CN102838145A - 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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- CN102838145A CN102838145A CN2011101706973A CN201110170697A CN102838145A CN 102838145 A CN102838145 A CN 102838145A CN 2011101706973 A CN2011101706973 A CN 2011101706973A CN 201110170697 A CN201110170697 A CN 201110170697A CN 102838145 A CN102838145 A CN 102838145A
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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, this method belongs to the improvement of petroleum refining technology.The technical characterstic of this method has been to use cheap pseudo-boehmite and magnesium nitrate as aluminium source and magnesium source; The magnesium-aluminium spinel for preparing rich magnesium and rich aluminium earlier; Handle with certain density salpeter solution then; With magnesium or al dissolution more than needed, make that the space between spinel particle increases, obtain the magnesium-aluminium spinel of the metering ratio of high-ratio surface.
Prior art
Magnesium-aluminium spinel is owing to have chemicalstability, thermostability and the higher physical strength of HMP, 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, need it to have high-ratio surface, little crystal grain and special active sites usually.For example, when being applied to the FCC system as sulfur transfer additive, it removes the SO in the revivifier
2The time, remove SO
2Activity and specific surface substantial connection is arranged, specific surface increases, SO
2The probability that contacts with the active site of spinel increases, and more helps SO
2Absorption.
A kind of solution is the nano level spinel particle of preparation.Preparing method and experiment condition have very important influence to the chemical property and the constitutional features of nano level magnesium-aluminium spinel, and then influence the catalysis and other physicochemical property of spinel.
Based on MOX with or salt roasting solid state reaction synthetic MgAl spinal be a kind of comparatively early stage traditional method, synthesis temperature is very high, even add mineralizer, ZnO auxiliary agent or sintering aid AlCl
3Help not quite Deng also, 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.Wang Jinan etc. use the magnesium-aluminium spinel of magnesium nitrate and the preparation of sodium metaaluminate coprecipitation method to be 147m
2g
-1Coprecipitation method needs the remaining Na of a large amount of deionized water wash
+, and also need be comparatively accurate to the control of pH value, be unwell to industrial mass production.Conventional sol-gel method forms gel with metal alkoxide hydrolysis, polymerization mostly, and synthetic spinel specific surface is mostly at 50-150m
2g
-1In the scope.The improved sol-gel method of employings such as Guo has been synthesized the nano spinel powder; This method has combined gel and precipitation process; The spinel that can under the high-temperature roasting condition, synthesize high-ratio surface, the spinel specific surface that obtains at 800 ℃ and 950 ℃ of roasting 8h are respectively 182 and 136m
2g
-1But this method need add a large amount of high molecular polymer PVA, and the PVA add-on increases, the also corresponding increase of the specific surface of the spinel that obtains.The adding of PVA makes the cost and the energy consumption of preparation magnesium-aluminium spinel increase greatly, and is only applicable to laboratory scale.
Summary of the invention
The objective of the invention is to magnesium-aluminium spinel, and raw materials cost and energy consumption are all lower with the synthetic high-ratio surface of a kind of comparatively simple method.
Respectively with pseudo-boehmite and magnesium nitrate as aluminium source and magnesium source, the magnesium-aluminium spinel of rich magnesium of preparation and rich aluminium is handled with certain density salpeter solution then earlier, with the magnesium or the al dissolution of having more than needed, obtains the magnesium-aluminium spinel of the metering ratio of high-ratio surface.
Concrete preparation process is:
1) prepares magnesium-aluminium spinel earlier: pseudo-boehmite is mixed with diluted hydrochloric acid aqueous solution stir 1h formation aluminium colloidal sol earlier.Again a certain amount of magnesium nitrate and deionized water are added to and stir 2h in the colloidal sol.Behind 120 ℃ of oven dryings, roasting 4h in 700 ℃ of retort furnaces.The solid abrasive that obtains is pulverized, and obtaining granularity is rich magnesium of 80-180 purpose or rich magnalium aluminate.The magnesium-aluminium spinel of the ratio of preparation metering in kind as a comparison simultaneously.
2) rich magnesium or rich magnalium aluminate are mixed with certain density salpeter solution stir 2h, filter, repeat after the drying identical step 3 time, at last with roasting 2h in 700 ℃ of retort furnaces of sample.
The drawing explanation
Accompanying drawing 1 is the XRD spectras of different magnaliums than following synthetic magnesium-aluminium spinel
Accompanying drawing 2 is different magnaliums N than following synthetic magnesium-aluminium spinel
2-adsorption/desorption curve
Accompanying drawing 3 is the N after the magnesium-aluminium spinel nitric acid treatment under the different magnaliums ratios
2-adsorption/desorption curve
Embodiment
To combine embodiment to come enumeration technical characterstic of the present invention below.
Earlier pseudo-boehmite (is contained Al
2O
3Massfraction be 68%) 30g mixes stirring with the 120g deionized water, dropwise splashes into 4.05g dilute hydrochloric acid solution (the HCl massfraction is 36.5%) again, continue to stir 1h and form aluminium colloidal sol.Again with 51.28gMg (NO
3)
26H
2O and deionized water are added to and stir 2h in the colloidal sol.Behind 120 ℃ of oven dryings, roasting 4h in 700 ℃ of retort furnaces obtains measuring the magnesium-aluminium spinel of ratio after grinding.
Earlier pseudo-boehmite (is contained Al
2O
3Massfraction be 68%) 30g mixes stirring with the 120g deionized water, dropwise splashes into 4.05g dilute hydrochloric acid solution (the HCl massfraction is 36.5%) again, continue to stir 1h and form aluminium colloidal sol.Again with 102.56gMg (NO
3)
26H
2O and deionized water are added to and stir 2h in the colloidal sol.Behind 120 ℃ of oven dryings, roasting 4h in 700 ℃ of retort furnaces obtains rich magnesium aluminate spinel MgAl after grinding
2O
4MgO.
Embodiment 3
Earlier pseudo-boehmite (is contained Al
2O
3Massfraction be 68%) 60g mixes stirring with the 240g deionized water, dropwise splashes into 8.10g dilute hydrochloric acid solution (the HCl massfraction is 36.5%) again, continue to stir 1h and form aluminium colloidal sol.Again with 51.28gMg (NO
3)
26H
2O and deionized water are added to and stir 2h in the colloidal sol.Behind 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 the 75g deionized water, dropwise splashes into 3.58g salpeter solution (HNO again
3Massfraction is 65%), behind the stirring 2h, filter, wash and drying under the room temperature, repeat this process 2 times again, roasting 2h obtains product and is designated as MgAl in last 700 ℃ of retort furnaces
2O
4MgO-HNO
3
Embodiment 5
Get rich magnalium aluminate MgAl
2O
4Al
2O
315g adds the 75g deionized water, dropwise splashes into 7.16g salpeter solution (HNO again
3Massfraction is 65%), behind the stirring 2h, filter, wash and drying under the room temperature, repeat this process 2 times again, roasting 2h obtains product and is designated as MgAl in last 700 ℃ of retort furnaces
2O
4Al
2O
3-HNO
3
The thing of sample adopts the X ' Pert PRO MPD diffractometer of Dutch PANalytical company to measure mutually, and CuK α, tube voltage are 40kV, and tube current is 40mA, 0.0167 ° of scanning wavelength.The XRD spectra of the magnesium-aluminium spinel of rich magnesium before and after the nitric acid treatment or rich magnalium aluminate and metering ratio is seen Fig. 1.
Can find out by Fig. 1, compare, occurred the characteristic peak of sharp-pointed free MgO in the magnesium-aluminium spinel of rich magnesium, and the characteristic peak intensity of spinel phase be lower slightly with the magnesium-aluminium spinel of metering; Do not occur mutually and there are other impurity in the magnesium-aluminium spinel of rich aluminium, the characteristic peak intensity of same spinel phase is lower than the spinel of metering ratio slightly, explains that the spinel Tipping Center spathous crystal grain of rich magnesium and rich aluminium is all less.Use HNO
3After solution was repeatedly handled, free MgO disappeared mutually in the magnesium-aluminium spinel of rich magnesium, and the characteristic peak intensity of spinel phase significantly strengthens; The magnesium-aluminium spinel phase of rich aluminium does not change, and only the peak intensity of spinel phase increases to some extent.Show through HNO
3The spinel Tipping Center spathous crystal grain of handling rich magnesium in back and rich aluminium all increases.
Carry out on ASAP 2010 physical adsorption appearances of the U.S. Micromeritics company that is determined at of the adsorption of sample and pore size distribution, with high-purity N
2Being adsorption medium, is cold-trap with liquid nitrogen (196 ℃).
N
2-adsorption/desorption curve (Fig. 2,3) shows that resulting spinel is mesoporous material.MgAl
2O
4And MgAl
2O
4The hysteresis loop shape approximation of MgO is in the H2 type, and the duct possibly be round shape; And MgAl
2O
4Al
2O
3Hysteresis loop then belong to the H3 type, should be the slit-shaped duct.The change in shape of hysteresis loop is little after the magnesium-aluminium spinel nitric acid treatment of rich magnesium and rich aluminium, but the starting point of hysteresis loop will be higher than the spinel before being untreated, and shows that the nitric acid treatment back aperture all increases.
The different magnaliums of table 1 are than the specific surface and the pore structure character of following synthetic magnesium-aluminium spinel
Can be known that by specific surface and pore structure character (table 1) specific surface of magnesium-rich spinel is only compared with the metering spinel slightly to be increased, and the specific surface of aluminium riched spinel is bigger, this possibly be owing to contain more Al in the solid of this moment
2O
3Relevant.The mean pore size of aluminium riched spinel is starkly lower than other both.But behind rich magnesium of nitric acid treatment and the aluminium riched spinel, 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
-1And Mg Al
2O
4Al
2O
3Specific surface then 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 novel method of a synthetic high-ratio surface magnesium-aluminium spinel; This method be respectively with pseudo-boehmite and magnesium nitrate as aluminium source and magnesium source; It is characterized in that preparing earlier the magnesium-aluminium spinel of rich magnesium and rich aluminium, handle with certain density salpeter solution then, with magnesium or al dissolution more than needed; Obtain the magnesium-aluminium spinel of the metering ratio of high-ratio surface, concrete preparation process is:
(1) prepares magnesium-aluminium spinel earlier: earlier pseudo-boehmite is mixed to stir forming aluminium colloidal sol in 1 hour with diluted hydrochloric acid aqueous solution; Again a certain amount of magnesium nitrate and deionized water are added in the colloidal sol and stirred 2 hours; Behind 120 ℃ of oven dryings, roasting is 4 hours in 700 ℃ of retort furnaces, and the solid abrasive that obtains is pulverized; Obtaining granularity is rich magnesium of 80～180 purposes or rich magnalium aluminate, and the magnesium-aluminium spinel of the ratio of preparation metering in kind as a comparison simultaneously;
(2) rich magnesium or rich magnalium aluminate are mixed with certain density salpeter solution stirred 2 hours, filter, repeat after the drying identical step 3 time,, can obtain the magnesium-aluminium spinel of high-ratio surface at last with roasting in 700 ℃ of retort furnaces of sample 2 hours.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861437A (en) * | 2014-03-20 | 2014-06-18 | 中国石油大学(华东) | Catalytic cracking flue gas sulfur transfer agent adopting mixed crystal phases as well as preparation method and application thereof |
| CN104549197A (en) * | 2015-01-30 | 2015-04-29 | 陕西科技大学 | Preparation method of MgAl2O4 spinel reforming catalyst 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- |
Citations (1)
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|---|---|---|---|---|
| CN101041142A (en) * | 2007-04-29 | 2007-09-26 | 沈阳化工学院 | Method of preparing Fumei type magnesia-alumina spinel by using brucite acid method |
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2011
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041142A (en) * | 2007-04-29 | 2007-09-26 | 沈阳化工学院 | Method of preparing Fumei type magnesia-alumina spinel by using brucite acid method |
Non-Patent Citations (1)
| Title |
|---|
| 李晓等: "镁铝尖晶石作为催化裂化双功能助剂的研究", 《石油学报(石油加工)》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861437A (en) * | 2014-03-20 | 2014-06-18 | 中国石油大学(华东) | Catalytic cracking flue gas sulfur transfer agent adopting mixed crystal phases as well as preparation method and application thereof |
| CN103861437B (en) * | 2014-03-20 | 2016-03-30 | 中国石油大学(华东) | Multiphase catalytic cracking fuel gas sulfur transfer additive prepared by secondary growth method and application |
| CN104549197A (en) * | 2015-01-30 | 2015-04-29 | 陕西科技大学 | Preparation method of MgAl2O4 spinel reforming catalyst carrier |
| 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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|---|---|
| CN102838145B (en) | 2014-10-15 |
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