CN103159249A - [La(EDTA)]<->-containing solid synthesis method - Google Patents
[La(EDTA)]<->-containing solid synthesis method Download PDFInfo
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- CN103159249A CN103159249A CN2011104059871A CN201110405987A CN103159249A CN 103159249 A CN103159249 A CN 103159249A CN 2011104059871 A CN2011104059871 A CN 2011104059871A CN 201110405987 A CN201110405987 A CN 201110405987A CN 103159249 A CN103159249 A CN 103159249A
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- edta
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Abstract
The present invention relates to a [La(EDTA)]<->-containing solid synthesis method, which comprises three steps such as La2O3 solid dissolving, EDTA dissolving and [La(EDTA)]<->-containing solid preparing so as to solve problems of complex process treatment process, low decomposition temperature, small specific surface area and other aspects of the conventional process using ammonium carbonate, urea and other hole expansion agents, wherein an EDTA decomposition temperature is improved, a hole expansion effect is excellent, and a specific surface area, a pore volume and a pore size of active alumina treated by the [La(EDTA)]<->-containing solid are significantly increased.
Description
Technical field
The present invention relates to a kind of synthetic contain [La (EDTA)]
-The method of solid is mainly used in the high-temperature catalytic field.
Background technology
Activated alumina typically refers to γ-A1
2O
3Or η-A1
2O
3, they are all defect spinel structure, and owing to having good surface properties, as larger in surface-area, strong surface adsorption property, and the surface acidity center, and how empty, large hollow structure, widely as catalyzer, carrier, dry sorbent material.Be mainly used in petrochemical complex, organic chemistry industry, rubber industry, chemical fertilizer industry and environment-protecting industrial.The thermostability of active aluminum oxide carrier is very important.Oriented α-Al during in temperature＞800 ℃
2O
3The trend that changes, such crystal conversion can cause its specific surface area to reduce, and have with active metal component have an effect reduce catalyst activity may.Therefore the meaning of this patent research is to improve γ-Al
2O
3To α-Al
2O
3The transformation temperature that changes suppresses γ-Al preferably
2O
3To α-Al
2O
3Phase transformation, make specific surface area keep stable, guarantee the activity of dispersion layer, make catalyzer that thermostability and work-ing life preferably be arranged.About the preparation of activated alumina thermostability and expanding agent, main thermally-stabilised auxiliary agent is generally selected ZrO abroad
2, TiO
2Deng perovskite composite oxide, alkaline earth metal oxide BaO, CaO, SrO; Domestic comparatively commonly used be rare earth metal such as Ce, Nd, the oxide compound of Pr etc. and the mixture of two or more rare earth oxides, to the introduction of expanding agent seldom.The solid matter that this patent adopts thermo-stabilizer and expanding agent to synthesize, operation to the aluminum oxide blend is succinct, the reaming effect is good, the advantage of Heat stability is good, change the preparation technology that traditional thermally-stabilised auxiliary agent and expanding agent separate, effectively improve the decomposition temperature of EDTA.
Summary of the invention
Goal of the invention:
The present invention proposes a kind of synthetic contain [La (EDTA)]
-The problem that the aspects such as the method for solid has solved the method that traditional technology adopts the expanding agents such as carbonic acid ammonia and urea, and process treatment process is complicated, and decomposition temperature is low, specific surface area is little exist.
Technical scheme:
A kind of synthetic contain [La (EDTA)]
-The method of solid is characterized in that: the method is carried out according to the following steps:
(1), La
2O
3The dissolving of solid: the La of weighing 16.3g
2O
3Solid is put into water, adds the 65% concentrated nitric acid dissolving of 10-20ml/L;
(2), the dissolving of EDTA: the La that contains of dissolving
3+Solution add 29.2gEDTA, La
3+With the mole ratio of EDTA be 1:1, then with the ammoniacal liquor of 40-50ml/L, solution being transferred to alkaline Ph value is 10, makes the EDTA dissolving, then to transfer to acid Ph value with nitric acid be 4-5, namely gets settled solution;
(3), the preparation of solid: with the settled solution low-grade fever evaporation that step (2) obtains, remove ammoniacal liquor and nitric acid, the cooling solid that namely gets.
After adding 65% concentrated nitric acid dissolving in step (1), stirred 15 minutes, make the solution clarification.
After with ammoniacal liquor, solution being transferred to alkaline Ph value and is 10 in step (2), EDTA slowly dissolves, then to transfer to acid Ph value with nitric acid be 4-5, until solution is clarified.
In step (3), evaporative process is carried out in low-grade fever, and temperature remains on 50-60 ℃.
Advantage and effect:
The present invention proposes a kind of synthetic contain [La (EDTA)]
-The method of solid has following advantage:
The present invention relates to a kind of water-soluble fabulous [La (EDTA)]
-The solid synthetic method of ion, it has solved La
2O
3Improve with simple and easy mixing of EDTA the problem that the stable on heating traditional method of activated alumina exists, a kind of better containing [La (EDTA)] is provided
-The method of solid.Process treatment process is simple, has improved the decomposition temperature of EDTA, and the reaming effect is splendid.Contain [La (EDTA)]
-Solid is a kind of high temperature expanding agent and thermo-stabilizer that the experiment proved that, can improve and the activity of stable alumina supporter under hot conditions.The present invention proposes a kind of new high-temperature thermal stability agent and expanding agent and (contain [La (EDTA)]
-Solid), study simultaneously its synthetic method.Through containing [La (EDTA)]
-The activated alumina that solids treatment is crossed, specific surface area and large pore volume aperture significantly improve, and are mainly used in the high-temperature catalytic field.
Description of drawings:
Fig. 1 is that prepared expanding agent is the surface topography map of sample under scanning electronic microscope of quality of alumina mark 1%.
In Fig. 1, (a) for the image of 300 times of amplifications, can see that particle is very thin, very broken, and granular size is uneven.(b) being the picture of 3000 times of amplifications, is typically there is no the particle of pulverizing, is clear that high temperature expanding agent [La (EDTA)] in figure
-Expand the hole that, hole size is uneven, and large have a um more than 30, and little also have a um more than 10, although the micropore of whether seeing and mesopore, wide-aperture hole is that carrier needs most.(c) be to amplify the picture of 5000 times, what see in figure is particle with pertusate pulverizing, and the aperture is greatly about the small-particle of 10um left and right.(d) be to amplify the picture of 3000 times, what see in figure is particle with pertusate pulverizing, and the aperture is greatly about the macroparticle of the left and right of um more than 30.
Fig. 2 is that prepared expanding agent is the surface topography map of sample under scanning electronic microscope of quality of alumina mark 2%.
In Fig. 2, (a) for the image of 300 times of amplifications, can see that particle is very thin, very broken, and granular size is uneven.(b) being the picture of 3000 times of amplifications, is the particle of pulverizing, and is clear that high temperature expanding agent [La (EDTA)] in figure
-Expand the hole that, hole is to amplify the picture of 3000 times about about 20um (c) greatly, and what see in figure is particle with pertusate pulverizing, and the aperture is greatly about the small-particle of 30um left and right.(d) be to amplify the picture of 3000 times, what see in figure is particle with pertusate pulverizing, and the aperture is greatly about the particle less than the 10um left and right.
Embodiment:
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not subjected to the restriction of embodiment.
Contain [La (EDTA)]
-Synthesizing of solid, at first La
2O
3The dissolving of solid is with La
2O
3The solid nitric acid dissolve, then use ammonia solvent EDTA, transfer to acidity with acid at last.The present invention is directed to activated alumina activity at high temperature, proposed a kind of New Heat Stabilizer and expanding agent, even activated alumina at high temperature has specific surface area and pore structure preferably, cancelled the low characteristics of common expanding agent decomposition temperature.
In order to obtain to contain [La (EDTA)]
-Solid, synthetic the containing [La (EDTA)] that the present invention adopts
-The method of solid is as follows:
(1), La
2O
3The dissolving of solid: the La of weighing 16.3g
2O
3Solid is put into water, adds the 65% concentrated nitric acid dissolving of 10-20ml/L;
(2), the dissolving of EDTA: the La that contains of dissolving
3+Solution add 29.2gEDTA, La
3+With the mole ratio of EDTA be 1:1, then with the ammoniacal liquor of 40-50ml/L, solution being transferred to alkaline Ph value is 10, makes the EDTA dissolving, has simultaneously a small amount of white precipitate to separate out, then to transfer to acid Ph value with nitric acid be 4-5, namely gets settled solution and (contains [La (EDTA)]
-Solution);
(3), the preparation of solid: with the settled solution low-grade fever evaporation that step (2) obtains, remove ammoniacal liquor and nitric acid, the cooling solid that namely gets.
After adding massfraction 65% concentrated nitric acid dissolving in step (1), stirred 15 minutes, make the solution clarification.
After with ammoniacal liquor, solution being transferred to alkaline Ph value and is 10 in step (2), EDTA dissolves, then to transfer to acid Ph value with nitric acid be 4-5, until solution is clarified.
In step (3), evaporative process is carried out in low-grade fever, and temperature remains on 50-60 ℃.
Operating process and content are as follows: lanthanum trioxide 16.3g, and EDTA29.2g, nitric acid 10-20ml/L, ammoniacal liquor 40-50ml/L, the pH value is 4-5, solvent is deionized water 200ml.Evaporative process is carried out in low-grade fever, and temperature remains on 50-60 ℃.
Use the SEM(scanning electron microscope), DTA(nitrogen adsorption/desorption) to the powder analysis of gained, result shows gained at high temperature alumina powder jointedly has higher specific surface area and a larger pore volume, namely at high temperature still has higher activity.
Embodiment 1:
Rare earth oxide La with 16.3g
2O
3(for the quality of alumina mark 1%) be put in the aqueous solution, then add 65% the concentrated nitric acid of 10ml/L, stirred 15 minutes, solution is clarified.Then add 29.2g 1% ethylenediamine tetraacetic acid (EDTA) (pure EDTA), La
3+With the mole ratio of EDTA be 1:1, transfer to alkaline Ph=10 with the ammoniacal liquor of 40ml/L, make the EDTA dissolving, have simultaneously a small amount of white precipitate to separate out, then transfer to acid Ph=5 with nitric acid, namely get settled solution.
Heating is removed ammoniacal liquor and nitric acid 50 ℃ of evaporations, and is then cooling, until separate out H[La (EDTA)] 16H
2The O crystal, amount and the final total solids of solid are calculated [La (EDTA)] according to adding
-Content.
The 180g exsiccated ammonium alum that weighs with scale specifies the expanding agent of making (to contain [La (EDTA)] with taking
-Solid) crystal prototype (being respectively the molar fraction 0.5%, 1%, 2%, 3% of aluminum oxide that exsiccated ammonium alum generates) blend is even.Then this material is placed in 600 ℃ of thermal degradation 1h of High Temperature Furnaces Heating Apparatus and obtains foam shape alumina powder sample, then install preservation etc. with packing bag to be tested.The rare earth sample of 4 kinds of ratios is respectively charged into plumbago crucible, puts into tube type high-temperature furnace and carry out high-temperature calcination, thermostatically heating was taken out sample after 1 hour when being heated to 1200 ℃ respectively.
Embodiment 2:
Rare earth oxide La with 16.3g
2O
3(for the quality of alumina mark 2%) be put in the aqueous solution, then add 65% the concentrated nitric acid of 20ml/L, stirred 15 minutes, solution is clarified.Then add 29.2g 1% ethylenediamine tetraacetic acid (EDTA) (pure EDTA), La
3+With the mole ratio of EDTA be 1:1, transfer to alkaline Ph=10 with the ammoniacal liquor of 50ml/L, then 50 ℃ of heating, EDTA is slowly dissolved, then transfers to acid Ph=4 with nitric acid, until the solution clarification.
Heating is removed ammoniacal liquor and nitric acid 60 ℃ of evaporations, and is then cooling, until separate out H[La (EDTA)] 16H
2The O crystal, amount and the final total solids of solid are calculated [La (EDTA)] according to adding
-Content.
The 180g exsiccated ammonium alum that weighs with scale specifies expanding agent crystal prototype (being respectively the molar fraction 0.5%, 1%, 2%, 3% of aluminum oxide that the exsiccated ammonium alum generates) blend of making even with taking.。Then this material is placed in 600 ℃ of thermal degradation 1h of High Temperature Furnaces Heating Apparatus and obtains foam shape alumina powder sample, then install preservation etc. with packing bag to be tested.The rare earth sample of 4 kinds of ratios is respectively charged into plumbago crucible, puts into tube type high-temperature furnace and carry out high-temperature calcination, thermostatically heating was taken out sample after 1 hour when being heated to 1200 ℃ respectively.
Embodiment 3:
Rare earth oxide La with 16.3g
2O
3(for the quality of alumina mark 1%) be put in the aqueous solution, then add 65% the nitric acid of 15ml/L, stirred 15 minutes, solution is clarified.Then add 29.2g 1% ethylenediamine tetraacetic acid (EDTA) (pure EDTA), La
3+With the mole ratio of EDTA be 1:1, transfer to alkaline Ph=10 with the ammoniacal liquor of 45ml/L, then 60 ℃ of heating, EDTA is slowly dissolved, then transfers to acid Ph=4.5 with nitric acid, namely get settled solution.
Heating is removed ammoniacal liquor and nitric acid 55 ℃ of evaporations, and is then cooling, until separate out H[La (EDTA)] 16H
2The O crystal, amount and the final total solids of solid are calculated [La (EDTA)] according to adding
-Content.
The 180g exsiccated ammonium alum that weighs with scale specifies expanding agent crystal prototype (being respectively the molar fraction 0.5%, 1%, 2%, 3% of aluminum oxide that the exsiccated ammonium alum generates) blend of making even with taking.Then this material is placed in 600 ℃ of thermal degradation 1h of High Temperature Furnaces Heating Apparatus and obtains foam shape alumina powder sample, then install preservation etc. with packing bag to be tested.The rare earth sample of 4 kinds of ratios is respectively charged into plumbago crucible, puts into tube type high-temperature furnace and carry out high-temperature calcination, thermostatically heating was taken out sample after 1 hour when being heated to 1200 ℃ respectively.
Embodiment 4:
Ammoniacal liquor with 40ml/L transfers to alkaline Ph=10, then 55 ℃ of heating, EDTA is slowly dissolved, and all the other conditions are with embodiment 3.
Add [La (EDTA)]
-The test data of 1200 ℃ is as shown in table 1.
Table 1 adds [La (EDTA)]
-1200 ℃ of test datas.
By as seen from Table 1, [La (EDTA)]
-Adding of component can obviously improve Al
2O
3Thermostability.Along with containing [La (EDTA)]
-The increasing of solid addition, there is certain Changing Pattern in its specific surface area and most probable aperture.As [La (EDTA)]
-When addition was 1%, the specific surface area of sample reached maximum value 150.36 m
2/ g.This explanation La in heat-processed
3+Ion is easy to form with aluminum oxide the LaAlO of perovskite structure
3, this structure forms at limit, angle, the stupefied place of aluminum oxide, due to its Thermodynamically stable, at high temperature stops the transformation of crystalline form, therefore at high temperature obtains thermodynamically stable activated alumina.
Claims (4)
1. synthetic contain [La (EDTA)]
-The method of solid is characterized in that: the method is carried out according to the following steps:
(1), La
2O
3The dissolving of solid: the La of weighing 16.3g
2O
3Solid is put into water, adds the 65% concentrated nitric acid dissolving of 10-20ml/L;
(2), the dissolving of EDTA: the La that contains of dissolving
3+Solution add 29.2gEDTA, La
3+With the mole ratio of EDTA be 1:1, then with the ammoniacal liquor of 40-50ml/L, solution being transferred to alkaline Ph value is 10, makes the EDTA dissolving, then to transfer to acid Ph value with nitric acid be 4-5, namely gets settled solution;
(3), the preparation of solid: with the settled solution low-grade fever evaporation that step (2) obtains, remove ammoniacal liquor and nitric acid, the cooling solid that namely gets.
2. a kind of synthetic contain [La (EDTA)] according to claim 1
-The method of solid is characterized in that: after adding 65% concentrated nitric acid dissolving in step (1), stirred 15 minutes, make the solution clarification.
3. a kind of synthetic contain [La (EDTA)] according to claim 1
-The method of solid is characterized in that: after with ammoniacal liquor, solution being transferred to alkaline Ph value and is 10 in step (2), EDTA dissolves, then to transfer to acid Ph value with nitric acid be 4-5, until solution is clarified.
4. a kind of synthetic contain [La (EDTA)] according to claim 1
-The method of solid is characterized in that: in step (3), evaporative process is carried out in low-grade fever, and temperature remains on 50-60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104059871A CN103159249A (en) | 2011-12-08 | 2011-12-08 | [La(EDTA)]<->-containing solid synthesis method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104059871A CN103159249A (en) | 2011-12-08 | 2011-12-08 | [La(EDTA)]<->-containing solid synthesis method |
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|---|---|
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|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1408645A (en) * | 2001-09-19 | 2003-04-09 | 川化集团有限责任公司 | Aluminium oxide maintaining high specific surface area under high temperature and its preparing method |
| CN101302023A (en) * | 2008-06-16 | 2008-11-12 | 沈阳工业大学 | Preparation of high temperature-resistant active aluminum oxide |
-
2011
- 2011-12-08 CN CN2011104059871A patent/CN103159249A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1408645A (en) * | 2001-09-19 | 2003-04-09 | 川化集团有限责任公司 | Aluminium oxide maintaining high specific surface area under high temperature and its preparing method |
| CN101302023A (en) * | 2008-06-16 | 2008-11-12 | 沈阳工业大学 | Preparation of high temperature-resistant active aluminum oxide |
Non-Patent Citations (3)
| Title |
|---|
| I. I. M. TIJBURG等: "Application of lanthanum to pseudo-boehmite and γ-Al2O3", 《JOURNAL OF MATERIALS SCIENCE》 * |
| LIU XIAOJUN等: "Influence of [La(EDTA)]– on pore structure of activated alumina carrier at high-temperature", 《JOURNAL OF RARE EARTHS》 * |
| 刘晓军等: "高温活性氧化铝的制备", 《矿冶工程》 * |
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Application publication date: 20130619 |