CN101418225A - Method for preparing biodiesel by using supported solid acid combining cosolvent - Google Patents
Method for preparing biodiesel by using supported solid acid combining cosolvent Download PDFInfo
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- CN101418225A CN101418225A CNA2007101762036A CN200710176203A CN101418225A CN 101418225 A CN101418225 A CN 101418225A CN A2007101762036 A CNA2007101762036 A CN A2007101762036A CN 200710176203 A CN200710176203 A CN 200710176203A CN 101418225 A CN101418225 A CN 101418225A
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The invention discloses a method for producing biodiesel in the presence of a supported solid acid catalyst and a solubilizing agent. The method is characterized in that: (1) a hydrophobic solid acid catalyst which is high in catalytic efficiency, recyclable, easily separable and simple in post treatment process is adopted; (2) a cosolvent is introduced during a reaction process to improve reaction conditions and reduce reaction temperature and pressure; (3) the cosolvent and lower alcohols used in the reaction can be recycled; and (4) equipment corrosion and environmental pollution are avoided and advantages of low requirements on equipment corrosion, short technical process, environmental-friendly production, low investment in equipment and low operation cost are achieved.
Description
Technical field
The present invention relates to technical field of green regenerative energy sources, specifically refer to adopt the method for load-type solid acid catalysis for preparing biodiesel oil.Owing to adopted solid acid, make final product be easy to handle and reached external existing biofuel quality standard.Use solubility promoter to make reaction conditions obtain big improvement in the reaction.
Background technology
Diesel oil occupies higher share as a kind of important refining of petroleum product in various countries' fuel structure, become important power fuel.Along with the quickening of vehicle diesel oil trend in the world wide, the demand of following diesel oil can be more and more big, and the raising of exhausted day by day and people's environmental consciousness of petroleum resources, people begin to pay close attention to oil-fired substitute.Biofuel is to be the renewable energy source of raw material production with plant or animal grease, can be used as fine petroleum diesel surrogate.China is a large agricultural country, and agricultural resource is anxious to be waited to develop.Produce the selling market that thing diesel oil is maximum next life with Vegetable oil lipoprotein, so both adjusted the farm crop economic structure, improved peasant's income simultaneously again.This Study on Technology is not only benefited the nation and the people, and has realistic meaning.
Biofuel is a fatty acid methyl ester, is by the preparation of homogeneous catalysis ester-interchange method at present mostly, adopts liquid acid or liquid alkali catalyst, is generally NaOH, the KOH or the vitriol oil.If adopt the liquid alkali as a catalyst, stock oil and methyl alcohol must strictly dewater, otherwise easily form milk, and the free acid in the stock oil has very big infringement to the activity of basic catalyst.Also there is the people under the condition that liquid acid catalyst exists, to prepare biofuel, CN 1 382762A adopts sulfuric acid or Phenylsulfonic acid to make catalyzer, CN 1412278A adopts sulfuric acid to make catalyzer, though liquid acid catalyst does not have particular requirement to the moisture and the free acid content of stock oil, but liquid acid has corrodibility, makes it very high to equipment requirements, and reaction end back methyl alcohol is difficult to separate with by-product glycerin, the last handling process complexity rises cost.In addition, adopt liquid acid or alkali, in last handling process, can discharge large amount of sewage, cause environmental pollution as catalyzer.Therefore, how to find a kind of appropriate catalyst, both reduced cost, simplify technical process, can reach the purpose of environmental protection again, become the focus that people pay close attention to.
Summary of the invention
The objective of the invention is to: a kind of method that adopts the load-type solid acid catalysis for preparing biodiesel oil is proposed, and in conjunction with cosolvent solved traditional employing liquid acid or liquid base complicated as the aftertreatment that catalyzer brings, problems such as contaminate environment.
Technology of the present invention is as follows: under the condition that load-type solid acid catalyst exists, low-carbon alcohol is mixed and add cosolvent place autoclave to stir with animal and vegetable oil, heating makes it that transesterification reaction take place, and after reacting completely, catalyst separating is gone out.With reaction mixture sat, two-layer about being divided into, the upper strata is a coarse products, is a series of fatty acid methyl esters (biofuel) and the mixture that is dissolved in small amount of methanol wherein, and lower floor is glycerine and the mixed solution that remains methyl alcohol.To get biofuel behind the thick ester water-bath distillation in upper strata, get purified glycerine behind lower floor's water-bath distillation.
Processing condition relevant in the above-mentioned technology are as follows:
Catalyst levels accounts for 0.1%～10% of stock oil weight;
The cosolvent consumption accounts for 5%～40% of the used alcohol of reaction;
Alcohol oil mole proportioning 3:1～32:1;
100～250 ℃ of transesterification reaction temperature;
Transesterification reaction time 10～90min;
Transesterification reaction pressure 0.1～3MP
In the technology of above-mentioned preparation biofuel, used load-type solid acid catalyst, it is characterized in that carrier degassing dehydration, the dissolving of active constituent metal inorganic salt is made into certain density solution, dipping, by normal temperature dipping method and backflow pickling process active constituent is flooded to carrier, drying is calcined certain hour at a certain temperature and is prepared load-type solid acid catalyst; This catalyzer has been simplified the aftertreatment technology of product in preparation biofuel process, reduced corrosion and environmental protection to equipment.
In the load-type solid acid catalyst of described preparation biofuel, the active ingredient of load-type solid acid is one or more in phospho-wolframic acid, silicotungstic acid, phospho-molybdic acid, tetrahydrated zirconium sulfate, sal epsom, ferric sulfate hydrate, iron(ic) chloride, two hydrated stannous chlorides, tosic acid, four water cesium sulfates, the titanium sulfate;
In the load-type solid acid catalyst of described preparation biofuel, the carrier of load-type solid acid is gac, silicon oxide, HZSM-5, diatomite, silica gel, aluminium phosphate molecular sieve, aluminium silicophosphate molecular sieve, polynite, wilkinite, ion exchange resin, TiO
2-ZrO
2, among the ZnO, ferric oxide one or more.
Described animal and plant grease is the mixture of one or more (comprising two kinds) in pig, sheep, ox, fox, chicken, duck oil and soybean oil, genetically engineered soybean oil, rapeseed oil, transgenosis rapeseed oil, Viscotrol C, plam oil, peanut oil, the sunflower seed oil.
Described low-carbon alcohol is a methyl alcohol, ethanol, the mixture of one or more in the butanols (comprising two kinds).
Described cosolvent is one or more the mixture in carbonic acid gas, methane, ethane, propane, normal butane, Trimethylmethane, methyl alcohol, ethanol, the thanomin.
The present invention compares with other method of production biofuel, and the advantage and the technical superiority that have are:
1) adopt load-type solid acid catalyst, postprocessing working procedures to significantly reduce in the ester-exchange reaction of the present invention, reaction process is simple and easy to control, has reduced cost.
2) the present invention has environment friendly, the production process non-pollutant discharge.
3) mutual solubility that vegetables oil and low charcoal alcohol have not only been strengthened in the adding of solubility promoter in the reaction process of the present invention low-carbon alcohol is better dissolved each other with vegetables oil, thereby accelerated reaction speed has shortened the reaction times greatly; Reduced temperature of reaction and pressure, made originally to be reflected to be easy in the industrial production realize having the favorable industrial using value.
Isolated low-carbon alcohol can purified repetition reuse when 4) the present invention reacted and finishes, and isolated raw glycerine is made with extra care and obtained the finished product pure glycerin or be used for other industrial production (as saponification etc.).The cosolvent that reaction adds also can treatedly reuse.
Embodiment
The present invention is a kind of novel method by animal and vegetable oil production biofuel, it is characterized in that: with animal and vegetable oil and low charcoal alcohols is reactant, adding solubility promoter, carry out transesterification reaction, glycerin fatty acid ester is converted into lipid acid small molecules alcohol ester (being biofuel).Wherein, low charcoal alcohol: the mol ratio of vegetables oil is 3～32:1, after reaction in 10～90 minutes, promptly produce biofuel, its production process and processing condition are: 1) reaction raw materials and cosolvent place can be temperature automatically controlled autoclave internal heating to 100 ℃～250 ℃; 2) the temperature control reaction finishes reaction after 10～90 minutes, reacting final product is separated can produce refined biometric diesel oil.
Described animal and plant grease is the mixture of one or more (comprising two kinds) in pig, sheep, ox, fox, chicken, duck oil and soybean oil, genetically engineered soybean oil, rapeseed oil, transgenosis rapeseed oil, Viscotrol C, plam oil, peanut oil, the sunflower seed oil.
In the load-type solid acid catalyst of described preparation biofuel, the active ingredient of load-type solid acid is one or more in phospho-wolframic acid, silicotungstic acid, phospho-molybdic acid, tetrahydrated zirconium sulfate, sal epsom, ferric sulfate hydrate, iron(ic) chloride, two hydrated stannous chlorides, tosic acid, four water cesium sulfates, the titanium sulfate;
The carrier of the load-type solid acid of described preparation biofuel is gac, silicon oxide, HZSM-5, diatomite, silica gel, aluminium phosphate molecular sieve, aluminium silicophosphate molecular sieve, polynite, wilkinite, ion exchange resin, TiO
2-ZrO
2, among the ZnO, ferric oxide one or more.
Described low-carbon alcohol is a methyl alcohol, ethanol, the mixture of one or more in the butanols (comprising two kinds).
Described cosolvent is one or more the mixture in carbonic acid gas, methane, ethane, propane, normal butane, Trimethylmethane, methyl alcohol, ethanol, the thanomin.
Below in conjunction with embodiment, the present invention is done the detailed description in a nearly step.
Embodiment one
With soybean oil 25 gram, it is 40% the gac autoclave of packing into that 22 gram methyl alcohol and 1 gram load tetrahydrated zirconium sulfate account for the total catalyst massfraction, and sealed reactor and with the air in the inert gas replacement reactor adds 8 gram cosolvent C
4H
10The pressure and temperature of reactor is implemented immediately monitoring by instrument.Autoclave pressure is heated by external heater, and temperature in the kettle is by Fe, the monitoring of Cu-Ni alloy thermopair.Regulating voltage makes and reaches 180 ℃ in 45 minutes, controls ± 5 ℃, 30 minutes, transesterification reaction during finish.Move into the water-bath stopped reaction at last.
React emission gases, the mixture in the autoclave pressure has been poured into collector, used the methanol wash reactor.Isolate catalyzer earlier, pending product sedimentation 60 minutes divides 3 layers, and the superiors are methyl alcohol phases, separates.Remaining two separate was also distilled 30 minutes at 60～80 ℃ respectively, steam remaining methyl alcohol, the quality of weighing residuum, use efficient liquid phase chromatographic analysis (column length 25cm, diameter 4.6mm, 40 ℃, 1.0ml/min methyl alcohol are 20ul for the solvent that loses shape, injection volume) respectively, differentiate that product is respectively vegetables oil methyl esters (biofuel) and glycerine.Measure product quality: vegetables oil methyl esters 24.5 grams, glycerine 2.53 grams, calculate reaction yield and reach 98%.
The quality and the performance of gained biofuel product are as follows after tested: viscosity 2.8-6csl (20 ℃), and similar with 2# diesel oil, calorific value is 10000kcal/kg, flash-point ≮ 85, cetane value is 54, ash 0.001%; The performance test of oil engine, the power that shows biofuel burning generation is a little less than 2# diesel oil, and the discharging of the concentration of cigarette, CO and unburned hydrocarbons reduces, and is a kind of renewable environmentally friendly alternative fuel of fossil diesel fuel.
Embodiment two
It is 40% the gac autoclave of packing into that soybean oil 20 gram and 17.6 gram methyl alcohol and 0.8 gram load tetrahydrated zirconium sulfate are accounted for the total catalyst massfraction, and sealed reactor and with the air in the inert gas replacement reactor adds 2gCO2.The pressure and temperature of reactor is implemented immediately monitoring by instrument.Autoclave pressure is heated by external heater, and temperature in the kettle is by Fe, Cu-Ni alloy thermopair monitoring.Regulating voltage makes and reaches 180 ℃ in 45 minutes, controls ± 5 ℃, 30 minutes, transesterification reaction during finish.Move into the water-bath stopped reaction at last.
React emission gases and collection, the mixture in the autoclave pressure has been poured into collector, used the methanol wash reactor.Isolate catalyzer earlier, pending product sedimentation 60 minutes divides 3 layers, and the superiors are methyl alcohol phases, separates.Remaining two separate was also distilled 30 minutes at 60～80 ℃ respectively, steam remaining methyl alcohol, the quality of weighing residuum, use efficient liquid phase chromatographic analysis (column length 25cm, diameter 4.6mm, 40 ℃, 1.0ml/min methyl alcohol are 20ul for the solvent that loses shape, injection volume) respectively, differentiate that product is respectively vegetables oil methyl esters (biofuel) and glycerine.Measure product quality: vegetables oil methyl esters 19.5 grams, glycerine 2.01 grams, calculate reaction yield and reach 97.5%.
The quality of gained biofuel product is identical with embodiment one with performance.
Embodiment three
With soybean oil 20 gram, it is 40% the gac autoclave of packing into that 17.6 gram methyl alcohol and 0.8 gram load tetrahydrated zirconium sulfate account for the total catalyst massfraction, and sealed reactor and with the air in the inert gas replacement reactor adds 3.8 gram solubility promoter CO2.The pressure and temperature of reactor is implemented immediately monitoring by instrument.Autoclave pressure is heated by external heater, and temperature in the kettle is by Fe, the monitoring of Cu-Ni alloy thermopair.Regulating voltage makes and reaches 140 ℃ in 30 minutes, controls ± 5 ℃, 30 minutes, transesterification reaction during finish.Move into the water-bath stopped reaction at last.
React emission gases, the mixture in the autoclave pressure has been poured into collector, used the methanol wash reactor.Isolate catalyzer earlier, pending product sedimentation 60 minutes divides 3 layers, and the superiors are methyl alcohol phases, separates.Remaining two separate was also distilled 30 minutes at 60～80 ℃ respectively, steam remaining methyl alcohol, the quality of weighing residuum, use efficient liquid phase chromatographic analysis (column length 25cm, diameter 4.6mm, 40 ℃, 1.0ml/min methyl alcohol are 20ul for the solvent that loses shape, injection volume) respectively, differentiate that product is respectively vegetables oil methyl esters (biofuel) and glycerine.Measure product quality: vegetables oil methyl esters 19.61 grams, glycerine 1.87 grams, calculate reaction yield and reach 98%.
The quality of gained biofuel product is identical with embodiment one with performance.
Embodiment four
With soybean oil 20 gram, it is 40% the silicon-dioxide autoclave of packing into that 17.6 gram methyl alcohol and 0.8 gram load tetrahydrated zirconium sulfate account for the total catalyst massfraction, and sealed reactor and with the air in the inert gas replacement reactor adds 2 gram solubility promoter CO2.The pressure and temperature of reactor is implemented immediately monitoring by instrument.Autoclave pressure is heated by external heater, and temperature in the kettle is by Fe, the monitoring of Cu-Ni alloy thermopair.Regulating voltage makes and reaches 180 ℃ in 45 minutes, controls ± 5 ℃, 30 minutes, transesterification reaction during finish.Move into the water-bath stopped reaction at last.
React emission gases, the mixture in the autoclave pressure has been poured into collector, used the methanol wash reactor.Isolate catalyzer earlier, pending product sedimentation 60 minutes divides 3 layers, and the superiors are methyl alcohol phases, separates.Remaining two separate was also distilled 30 minutes at 60～80 ℃ respectively, steam remaining methyl alcohol, the quality of weighing residuum, use efficient liquid phase chromatographic analysis (column length 25cm, diameter 4.6mm, 40 ℃, 1.0ml/min methyl alcohol are 20ul for the solvent that loses shape, injection volume) respectively, differentiate that product is respectively vegetables oil methyl esters (biofuel) and glycerine.Measure product quality: vegetables oil methyl esters 20.3 grams, glycerine 1.996 grams.
The quality of gained biofuel product is identical with embodiment one with performance.
Claims (9)
1, a kind of load-type solid acid catalyst prepares method of bio-diesel oil in conjunction with cosolvent, it is characterized in that: under the condition that solid acid catalyst exists, low-carbon alcohol is mixed the injection autoclave with the animal and plant grease, then add solubility promoter, continue to stir and heating, make it that transesterification reaction take place.After reaction finishes, reclaim cosolvent, filter and also reclaim solid acid catalyst, the product after filtering is boiled off low-carbon alcohol after, the residuum static layering, the upper strata is a biofuel, lower floor is a glycerine.
2, be the method for biodiesel according to claim 1 described load-type solid acid, it is characterized in that: the active ingredient of load-type solid acid is one or more in phospho-wolframic acid, silicotungstic acid, phospho-molybdic acid, tetrahydrated zirconium sulfate, sal epsom, ferric sulfate hydrate, iron(ic) chloride, two hydrated stannous chlorides, tosic acid, four water cesium sulfates, the titanium sulfate; The carrier of load-type solid acid is gac, silicon oxide, HZSM-5, diatomite, silica gel, aluminium phosphate molecular sieve, aluminium silicophosphate molecular sieve, polynite, wilkinite, ion exchange resin, TiO
2-ZrO
2, among the ZnO, ferric oxide one or more.
3, according to claim 1 is the method for biodiesel with the load-type solid acid, it is characterized in that: described cosolvent is one or more the mixture in carbonic acid gas, methane, ethane, propane, normal butane, Trimethylmethane, methyl alcohol, ethanol, the thanomin.
4, according to claim 1 is that catalyst prepares method of bio-diesel oil with the load-type solid acid, and it is characterized in that: catalyst levels accounts for 0.1%～10% of reaction raw materials total mass.
5, load-type solid acid according to claim 1 is the method for biodiesel, it is characterized in that: the optimum molar proportioning of low-carbon alcohol and animal and vegetable oil is 3:1～32:1.
6, load-type solid acid catalyst according to claim 1 prepares method of bio-diesel oil, it is characterized in that: transesterification reaction is carried out under 100 ℃-250 ℃, and the reaction times is 0.5 hour～3 hours, and reaction pressure is 0.1MP～3MP
7, load-type solid acid catalyst according to claim 1 prepares method of bio-diesel oil, it is characterized in that: purified the reusing of the pure and mild cosolvent of isolated low charcoal when described reaction finishes, solid acid recycle after the filtration gets purified glycerine and is used for industrial production behind the mixture distillation.
8, load-type solid acid catalyst according to claim 1 prepares method of bio-diesel oil, it is characterized in that: described animal and plant grease is the mixture of one or more (comprising two kinds) in pig, sheep, ox, fox, chicken, duck oil and soybean oil, genetically engineered soybean oil, rapeseed oil, transgenosis rapeseed oil, Viscotrol C, plam oil, peanut oil, the sunflower seed oil.
9, load-type solid acid catalyst according to claim 1 prepares method of bio-diesel oil, it is characterized in that: described low-carbon alcohol is a methyl alcohol, ethanol, the mixture of one or more in the butanols (comprising two kinds).
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| CN101787303A (en) * | 2010-03-12 | 2010-07-28 | 江苏卡特新能源有限公司 | Method for preparing alkane from acidized oil |
| CN102703223A (en) * | 2012-05-31 | 2012-10-03 | 源华能源科技（福建）有限公司 | Process for preparing biodiesel by catalytic esterification and alcoholysis of gas-phase methanol |
| CN102850157A (en) * | 2012-07-30 | 2013-01-02 | 华东理工大学 | Novel technique for preparing long-chain alkane efficiently through multifunctional catalyst in one-step method |
| CN103013678A (en) * | 2011-09-20 | 2013-04-03 | 中国石油化工股份有限公司 | Method for reducing biodiesel crude product acid value, and biodiesel preparation method |
| CN103382417A (en) * | 2013-01-14 | 2013-11-06 | 江苏卡特新能源有限公司 | Biodiesel transesterification technology |
| CN103382416A (en) * | 2013-01-14 | 2013-11-06 | 江苏卡特新能源有限公司 | Biodiesel esterification reaction technology |
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