroxide MAl-LDHs.
Tertiary structure layered double hydroxide MAl-LDHs is applied to as solid base catalyst in the ester exchange reaction of tributyrin and methyl alcohol and prepares methyl butyrate, reaction conversion ratio is 80-100%, and the productive rate of methyl butyrate is 85-95 %.
Secondary that embodiment 1 is prepared and tertiary structure LDHs carry out XRD and SEM respectively and characterize, and the results are shown in Figure 1 and Fig. 2.By the XRD spectra of secondary structure MgAl-LDHs among Fig. 1 a as can be seen, the 2 θ angles of (00l) serial diffraction maximum on the c axialite face of hydrotalcite ((003), (006), (009), (0012), (0015), (0018) and (0021)) are good multiple relation, crystal formation is good, be typical layer structure, the rose-shaped secondary structure form (as Fig. 2 a shown in) of its pattern for being assembled into by primary structure LDHs.By the XRD spectra of the tertiary structure MgAl-LDHs of Fig. 1 b as can be seen, magnalium bimetallic oxide characteristic peak disappears, and the characteristic diffraction peak of LDHs occurs once again, but broadens and die down than the characteristic diffraction peak of secondary structure LDHs, illustrates that the crystalline size of LDHs reduces.Find out that from Fig. 2 b hydration has generated the nanometer sheet of structure many times after restoring on the LDHs of primary structure sheet, obtained having the tertiary structure anionic type laminated material.
Get 15mL methyl alcohol with graduated cylinder and be put in the autoclave, get the 3mL butyrin with pipette again and place autoclave, magneton stirs 3min.Add 0.25g tertiary structure catalyst in still, sealed environment charges into nitrogen in still, venting, to such an extent as to so exchange the interior normal pressure nitrogen environment of stills No. three times, oil bath is reacted 12h down for 65 ℃, makes the conversion ratio of ester exchange reaction and the productive rate of methyl butyrate be respectively 80-100 % and 85-95 %.The conversion ratio of the ester exchange reaction that the anionic type laminated material of the tertiary structure that Fig. 3 obtains for embodiment 2 records as solid base catalyst and the time dependent curve of productive rate of methyl butyrate.
The present invention has following remarkable result: (1) is under the condition that surfactant exists, prepare the LDHs of rose-shaped secondary structure by hydrothermal synthesis method, and utilize the memory effect characteristic of LDHs, adopt roasting-hydration restored method to prepare the anionic type laminated material of tertiary structure; (2) the staggered multilevel hierarchy that interts of LDHs material allows more basic active center be exposed and makes material have higher basic active bit density, helps base catalyzed reactions; (3) anionic type laminated material of tertiary structure is applied to as solid base catalyst in the ester exchange reaction of tributyrin and methyl alcohol and prepares methyl butyrate, reaction conversion ratio is 80-100 %, the productive rate of methyl butyrate is 85-95 %, has potential actual application value.
Description of drawings
Fig. 1 is the secondary for preparing in the embodiment of the invention 1 and the XRD spectra of tertiary structure LDHs.
Fig. 2 is the secondary for preparing in the embodiment of the invention 1 and the SEM photo of tertiary structure LDHs.
Fig. 3 is the curve of the productive rate of the conversion ratio of ester exchange reaction in the embodiment of the invention 2 and methyl butyrate with the reaction time.
The specific embodiment
Embodiment 1
Taking by weighing the 0.9870g odium stearate is dissolved in the 40ml deionized water and is formulated as solution A; Take by weighing 2.0512gMg (NO
3)
26H
2O and 1.5005gAl (NO
3)
39H
2O is dissolved in the 40mL deionized water and is mixed with metal salt solution, is stirred to dissolve fully in the back adding solution A, evenly mixes; Take by weighing the 3.9254g hexamethylenetetramine, be dissolved in the above-mentioned mixed solution; The mixed solution that obtains is transferred in the 100ml water heating kettle, 150 ℃ of following crystallizations 6 hours.Gained precipitation is centrifugal to upper strata clear liquid pH value=7 through washing, and filter cake is placed 70 ℃ oven drying 12 hours, can obtain secondary structure MgAl-LDHs.
Secondary structure MgAl-LDHs is placed high temperature resistance furnace (Muffle furnace), under air atmosphere, slowly be warmed up to 500 ℃ and roasting insulation 8h with the heating rate of 2 ℃/min.To be cooled to room temperature, obtain product of roasting.Take by weighing the 1g product of roasting and join in the 250ml four-hole boiling flask, in bottle, add 100ml again and remove CO
2Deionized water, at N
2Protection is fully stirred 6h with the rotating speed of 1200rpm down.After reaction finishes, cool to room temperature, centrifugation obtains precipitation, and places 40 ℃ of dry 12h of vacuum drying chamber, obtains tertiary structure MgAl-LDHs.Its primary structure LDHs chip size is distributed as 0.7 μ m, and the secondary particle particle diameter of being assembled by primary structure is distributed as 3 μ m, and the LDHs nanometer sheet Size Distribution of aggregated(particle) structure is 78nm on the primary structure LDHs sheet, and the material specific area is 83m
2/ g, basic sites density is 0.2178mmol/g.
Get 15mL methyl alcohol with graduated cylinder and be put in the autoclave, get the 3mL butyrin with pipette again and place autoclave, magneton stirs 3min.Add 0.25g tertiary structure catalyst in still, sealed environment charges into nitrogen in still, venting, to such an extent as to so exchange the interior normal pressure nitrogen environment of still No. three times, oil bath is reacted 12h down for 65 ℃.After reaction finished, the conversion ratio of ester exchange reaction was 90.63%, and the productive rate of methyl butyrate is 89.12 %.
Embodiment 2
Taking by weighing the 0.4935g odium stearate is dissolved in the 40ml deionized water and is formulated as solution A; Take by weighing 2.3076gMg (NO
3)
26H
2O and 1.1256gAl (NO
3)
39H
2O is dissolved in the 40mL deionized water and is mixed with metal salt solution, is stirred to dissolve fully in the back adding solution A, evenly mixes; Take by weighing the 3.9254g hexamethylenetetramine, be dissolved in the above-mentioned mixed solution; The mixed solution that obtains is transferred in the 100ml water heating kettle, 120 ℃ of following crystallizations 12 hours.Gained precipitation is centrifugal to upper strata clear liquid pH value=7 through washing, and filter cake is placed 70 ℃ oven drying 12 hours, can obtain secondary structure MgAl-LDHs.
Secondary structure MgAl-LDHs is placed high temperature resistance furnace (Muffle furnace), under air atmosphere, slowly be warmed up to 600 ℃ and roasting insulation 12h with the heating rate of 5 ℃/min.To be cooled to room temperature, obtain product of roasting.Take by weighing the 1g product of roasting and join in the 250ml four-hole boiling flask, in bottle, add 100ml again and remove CO
2Deionized water, at N
2Protection is fully stirred 3h with the rotating speed of 1200rpm down.After reaction finishes, cool to room temperature, centrifugation obtains precipitation, and places 40 ℃ of dry 12h of vacuum drying chamber, obtains tertiary structure MgAl-LDHs.Its primary structure LDHs chip size is distributed as 0.4 μ m, and the secondary particle particle diameter of being assembled by primary structure is distributed as 2 μ m, and the LDHs nanometer sheet Size Distribution of aggregated(particle) structure is 62nm on the primary structure LDHs sheet, and the material specific area is 96m
2/ g, basic sites density is 0.2563mmol/g.
Get 15mL methyl alcohol with graduated cylinder and be put in the autoclave, get the 3mL butyrin with pipette again and place autoclave, magneton stirs 3min.Add 0.25g tertiary structure catalyst in still, sealed environment charges into nitrogen in still, venting, to such an extent as to so exchange the interior normal pressure nitrogen environment of still No. three times, oil bath is reacted 12h down for 65 ℃.After reaction finished, the conversion ratio of ester exchange reaction was 97.12%, and the productive rate of methyl butyrate is 86.69 %.
Embodiment 3
Taking by weighing the 0.9870g odium stearate is dissolved in the 40ml deionized water and is formulated as solution A; Take by weighing 2.3076gMg (NO
3)
26H
2O and 1.1256gAl (NO
3)
39H
2O is dissolved in the 40mL deionized water and is mixed with metal salt solution, is stirred to dissolve fully in the back adding solution A, evenly mixes; Take by weighing 1.9627g hexamethylenetetramine (HMT), be dissolved in the above-mentioned mixed solution; The mixed solution that obtains is transferred in the 100ml water heating kettle, 130 ℃ of following crystallizations 10 hours.Gained precipitation is centrifugal to upper strata clear liquid pH value=7 through washing, and filter cake is placed 70 ℃ oven drying 12 hours, can obtain secondary structure MgAl-LDHs.
Secondary structure MgAl-LDHs is placed high temperature resistance furnace (Muffle furnace), under air atmosphere, slowly be warmed up to 450 ℃ and roasting insulation 3h with the heating rate of 3 ℃/min.To be cooled to room temperature, obtain product of roasting.Take by weighing the 1g product of roasting and join in the 250ml four-hole boiling flask, in bottle, add 100ml again and remove CO
2Deionized water, at N
2Protection is fully stirred 6h with the rotating speed of 1200rpm down.After reaction finishes, cool to room temperature, centrifugation obtains precipitation, and places 40 ℃ of dry 12h of vacuum drying chamber, obtains tertiary structure MgAl-LDHs.Its primary structure LDHs chip size is distributed as 0.8 μ m, and the secondary particle particle diameter of being assembled by primary structure is distributed as 4 μ m, and the LDHs nanometer sheet Size Distribution of aggregated(particle) structure is 84nm on the primary structure LDHs sheet, and the material specific area is 73m
2/ g, basic sites density is 0.1815mmol/g.
Get 15mL methyl alcohol with graduated cylinder and be put in the autoclave, get the 3mL butyrin with pipette again and place autoclave, magneton stirs 3min.Add 0.25g tertiary structure catalyst in still, sealed environment charges into nitrogen in still, venting, to such an extent as to so exchange the interior normal pressure nitrogen environment of still No. three times, oil bath is reacted 12h down for 65 ℃.After reaction finished, the conversion ratio of ester exchange reaction was 86.30%, and the productive rate of methyl butyrate is 92.63 %.
Embodiment 4
Taking by weighing the 0.9870g odium stearate is dissolved in the 40ml deionized water and is formulated as solution A; Take by weighing 1.8892gCa (NO
3)
24H
2O and 1.1256gAl (NO
3)
39H
2O is dissolved in the 40mL deionized water and is mixed with metal salt solution, is stirred to dissolve fully in the back adding solution A, evenly mixes; Take by weighing the 3.9254g hexamethylenetetramine, be dissolved in the above-mentioned mixed solution; The mixed solution that obtains is transferred in the 100ml water heating kettle, 160 ℃ of following crystallizations 8 hours.Gained precipitation is centrifugal to upper strata clear liquid pH value=7 through washing, and filter cake is placed 70 ℃ oven drying 12 hours, can obtain secondary structure CaAl-LDHs.
Secondary structure CaAl-LDHs is placed high temperature resistance furnace (Muffle furnace), under air atmosphere, slowly be warmed up to 500 ℃ and roasting insulation 6h with the heating rate of 2 ℃/min.To be cooled to room temperature, obtain product of roasting.Take by weighing the 1g product of roasting and join in the 250ml four-hole boiling flask, in bottle, add 100ml again and remove CO
2Deionized water, at N
2Protection is fully stirred 3h with the rotating speed of 1200rpm down.After reaction finishes, cool to room temperature, centrifugation obtains precipitation, and places 40 ℃ of dry 12h of vacuum drying chamber, obtains tertiary structure CaAl-LDHs.Its primary structure LDHs chip size is distributed as 0.5 μ m, and the secondary particle particle diameter of being assembled by primary structure is distributed as 3 μ m, and the LDHs nanometer sheet Size Distribution of aggregated(particle) structure is 70nm on the primary structure LDHs sheet, and the material specific area is 85m
2/ g, basic sites density is 0.2265mmol/g.
Get 15mL methyl alcohol with graduated cylinder and be put in the autoclave, get the 3mL butyrin with pipette again and place autoclave, magneton stirs 3min.Add 0.25g tertiary structure catalyst in still, sealed environment charges into nitrogen in still, venting, to such an extent as to so exchange the interior normal pressure nitrogen environment of still No. three times, oil bath is reacted 12h down for 65 ℃.After reaction finished, the conversion ratio of ester exchange reaction was 94.12%, and the productive rate of methyl butyrate is 88.69 %.
Claims (3)
1. one kind has the tertiary structure layered double hydroxide, it is characterized in that, utilize hexamethylenetetramine to be precipitating reagent, under the odium stearate guiding, prepare the rose-shaped micron particles of secondary structure that is assembled into by primary structure LDHs sheet, again it is carried out roasting-hydration and restore processing, utilize the structure memory effect characteristic of LDHs self, on the LDHs sheet, generate the nanometer sheet of aggregated(particle) structure, obtain having the MAl-LDHs of tertiary structure, M is Mg or Ca;
Wherein, primary structure LDHs chip size is distributed as 0.5-1 μ m, and the secondary particle particle diameter of being assembled by primary structure is distributed as 1-5 μ m, and the nanometer sheet Size Distribution of aggregated(particle) structure is 50-100nm on the LDHs sheet, and the specific area of MAl-LDHs is 70-150 m
2/ g, the alkali bit density is 0.1-0.5 mmol/g.
2. described preparation method with tertiary structure layered double hydroxide of claim 1 is characterized in that processing step is as follows:
(1) odium stearate is dissolved in compound concentration is 0.01～0.1mol/L solution A in the deionized water;
(2) obtain M (NO with the deionized water preparation
3)
2And Al (NO
3)
3Mixing salt solution, wherein divalent metal M represents a kind of among Mg and the Ca, M
2+Concentration be 0.01～0.5mol/L, M
2+With Al
3+Molar concentration rate is 1～10; Again solution A is joined in this solution to stir and obtain mixed solution B, and make M in the mixed solution
2+With the molar concentration rate of odium stearate be 1～50:1;
(3) hexamethylenetetramine is added in the solution B, make that hexamethylenetetramine concentration is 0.1～1mol/L in the solution, stir it is fully dissolved;
(4) above-mentioned mixed solution is transferred in the autoclave, 80～180 ℃ of following crystallization 1～48 hour, preferable crystallization condition is 120～160 ℃ of following crystallization 4～12 hours, and reaction naturally cools to room temperature after finishing, centrifugation goes out solid product, centrifuge washing is used ethanol, the residual odium stearate of acetone soln flush away again to upper strata clear liquid pH value=7～8, and filter cake is placed baking oven, 60～120 ℃ of dryings 8～24 hours, obtain the secondary structure layered double hydroxide.
(5) the secondary structure layered double hydroxide that previous step is obtained places high temperature resistance furnace, under air atmosphere, slowly is warmed up to 400-700 ℃ and roasting insulation 3-12h with the heating rate of 1-10 ℃/min.To be cooled to room temperature, obtain product of roasting.
(6) take by weighing the 1g product of roasting and join in the 250ml four-hole boiling flask, in bottle, add 100ml again and remove CO
2Deionized water, at N
2Protection is fully stirred 3-12h with the rotating speed of 1200rpm down.After reaction finished, cool to room temperature with the products therefrom centrifugation, took off layer precipitation and places the 40-120 ℃ of dry 3-12h of baking oven, obtains the tertiary structure layered double hydroxide.
3. the using method of the layered double hydroxide of the described tertiary structure of claim 1, it is characterized in that, MAl-LDHs is applied to as solid base catalyst in the ester exchange reaction of tributyrin and methyl alcohol and prepares methyl butyrate, reaction conversion ratio is 80-100%, and the productive rate of methyl butyrate is 85-95 %.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105642263A (en) * | 2014-11-14 | 2016-06-08 | 辽宁奥克化学股份有限公司 | A preparing method of a modified layered bi-metal oxide |
| CN106944028A (en) * | 2017-03-21 | 2017-07-14 | 北京化工大学 | A kind of preparation method of the graphene-based complex solid base catalyst of 3D structures |
| CN108585064A (en) * | 2018-05-14 | 2018-09-28 | 北京化工大学 | A kind of multilevel hierarchy metal oxide gas sensitive and preparation method thereof |
| CN110586079A (en) * | 2019-09-23 | 2019-12-20 | 湘潭大学 | Preparation and application of layered CaMnAl hydrotalcite solid base catalyst |
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| CN101096015A (en) * | 2006-06-30 | 2008-01-02 | 北京化工大学 | Sphericity spinel material with cage construction and method for preparing the same |
| CN101456566A (en) * | 2007-12-13 | 2009-06-17 | 北京理工大学 | Method for preparing regeneration circular used acid wastewater treating agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101096015A (en) * | 2006-06-30 | 2008-01-02 | 北京化工大学 | Sphericity spinel material with cage construction and method for preparing the same |
| CN101456566A (en) * | 2007-12-13 | 2009-06-17 | 北京理工大学 | Method for preparing regeneration circular used acid wastewater treating agent |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105642263A (en) * | 2014-11-14 | 2016-06-08 | 辽宁奥克化学股份有限公司 | A preparing method of a modified layered bi-metal oxide |
| CN106944028A (en) * | 2017-03-21 | 2017-07-14 | 北京化工大学 | A kind of preparation method of the graphene-based complex solid base catalyst of 3D structures |
| CN108585064A (en) * | 2018-05-14 | 2018-09-28 | 北京化工大学 | A kind of multilevel hierarchy metal oxide gas sensitive and preparation method thereof |
| CN110586079A (en) * | 2019-09-23 | 2019-12-20 | 湘潭大学 | Preparation and application of layered CaMnAl hydrotalcite solid base catalyst |
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