CN101780415A - Coal cinder supported solid base catalyst and preparation method and use thereof - Google Patents
Coal cinder supported solid base catalyst and preparation method and use thereof Download PDFInfo
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- CN101780415A CN101780415A CN201010103643A CN201010103643A CN101780415A CN 101780415 A CN101780415 A CN 101780415A CN 201010103643 A CN201010103643 A CN 201010103643A CN 201010103643 A CN201010103643 A CN 201010103643A CN 101780415 A CN101780415 A CN 101780415A
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- solid base
- base catalyst
- coal cinder
- supported solid
- cinder
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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 coal cinder supported solid base catalyst and a preparation method and use thereof. The coal cinder supported solid base catalyst is prepared by soaking a dried coal cinder carrier with a certain particle diameter in aqueous solution of K2CO3 with the concentration of 0.3 to 1 g/ml, and filtering, drying and calcining after adsorption equilibrium. The coal cinder supported solid base catalyst can efficiently catalyze various vegetable oils to produce biodiesel under mild reaction conditions (normal pressure and the temperature of less than 70 DEG C). The yield of the coal cinder supported solid base catalyst can reach over 93 percent and over 99 percent maximally. The coal cinder supported solid base catalyst has the advantages of having simple preparation method and low cost, facilitating continuous production of the biodiesel, saving the production cost, reducing the operating cost, and simplifying the production process flow and the purification process of the biodiesel.
Description
Technical field
The present invention relates to a kind of coal cinder supported solid base catalyst and preparation method thereof and under the methyl alcohol boiling point catalysis vegetable oil (fatty glyceride) and methyl alcohol carry out the purposes that ester exchange reaction prepares biodiesel.
Background technology
Biodiesel is meant by reproducible animal and plant fat and short chain alcohol (methyl alcohol or ethanol) carries out the prepared fatty acid methyl ester of ester exchange reaction, is a kind of regenerative resource that can substitute the cleaning of petrifaction diesel use.Biodiesel does not contain aromatic hydrocarbon and sulfur content is very low, compares with petrifaction diesel, and the discharge capacity of major pollutants reduces, toxic emission index symbol and European standard; The what is more important biodiesel has recyclability, and greasy property is good, sufficient combustion, and transportation is with safe in utilization.
At present, the main production method of biodiesel has four kinds of blending methods, mini-emulsion process, high temperature pyrolytic cracking (HTP), ester-interchange method.Wherein admix method and mini-emulsion process and belong to the physics method, high temperature pyrolytic cracking (HTP) and ester-interchange method belong to chemical method.Mix use or mini-emulsion process and can reduce the animals and plants oil viscosity, but problems such as carbon deposit and lubricant pollution are difficult to solve; And the major product of high temperature pyrolytic cracking is a biogasoline, and biodiesel is its byproduct.By contrast, ester-interchange method is a kind of better preparation method, will simply introduce research situation and products thereof the characteristics of this kind method below.
Ester-interchange method is also referred to as alcoholysis method, is the method that present industrial production biodiesel is used at most, technology is the most ripe, and this method is simple because of production technology, cost is low, easy to control, is subjected to the common concern of Chinese scholars.Ester-interchange method commonly used mainly contains soda acid homogeneous catalysis transesterification reaction, lipase-catalyzed transesterification reaction, heterogeneous catalyzed by solid base transesterification reaction etc.
The acid catalysis transesterification reaction, reaction temperature and pressure height, methanol usage is big, and reaction speed is slow, and consersion unit needs stainless steel material, and industrial acid catalyzed process receives publicity degree much smaller than the base catalysis method.Advantages such as alkali homogeneous catalysis transesterification reaction has the reaction condition gentleness, and the catalyst cost is very low, and reaction afterproduct yield is higher, and the reaction time is short.But reaction finishes rear catalyst and product separation difficulty, and has a large amount of spent acid, alkali lye to discharge, and has increased running cost and Environmental costs.
Lipase-catalyzed transesterification reaction has that mild condition, pure consumption are little, product is easy to purify, the free fatty in the non-pollutant discharge, grease can change into advantages such as methyl esters fully, therefore, adopt enzymatic to prepare biodiesel and caused that people more and more pay close attention to.But because lipase easy inactivation in high concentration methanol and ethanol, and the carbon number of alcohol is few more, causes the ability of the irreversible inactivation of enzyme just strong more, cause the enzymatic conversion method rate very low, and enzyme deactivation is serious, and the conversion ratio of Production by Enzymes biodiesel is lower so far.
Solid base mainly is meant the solid that can provide electronics to reactant, has extremely strong power supply or accepts electronic capability as its activated centre of catalyst.Solid base just refers to the acid of energy chemisorbed or makes the solid of acid indicator variable color.Solid base catalyst can be divided into multiple catalyst system and catalyzing by different sorting techniques, mainly is divided into non-loading type solid base and load-type solid.Wherein, non-loading type mainly comprises metal oxide solid alkali, molecular sieve, clay mineral and deacidite etc., and is relatively stricter to the requirement of the factors such as reaction temperature, reaction time, the process complexity, the Catalyst Production cost is limited to its industrial application value than higher.At present, in solid base catalyst commonly used, load-type solid has because of it that preparation is simple, specific area is relatively large, alkalescence is strong and the aperture is even etc. that advantage becomes most popular a kind of catalyst.Material as catalyst carrier mostly is at present: Al
2O
3, CaO, activated carbon etc., the main feature of this class carrier is inner porous, has bigger specific area, can play peptizaiton preferably.But solid base catalyst catalyzed transesterification commonly used at present mainly contains following shortcoming: molar ratio of methanol to oil is big (being more common in 15: 1), the ester exchange reaction time is grown (being more common in more than the 2h), reaction temperature higher (being more common in more than 80 ℃), esterification yield is rarely in more than 95%.
China is the production of energy and consumption big country based on coal.Thermal power plant, industry and civil boiler and other coal combustion equipments are all discharged a large amount of cinders every year.If be not used, the long-term stacking, appropriation of land, the land resources of serious waste preciousness threaten to the environment and the mankind.Along with the minimizing of resource, the energy, it is particularly important that the comprehensive utilization of refuse seems, turns waste into wealth and promptly protect environment to increase resource regeneration again, and economy and environment are improved synchronously.Cinder is grey or linen solid particulate matter, contains a large amount of activating oxide (Al
2O
3, SiO
2Deng), have loose structure than bigger serface.When cinder is used as catalyst carrier, except the effect that can play dispersion and stabilizing active component, itself can also provide acid, basic active center and catalytic component synergy.And relevant cinder is done the correlative study of catalyst carrier and is not appeared in the newspapers.
Summary of the invention
The objective of the invention is to remedy the deficiency of above-mentioned prior art, provide a kind of can be under the reaction condition of gentleness, promote ester exchange reaction efficiently to carry out, the purposes of coal cinder supported solid base catalyst that technology is simple, cost is low and preparation method thereof and this biodiesel, can avoid the subtractive process of homogeneous phase method complexity and the problem of environmental pollution that is brought, also effectively utilized discarded cinder, turned waste into wealth, the most important alternative energy that provides green cleaning.
The technical scheme that realizes the object of the invention is: a kind of coal cinder supported solid base catalyst, its preparation method are to be that the dry cinder carrier of 1mm～10mm is immersed in the K that concentration is 0.3g/ml～1g/ml with particle diameter
2CO
3In the aqueous solution, filter after reaching adsorption equilibrium, solid sample oven dry back in 300 ℃～800 ℃ calcinings 0.5～6 hour down, is obtained coal cinder supported solid base catalyst.
Described cinder and K
2CO
3The mass volume ratio of water is 0.2g/ml～0.6g/ml in the aqueous solution.
Coal cinder supported solid base catalyst of the present invention is used to prepare biodiesel.
The present invention is the K that charge density is higher
2CO
3Introducing cinder surface, high-temperature roasting help carrier and active component takes place to interact and form new crystalline phase, promptly new activity centre, thus the purpose of ester exchange reaction is quickened in realization, improves the activity of solid base catalyst, and then improve the productive rate of biodiesel.Therefore, advantage of the present invention is:
Coal cinder supported solid base catalyst of the present invention has effectively utilized discarded cinder, turn waste into wealth, can be under the reaction condition of gentleness (normal pressure, temperature＜70 ℃) promote ester exchange reaction efficiently to carry out, catalytic efficiency is near homogeneous liquid base catalysts such as sodium methoxides, biodiesel production rate reaches more than 93%, reaches as high as more than 99%; Product can satisfy the main performance index of biodiesel standard after separation and purification, and this catalyst is to participate in reaction with heterogeneous form, simple with separating of biodiesel product, postprocessing working procedures obtains simplifying, catalyst can reclaim repeated use, greatly reduces the job costs and the Environmental costs of production of biodiesel.
The specific embodiment
The invention will be further described below by specific embodiment, but protection content of the present invention is not limited to following examples.
Embodiment 1
Take by weighing potash 35g in beaker, be dissolved in the 100mL deionized water, stirring is fully dissolved it, gets solution of potassium carbonate.Taking by weighing and pass through the dry particle diameter of crossing of screening the cinder carrier 30 as one kind g that is 5mm～7mm is immersed in the above-mentioned wet chemical, filter after reaching adsorption equilibrium, generally left standstill 1 hour and abovely can reach adsorption equilibrium, be to leave standstill after 12 hours to refilter in the present embodiment, to filter gained solid sample oven dry back in 600 ℃ of calcining 1h, obtain coal cinder supported solid base catalyst.
In the 250ml there-necked flask, add above-mentioned catalyst 8g, methyl alcohol 0.6mol, soybean oil 0.05mol successively, at 65 ℃ of following stirring and refluxing reaction 1h.Steam residue methyl alcohol after reaction finishes to reclaim, reacting liquor while hot is filtered, and isolates solid base catalyst to reclaim.Then filtrate is moved in the separatory funnel, leave standstill 10min, treat the product on separation upper strata, the stable back of layering and the crude glycerine of lower floor.The coarse biodiesel on upper strata is carried out centrifugal layering, finally obtain the biodiesel of yellow light tone.Through liquid chromatographic detection, biodiesel production rate is 96.7%.
Embodiment 2
Take by weighing potash 50g and be dissolved in the 100mL deionized water, stirring is fully dissolved it, gets solution of potassium carbonate.The cinder carrier 40g that to take by weighing through the dry particle diameter of crossing of screening be 2mm～5mm is immersed in the above-mentioned wet chemical, filters after leaving standstill 24h, and solid sample oven dry back in 500 ℃ of calcining 5h, is obtained coal cinder supported solid base catalyst.
In the 250ml there-necked flask, add above-mentioned catalyst 8g, methyl alcohol 0.6mol, rapeseed oil 0.05mol successively, at 65 ℃ of following stirring and refluxing reaction 1h.Steam residue methyl alcohol after reaction finishes to reclaim, reacting liquor while hot is filtered, and isolates solid base catalyst to reclaim.Then filtrate is moved in the separatory funnel, leave standstill 10min, treat the product on separation upper strata, the stable back of layering and the crude glycerine of lower floor.The coarse biodiesel on upper strata being carried out centrifugal layering, obtain the bigger biodiesel of purity, then biodiesel is washed in separatory funnel, is colourless until lower floor.Put it into Rotary Evaporators at last and carry out air-distillation, finally obtain the biodiesel of yellow light tone.Through liquid chromatographic detection, biodiesel production rate is 99.2%.
Embodiment 3
Take by weighing potash 90g and be dissolved in the 100mL deionized water, stirring is fully dissolved it, gets solution of potassium carbonate.The cinder carrier 50g that to take by weighing through the dry particle diameter of crossing of screening be 1～2mm is immersed in the above-mentioned wet chemical, filters after leaving standstill 6h, and solid sample oven dry back in 400 ℃ of calcining 3h, is obtained coal cinder supported solid base catalyst.
In the 250ml there-necked flask, add above-mentioned catalyst 8g, methyl alcohol 0.6mol, tung oil 0.05mol successively, at 65 ℃ of following stirring and refluxing reaction 1h.Steam residue methyl alcohol after reaction finishes to reclaim, reacting liquor while hot is filtered, and isolates solid base catalyst to reclaim.Then filtrate is moved in the separatory funnel, leave standstill 10min, treat the product on separation upper strata, the stable back of layering and the crude glycerine of lower floor.The coarse biodiesel on upper strata being carried out centrifugal layering, obtain the bigger biodiesel of purity, then biodiesel is washed in separatory funnel, is colourless until lower floor.Put it at last and carry out air-distillation in the Rotary Evaporators, finally obtain the biodiesel of yellow light tone.Through liquid chromatographic detection, biodiesel production rate is 95.2%.
Claims (5)
1. coal cinder supported solid base catalyst is characterized in that: this catalyst is to be that the dry cinder carrier of 1mm～10mm is immersed in the K that concentration is 0.3g/ml～1g/ml with particle diameter
2CO
3In the aqueous solution, filter after reaching adsorption equilibrium, solid sample oven dry back was formed in 300 ℃～800 ℃ calcinings in 0.5～6 hour.
2. coal cinder supported solid base catalyst according to claim 1 is characterized in that: described cinder and K
2CO
3The mass volume ratio of water is 0.2g/ml～0.6g/ml in the aqueous solution.
3. the preparation method of the described coal cinder supported solid base catalyst of claim 1 is characterized in that: with particle diameter is that the dry cinder carrier of 1mm～10mm is immersed in the K that concentration is 0.3g/ml～1g/ml
2CO
3In the aqueous solution, filter after reaching adsorption equilibrium, solid sample oven dry back in 300 ℃～800 ℃ calcinings 0.5～6 hour down, is obtained coal cinder supported solid base catalyst.
4. the preparation method of coal cinder supported solid base catalyst according to claim 3 is characterized in that: described cinder and K
2CO
3The mass volume ratio of water is 0.2g/ml～0.6g/ml in the aqueous solution.
5. coal cinder supported solid base catalyst as claimed in claim 1 is used to prepare biodiesel.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010103643A CN101780415A (en) | 2010-01-27 | 2010-01-27 | Coal cinder supported solid base catalyst and preparation method and use thereof |
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| CN201010103643A CN101780415A (en) | 2010-01-27 | 2010-01-27 | Coal cinder supported solid base catalyst and preparation method and use thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103182300A (en) * | 2013-03-25 | 2013-07-03 | 江苏大学 | Attapulgite-supported potassium carbonate heterogeneous catalyst and preparation method and application thereof in biodiesel catalyzed synthesis |
| CN103191709A (en) * | 2013-03-25 | 2013-07-10 | 江苏大学 | Attapulgite-loading potassium hydroxide heterogeneous catalyst and preparation method of heterogeneous catalyst and application of heterogeneous catalyst in biodiesel catalytic synthesis |
| CN106000436A (en) * | 2015-12-14 | 2016-10-12 | 合肥工业大学 | Preparation method of heterogeneous catalyst with camphor tree ash as carrier and application thereof |
-
2010
- 2010-01-27 CN CN201010103643A patent/CN101780415A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103182300A (en) * | 2013-03-25 | 2013-07-03 | 江苏大学 | Attapulgite-supported potassium carbonate heterogeneous catalyst and preparation method and application thereof in biodiesel catalyzed synthesis |
| CN103191709A (en) * | 2013-03-25 | 2013-07-10 | 江苏大学 | Attapulgite-loading potassium hydroxide heterogeneous catalyst and preparation method of heterogeneous catalyst and application of heterogeneous catalyst in biodiesel catalytic synthesis |
| CN103182300B (en) * | 2013-03-25 | 2015-08-26 | 江苏大学 | Heterogeneous catalysis of Attapulgite-supportepotassium potassium carbonate and preparation method thereof and the application in biodiesel catalyzes and synthesizes |
| CN106000436A (en) * | 2015-12-14 | 2016-10-12 | 合肥工业大学 | Preparation method of heterogeneous catalyst with camphor tree ash as carrier and application thereof |
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Application publication date: 20100721 |