CN103894168A - Magnesium oxide solid base catalyst as well as preparation method and application thereof - Google Patents
Magnesium oxide solid base catalyst as well as preparation method and application thereof Download PDFInfo
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- CN103894168A CN103894168A CN201410155953.5A CN201410155953A CN103894168A CN 103894168 A CN103894168 A CN 103894168A CN 201410155953 A CN201410155953 A CN 201410155953A CN 103894168 A CN103894168 A CN 103894168A
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- 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 relates to a magnesium oxide solid base catalyst as well as a preparation method and an application thereof, and relates to solid base catalysts. The magnesium oxide solid base catalyst consists of magnesium element and oxygen element, the grain size of the catalyst is 50-100 nm, and the catalyst is nearly spherical in form and uniform in distribution. The preparation method comprises the following steps: dissolving magnesium salt in water to prepare a 0.01-3.00 mol/L solution; adding a dispersing agent; after stirring, adding a precipitant in a water bath environment until the pH is 10-11; after stirring again, carrying out combined treatment through microwave and ultrasonic; after standing for aging, filtering turbid liquid and washing until filtrate is neutral; obtaining white solid after drying; then grinding and sieving, thereby obtaining the magnesium oxide solid base catalyst after roasting. The magnesium oxide solid base catalyst can be applied in the preparation of biodiesel. Grease, low carbon alcohol and the magnesium oxide solid base catalyst are added in a reaction kettle, and under the atmosphere of N2, a reaction is carried out through heating, stirring, suction filtration and standing for hierarchy, and the biodiesel is obtained by taking crude diesel oil on the upper layer for reduced pressure distillation.
Description
Technical field
The present invention relates to solid base catalyst, especially relate to a kind of magnesia solid base catalyst and preparation method thereof and application.
Background technology
Along with the continuous consumption of fossil resource and going from bad to worse of ecological environment, finding a kind of clean, eco-friendly reproducible alternative energy source becomes the major issue that people face.Biodiesel is a kind of regeneratable liquors fuel of environmental protection, and it possesses good flammability, security and greasy property, can effectively reduce the discharge of carbon dioxide and sulfide in Vehicular waste gas, has important strategic importance to controlling urban atmospheric pollution.This makes biodiesel be acknowledged as the desirable alternative energy source of petrifaction diesel, becomes the focus that people study.
Biodiesel is taking animal and plant fat, oil plant leftover bits and pieces or waste cooking oil etc. as raw material, and the fatty acid ester that generates by esterification or ester exchange reaction under catalyst action of low-carbon alcohols.At present, industrial main use homogenous acid or base catalysts, as HCl, H
2sO
4, KOH, NaOH, CH
3oNa, CH
3oK etc., that these catalyst exist is perishable, the difficult recovery of catalyst, product separation and refining difficulty, by-product glycerin separating-purifying difficulty, generates the too much problem of waste liquid, has reduced raw material availability, has increased production cost.The problem existing in order to overcome homogenous acid or base catalysts, the heterogeneous solid catalyst of preparing a kind of efficient stable is subject to scholar's extensive concern.Magnesia solid base catalyst has higher catalyzed transesterification activity, easily separated, reusable, and cheap, and wide material sources are clean solid base catalysts that a class has application prospect.In addition, it is neutral that product ester class and by-product glycerin are all, and without washing, effectively avoided the generation of waste liquid.
Chinese patent 200610053324.7 has been introduced a kind of method that uses solid base catalyst to prepare biodiesel, and described solid base catalyst is that rare-earth oxide is as La
2o
3, CeO
2, Sm
2o
3, Eu
3o
3, Y
2o
3, Ln
2o
3in one or more, and the rare-earth oxide of load KF taking rare-earth oxide as carrier, as KF/La
2o
3, KF/CeO
2, KF/Sm
2o
3, KF/Eu
3o
3, KF/Y
2o
3, KF/Ln
2o
3in one.It is neutral that product ester class and by-product glycerin are all, and do not need neutralization washing, and catalyst can be repeatedly used simultaneously.But this type of catalyst preparation process complexity, cost of material is higher.
(Ji Junmin, Yang Guolong, the Bi Yanlan such as Ji Junmin, Jing Yanrong, Wu Dongxiao. fatty acid methyl ester [J] is prepared in ionic liquid ([BMIM] BF4) catalysis soybean oil ester exchange. Chinese grain and oil journal, 2010,25 (10): 65 – 68) introduce use ionic liquid [BMIM] BF
4the ester exchange reaction of (1-butyl-3-methyl imidazolium tetrafluoroborate) catalysis soybean oil and methyl alcohol.Result shows: optimum reaction condition is 69 DEG C of reaction temperatures, reaction time 4h, n (methyl alcohol): n (soybean oil)=6: 1, catalyst amount is 1% of soybean oil quality, the conversion ratio of soybean oil can reach more than 96% with this understanding, [BMIM] BF
4easily and product separation, reusable 3 times, but higher with ionic liquid price, be unfavorable for reducing production costs.
(the Zhang Shouhua such as Zhang Shouhua, Zhang Xinhai, Zhang Honghao .K2O/Ti – HMS catalyzed by solid base Study on Preparation of Biodiesel from Soybean oil [J]. Soybean Science, 2010,6(29): 1043 – 1046) introduce 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 DEG C 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.
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, 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 DEG C, 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, a kind of efficient stable of research preparation, magnesia solid base catalyst with low cost have certain economic and social profit.
Summary of the invention
The object of this invention is to provide a kind of magnesia solid base catalyst and preparation method thereof.
Another object of the present invention is to provide the application of a kind of magnesia solid base catalyst in preparation biodiesel.
Described magnesia solid base catalyst is made up of magnesium elements and oxygen element, and the particle diameter of catalyst is 50～100nm, and form is subsphaeroidal, is evenly distributed.
Described magnesia solid base catalyst raw material can be selected from Mg (NO
3)
26H
2o, Mg (NO
3)
2, MgCl
26H
2o, MgCl
2, MgSO
47H
2o, MgSO
4deng in one.
The preparation method of described a kind of magnesia solid base catalyst, concrete steps are as follows:
Be mixed with by soluble in water magnesium salts the solution that concentration is 0.01～3.00mol/L, add dispersant, after stirring, under water-bath environment, add precipitating reagent to pH10～11, after again stirring, through microwave and ultrasonic coupling processing, leave standstill aging after, suspension is filtered and is washed to filtrate be neutrality, after dry, obtain white solid, grind and sieve again, after roasting, obtain magnesia solid base catalyst.
In suspension filtration washing process, dispersant and precipitating reagent abandon or reclaim with filtrate.
Optional at least one in polyethylene glycol, isopropyl alcohol etc. of described dispersant; The addition of described dispersant can be 1%～10% of magnesium salts by mass percentage; The speed of described stirring can be 400～1000r/min; The temperature of described water-bath can be 30～80 DEG C; Described precipitating reagent can be selected from NH
3h
2at least one in O, NaOH, carbonate etc.; The described time of again stirring can be 5min～1h; The power of described microwave can be 50～1000W, and described ultrasonic power can be 100～1000W, and the time of described microwave and ultrasonic coupling processing can be 0.5～10min; The described standing aging time can be 0.5～12h; Described dry condition can be at 50～105 DEG C of vacuum drying 2～12h; Described sieving can be crossed 100～200 eye mesh screens; The temperature of described roasting can be 500～900 DEG C, and the time of roasting can be 1～5h.
Described magnesia solid base catalyst can be applied in preparation biodiesel.
The method of preparing biodiesel with magnesia solid base catalyst is as follows:
In reactor, add grease, low-carbon alcohols and magnesia solid base catalyst, at N
2under atmosphere, reaction, through heating, stirring, suction filtration, stratification, gets upper strata gas-oil decompression distillation and obtains biodiesel.
Described grease can be selected from least one in palm oil, soybean oil, cottonseed oil, Jatropha oil, algae grease, waste grease etc.Described low-carbon alcohols can be selected from least one in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, sec-butyl alcohol, the tert-butyl alcohol etc.The temperature of described reaction can be 120～260 DEG C, and the time of reaction can be 1～8h; The mol ratio of methyl alcohol and grease can be (6～15): 1, the quality of magnesia solid base catalyst can account for grease quality 0.5%～5%, stir speed (S.S.) can be 300～1000r/min.
Major advantage of the present invention is: magnesium raw material wide material sources, and cheap.Described catalyst preparation process is simple, and under dispersant, microwave ultrasound acting in conjunction, catalyst precarsor is uniformly dispersed, and the catalyst particle size that roasting obtains is 50～100nm, and form is subsphaeroidal, is evenly distributed.This magnesia solid base catalyst has higher catalytic activity in ester exchange reaction, easily and separation of products, through reclaim for three times use after catalytic activity obviously do not reduce, and biodiesel and glycerine is neutrality, without washing, can not produce industrial wastewater.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of the precursor magnesium hydroxide of magnesia solid base catalyst.
Fig. 2 is the stereoscan photograph of the magnesia solid base catalyst that makes of laboratory.
Fig. 3 is the stereoscan photograph that repeats expendable magnesia solid base catalyst.
Fig. 4 is the stereoscan photograph of reusing the magnesia solid base catalyst of twice.
Fig. 5 is the stereoscan photograph of reusing the magnesia solid base catalyst of three times.
Detailed description of the invention
Below in conjunction with concrete embodiment and accompanying drawing, the invention will be further elaborated, but not thereby limiting the invention.
Embodiment 1:
Magnesium salts is dissolved in to the solution that is mixed with 0.05mol/L in deionized water, adds Mg (NO
3)
23% dispersant PEG10000 of quality adds precipitating reagent NH under 30 DEG C of water-baths and 600r/min stir
3h
2o, stir 10min, then process 3min through 200W microwave and the ultrasonic coupling of 500W, under room temperature, leave standstill aging 12h, suspension is filtered and washed to filtrate and be neutral, 105 DEG C of vacuum drying 4h obtain white solid, are ground 200 eye mesh screens, roasting 2h at 900 DEG C, obtains magnesia solid base catalyst.
In 100mL autoclave, be to add 30.03g palm oil at 9: 1 according to molar ratio of methanol to oil, 10.23g methyl alcohol, adds 1% magnesia solid base catalyst of palm oil quality, at N
2under atmosphere, be heated to 240 DEG C, 600r/min reacts 2h.Then suction filtration, stratification, gets upper strata gas-oil decompression distillation removal methyl alcohol and obtains biodiesel; Take off a layer crude glycerine decompression distillation and obtain glycerine.It is neutral that biodiesel and glycerine are all, and product is through gas chromatographic detection, and the content of gained fatty acid methyl ester is 95.11%.
Embodiment 2:
Magnesium salts is dissolved in to the solution that is mixed with 0.1mol/L in deionized water, adds Mg (NO
3)
25% dispersant PEG10000 of quality adds precipitating reagent NH under 30 DEG C of water-baths and 600r/min stir
3h
2o, stir 20min, then process 6min through 200W microwave and the ultrasonic coupling of 600W, under room temperature, leave standstill aging 6h, suspension is filtered and washed to filtrate and be neutral, 105 DEG C of vacuum drying 4h obtain white solid, are ground 200 eye mesh screens, roasting 3h at 800 DEG C, obtains magnesia solid base catalyst.
In 100mL autoclave, be to add 30.04g palm oil at 9: 1 according to molar ratio of methanol to oil, 10.27g methyl alcohol, adds 1% magnesia solid base catalyst of palm oil quality, at N
2under atmosphere, be heated to 180 DEG C, 600r/min reacts 2h.Then suction filtration, stratification, gets upper strata gas-oil decompression distillation removal methyl alcohol and obtains biodiesel; Take off a layer crude glycerine decompression distillation and obtain glycerine.It is neutral that biodiesel and glycerine are all, and product is through gas chromatographic detection, and the content of gained fatty acid methyl ester is 80.06%.
Embodiment 3:
Magnesium salts is dissolved in to the solution that is mixed with 0.1mol/L in deionized water, adds Mg (NO
3)
25% dispersant PEG6000 of quality adds precipitating reagent NH under 30 DEG C of water-baths and 600r/min stir
3h
2o, stir 10min, then process 3min through 200W microwave and the ultrasonic coupling of 500W, under room temperature, leave standstill aging 3h, suspension is filtered and washed to filtrate and be neutral, 105 DEG C of vacuum drying 4h obtain white solid, are ground 200 eye mesh screens, roasting 3h at 700 DEG C, obtains magnesia solid base catalyst.
In 100mL autoclave, be to add 29.97g palm oil at 9: 1 according to molar ratio of methanol to oil, 10.28g methyl alcohol, adds 1% magnesia solid base catalyst of palm oil quality, at N
2under atmosphere, be heated to 180 DEG C, 600r/min reacts 6h.Then suction filtration, stratification, gets upper strata gas-oil decompression distillation removal methyl alcohol and obtains biodiesel; Take off a layer crude glycerine decompression distillation and obtain glycerine.It is neutral that biodiesel and glycerine are all, and product is through gas chromatographic detection, and the content of gained fatty acid methyl ester is 95.68%.
Embodiment 4:
Magnesium salts is dissolved in to the solution that is mixed with 0.5mol/L in deionized water, adds Mg (NO
3)
210% dispersant PEG6000 of quality, under 50 DEG C of water-baths and 600r/min stirring, add precipitating reagent NaOH, stir 30min, then process 2min through 300W microwave and the ultrasonic coupling of 800W, under room temperature, leave standstill aging 6h, suspension is filtered and washed to filtrate and be neutrality, 105 DEG C of vacuum drying 4h obtain white solid, ground 200 eye mesh screens, roasting 4h at 600 DEG C, obtains magnesia solid base catalyst.
In 100mL autoclave, be to add 30.12g palm oil at 6: 1 according to molar ratio of methanol to oil, 6.91g methyl alcohol, adds 2% magnesia solid base catalyst of palm oil quality, at N
2under atmosphere, be heated to 180 DEG C, 600r/min reacts 6h.Then suction filtration, stratification, gets upper strata gas-oil decompression distillation removal methyl alcohol and obtains biodiesel; Take off a layer crude glycerine decompression distillation and obtain glycerine.It is neutral that biodiesel and glycerine are all, and product is through gas chromatographic detection, and the content of gained fatty acid methyl ester is 96.23%.
Embodiment 5:
Magnesium salts is dissolved in to the solution that is mixed with 1mol/L in deionized water, adds Mg (NO
3)
25% dispersant PEG10000 of quality, under 50 DEG C of water-baths and 600r/min stirring, add precipitating reagent NaOH, stir 10min, then process 10min through 200W microwave and the ultrasonic coupling of 500W, under room temperature, leave standstill aging 9h, suspension is filtered and washed to filtrate and be neutrality, 105 DEG C of vacuum drying 3h obtain white solid, ground 200 eye mesh screens, roasting 1h at 900 DEG C, obtains magnesia solid base catalyst.
In 100mL autoclave, be to add 30.07g palm oil at 12: 1 according to molar ratio of methanol to oil, 13.64g methyl alcohol, adds 1% magnesia solid base catalyst of palm oil quality, at N
2under atmosphere, be heated to 180 DEG C, 600r/min reacts 6h.Then suction filtration, stratification, gets upper strata gas-oil decompression distillation removal methyl alcohol and obtains biodiesel; Take off a layer crude glycerine decompression distillation and obtain glycerine.It is neutral that biodiesel and glycerine are all, and product is through gas chromatographic detection, and the content of gained fatty acid methyl ester is 97.08%.
Fig. 1 is the precursor Mg (OH) of magnesia solid base catalyst
2scanning electron microscope (SEM) photograph; Fig. 2 is the scanning electron microscope (SEM) photograph of the MgO that makes after 900 DEG C of roasting 2h of magnesia solid base catalyst precursor magnesium hydroxide; Fig. 3 is the scanning electron microscope (SEM) photograph that repeats expendable magnesia solid base catalyst; Fig. 4 is the scanning electron microscope (SEM) photograph of reusing the magnesia solid base catalyst of twice; Fig. 5 is the scanning electron microscope (SEM) photograph of reusing the magnesia solid base catalyst of three times.As can be seen from Figure 1, catalyst precarsor Mg (OH)
2have club shaped structure and layer structure, obtain magnesia solid base catalyst sphere diameter and be about 50～100nm after 900 DEG C of roastings, form is subsphaeroidal, is evenly distributed.Through three catalyst recovery experiments, find that magnesia solid base catalyst is still keeping higher catalytic activity in course of reaction.Can find out by scanning electron microscope (SEM) photograph, there is not significant variation in the granularity of catalyst and surface topography, and through after catalyzed transesterification repeatedly, in catalyst, magnesia disperses more even.Adopt the surface topography of Hitachi S-4800 type scanning electron microscope analysis magnesia solid base catalyst, observing catalyst particle size is 50～100nm, form is subsphaeroidal, be evenly distributed, reusing through three times, there is not marked change in the surface topography of magnesia solid base catalyst.
Reusing of magnesia solid base catalyst tested referring to table 1.
Table 1
a: the addition of catalyst represents with the mass fraction of raw oil material.
Can find out by table 1, the magnesia solid base catalyst of preparation has stronger catalytic activity in ester exchange reaction, and after three times are reclaimed use, catalytic activity does not obviously reduce.
Claims (10)
1. a magnesia solid base catalyst, is characterized in that being made up of magnesium elements and oxygen element.
2. a kind of magnesia solid base catalyst as claimed in claim 1, is characterized in that the raw material of described magnesia solid base catalyst is selected from Mg (NO
3)
26H
2o, Mg (NO
3)
2, MgCl
26H
2o, MgCl
2, MgSO
47H
2o, MgSO
4in one.
3. a kind of preparation method of magnesia solid base catalyst as claimed in claim 1, is characterized in that its concrete steps are as follows:
Be mixed with by soluble in water magnesium salts the solution that concentration is 0.01～3.00mol/L, add dispersant, after stirring, under water-bath environment, add precipitating reagent to pH10～11, after again stirring, through microwave and ultrasonic coupling processing, leave standstill aging after, suspension is filtered and is washed to filtrate be neutrality, after dry, obtain white solid, grind and sieve again, after roasting, obtain magnesia solid base catalyst.
4. a kind of preparation method of magnesia solid base catalyst as claimed in claim 3, is characterized in that described dispersant is selected from least one in polyethylene glycol, isopropyl alcohol; The addition of described dispersant can be 1%～10% of magnesium salts by mass percentage.
5. a kind of preparation method of magnesia solid base catalyst as claimed in claim 3, the speed that it is characterized in that described stirring is 400～1000r/min; The temperature of described water-bath can be 30～80 DEG C.
6. a kind of preparation method of magnesia solid base catalyst as claimed in claim 3, is characterized in that described precipitating reagent is selected from NH
3h
2at least one in O, NaOH, carbonate; The described time of again stirring is 5min～1h; The power of described microwave can be 50～1000W, and described ultrasonic power can be 100～1000W, and the time of described microwave and ultrasonic coupling processing can be 0.5～10min; The described standing aging time can be 0.5～12h; Described dry condition can be at 50～105 DEG C of vacuum drying 2～12h; Described sieving can be crossed 100～200 eye mesh screens; The temperature of described roasting can be 500～900 DEG C, and the time of roasting can be 1～5h.
7. a kind of magnesia solid base catalyst is applied in preparation biodiesel as claimed in claim 1.
8. application as claimed in claim 7, is characterized in that the described method of preparing biodiesel is as follows:
In reactor, add grease, low-carbon alcohols and magnesia solid base catalyst, at N
2under atmosphere, reaction, through heating, stirring, suction filtration, stratification, gets upper strata gas-oil decompression distillation and obtains biodiesel.
9. application as claimed in claim 8, is characterized in that described grease is selected from least one in palm oil, soybean oil, cottonseed oil, Jatropha oil, algae grease, waste grease; Described low-carbon alcohols can be selected from least one in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, sec-butyl alcohol, the tert-butyl alcohol.
10. application as claimed in claim 8, the temperature that it is characterized in that described reaction is 120～260 DEG C, the time of reaction is 1～8h; The mol ratio of methyl alcohol and grease can be (6～15): 1, the quality of magnesia solid base catalyst can account for grease quality 0.5%～5%, stir speed (S.S.) can be 300～1000r/min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106861668A (en) * | 2017-02-13 | 2017-06-20 | 杭州诚洁环保有限公司 | A kind of MgO/HC solid base catalysts and its catalysis ozone process the purposes and method of waste water |
| CN106955690A (en) * | 2017-04-20 | 2017-07-18 | 曲阜师范大学 | A kind of catalysis ethanol prepares the solid basic catalyst and preparation method of butanol |
| CN107442095A (en) * | 2017-08-25 | 2017-12-08 | 哈尔滨工业大学 | A kind of preparation method of nano magnesia ozone catalyst and the deep treatment method with its catalysis oxidation coal chemical industrial waste water |
| CN109701564A (en) * | 2018-09-18 | 2019-05-03 | 湘潭大学 | A kind of chondritic solid base KF/MgO-CeO2The method of catalytically synthesizing biological diesel oil |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106861668A (en) * | 2017-02-13 | 2017-06-20 | 杭州诚洁环保有限公司 | A kind of MgO/HC solid base catalysts and its catalysis ozone process the purposes and method of waste water |
| CN106955690A (en) * | 2017-04-20 | 2017-07-18 | 曲阜师范大学 | A kind of catalysis ethanol prepares the solid basic catalyst and preparation method of butanol |
| CN106955690B (en) * | 2017-04-20 | 2020-05-01 | 曲阜师范大学 | Solid alkaline catalyst for preparing butanol by catalyzing ethanol and preparation method thereof |
| CN107442095A (en) * | 2017-08-25 | 2017-12-08 | 哈尔滨工业大学 | A kind of preparation method of nano magnesia ozone catalyst and the deep treatment method with its catalysis oxidation coal chemical industrial waste water |
| CN109701564A (en) * | 2018-09-18 | 2019-05-03 | 湘潭大学 | A kind of chondritic solid base KF/MgO-CeO2The method of catalytically synthesizing biological diesel oil |
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