CN103112884A - Preparation method for synthesizing spinel material by using micromolecule as template - Google Patents

Preparation method for synthesizing spinel material by using micromolecule as template Download PDF

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CN103112884A
CN103112884A CN2013100514759A CN201310051475A CN103112884A CN 103112884 A CN103112884 A CN 103112884A CN 2013100514759 A CN2013100514759 A CN 2013100514759A CN 201310051475 A CN201310051475 A CN 201310051475A CN 103112884 A CN103112884 A CN 103112884A
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spinel
template
preparation
salt
solubility
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董立春
刘雄
唐成黎
李俊宏
陈文�
王竸
谭芸妃
杨倩
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Chongqing University
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Abstract

The invention relates to a preparation method for synthesizing spinel material by using a micromolecule as a template, belonging to the technical field of preparation of chemical materials. The preparation method comprises the following steps: preparing a metallic ion mixed solution from raw materials soluble salt A and soluble salt B by using micromolecule glucose or sucrose as a template, refluxing, crystallizing, carrying out vacuum filtration, washing, and roasting to obtain the product. The preparation method has the characteristics of simple production equipment, low investment, simple technique, low reaction temperature, low energy consumption, high production safety and low production cost, is convenient for popularization, and can be used for preparing good spinel products with large specific area; and the spinel product has the characteristics of adjustable specific area and pore size, and wide application range. The invention can be widely used for preparing spinel materials, and is especially suitable for preparing MgA12O4 and ZnAl2O4 spinel materials. The product prepared by the method can be widely used as ceramic and fireproof materials and the like, and is especially suitable to be used as a catalyst support for high temperature reaction.

Description

A kind of take small molecules as template synthetic spinel material preparation method
Technical field
The invention belongs to technical field of chemical material preparation, be specifically related to the preparation method of spinel.
Technical background
Spinel AB 2O 4(A, B represent two kinds of metals) material has special physicochemical property, and as 1. material hardness is large, fusing point is high, stable chemical performance, under high temperature, anti-etch ability is strong; 2. crystal belongs to isometric system, and its thermal conductivity and thermal expansivity are all identical on all directions, and the coefficient of expansion is little, and good thermostability is arranged; 3. in crystal lattice, A ion and B ion can be respectively many kinds of metal ions, cause it to have the character polytropy, as magnetic performance etc.; 4. lattice tightness is large, and water molecules is difficult to enter crystals, has very high hydrothermal stability.Spinel all has a wide range of applications at numerous areas thus, as magneticsubstance, stupalith, fire-retardant material, stealth material etc., has especially received increasing concern as catalytic material.
The preparation method of existing spinel is as publication number in 2009 " a kind of preparation method of the superfine mesoporous magnesium aluminate spinel " patent that is CN101565194A.Its disclosed method is: take aluminum soluble salt and solubility magnesium salts as raw material, take ammoniacal liquor or organic amine as basic solution, take cats product or organic polymer as template; First basic solution is joined in the mixing solutions of aluminum soluble salt and solubility magnesium salts, and adds template, then ageing, crystallization, washing, filtration, drying, roasting and magnesium-aluminium spinel powder product.The main drawback of the method is: the organic amine that 1. uses in alkali lye all has toxicity in various degree; 2. the template that adopts is cats product and organic polymer, and its price is more expensive, is not suitable for industrialized mass production; 3. wash and filter waste liquid and do not do any processing and directly discharge, organism wherein is unfavorable for environment protection easily to environment.And for example the report such as Mehran Rezaei prepares mesoporous magnesium aluminate spinel (Powder Technology take tensio-active agent as template, 2010198:275), its method is: the magnesium nitrate of stoichiometric ratio, aluminum nitrate, CTAB (cetyl trimethylammonium bromide) are dissolved in deionized water and make slurries and drip ammoniacal liquor adjusting pH to 9 left and right, wait to precipitate to complete and continue to stir 30min, and reflux under 80 ℃ and continue to stir 24h, the magnesium-aluminium spinel product is after filtration, washing, drying and roasting obtain.The main drawback of the method is: the magnesium-aluminium spinel (MgAl of preparation 2O 4) specific surface area 65～203m only 2/ g, less, practicality is relatively poor.
Summary of the invention
The objective of the invention is the weak point for existing spinel preparation method, provide a kind of take the preparation method of small molecules as the template synthetic spinel.Have the characteristics such as the spinel specific surface area of preparing is large, the aperture is larger, practical; The method is simple, raw material is easy to get, cost is low, easy to utilize, be easy to the industrialization expanding production.
The technical scheme that realizes the object of the invention is: a kind of take small molecules as template synthetic spinel material preparation method.Take solubility A salt (being magnesium nitrate hexahydrate or zinc nitrate hexahydrate etc.) and solubility B salt (i.e. nine water aluminum nitrates or nine water iron nitrates etc.) as raw material, take small molecules glucose, sucrose etc. as template, first prepare the metal ion mixed solution, then through the simple procedures of backflow, crystallization, suction filtration, washing, roasting and obtain product.The concrete steps of described method are as follows:
(1) preparation metallic ion mixed liquor
[be magnesium nitrate hexahydrate Mg (NO with solubility A salt 3) 26H 2O) or zinc nitrate hexahydrate (Zn (NO 3) 26H 2] and solubility B salt [i.e. nine water aluminum nitrate (Al (NO O) etc. 3) 39H 2O) or nine water iron nitrate (Fe (NO 3) 39H 2O) etc.] be raw material; A kind of with in glucose, sucrose, citric acid, CTAB perhaps adds the mixture of CTAB in glucose or sucrose or citric acid, in described mixture, the mol ratio of glucose or sucrose or citric acid: CTAB is 1: 0.2～2.According to solubility A salt: solubility B salt: template: the mol ratio of deionized water is 1: 2: 0.03～1: 220～450 ratio, first template is joined in deionized water, obtain transparent template solution till being stirred to dissolving, then add solubility A salt and solubility B salt in template solution, be stirred to and mix; Prepare the metal ion mixed solution of transparent thickness, standby.
(2) preparation spinel finished product
(1) step complete after, first (1) the metal ion mixed solution prepared of step is positioned in the oil bath pan with magnetic agitation, under agitation condition according to solubility A salt in the metal ion mixed solution: the mol ratio of ammoniacal liquor is 1: 3～6 ratio, drip ammoniacal liquor in the metal ion mixed solution, then be warming up to and reflux under 80～120 ℃ of constant temperature and continue to stir 12～48h.Then the mixed solution that just dripped ammoniacal liquor is transferred to and obtains thick product in the teflon-lined reactor after 80～170 ℃ of lower crystallization 12h～48h.The thick product that will make at last carries out suction filtration, is neutral with deionized water wash to filtrate in the time of suction filtration, collects respectively scrub raffinate and crosses filter solid.The treated rear discharging up to standard of scrub raffinate of collecting, with collect cross filter solid in loft drier in 110～120 ℃ of drying 8～12h.With the solid that obtains after drying, be placed in mortar and grind, levigate solid is positioned in retort furnace at 700～1000 ℃ of lower roasting 4～5h, just prepare the spinel product.
After the present invention adopts technique scheme, mainly contain following effect:
1. the template of the inventive method employing is glucose sugar, sucrose, citric acid, it is cheap and easy to get, compare tensio-active agent, the polymer that tradition preparation bigger serface spinel uses and have obvious price advantage, so production cost is low, is beneficial to industrial application; Template used dose substantially pollution-free to environment, is conducive to environment protection;
2. adopt spinel specific surface area that the inventive method prepares up to 190～330m 2/ g, the aperture is 40～60nm, belongs to good spinel;
3. specific surface area and the aperture of the spinel of employing the inventive method preparation are adjustable.The present invention as the mixture of glucose and CTAB, and regulates its blending ratio by selecting two kinds of mixed templates, just can regulate specific surface area and the aperture of spinel, prepare the spinel of different premium propertiess, satisfy the demand of different application, be widely used;
4. the present invention adopts the precipitator method to prepare spinel, and technique is simple, and crystallization and reflux temperature are low, and energy consumption is low, and production safety has further reduced production cost;
5. the production unit of the inventive method is simple, invests little.The inventive method has only been used the instrument simply commonly used such as oil bath pan, loft drier, retort furnace, thereby has further reduced production cost again, and is easy to utilize, is suitable for large-scale industrialization production.
The inventive method can be widely used in the preparation spinel, is particularly useful for making MgAl 2O 4And ZnAl 2O 4Spinel adopts the spinel of the present invention's preparation can be widely used as magneticsubstance, stupalith, fire-retardant material, stealth material etc., is particularly useful as the carrier that pyroreaction is used catalyzer.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment 1
A kind of take small molecules as template synthetic spinel material preparation method, feature is synthetic MgAl 2O 4The concrete steps of spinel are as follows:
(1) preparation metal ion mixed solution
According to Mg (NO 3) 26H 2O: Al (NO 3) 39H 2O: glucose: distilled water=1: 2: 1: 380 ratio prepares MgAl 2O 4, concrete steps are as follows: take 1.98g glucose and be dissolved in 68ml distilled water and be stirred to transparent liquid; Take 7.5g nine water aluminum nitrates, it is standby that the 2.56g magnesium nitrate hexahydrate adds in mentioned solution stirring and evenly mixing to get the metal ion mixed solution.
(2) preparation MgAl 2O 4Finished product
(1) step first went on foot with (1) the metal ion mixed solution of preparing and is positioned in the oil bath pan of magnetic agitation, according to Mg in the metal ion mixed solution after completing 2+: the ratio of ammoniacal liquor=1: 5 under agitation is added drop-wise to ammoniacal liquor in the metal ion mixed solution; The mixed solution that will drip ammoniacal liquor after dropwising is warming up to 120 ℃, and 12h refluxes under continuously stirring.The mixed solution that then will drip ammoniacal liquor is transferred to that in the teflon-lined reactor, 80 ℃ of lower crystallization 48h obtain thick product.The thick product that will make at last carries out suction filtration, is neutral with deionized water wash to filtrate in the time of suction filtration, collects respectively scrub raffinate and crosses filter solid.The treated rear discharging up to standard of scrub raffinate of collecting, with collect cross filter solid in loft drier in 110 ℃ of dry 8h, with the solid that obtains after drying, be placed in mortar and grind, the solid of porphyrize is positioned in retort furnace at 800 ℃ of lower roasting 4h, just prepares spinel MgAl 2O 4Product.
Embodiment 2
A kind of take small molecules as template synthetic spinel material preparation method, feature is synthetic MgAl 2O 4Spinel, with embodiment 1, wherein:
In (1) step, material Mg (NO 3) 26H 2O: Al (NO 3) 39H 2O: citric acid: the mol ratio of distilled water is 1: 2: 1: 400, and the quality of citric acid is 1.92g, the volume of distilled water is 72ml.
In (2) step, Mg 2+: the mol ratio of ammoniacal liquor is 1: 6, mixed solution is warming up to 100 ℃ after ammoniacal liquor dropwises, and return time is 30h, and crystallization temperature is 160 ℃, and crystallization time is 24h, and be 12h time of drying, and maturing temperature is 900 ℃.
Embodiment 3
A kind of take small molecules as template synthetic spinel material preparation method, feature is synthetic MgAl 2O 4Spinel, with embodiment 1, wherein:
In (1) step, material Mg (NO 3) 26H 2O: Al (NO 3) 3H 2O: sucrose: the mol ratio of distilled water is 1: 2: 1: 450, and the quality of sucrose is 3.42g, the volume of distilled water is 81ml.
In (2) step, mixed solution is warming up to 90 ℃ after ammoniacal liquor dropwises, return time is 20h, and crystallization temperature is 150 ℃, and crystallization time is 24h, and be 10h time of drying, and maturing temperature is 900 ℃.
Embodiment 4
A kind of take small molecules as template synthetic spinel material preparation method, feature is synthetic MgAl 2O 4Spinel, with embodiment 1, wherein:
In (1) step, material Mg (NO 3) 26H 2O: Al (NO 3) 39H 2O: CTAB: the mol ratio of distilled water is 1: 2: 0.5: the quality of 450, CTAB is 3.64g, and the volume of distilled water is 81ml.
In (2) step, mixed solution is warming up to 100 ℃ after ammoniacal liquor dropwises, return time is 20h, and crystallization temperature is 170 ℃, and crystallization time is 24h, and be 10h time of drying, and maturing temperature is 700 ℃.
Embodiment 5
A kind of take small molecules as template synthetic spinel material preparation method, feature is synthetic MgAl 2O 4Spinel, with embodiment 1, wherein:
In (1) step, material Mg (NO 3) 26H 2O: Al (NO 3) 39H 2O: glucose: CTAB: the mol ratio of distilled water is 1: 2: 1: 0.5: 450, the volume of distilled water was 81ml, and the quality of CTAB is 1.82g.
In (2) step, Mg 2+: the mol ratio of ammoniacal liquor is 1: 6, mixed solution is warming up to 90 ℃ after ammoniacal liquor dropwises, and return time is 20h, and crystallization temperature is 150 ℃, and crystallization time is 24h, and be 10h time of drying, and maturing temperature is 1000 ℃.
Embodiment 6
A kind of take small molecules as template synthetic spinel material preparation method, feature is synthetic MgAl 2O 4Spinel, with embodiment 1, wherein:
In (1) step, material Mg (NO 3) 26H 2O: Al (NO 3) 39H 2O: glucose: CTAB: the mol ratio of distilled water is 1: 2: 1: 0.2: 450, the volume of distilled water was 81ml, and the quality of CTAB is 1.82g.
In (2) step, Mg 2+: the mol ratio of ammoniacal liquor is 1: 6, mixed solution is warming up to 90 ℃ after ammoniacal liquor dropwises, and return time is 20h, and crystallization temperature is 150 ℃, and crystallization time is 24h, and be 10h time of drying, and maturing temperature is 1000 ℃.
Embodiment 7
A kind of take small molecules as template synthetic spinel material preparation method, feature is synthetic MgAl 2O 4Spinel, with embodiment 1, wherein:
In (1) step, material Mg (NO 3) 26H 2O: Al (NO 3) 39H 2O: glucose: CTAB: the mol ratio of distilled water is 1: 2: 1: 2: 450, the volume of distilled water was 81ml, and the quality of CTAB is 1.82g.
In (2) step, MgAl 2O 4: the mol ratio of ammoniacal liquor is 1: 6, mixed solution is warming up to 90 ℃ after ammoniacal liquor dropwises, and return time is 20h, and crystallization temperature is 150 ℃, and crystallization time is 24h, and be 10h time of drying, and maturing temperature is 1000 ℃.
Embodiment 8
A kind of take small molecules as template synthetic spinel material preparation method, feature is synthetic ZnAl 2O 4Spinel, lower with embodiment 1, wherein:
In (1) step, material Zn (NO 3) 26H 2O: Al (NO 3) 39H 2O: glucose: the mol ratio of distilled water is 1: 2: 1: 330, and the volume of distilled water is 60ml, the quality of zinc nitrate hexahydrate is 2.97g.
In (2) step, Zn 2+: the mol ratio of ammoniacal liquor is 1: 4, mixed solution is warming up to 100 ℃ after ammoniacal liquor dropwises, and return time is 18h, and crystallization temperature is 170 ℃, and crystallization time is 12h, and maturing temperature is 1000 ℃.
Experimental result
1. the MgAl that uses the different templates agent to prepare to the present embodiment 1～4 2O 4Spinel carries out the BET test, and result is as shown in table 1.
The MgAl that the agent of table 1 different templates is prepared 2O 4The BET result of spinel
Figure BSA00000855495800051
2. the MgAl that the present embodiment 5～7 is prepared under the glucose of different ratios and CTAB condition 2O 4Spinel carries out the BET test, and result is as shown in table 2.
The MgAl that the glucose of table 2 different ratios and CTAB prepare 2O 4The BET result of spinel
Figure BSA00000855495800052
3. the ZnAl that the present embodiment 8 is prepared 2O 4Spinel carries out BET test, and the MgAl for preparing with embodiment 1 2O 4Spinel compares, and result is as shown in table 3.
The MgAl that table 3 is prepared take glucose as template 2O 4With ZnAl 2O 4The BET result of spinel
Figure BSA00000855495800061
From above-mentioned test-results as can be known:
1. as known from Table 1, the specific surface area of the present invention's synthetic dimension stone of magnesia alumina spinel take small molecules such as glucose as template is up to 190～250m 2/ g, with existing Surfactant CTAB be the synthetic MgAl of template 2O 4The specific surface area of spinel is identical, can satisfy the requirement of using.But the cheap of small molecules template such as glucose that the present invention selects are easy to get, synthetic MgAl 2O 4The cost of spinel is low, is conducive to commercial scale production;
2. the MgAl for preparing of the present invention as known from Table 1, 2O 4The aperture of spinel is 40～60nm, the MgAl that only has Surfactant CTAB to prepare 2O 4/ 2nd of an aperture of spinel;
3. as known from Table 2, regulate the ratio of small molecules template glucose and CTAB mixture, can prepare specific surface area up to 270～300m 2The MgAl of the excellent property of/g 2O 4Spinel;
4. as known from Table 3, take glucose as template, can not only prepare the MgAl of excellent property 2O 4Spinel can also be prepared specific surface area up to 290～330m 2/ g, the aperture is the ZnAl of the excellent property of 40～50nm 2O 4Spinel.

Claims (2)

1. one kind take small molecules as template synthetic spinel material preparation method, it is characterized in that the concrete steps of described method are as follows:
(1) preparation metallic ion mixed liquor
Take solubility A salt and solubility B salt as raw material; According to solubility A salt: solubility B salt: template: the mol ratio of deionized water is 1: 2: 0.03～1: 220～450 ratio, first template is joined in deionized water, obtain transparent template solution till being stirred to dissolving, then add solubility A salt and solubility B salt in template solution, be stirred to and mix; Prepare the metal ion mixed solution of transparent thickness;
(2) preparation spinel finished product
(1) step complete after, first (1) the metal ion mixed solution prepared of step is positioned in the oil bath pan with magnetic agitation, under agitation condition according to solubility A salt in the metal ion mixed solution: the mol ratio of ammoniacal liquor is 1: 3～6 ratio, drips ammoniacal liquor in the metal ion mixed solution, be warming up to again and reflux under 80～120 ℃ of constant temperature and continue to stir 12～48h, the mixed solution that then will drip ammoniacal liquor is transferred to and obtains thick product in the teflon-lined reactor after 80～170 ℃ of lower crystallization 12h～48h, the thick product that will make at last carries out suction filtration, be neutral with deionized water wash to filtrate in the time of suction filtration, collect respectively scrub raffinate and cross filter solid, the treated rear discharging up to standard of scrub raffinate of collecting, with collect cross filter solid in loft drier in 110～120 ℃ of drying 8～12h, with the solid that obtains after drying, being placed in mortar grinds, levigate solid is positioned in retort furnace at 700～1000 ℃ of lower roasting 4～5h, just prepare the spinel product.
2. according to claimed in claim 1 a kind of take small molecules as template synthetic spinel material preparation method, it is characterized in that described solubility A salt is six water iron nitrate or zinc nitrate hexahydrates, described solubility B salt is nine water aluminum nitrates or nine water iron nitrates; Described template is glucose or sucrose or citric acid, perhaps add CTAB in glucose or sucrose or citric acid and mixture, in described mixture, glucose or sucrose or mol ratio citric acid: CTAB is 1: 0.2～2.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112010331A (en) * 2020-09-08 2020-12-01 江西省科学院应用物理研究所 Industrial preparation method and preparation device of magnesium aluminate spinel powder
CN114538491A (en) * 2020-11-25 2022-05-27 中国石油天然气股份有限公司 Preparation method of magnesium aluminate spinel

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Publication number Priority date Publication date Assignee Title
CN101565194A (en) * 2009-06-01 2009-10-28 西北大学 Method for preparing superfine mesoporous magnesium aluminate spinel

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Publication number Priority date Publication date Assignee Title
CN101565194A (en) * 2009-06-01 2009-10-28 西北大学 Method for preparing superfine mesoporous magnesium aluminate spinel

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Title
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ESMAEIL NAVAEI ALVAR ET AL.: "Synthesis of mesoporous nanocrystalline MgAl2O4 spinel via surfactant assisted precipitation route", 《POWDER TECHNOLOGY》 *
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112010331A (en) * 2020-09-08 2020-12-01 江西省科学院应用物理研究所 Industrial preparation method and preparation device of magnesium aluminate spinel powder
CN114538491A (en) * 2020-11-25 2022-05-27 中国石油天然气股份有限公司 Preparation method of magnesium aluminate spinel

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