CN103920481A - Compound solid base catalyst as well as preparation method and application thereof - Google Patents
Compound solid base catalyst as well as preparation method and application thereof Download PDFInfo
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- CN103920481A CN103920481A CN201410156487.2A CN201410156487A CN103920481A CN 103920481 A CN103920481 A CN 103920481A CN 201410156487 A CN201410156487 A CN 201410156487A CN 103920481 A CN103920481 A CN 103920481A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention discloses a compound solid base catalyst as well as a preparation method and application thereof. The catalyst is prepared from 0.4%-2.2% of Ca, 53%-59% of Mg and 40%-45% of O, and the particle size of the catalyst is 30-100nm. The reparation method comprises the steps of dissolving calcium salt and magnesium salt in deionized water to obtain a solution, adding a dispersing agent, adding a precipitator in a water bath environment till the pH value is 10-11, stirring, performing ultrasonic treatment, standing for aging, filtering suspension, washing till filtrate is neutral, drying white precipitate, grinding, sieving, and baking to obtain the compound solid base catalyst which can be applied to the preparation of biodiesel. The application comprises the steps of adding raw grease, methyl alcohol and the compound solid base catalyst into a reaction kettle, reacting in an N2 atmosphere, heating, stirring, performing suction filtration, standing for layering, and performing reduced pressure distillation on crude diesel oil on the upper layer, so as to obtain the biodiesel.
Description
Technical field
The present invention relates to solid base catalyst, especially relate to a kind of complex solid base catalyst and preparation method thereof and application.
Background technology
Along with the shortage of fossil resource and going from bad to worse of ecological environment, finding a kind of clean, eco-friendly renewable alternative energy source becomes the huge challenge that people face.Biodiesel, as a kind of regeneratable liquors fuel of environmental protection, has caused countries in the world and regional extensive concern.Biodiesel has good flammability, security and greasy property, can effectively reduce the discharge of carbon dioxide and sulfide in Vehicular waste gas, to controlling urban atmospheric pollution, has important strategic importance, is acknowledged as the desirable alternative energy source of petrifaction diesel.
Biodiesel is a kind of fatty acid ester being generated by esterification or ester exchange reaction under catalyst action by animal and plant fat, oil plant leftover bits and pieces or waste cooking oil and low-carbon alcohols.At present, homogenous acid or base catalysts HCl, the H of industrial main use
2sO
4, KOH, NaOH etc., the problem such as not only easy corrosion reaction container, also exists the difficult recovery of catalyst, product separation and refining difficulty, and the difficult separating-purifying of by-product glycerin, waste liquid are too much, causes raw material availability low, production cost increases.The problem existing in order to overcome homogenous acid or base catalysts, the heterogeneous solid catalyst of preparing a kind of efficient stable becomes the focus of scholar's concern.It is active that calcium solid magnesium compound base catalyst has higher catalyzed transesterification, good to target product selectivity, and easy and product separation is reusable, and cheap, and wide material sources, are the clean complex solid base catalysts that a class has application prospect.
(Zhang Shouhua, Zhang Xinhai, the Zhang Honghao .K such as Zhang Shouhua
2o/Ti – HMS catalyzed by solid base Study on Preparation of Biodiesel from Soybean oil [J]. Soybean Science, 2010,6(29): 1043 – 1046) introduced the complex solid base catalyst K that equi-volume impregnating has been prepared molecular sieve Ti-HMS carrying alkali metal oxide
2o/Ti-HMS.Result shows: optimum reaction condition is 60 ℃ of reaction temperatures, reaction time 3h, and n (methyl alcohol): n (soybean oil)=16: 1, catalyst amount is 3% of soybean oil quality, the conversion ratio of soybean oil is more than 75% with this understanding.But this ester interchange conversion rate is lower.
Lixia ZHANG (Lixia ZHANG. attapulgite modified immobilized phosphotungstic acid (salt) and catalytic esterification thereof research [J]. the .2010 of Southern Yangtze University) studied the load-type solid acid catalyst CsHPW/Pa for preparing attapulgite modified load phosphotungstic acid cesium salt with infusion process.Result shows: optimum reaction condition is reaction time 6h, 100 ℃ of reaction temperatures, and catalyst amount is 8% of oleic acid quality, the conversion ratio of oleic acid can reach 80% left and right with this understanding.The shortcomings such as catalyst preparation process is complicated but exist, and oleic acid conversion ratio is lower.
Wei Rui equality (Wei Ruiping, slow wave, the national .K of Xiao
2cO
3/
γ-Al
2o
3catalysis palm oil and methyl alcohol ester exchange reaction are prepared biodiesel [J]. biological processing, and 2010,6(8): 10 – 13) adopt infusion process to prepare K
2cO
3/ γ-Al
2o
3load type solid body base catalyst.Result shows: work as K
2cO
3load capacity is 22.6% of carrier mass fraction, reaction temperature is 65 ℃, reaction time 3h, catalyst quality is 3% of oily quality, n (methyl alcohol): n (palm oil)=12: 1, palmitic productive rate reaches as high as 91.60% with this understanding, but the repeat performance of catalyst needs further to be studied.
For this reason, the complex solid base catalyst of a kind of efficient stable of research preparation has certain economic and social profit.
Summary of the invention
The object of this invention is to provide a kind of complex solid base catalyst and preparation method thereof.
Another object of the present invention is to provide the application of complex solid base catalyst in preparation biodiesel.
Described complex solid base catalyst is comprised of Ca, Mg, O, and Ca content is that 0.4%～2.2%, Mg content is that 53%～59%, O content is 40%～45%, and the particle diameter of catalyst is 30～100nm, and form is subsphaeroidal, is evenly distributed.
The raw material of described complex solid base catalyst is calcium salt and magnesium salts; Calcium salt can be selected from Ca (NO
3)
24H
2o, Ca (NO
3)
2, CaCl
2deng in a kind of; Magnesium salts can be selected from Mg (NO
3)
26H
2o, Mg (NO
3)
2, MgCl
26H
2o, MgCl
2, MgSO
47H
2o, MgSO
4deng in a kind of.
The preparation method of described a kind of complex solid base catalyst, concrete steps are as follows:
Calcium salt and magnesium salts are dissolved in and in deionized water, are mixed with solution, add again dispersant, under water-bath environment, add precipitating reagent to pH10～11, through stirring, ultrasonic wave is processed, standing aging after, suspension is filtered and washed to filtrate and be neutral, dry white depositions is also ground and is sieved, and obtains calcium Magnesium coumpoud oxide, i.e. complex solid base catalyst finally by roasting.
In suspension filtration washing process, dispersant and precipitating reagent abandon or reclaim with filtrate.
The ratio that described calcium salt and magnesium salts can be 0.2～5 by Ca/Mg mol ratio adds.
Optional at least one in polyethylene glycol, isopropyl alcohol etc. of described dispersant, dispersant dosage is 1%～10% of magnesium salts mass percent.
Described precipitating reagent can be selected from NH
3h
2at least one in O, NaOH etc.
The temperature of described water-bath can be 30～70 ℃; The speed of described stirring can be 300～1000r/min, and the time of stirring can be 1～30min; The time that described ultrasonic wave is processed can be 1～60min; The described standing aging time can be 10min～12h.
Described dry temperature can be 50～80 ℃, and the dry time can be 3～24h; Described sieving can be crossed 100～200 mesh sieves.
The temperature of described roasting can be 500～900 ℃, and the time of roasting can be 1～5h.
Described complex solid base catalyst can be applied in preparation biodiesel.
The method of preparing biodiesel with complex solid base catalyst is as follows:
In reactor, add grease, methyl alcohol and complex solid base catalyst, at N
2under atmosphere, react; Through heating, stirring, suction filtration, stratification, get upper strata gas-oil decompression distillation and obtain biodiesel.
Described grease can be selected from least one in palm oil, soybean oil, cottonseed oil, Jatropha oil, algae grease, waste grease etc.; The temperature of described reaction can be 120～260 ℃, and the time of reaction can be 1～8h; The mol ratio of described methyl alcohol and grease can be (6～15): 1; The mass percent that the complex solid base catalyst using accounts for grease is 0.5%～5%; The speed of described stirring can be 300～1000r/min.
Major advantage of the present invention is: 1. calcium magnesium raw material wide material sources, and cheap; 2. this catalyst preparation process is simple, easily operation, and reaction finishes rear catalyst and is easy to separated with product; 3. dispersant and the ultrasonic processing added are uniformly dispersed complex solid base catalyst, and the catalyst particle size that roasting obtains is 30～100nm, has higher catalytic activity in ester exchange reaction, can be repeatedly used, and activating and regenerating method is easy; 4. biodiesel and glycerine are neutrality, reduce the industrial wastewater that neutralization washing produces.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the complex solid base catalyst prepared of the present invention.
The specific embodiment
Below in conjunction with specific embodiments and the drawings, the invention will be further elaborated, but not thereby limiting the invention.
Embodiment 1:
By Ca (NO
3)
24H
2o and Mg (NO
3)
26H
2o is dissolved in and in deionized water, is mixed with solution by Ca/Mg mass ratio 8.33, and adds Mg (NO
3)
25% dispersant PEG10000 of quality adds alkaline precipitating agent NH under 30 ℃ of water-baths and 600r/min
3h
2o, stirs 20min, and ultrasonic processings 5min then, after standing 12h, filters suspension wash to filtrate and be neutrality, and 65 ℃ of white solids that dry 12h obtains, ground 200 eye mesh screens, and roasting 2h at 900 ℃ obtains calcium solid magnesium compound base catalyst.
In reactor, according to molar ratio of methanol to oil 12: 1, add 30.11g palm oil, 13.69g methyl alcohol, adds 1% complex solid base catalyst of palm oil quality, at N
2under atmosphere, be heated to 180 ℃, 600r/min reacts 2h.Then suction filtration, stratification, get upper strata gas-oil decompression distillation removal methyl alcohol and obtain biodiesel; Lower floor is crude glycerine.Product is through gas chromatographic detection, and the content of gained fatty acid methyl ester is 79.71%.
Embodiment 2:
By Ca (NO
3)
24H
2o and Mg (NO
3)
26H
2o is dissolved in and in deionized water, is mixed with solution by Ca/Mg mass ratio 8.33, and adds Mg (NO
3)
210% dispersant PEG10000 of quality adds alkaline precipitating agent NH under 30 ℃ of water-baths and 600r/min
3h
2o, stirs 20min, and ultrasonic processings 10min then, after standing 12h, filters suspension wash to filtrate and be neutrality, and 65 ℃ of white solids that dry 12h obtains, ground 200 eye mesh screens, and roasting 2h at 900 ℃ obtains calcium solid magnesium compound base catalyst.
In reactor, according to molar ratio of methanol to oil 12: 1, add 30.08g palm oil, 13.76g methyl alcohol, adds 1% complex solid base catalyst of palm oil quality, at N
2under atmosphere, be heated to 180 ℃, 600r/min reacts 6h.Then suction filtration, stratification, get upper strata gas-oil decompression distillation removal methyl alcohol and obtain biodiesel; Lower floor is crude glycerine.Product is through gas chromatographic detection, and the content of gained fatty acid methyl ester is 99.97%.
Embodiment 3:
By Ca (NO
3)
24H
2o and Mg (NO
3)
26H
2o is dissolved in and in deionized water, is mixed with solution by Ca/Mg mass ratio 5.00, and adds Mg (NO
3)
2the dispersant PEG6000 of quality 8% adds alkaline precipitating agent NH under 30 ℃ of water-baths and 600r/min
3h
2o, stirs 20min, and ultrasonic processings 20min then, after standing 6h, filters suspension wash to filtrate and be neutrality, and 65 ℃ of white solids that dry 6h obtains, ground 200 eye mesh screens, and roasting 2h at 800 ℃ obtains calcium solid magnesium compound base catalyst.
In reactor, according to molar ratio of methanol to oil 12: 1, add 30.15g palm oil, 13.62g methyl alcohol, adds 1% complex solid base catalyst of palm oil quality, at N
2under atmosphere, be heated to 180 ℃, 600r/min reacts 6h.Then suction filtration, stratification, get upper strata gas-oil decompression distillation removal methyl alcohol and obtain biodiesel; Lower floor is crude glycerine.Product is through gas chromatographic detection, and the content of gained fatty acid methyl ester is 99.96%.
Embodiment 4:
By Ca (NO
3)
24H
2o and Mg (NO
3)
26H
2o is dissolved in and in deionized water, is mixed with solution by Ca/Mg mass ratio 1.67, and adds Mg (NO
3)
210% dispersant PEG8000 of quality, under 50 ℃ of water-baths and 800r/min, add alkaline precipitating agent NaOH, stir 5min, then ultrasonic processing 10min, after standing 3h, filters suspension wash to filtrate and be neutral, 65 ℃ of white solids that dry 6h obtains, ground 200 eye mesh screens, roasting 3h at 800 ℃, obtains calcium solid magnesium compound base catalyst.
In reactor, according to molar ratio of methanol to oil 12: 1, add 30.15g palm oil, 10.34g methyl alcohol, adds 1% complex solid base catalyst of palm oil quality, at N
2under atmosphere, be heated to 180 ℃, 600r/min reacts 6h.Then suction filtration, stratification, get upper strata gas-oil decompression distillation removal methyl alcohol and obtain biodiesel; Lower floor is crude glycerine.Product is through gas chromatographic detection, and the content of gained fatty acid methyl ester is 98.23%.
Embodiment 5:
By Ca (NO
3)
24H
2o and Mg (NO
3)
26H
2o is dissolved in and in deionized water, is mixed with solution by Ca/Mg mass ratio 0.33, and adds Mg (NO
3)
25% isopropyl alcohol dispersant of quality, under 30 ℃ of water-baths and 600r/min, add alkaline precipitating agent NaOH, stir 10min, then ultrasonic processing 15min, after standing 3h, filters suspension wash to filtrate and be neutral, 65 ℃ of white solids that dry 12h obtains, ground 200 eye mesh screens, roasting 1h at 900 ℃, obtains calcium solid magnesium compound base catalyst.
In reactor, according to molar ratio of methanol to oil 12: 1, add 30.21g palm oil, 13.64g methyl alcohol, adds 2% complex solid base catalyst of palm oil quality, at N
2under atmosphere, be heated to 160 ℃, 600r/min reacts 6h.Then suction filtration, stratification, get upper strata gas-oil decompression distillation removal methyl alcohol and obtain biodiesel; Lower floor is crude glycerine.Product is through gas chromatographic detection, and the content of gained fatty acid methyl ester is 99.20%.
The specific area of the complex solid base catalyst of Different Ca/Mg mass ratio is referring to table 1.
The specific area of the complex solid base catalyst of table 1 Different Ca/Mg mass ratio
a: Ca/Mg8.33, represent that the ratio that catalyst raw material calcium salt and magnesium salts are 8.33 according to Ca/Mg mass ratio adds, precipitating reagent is NH
3h
2o.
By table 1, can find out, under the same terms, the specific area of CaO pressed powder prepared by laboratory is 6.736m
2/ g, and the specific area of the calcium solid magnesium compound base catalyst of preparation is at 26.631～33.747m
2between/g.The specific area of calcium solid magnesium compound base catalyst increases, and has improved its catalytic activity in ester exchange reaction.
The Ca of complex solid base catalyst, Mg, O content are referring to table 2.
Ca, the Mg of table 2 complex solid base catalyst, O content a
a: with this element, the mass fraction in catalyst represents (%) to the constituent content of catalyst.
b: adopt Energy Dispersive X-Ray Spectroscopy to detect.
By table 2, can find out, calcium solid magnesium compound base catalyst prepared by laboratory is comprised of Ca, Mg, O, and the Ca/Mg mass ratio of catalyst is 0.008～0.08, and wherein Ca content is 0.4～2.2%, Mg content is that 53.0～59.0%, O content is 40.0%～45.0%.
Fig. 1 provides the scanning electron microscope (SEM) photograph of complex solid base catalyst prepared by the present invention.The surface topography that adopts Hitachi S-4800 type scanning electron microscope analysis complex solid base catalyst, is used X-ray energy spectrum (EDX) to detect Ca/Mg mass ratio in solid base catalyst.By scanning electron microscope (SEM) photograph, can find out that catalyst particle size is 30～100nm, form is subsphaeroidal, is evenly distributed.
Claims (10)
1. a complex solid base catalyst, is characterized in that being comprised of Ca, Mg, O, and Ca content is that 0.4%～2.2%, Mg content is that 53%～59%, O content is 40%～45%.
2. a kind of complex solid base catalyst as claimed in claim 1, the raw material that it is characterized in that described complex solid base catalyst is calcium salt and magnesium salts; Calcium salt is selected from Ca (NO
3)
24H
2o, Ca (NO
3)
2, CaCl
2in a kind of; Magnesium salts is selected from Mg (NO
3)
26H
2o, Mg (NO
3)
2, MgCl
26H
2o, MgCl
2, MgSO
47H
2o, MgSO
4in a kind of.
3. a kind of preparation method of complex solid base catalyst as claimed in claim 1, is characterized in that concrete steps are as follows:
Calcium salt and magnesium salts are dissolved in and in deionized water, are mixed with solution, add again dispersant, under water-bath environment, add precipitating reagent to pH10～11, through stirring, ultrasonic wave is processed, standing aging after, suspension is filtered and washed to filtrate and be neutral, dry white depositions is also ground and is sieved, and obtains calcium Magnesium coumpoud oxide, i.e. complex solid base catalyst finally by roasting.
4. a kind of preparation method of complex solid base catalyst as claimed in claim 3, is characterized in that the ratio that described calcium salt and magnesium salts are 0.2～5 by Ca/Mg mol ratio adds.
5. a kind of preparation method of complex solid base catalyst as claimed in claim 3, is characterized in that described dispersant is selected from least one in polyethylene glycol, isopropyl alcohol, and dispersant dosage is 1%～10% of magnesium salts mass percent; Described precipitating reagent can be selected from NH
3h
2at least one in O, NaOH.
6. a kind of preparation method of complex solid base catalyst as claimed in claim 3, the temperature that it is characterized in that described water-bath is 30～70 ℃; The speed of described stirring can be 300～1000r/min, and the time of stirring can be 1～30min; The time that described ultrasonic wave is processed can be 1～60min; The described standing aging time can be 10min～12h.
7. a kind of preparation method of complex solid base catalyst as claimed in claim 3, is characterized in that described dry temperature is 50～80 ℃, and the dry time is 3～24h; Described sieving can be crossed 100～200 mesh sieves; The temperature of described roasting can be 500～900 ℃, and the time of roasting can be 1～5h.
8. complex solid base catalyst is applied in preparation biodiesel as claimed in claim 1.
9. application as claimed in claim 8, is characterized in that the described method of preparing biodiesel is as follows:
In reactor, add grease, methyl alcohol and complex solid base catalyst, at N
2under atmosphere, react; Through heating, stirring, suction filtration, stratification, get upper strata gas-oil decompression distillation and obtain biodiesel.
10. application as claimed in claim 9, is characterized in that described grease is selected from least one in palm oil, soybean oil, cottonseed oil, Jatropha oil, algae grease, waste grease; The temperature of described reaction can be 120～260 ℃, and the time of reaction can be 1～8h; The mol ratio of described methyl alcohol and grease can be (6～15): 1; The mass percent that the complex solid base catalyst using accounts for grease is 0.5%～5%; The speed of described stirring can be 300～1000r/min.
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| CN201410156487.2A CN103920481B (en) | 2014-04-18 | A kind of complex solid base catalyst and preparation method and application |
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|---|---|---|---|
| CN201410156487.2A CN103920481B (en) | 2014-04-18 | A kind of complex solid base catalyst and preparation method and application |
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| CN103920481A true CN103920481A (en) | 2014-07-16 |
| CN103920481B CN103920481B (en) | 2016-11-30 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226343A (en) * | 2014-09-28 | 2014-12-24 | 佛山市天晟隆油脂化工有限公司 | Preparation method for solid base catalyst |
| CN104226346A (en) * | 2014-09-28 | 2014-12-24 | 佛山市天晟隆油脂化工有限公司 | Preparation method for solid base catalyst |
| CN104258882A (en) * | 2014-09-28 | 2015-01-07 | 佛山市天晟隆油脂化工有限公司 | Preparation method of solid base catalyst |
| CN109876790A (en) * | 2019-01-02 | 2019-06-14 | 湘潭大学 | A kind of CaO-MgO-Al2O3The method of catalyzed by solid base biodiesel synthesis |
| CN111167453A (en) * | 2020-02-18 | 2020-05-19 | 山西大学 | Preparation method and application method of catalyst for removing ammonia nitrogen in water |
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| CN101811038A (en) * | 2010-04-30 | 2010-08-25 | 太原理工大学 | Method for synthesizing biodiesel solid base catalyst and application |
| CN102172521A (en) * | 2011-03-04 | 2011-09-07 | 北京林业大学 | Solid basic catalyst and preparation method and application thereof |
| CN102824903A (en) * | 2012-09-07 | 2012-12-19 | 贵州大学 | Porous solid alkali catalyst prepared by using dolomite as raw material and application of porous solid alkali catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226343A (en) * | 2014-09-28 | 2014-12-24 | 佛山市天晟隆油脂化工有限公司 | Preparation method for solid base catalyst |
| CN104226346A (en) * | 2014-09-28 | 2014-12-24 | 佛山市天晟隆油脂化工有限公司 | Preparation method for solid base catalyst |
| CN104258882A (en) * | 2014-09-28 | 2015-01-07 | 佛山市天晟隆油脂化工有限公司 | Preparation method of solid base catalyst |
| CN109876790A (en) * | 2019-01-02 | 2019-06-14 | 湘潭大学 | A kind of CaO-MgO-Al2O3The method of catalyzed by solid base biodiesel synthesis |
| CN111167453A (en) * | 2020-02-18 | 2020-05-19 | 山西大学 | Preparation method and application method of catalyst for removing ammonia nitrogen in water |
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Inventor after: Zeng Xianhai Inventor after: Li Weifeng Inventor after: Guo Xiaoyi Inventor after: Hao Weiwei Inventor after: Sun Yong Inventor after: Lin Lu Inventor before: Zeng Xianhai Inventor before: Li Weifeng Inventor before: Sun Yong Inventor before: Lin Lu |
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