CN103586012A - Method for preparing calcium zirconium composite oxide - Google Patents
Method for preparing calcium zirconium composite oxide Download PDFInfo
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- CN103586012A CN103586012A CN201310618531.2A CN201310618531A CN103586012A CN 103586012 A CN103586012 A CN 103586012A CN 201310618531 A CN201310618531 A CN 201310618531A CN 103586012 A CN103586012 A CN 103586012A
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- nitrate
- zirconium
- calcium
- urea
- mixed oxide
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Abstract
The invention relates to a method for preparing a calcium zirconium composite oxide, which comprises the following steps: weighting calcium nitrate, zirconium nitrate and urea according to mass ratio, wherein the mol ratio of zirconium nitrate to calcium nitrate is 0.11-0.67 and mole number of urea is 1.8-3.5 times of total mole number of calcium nitrate and zirconium nitrate, mixing calcium nitrate, zirconium nitrate and urea, adding deionized water, performing ultrasonic for 20-60 minutes in an ultrasonic device to form a slurry mixture; putting the above mixture in a preheat muffle furnace with temperature of 300-500 DEG C to obtain a bulky white solid, and roasting the white solid at 550-800 DEG C for 2-8 hours. The preparation method has the advantages of simple and rapid process, the disadvantages that the pH value should be strictly controlled, the washing process is long and the components easily deviates the raw material ratio in a traditional coprecipitation method can be avoided. The prepared CaO-ZrO2 has high activity for preparing biodiesel through catalyzing ester exchange reaction.
Description
Technical field
The invention belongs to chemical field, relate in particular to a kind of preparation method of calcium zirconium mixed oxide, is a kind of method that adopts nitrate-urea combustion to prepare calcium zirconium mixed oxide specifically.
Background technology
Compare biodiesel with fossil fuel and have the advantages such as nontoxic, biodegradable, renewable, under the energy and the increasingly serious situation of environmental problem, research and the production of biodiesel receive much attention.The homogeneous catalyst catalysis vegetable oil such as industrial general employing NaOH, KOH and methyl alcohol generation ester exchange reaction are carried out production biodiesel.This approach has the features such as the simple and reaction condition gentleness of technique, but product is complicated with catalyst separation process, need to pass through neutralization, washing, the series of steps such as standing, and in product washing process, understand a large amount of waste liquid of generation.Solid base catalyst has not only retained the advantage of homogeneous phase alkali, and product and catalyst be easy to separatedly, is the development trend of catalyst for ester exchange reaction.That calcium based solid alkali has advantages of is inexpensive, non-toxic, catalyzed transesterification efficiency is high, is that a class has solid base catalyst application prospect, production biodiesel.
Current normal employing coprecipitation (document: Applied Catalysis A:General, 2013,466:272 – 281), infusion process (document: Applied Catalysis A:General, 2013,452:189-202) prepare calcium based solid alkali catalyst.Also have employing hydro-thermal method (document: Catalysis Communications, 2011,12:1005 – 1008) and sol-gel process (document: Catalysis communications, 2011,12:606-610) prepare the report of calcium based solid alkali.Yet these preparation methods also come with some shortcomings, as coprecipitation requires strict pH value, control, and washing process is long, component easily departs from raw material proportioning, sol-gel process needs expensive organometallic reagent conventionally.
Summary of the invention
For the defect existing in above-mentioned prior art, technical problem to be solved by this invention is to provide a kind of method of preparing calcium zirconium mixed oxide, adopts nitrate-urea combustion to prepare CaO-ZrO
2composite oxides, for coprecipitation, the method has simply, advantage fast, the CaO-ZrO of preparation
2composite oxides have good effect for catalyzed transesterification biodiesel processed.
A kind of method of preparing calcium zirconium mixed oxide of the present invention, comprises the following steps:
(1) according to quality proportioning, take calcium nitrate, zirconium nitrate and urea, the mol ratio of zirconium nitrate and calcium nitrate is 0.11 ~ 0.67, the molal quantity of urea is calcium nitrate, zirconium nitrate total mole number 1.8 ~ 3.5 times, then calcium nitrate, zirconium nitrate and urea are mixed, add deionized water, in ultrasonic device, ultrasonic 20-60 min, forms a paste mixture;
(2) said mixture is added in the Muffle furnace that is preheating to 300 ~ 500 ℃, obtain bulk white solid, by white solid roasting at 550 ~ 800 ℃, roasting time is 2-8 hour.
Concrete, mixture through moisture evaporation, foaming, expansion after-combustion, obtains bulk white solid in Muffle furnace.
Concrete, roasting is in order to remove residual nitrate.
Further, the mol ratio of described zirconium nitrate and calcium nitrate is 0.25.
Further, the molal quantity of described urea is calcium nitrate, zirconium nitrate total mole number 2.0 times.
Further, the described amount that adds deionized water be calcium nitrate, zirconium nitrate total mole number 20-35 doubly.
Further, the temperature of described Muffle furnace is 450 ℃.
Further, described sintering temperature is 600 ℃.
Further, described roasting time is 4 hours.
Combustion reaction between nitrate and urea is a redox reaction in essence, and nitrate anion is oxidant, and urea is reducing agent.Reaction is an exothermic reaction, generates a large amount of gas simultaneously.When the mol ratio of zirconium nitrate and calcium nitrate is 0.25, when the molal quantity of urea is calcium nitrate, zirconium nitrate total mole number 2.0 times, reaction equation is as follows:
0.8 Ca(NO
3)
2·4H
2O + 0.2 Zr(NO
3)
4·5H
2O + 2 CO(NH
2)
2 
0.8 CaO + 0.2 ZrO
2 + 3.2 N
2 + 2 CO
2 + 8.2 H
2O
The present invention compares with prior art, and its technological progress is significant.The present invention adopts nitrate-urea combustion, and preparation process is simple, quick, has avoided traditional coprecipitation method to need the strict pH of control value, the shortcoming that washing process is long, component easily departs from raw material proportioning.CaO-ZrO prepared by this method
2for catalyzed transesterification biodiesel processed, there is higher activity.Preparation method of the present invention is simple and quick, be easy to control.
Accompanying drawing explanation
Fig. 1 is the XRD figure that adopts the calcium zirconium mixed oxide of the present invention's acquisition.
The specific embodiment
Below by embodiment, the present invention is described in further detail, but do not limit the present invention.
The present invention's reagent used is all purchased from Shanghai reagent company of traditional Chinese medicines group, reagent be analyze pure.
Instrument model, specification, manufacturer that the present invention is used
| Instrument model | Specification | Manufacturer |
| Muffle furnace | SX2-4 | Shanghai Suo Pu Instrument Ltd. |
| X-ray diffractometer | X'pert Pro MRD | Holland PANalytical company |
embodiment 1
(1) take 2.86 g Zr (NO
3)
45H
2o, 6.29 g Ca (NO
3)
24H
2o and 4 g CO (NH
2)
2in crucible, (mol ratio of zirconium and calcium is 0.25, and the amount of urea is calcium and zirconium total mole number 2.0 times), adds 18 ml deionized waters, stirs, and ultrasonic 30 min in ultrasonic device, form a white paste mixture.
(2) paste mixture of step (1) is transferred in the Muffle furnace that is preheating to 450 ° of C.Mixture, through moisture evaporation, foaming, expansion after-combustion, obtains bulk white solid.
(3) by step (2) gained white solid further 600 ° of C roastings 4 hours.The XRD figure of the catalyst of gained as shown in Figure 1.
embodiment 2
With embodiment 1, just by Zr (NO
3)
45H
2o and Ca (NO
3)
24H
2the mol ratio of O changes 0.43 into, and urea molal quantity is calcium and zirconium total mole number 2.2 times, makes CaO-ZrO
2catalyst.
embodiment 3
With embodiment 1, just by Zr (NO
3)
45H
2o and Ca (NO
3)
24H
2the mol ratio of O changes 0.67 into, and urea molal quantity is calcium and zirconium total mole number 2.3 times, makes CaO-ZrO
2catalyst.
embodiment 4
With embodiment 1, just by Zr (NO
3)
45H
2o and Ca (NO
3)
24H
2the mol ratio of O changes 0.11 into, and urea molal quantity is calcium and zirconium total mole number 1.8 times, makes CaO-ZrO
2catalyst.
embodiment 5
With embodiment 1, just by Zr (NO
3)
45H
2o and Ca (NO
3)
24H
2the mol ratio of O changes 0.50 into, and urea molal quantity is calcium and zirconium total mole number 2.2 times, makes CaO-ZrO
2catalyst.
embodiment 6
With embodiment 1, just by Zr (NO
3)
45H
2o and Ca (NO
3)
24H
2the mol ratio of O changes 0.11 into, and urea molal quantity is calcium and zirconium total mole number 2.7 times, makes CaO-ZrO
2catalyst.
embodiment 7
With embodiment 1, the molal quantity that is urea is calcium and zirconium total mole number 3.5 times, makes CaO-ZrO
2catalyst.
embodiment 8
Calcium zirconium mixed oxide prepared by the present invention is below described for an example of catalysis soybean oil and methyl alcohol ester exchange reaction biodiesel processed.
Take 1.5 g CaO-ZrO
2solid base catalyst (condition and step by above-described embodiment 1 are obtained) and 40 ml methyl alcohol, put into round-bottomed flask, add 80 ml soybean oils (the gold dragon fish soybean oil of beneficial Hai Jiali food marketing Co., Ltd), be heated to 65 ° of C reactions after 6 hours, use Buchner funnel filtering recovering catalyst, filtrate steams unreacted methyl alcohol with Rotary Evaporators, then puts into separatory funnel stratification, lower floor is glycerine, and upper strata is product.According to document (regenerative resource, 2005, the method that 3:14-16) provides is measured lower floor's glycerol content, calculating ester interchange conversion rate is 96.0%.
The above is only giving an example of embodiments of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the technology of the present invention principle; can also make some improvement and modification, these improve and modification is considered as protection scope of the present invention.
Claims (7)
1. a method of preparing calcium zirconium mixed oxide, is characterized in that comprising the following steps:
(1) according to quality proportioning, take calcium nitrate, zirconium nitrate and urea, the mol ratio of zirconium nitrate and calcium nitrate is 0.11 ~ 0.67, the molal quantity of urea is calcium nitrate, zirconium nitrate total mole number 1.8 ~ 3.5 times, then calcium nitrate, zirconium nitrate and urea are mixed, add deionized water, in ultrasonic device, ultrasonic 20-60 min, forms a paste mixture;
(2) said mixture is put into the Muffle furnace that is preheating to 300 ~ 500 ℃, obtained bulk white solid, by white solid roasting at 550 ~ 800 ℃, roasting time is 2-8 hour.
2. a kind of method of preparing calcium zirconium mixed oxide as claimed in claim 1, is characterized in that: described zirconium nitrate and the mol ratio of calcium nitrate are 0.25.
3. a kind of method of preparing calcium zirconium mixed oxide as claimed in claim 1, is characterized in that: the molal quantity of described urea is calcium nitrate, zirconium nitrate total mole number 2.0 times.
4. a kind of method of preparing calcium zirconium mixed oxide as claimed in claim 1, is characterized in that: the preheat temperature of described Muffle furnace is 450 ℃.
5. a kind of method of preparing calcium zirconium mixed oxide as claimed in claim 1, is characterized in that: described sintering temperature is 600 ℃.
6. a kind of method of preparing calcium zirconium mixed oxide as claimed in claim 1, is characterized in that: described roasting time is 4 hours.
7. a kind of method of preparing calcium zirconium mixed oxide as claimed in claim 1, is characterized in that: the amount that adds deionized water is calcium nitrate, zirconium nitrate total mole number 20-35 times.
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ID=50076451
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|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000246100A (en) * | 1999-03-02 | 2000-09-12 | Kao Corp | Catalyst for alkylene oxide addition |
| CN103359787A (en) * | 2013-07-15 | 2013-10-23 | 江西理工大学 | Method for preparing fully-stabilized nano-zirconia powder at low temperature by using combustion method |
-
2013
- 2013-11-29 CN CN201310618531.2A patent/CN103586012A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000246100A (en) * | 1999-03-02 | 2000-09-12 | Kao Corp | Catalyst for alkylene oxide addition |
| CN103359787A (en) * | 2013-07-15 | 2013-10-23 | 江西理工大学 | Method for preparing fully-stabilized nano-zirconia powder at low temperature by using combustion method |
Non-Patent Citations (2)
| Title |
|---|
| XIAOMING GUO等: "Glycine–nitrate combustion synthesis of CuO-ZnO-ZrO2 catalysts for methanol synthesis from CO2 hydrogenation", 《JOURNAL OF CATALYSIS》, vol. 271, 1 February 2010 (2010-02-01) * |
| 陈杰博等: "纳米固体碱CaO-ZrO2催化红麻籽油制备生物柴油", 《应用化学》, vol. 28, no. 3, 31 March 2011 (2011-03-31) * |
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Application publication date: 20140219 |