CN102838145B - New method for synthesizing high specific surface magnesium-aluminum spinel - Google Patents
New method for synthesizing high specific surface magnesium-aluminum spinel Download PDFInfo
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- CN102838145B CN102838145B CN201110170697.3A CN201110170697A CN102838145B CN 102838145 B CN102838145 B CN 102838145B CN 201110170697 A CN201110170697 A CN 201110170697A CN 102838145 B CN102838145 B CN 102838145B
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- magnesium
- spinel
- aluminium
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Abstract
The invention relates to a new method for synthesizing high specific surface magnesium-aluminum spinel. A specific surface of the magnesium-aluminum spinel synthesized by the method of the present invention can be up to 301.13 m<2>g<-1> and 310.95 m<2>g<-1>. Technical characteristics of the synthesis method of the present invention comprise: adopting inexpensive pseudo boehmite and magnesium nitrate as an aluminum source and a magnesium source, firstly preparing magnesium-rich and aluminum-rich spinel, then carrying out a treatment by using a nitric acid solution with a certain concentration, and dissolving the surplus magnesium or the surplus aluminum, such that gaps between the spinel particles are increased so as to obtain the high specific surface magnesium-aluminum spinel with a stoichiometric ratio.
Description
Technical field
The present invention relates to a kind of novel method of synthetic high-ratio surface magnesium-aluminium spinel, the method belongs to the improvement of petroleum refining technology.The technical characterstic of the method has been to use cheap pseudo-boehmite and magnesium nitrate as He Mei source, aluminium source, the magnesium-aluminium spinel of first preparing rich magnesium and rich aluminium, then with certain density salpeter solution, process, by magnesium more than needed or al dissolution, space between spinel particle is increased, obtain the magnesium-aluminium spinel of the metering ratio of high-ratio surface.
Prior art
Magnesium-aluminium spinel is owing to having chemical stability, thermostability and the higher physical strength of high-melting-point, excellence, and it is applied to environmental catalysis, refining of petroleum and field of fine chemical more and more as catalyzer or support of the catalyst.When it is used as support of the catalyst or catalyzer, conventionally need it to there is high-ratio surface, little crystal grain and special active sites.For example, when being applied to FCC system as sulfur transfer additive, it removes the SO in revivifier
2time, remove SO
2activity and specific surface have substantial connection, specific surface increases, SO
2the probability contacting with the active centre of spinel increases, and is more conducive to SO
2absorption.
A kind of solution is the nano level spinel particle of preparation.Preparation method and experiment condition have very important impact to the chemical property of nano level magnesium-aluminium spinel and constitutional features, and then affect catalysis and other physicochemical property of spinel.
Based on metal oxide and or salt roasting solid state reaction synthetic MgAl spinal be a kind of comparatively early stage traditional method, synthesis temperature is very high, even if add mineralizer, ZnO auxiliary agent or sintering aid AlCl
3deng also, help not quite, synthetic spinel particle easy-sintering, specific surface is lower.In addition, it is synthetic that spinel particle also can adopt the decomposition etc. of sol-gel method, spray-drying process, complexometry, the precipitator method and metal alkoxide.Magnesium-aluminium spinel prepared by the use magnesium nitrates such as Wang Jinan and sodium metaaluminate coprecipitation method is 147m
2g
-1.Coprecipitation method needs the Na of a large amount of deionized water wash remnants
+, and the control of pH value is also needed comparatively accurate, be unwell to industrial mass production.Conventional sol-gel method forms gel mainly with metal alkoxide hydrolysis, polymerization greatly, and synthetic spinel specific surface is mostly at 50-150m
2g
-1in scope.The improved sol-gel method of the employings such as Guo has been synthesized nano spinel powder, this method combines gel and precipitation process, can under high-temperature roasting condition, synthesize the spinel of high-ratio surface, the spinel specific surface obtaining at 800 ℃ and 950 ℃ of roasting 8h is respectively 182 and 136m
2g
-1.But this method need to add a large amount of high molecular polymer PVA, and PVA add-on increases, and the specific surface of the spinel obtaining is corresponding increase also.Adding of PVA increases cost and the energy consumption of preparing magnesium-aluminium spinel greatly, and is only applicable to laboratory scale.
Summary of the invention
The object of the invention is to the magnesium-aluminium spinel with the synthetic high-ratio surface of a kind of comparatively simple method, and raw materials cost and energy consumption all lower.
Using pseudo-boehmite and magnesium nitrate respectively as He Mei source, aluminium source, first prepare the magnesium-aluminium spinel of rich magnesium and rich aluminium, then with certain density salpeter solution, process, by magnesium more than needed or al dissolution, obtain the magnesium-aluminium spinel of the metering ratio of high-ratio surface.
Concrete preparation process is:
1) first prepare magnesium-aluminium spinel: first pseudo-boehmite and diluted hydrochloric acid aqueous solution mix and blend 1h are formed to aluminium colloidal sol.Again a certain amount of magnesium nitrate and deionized water are added to and in colloidal sol, stir 2h.After 120 ℃ of oven dryings, roasting 4h in 700 ℃ of retort furnaces.The solid abrasive obtaining is pulverized, and obtaining granularity is the rich magnesium of 80-180 object or rich magnalium aluminate.The magnesium-aluminium spinel of in kind preparation metering ratio as a comparison simultaneously.
2), by rich magnesium or rich magnalium aluminate and certain density salpeter solution mix and blend 2h, after filtering, being dried, repeat identical step 3 time, finally by roasting 2h in 700 ℃ of retort furnaces of sample.
Drawing explanation
Accompanying drawing 1 is that different magnaliums are than the XRD spectra of lower synthetic magnesium-aluminium spinel
Accompanying drawing 2 is that different magnaliums are than the N of lower synthetic magnesium-aluminium spinel
2-adsorption/desorption curve
Accompanying drawing 3 are different magnaliums than under magnesium-aluminium spinel nitric acid treatment after N
2-adsorption/desorption curve
Embodiment
Below in conjunction with embodiment, carry out enumeration technical characterstic of the present invention.
Embodiment 1
First pseudo-boehmite (is contained to Al
2o
3massfraction be 68%) 30g and 120g deionized water mix and blend, more dropwise splash into 4.05g dilute hydrochloric acid solution (HCl massfraction is 36.5%), continue to stir 1h and form aluminium colloidal sol.Again by 51.28gMg (NO
3)
26H
2o and deionized water are added to and in colloidal sol, stir 2h.After 120 ℃ of oven dryings, roasting 4h in 700 ℃ of retort furnaces, obtains measuring the magnesium-aluminium spinel of ratio after grinding.
Embodiment 2
First pseudo-boehmite (is contained to Al
2o
3massfraction be 68%) 30g and 120g deionized water mix and blend, more dropwise splash into 4.05g dilute hydrochloric acid solution (HCl massfraction is 36.5%), continue to stir 1h and form aluminium colloidal sol.Again by 102.56gMg (NO
3)
26H
2o and deionized water are added to and in colloidal sol, stir 2h.After 120 ℃ of oven dryings, roasting 4h in 700 ℃ of retort furnaces, obtains rich magnesium aluminate spinel MgAl after grinding
2o
4mgO.
Embodiment 3
First pseudo-boehmite (is contained to Al
2o
3massfraction be 68%) 60g and 240g deionized water mix and blend, more dropwise splash into 8.10g dilute hydrochloric acid solution (HCl massfraction is 36.5%), continue to stir 1h and form aluminium colloidal sol.Again by 51.28gMg (NO
3)
26H
2o and deionized water are added to and in colloidal sol, stir 2h.After 120 ℃ of oven dryings, roasting 4h in 700 ℃ of retort furnaces, obtains rich magnalium aluminate MgAl after grinding
2o
4al
2o
3.
Embodiment 4
Get rich magnesium aluminate spinel MgAl
2o
4mgO 15g, adds 75g deionized water, more dropwise splashes into 3.58g salpeter solution (HNO
3massfraction is 65%), under room temperature, stir after 2h, filter, wash and be dried, then repeat this process 2 times, in last 700 ℃ of retort furnaces, roasting 2h obtains product and is designated as MgAl
2o
4mgO-HNO
3.
Embodiment 5
Get rich magnalium aluminate MgAl
2o
4al
2o
315g, adds 75g deionized water, more dropwise splashes into 7.16g salpeter solution (HNO
3massfraction is 65%), under room temperature, stir after 2h, filter, wash and be dried, then repeat this process 2 times, in last 700 ℃ of retort furnaces, roasting 2h obtains product and is designated as MgAl
2o
4al
2o
3-HNO
3.
The thing of sample adopts the X ' Pert PRO MPD diffractometer of Dutch PANalytical company to measure mutually, CuK α, and tube voltage is 40kV, tube current is 40mA, 0.0167 ° of scanning wavelength.The XRD spectra of the magnesium-aluminium spinel of the rich magnesium before and after nitric acid treatment or rich magnalium aluminate and metering ratio is shown in Fig. 1.
As seen from Figure 1, compare with the magnesium-aluminium spinel of metering, in the magnesium-aluminium spinel of rich magnesium, occurred the characteristic peak of sharp-pointed free MgO, and the characteristic peak intensity of Spinel is lower slightly; And without other impurity phases, occur in the magnesium-aluminium spinel of rich aluminium, the characteristic peak intensity of same Spinel is slightly lower than the spinel of metering ratio, illustrates that the crystal grain of spinel in the spinel of rich magnesium and rich aluminium is all less.Use HNO
3after solution is repeatedly processed, in the magnesium-aluminium spinel of rich magnesium, free MgO disappears mutually, and the characteristic peak intensity of Spinel significantly strengthens; The magnesium-aluminium spinel phase of rich aluminium does not change, and only the peak intensity of Spinel increases to some extent.Show through HNO
3after processing, in the spinel of rich magnesium and rich aluminium, the crystal grain of spinel all increases.
On ASAP 2010 physical adsorption appearances of the U.S. Micromeritics company that is determined at of the adsorption/desorption isotherms of sample and pore size distribution, carry out, with high-purity N
2for adsorption medium, the liquid nitrogen (196 ℃) of take is cold-trap.
N
2-adsorption/desorption curve (Fig. 2,3) shows, resulting spinel is mesoporous material.MgAl
2o
4and MgAl
2o
4the hysteresis loop shape approximation of MgO is in H2 type, and duct may be round shape; And MgAl
2o
4al
2o
3hysteresis loop belong to H3 type, should be slit-shaped duct.After the magnesium-aluminium spinel nitric acid treatment of rich magnesium and rich aluminium, the change in shape of hysteresis loop is little, but the starting point of hysteresis loop will, higher than the spinel before untreated, show that nitric acid treatment back aperture all increases.
The different magnaliums of table 1 are than the specific surface of lower synthetic magnesium-aluminium spinel and pore structure character
From specific surface and pore structure character (table 1), the specific surface of magnesium-rich spinel only slightly increases with metering Spinel ratio, and the specific surface of aluminium riched spinel is larger, and this may be owing to containing more Al in solid now
2o
3relevant.The mean pore size of aluminium riched spinel is starkly lower than other both.But after the rich magnesium of nitric acid treatment and aluminium riched spinel, the specific surface of the two and aperture all obviously increase.MgAl wherein
2o
4the specific surface of MgO is by 100.49m
2g
-1increase to 301.13m
2g
-1, pore volume is by 0.195cm
3g
-1increase to 0.555cm
3g
-1.And Mg Al
2o
4al
2o
3specific surface by 133.28m
2g
-1increase to 310.95m
2g
-1, pore volume is by 0.203cm
3g
-1increase to 0.450cm
3g
-1.
Claims (1)
1. the method for a synthetic high-ratio surface magnesium-aluminium spinel, the method is to using respectively pseudo-boehmite and magnesium nitrate as He Mei source, aluminium source, it is characterized in that first preparing the magnesium-aluminium spinel of rich magnesium and rich aluminium, then with certain density salpeter solution, process, by magnesium more than needed or al dissolution, obtain the magnesium-aluminium spinel of the metering ratio of high-ratio surface, concrete preparation process is:
(1) first prepare magnesium-aluminium spinel: first pseudo-boehmite and diluted hydrochloric acid aqueous solution mix and blend are formed to aluminium colloidal sol for 1 hour, again a certain amount of magnesium nitrate and deionized water are added in colloidal sol and are stirred 2 hours, after 120 ℃ of oven dryings, in 700 ℃ of retort furnaces, roasting is 4 hours, the solid abrasive obtaining is pulverized, obtaining granularity is the rich magnesium of 80～180 objects or rich magnalium aluminate, and the magnesium-aluminium spinel of in kind preparation metering ratio as a comparison simultaneously;
(2) by rich magnesium or rich magnalium aluminate and certain density salpeter solution mix and blend 2 hours, filter, repeat identical step 3 time after dry, finally by roasting in 700 ℃ of retort furnaces of sample 2 hours, can obtain the magnesium-aluminium spinel of high-ratio surface.
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| CN104549197B (en) * | 2015-01-30 | 2017-03-29 | 陕西科技大学 | A kind of MgA12O4The preparation method of spinelle Reforming catalyst agent carrier |
| CN106187228A (en) * | 2016-07-11 | 2016-12-07 | 河南和成无机新材料股份有限公司 | A kind of high magnesia spinel and its preparation method and application |
| CN106478088A (en) * | 2016-10-27 | 2017-03-08 | 张旭 | The preparation method of the magnesium aluminate spinel of controllable oxidization aluminium content |
| CN108658740A (en) * | 2018-06-25 | 2018-10-16 | 徐州得铸生物科技有限公司 | A kind of synthetic method of the chloro- 1- chloracetyls cyclopropane of 1- |
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