CN102335632A - Method for preparing solid base catalyst with porous SiO2 material as carrier and application of solid base catalyst - Google Patents
Method for preparing solid base catalyst with porous SiO2 material as carrier and application of solid base catalyst Download PDFInfo
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- CN102335632A CN102335632A CN201110204219XA CN201110204219A CN102335632A CN 102335632 A CN102335632 A CN 102335632A CN 201110204219X A CN201110204219X A CN 201110204219XA CN 201110204219 A CN201110204219 A CN 201110204219A CN 102335632 A CN102335632 A CN 102335632A
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Abstract
The invention relates to a method for preparing a solid base catalyst with a porous SiO2 material as a carrier and application of the solid base catalyst, belonging to the technical field of environmental catalysis and energy resources. The catalyst is prepared with the double-model mesoporous SiO2 material as the carrier and an alkaline component as an active component by adopting an impregnating method. The catalyst has the characteristics of simple preparation process, good catalysis effect and the like; the catalyst is easy to be separated from a reaction system after the ester exchange reaction is finished, and can be recycled, therefore the pollution of the catalyst to the environment is greatly reduced. After vegetable oil, animal oil and fat, catering waste oil or illegal cooking oil is adopted as a raw material and subjected to alcohol ester exchange reaction, the yield of the target product reaches more than 85.0 wt%.
Description
Technical field:
The invention belongs to environmental catalysis and energy technology field, be specifically related to a kind of to have the SiO of dual model pore passage structure
2Material is the load type solid body base catalyst preparation method and the application in the preparation biodiesel thereof of carrier.
Background technology:
Biodiesel be a kind of be primary raw material with the animal and plant fat, the fatty acid material that obtains through alcohol transesterification reaction, its performance and mineral matter diesel oil are very approaching, are acknowledged as a kind of reproducible clean fuel.
Prepare the used catalyst system and catalyzing of biodiesel through ester exchange reaction and can be divided into homogeneous catalysis system and heterogeneous catalysis system.Though lot of documents report and production experience show that the homogeneous catalysis system catalytic efficiency is higher, reaction finishes rear catalyst and product separation difficulty, has a large amount of waste liquids to discharge and contaminated environment in the last handling process.Heterogeneous solid catalyst can solve the existing problem of homogeneous catalyst well.But the solid acid catalyst reaction efficiency is lower, compares with it, and solid base catalyst then has the reaction condition gentleness, selectivity is high, and product is easy to separate characteristics such as catalyst reusable edible.
The more solid base catalyst of research mainly contains micropore and mesoporous molecular sieve carried potassium fluoride, alkali metal, the oxide of alkaline-earth metal and rare-earth oxide at present.People such as the Zhu Jianhua professor of Nanjing University have commented basic zeolite molecular sieve (is main with micropore) Preparation of catalysts method and application (Science Bulletin thereof since the nineties in last century; 1999; 44 (9): 897-903); The research of pointing out the super base molecular sieve mainly is how to improve its intensity, simplifies preparation technology and reduces cost.Chinese patent CN10113873A, CN101402875A, CN1821195A, CN101148396A and United States Patent (USP) 7357983B2 have reported to be the preparation method of the doping type solid base catalyst of carrier with the mesopore molecular sieve.As stated, no matter micro porous molecular sieve, or mesopore molecular sieve is introduced active component through methods such as framework modification and finishinges, all can obtain solid base catalyst.But in preparation process and practical application, generally be the base strength of stressing load alkali center, and ignored the influence of the pore passage structure of porous material carrier own.Because ester exchange reaction belongs to macromolecular reaction, the pore passage structure characteristic of porous material must be brought very big influence to molecular diffusion in the reaction system and absorption, thereby influences its reaction efficiency.
Summary of the invention:
The object of the invention is intended to be directed against the problem that exists among the existing preparation method, provides a kind of to have the SiO of dual model pore passage structure
2Material is the load type solid body base catalyst preparation method and the application in the preparation biodiesel thereof of carrier.
Technical scheme of the present invention is following:
A kind of with porous SiO
2Material is the solid base catalyst preparation method of carrier, it is characterized in that this method may further comprise the steps:
(1) with porous SiO
2Material naturally cooled to room temperature in drier after 100-150 ℃ of dry 3-5 hour, and airtight preservation.
Described porous SiO
2Material is meant the SiO of two meso-hole structures of the second hole of the one-level hole that has 2-5nm simultaneously and 10-30nm
2Material, its specific area are 500-1500m
2/ g, pore volume are 0.8-3.5cm
3/ g.
(2) source that will contain the compound of basic component is dissolved in the deionized water, is made into the solution that concentration is 10-40wt%.
The described compound that contains basic component is meant alkali metal, and one or both in the alkaline earth oxide derive from their nitrate, carbonate or acetate.
(3) the porous SiO that step (1) is obtained
2Material joins in the solution that step (2) obtains and floods, and continues down to stir 1-12 hour at 25 ℃, and reaction finishes the back and under 25-80 ℃, carries out the solvent evaporation, obtains solid product.
(4) solid product that step (3) is obtained is under nitrogen atmosphere; Programming rate with 5-10 ℃/min rises to certain temperature between 150-600 ℃ from room temperature; And after constant temperature 3-6 under this temperature hour, cooling naturally obtains solid base catalyst under nitrogen atmosphere.
The described compound that contains basic component accounts for the 1.0wt%-10.0wt% that is of solid base catalyst quality.
Described catalyst applications is in the preparation biodiesel; It is characterized in that feedstock oil, methyl alcohol and prepared solid base catalyst are mixed; Stirring reaction under 57-67 ℃ of temperature, the reaction time is 2-6 hour, reaction finishes the back standing demix; Obtain biodiesel after the separation, yield is more than 85.0%.Wherein catalyst amount is the 1.0-5.0wt% of feedstock oil, and the mol ratio of methyl alcohol and feedstock oil is 5-20: 1.
Further, described feedstock oil is vegetable oil, animal fat or waste cooking oil or waste oil.
It is simple that the present invention has preparation technology, characteristics such as excellent catalytic effect.
The specific embodiment
Embodiment 1:
Take by weighing 0.86g KNO
3With 0.59g Ca (NO
3)
2Be dissolved in the 10ml deionized water, then with 1g through 3 hours SiO of 150 ℃ of dryings
2(it is mesoporous mesoporous with 20nm to have 3nm simultaneously, and specific area is 1000m for porous material
2/ g and pore volume are 2.0cm
3/ g) immerse wherein, after stirring 12 hours under the room temperature, 80 ℃ of evaporates to dryness obtain solid sample.After solid sample fully ground, under nitrogen protection, rise to 250 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 6 hours, obtain load type solid body base catalyst with 5 ℃/min.
In the there-necked flask of 250ml; With soybean oil, methyl alcohol is raw material, and molar ratio of methanol to oil is 5: 1, is heated to temperature when being 62 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 2.5wt% of soybean oil weight; Speed with greater than 400 rev/mins stirs, and reacts after 2 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 95.0%.
Embodiment 2:
Take by weighing 1.00g KNO
3Be dissolved in the 10ml deionized water, then with 1g through 5 hours SiO of 100 ℃ of dryings
2(it is mesoporous mesoporous with 15nm to have 2nm simultaneously, and specific area is 1200m for porous material
2/ g and pore volume are 3.0cm
3/ g) immerse wherein, after stirring 12 hours under the room temperature, evaporate to dryness obtains solid sample under the room temperature.After solid sample fully ground, under nitrogen protection, rise to 600 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 3 hours, obtain load type solid body base catalyst with 10 ℃/min programming rate.
In the there-necked flask of 250ml; With rapeseed oil, methyl alcohol is raw material, and molar ratio of methanol to oil is 10: 1, is heated to temperature when being 57 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 1.0wt% of rapeseed oil weight; Speed with greater than 400 rev/mins stirs, and reacts after 6 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 95.0%.
Embodiment 3:
Take by weighing 1.11g CsNO
3With 0.52g Ba (CO
3)
2Be dissolved in the 10ml deionized water, then with 1g through 3 hours SiO of 120 ℃ of dryings
2(it is mesoporous mesoporous with 30nm to have 5nm simultaneously, and specific area is 500m for porous material
2/ g and pore volume are 0.8cm
3/ g) immerse wherein, after stirring 12 hours under the room temperature, 60 ℃ of following evaporates to dryness obtain solid sample.After solid sample fully ground, under nitrogen protection, rise to 600 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 3 hours, obtain load type solid body base catalyst with 10 ℃/min programming rate.
In the there-necked flask of 250ml; With waste oil, methyl alcohol is raw material, and molar ratio of methanol to oil is 10: 1, is heated to temperature when being 60 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 3.0wt% of waste oil weight; Speed with greater than 400 rev/mins stirs, and reacts after 6 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 85.0%.
Embodiment 4:
Take by weighing 1.38g CsNO
3Be dissolved in the 10ml deionized water, then with 1g through 3 hours SiO of 120 ℃ of dryings
2(it is mesoporous mesoporous with 30nm to have 3nm simultaneously, and specific area is 600m for porous material
2/ g and pore volume are 1.2cm
3/ g) immerse wherein, after stirring 1 hour under the room temperature, evaporate to dryness obtains solid sample under the room temperature.After solid sample fully ground, under nitrogen protection, rise to 400 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 5 hours, obtain load type solid body base catalyst with 5 ℃/min programming rate.
In the there-necked flask of 250ml; With waste cooking oil, methyl alcohol is raw material, and molar ratio of methanol to oil is 20: 1, is heated to temperature when being 67 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 5.0wt% of waste cooking oil weight; Speed with greater than 400 rev/mins stirs, and reacts after 6 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 90.0%.
Embodiment 5:
Take by weighing 4.62g Cs
2CO
3With 1.69g Ba (AC)
2Be dissolved in the 20ml deionized water, then with 1g through 5 hours SiO of 120 ℃ of dryings
2(it is mesoporous mesoporous with 30nm to have 2nm simultaneously, and specific area is 900m for porous material
2/ g and pore volume are 2.4cm
3/ g) immerse wherein, after stirring 5 hours under the room temperature, 50 ℃ of following evaporates to dryness obtain solid sample.After solid sample fully ground, under nitrogen protection, rise to 300 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 6 hours, obtain load type solid body base catalyst with 8 ℃/min programming rate.
In the there-necked flask of 250ml; With rapeseed oil, methyl alcohol is raw material, and molar ratio of methanol to oil is 5: 1, is heated to temperature when being 57 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 5.0wt% of rapeseed oil weight; Speed with greater than 400 rev/mins stirs, and reacts after 6 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 95.0%.
Embodiment 6:
Take by weighing 8.00g Cs
2CO
3Be dissolved in the 20ml deionized water, then with 1g through 3 hours SiO of 150 ℃ of dryings
2(it is mesoporous mesoporous with 20nm to have 3nm simultaneously, and specific area is 1000m for porous material
2/ g and pore volume are 2.0cm
3/ g) immerse wherein, after stirring 10 hours under the room temperature, 80 ℃ of following evaporates to dryness obtain solid sample.After solid sample fully ground, under nitrogen protection, rise to 500 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 3 hours, obtain load type solid body base catalyst with 5 ℃/min programming rate.
In the there-necked flask of 250ml; With industrial lard, methyl alcohol is raw material, and molar ratio of methanol to oil is 15: 1, is heated to temperature when being 67 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 2.0wt% of industrial lard weight; Speed with greater than 400 rev/mins stirs, and reacts after 6 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 90.0%.
Embodiment 7:
Take by weighing 6.67g KAC and 2.86g CaCO
3Be dissolved in the 30ml deionized water, then with 1g through 3 hours SiO of 150 ℃ of dryings
2(it is mesoporous mesoporous with 10nm to have 2nm simultaneously, and specific area is 1500m for porous material
2/ g and pore volume are 3.5cm
3/ g) immerse wherein, after stirring 1 hour under the room temperature, 80 ℃ of following evaporates to dryness obtain solid sample.After solid sample fully ground, under nitrogen protection, rise to 150 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 6 hours, obtain load type solid body base catalyst with 5 ℃/min programming rate.
In the there-necked flask of 250ml; With soybean oil, methyl alcohol is raw material, and molar ratio of methanol to oil is 10: 1, is heated to temperature when being 57 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 1.0wt% of soybean oil weight; Speed with greater than 400 rev/mins stirs, and reacts after 2 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 92.0%.
Embodiment 8:
Take by weighing 8.00g KAC and be dissolved in the 20ml deionized water, then with 1g through 4 hours SiO of 130 ℃ of dryings
2(it is mesoporous mesoporous with 25nm to have 5nm simultaneously, and specific area is 550m for porous material
2/ g and pore volume are 1.0cm
3/ g) immerse wherein, after stirring 8 hours under the room temperature, 30 ℃ of following evaporates to dryness obtain solid sample.After solid sample fully ground, under nitrogen protection, rise to 150 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 6 hours, obtain load type solid body base catalyst with 8 ℃/min programming rate.
In the there-necked flask of 250ml; With industrial lard, methyl alcohol is raw material, and molar ratio of methanol to oil is 20: 1, is heated to temperature when being 67 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 3.0wt% of industrial lard weight; Speed with greater than 400 rev/mins stirs, and reacts after 4 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 90.0%.
Embodiment 9:
Take by weighing 10.58g NaAC and 4.21g MgCO
3Be dissolved in the 50ml deionized water, then with 1g through 5 hours SiO of 100 ℃ of dryings
2(it is mesoporous mesoporous with 15nm to have 2nm simultaneously, and specific area is 1200m for porous material
2/ g and pore volume are 3.0cm
3/ g) immerse wherein, after stirring 12 hours under the room temperature, evaporate to dryness obtains solid sample under the room temperature.After solid sample fully ground, under nitrogen protection, rise to 150 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 6 hours, obtain load type solid body base catalyst with 5 ℃/min programming rate.
In the there-necked flask of 250ml; With waste cooking oil, methyl alcohol is raw material, and molar ratio of methanol to oil is 8: 1, is heated to temperature when being 65 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 4.0wt% of waste cooking oil weight; Speed with greater than 400 rev/mins stirs, and reacts after 4 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 85.0%.
Embodiment 10:
Take by weighing 13.22g NaAC and be dissolved in the 40ml deionized water, then with 1g through 4 hours SiO of 120 ℃ of dryings
2(it is mesoporous mesoporous with 25nm to have 2nm simultaneously, and specific area is 1100m for porous material
2/ g and pore volume are 2.8cm
3/ g) immerse wherein, after stirring 6 hours under the room temperature, 40 ℃ of following evaporates to dryness obtain solid sample.After solid sample fully ground, under nitrogen protection, rise to 350 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 3 hours, obtain load type solid body base catalyst with 5 ℃/min programming rate.
In the there-necked flask of 250ml; With industrial lard, methyl alcohol is raw material, and molar ratio of methanol to oil is 12: 1, is heated to temperature when being 65 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 4.0wt% of industrial lard weight; Speed with greater than 400 rev/mins stirs, and reacts after 4 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 91.0%.
Embodiment 11:
Take by weighing 5.06g RbNO
3With 3.26g Sr (CO
3)
2Be dissolved in the 30ml deionized water, then with 1g through 3 hours SiO of 120 ℃ of dryings
2(it is mesoporous mesoporous with 30nm to have 2nm simultaneously, and specific area is 900m for porous material
2/ g and pore volume are 2.0cm
3/ g) immerse wherein, after stirring 1 hour under the room temperature, evaporate to dryness obtains solid sample under the room temperature.After solid sample fully ground, under nitrogen protection, rise to 600 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 3 hours, obtain load type solid body base catalyst with 5 ℃/min programming rate.
In the there-necked flask of 250ml; With rapeseed oil, methyl alcohol is raw material, and molar ratio of methanol to oil is 20: 1, is heated to temperature when being 60 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 1.0wt% of rapeseed oil weight; Speed with greater than 400 rev/mins stirs, and reacts after 3 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 95.0%.
Embodiment 12:
Take by weighing 5.53g RbNO
3Be dissolved in the 20ml deionized water, then with 1g through 3 hours SiO of 140 ℃ of dryings
2(it is mesoporous mesoporous with 30nm to have 5nm simultaneously, and specific area is 500m for porous material
2/ g and pore volume are 0.8cm
3/ g) immerse wherein, after stirring 12 hours under the room temperature, 80 ℃ of following evaporates to dryness obtain solid sample.After solid sample fully ground, under nitrogen protection, rise to 500 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 4 hours, obtain load type solid body base catalyst with 5 ℃/min programming rate.
In the there-necked flask of 250ml; With waste oil, methyl alcohol is raw material, and molar ratio of methanol to oil is 15: 1, is heated to temperature when being 60 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 3.0wt% of waste oil weight; Speed with greater than 400 rev/mins stirs, and reacts after 6 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 92.0%.
Embodiment 13:
Take by weighing 10.97g NaAC and 7.1g MgCO
3Be dissolved in the 60ml deionized water, then with 1g through 3 hours SiO of 140 ℃ of dryings
2(it is mesoporous mesoporous with 30nm to have 2nm simultaneously, and specific area is 900m for porous material
2/ g and pore volume are 2.4cm
3/ g) immerse wherein, after stirring 12 hours under the room temperature, 50 ℃ of following evaporates to dryness obtain solid sample.After solid sample fully ground, under nitrogen protection, rise to 500 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 4 hours, obtain load type solid body base catalyst with 5 ℃/min programming rate.
In the there-necked flask of 250ml; With industrial lard, methyl alcohol is raw material, and molar ratio of methanol to oil is 10: 1, is heated to temperature when being 60 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 5.0wt% of industrial lard weight; Speed with greater than 400 rev/mins stirs, and reacts after 4 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 85.0%.
Embodiment 14:
Take by weighing 8.82g Li
2CO
3With 1.69g BeCO
3Be dissolved in the 30ml deionized water, then with 1g through 5 hours SiO of 120 ℃ of dryings
2(it is mesoporous mesoporous with 30nm to have 2nm simultaneously, and specific area is 900m for porous material
2/ g and pore volume are 2.4cm
3/ g) immerse wherein, after stirring 5 hours under the room temperature, 50 ℃ of following evaporates to dryness obtain solid sample.After solid sample fully ground, under nitrogen protection, rise to 300 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 6 hours, obtain load type solid body base catalyst with 8 ℃/min programming rate.
In the there-necked flask of 250ml; With waste cooking oil, methyl alcohol is raw material, and molar ratio of methanol to oil is 12: 1, is heated to temperature when being 60 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 3.0wt% of waste cooking oil weight; Speed with greater than 400 rev/mins stirs, and reacts after 4 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 90.0%.
Embodiment 15:
Take by weighing 12.33g Li
2CO
3Be dissolved in the 50ml deionized water, then with 1g through 3 hours SiO of 150 ℃ of dryings
2(it is mesoporous mesoporous with 30nm to have 5nm simultaneously, and specific area is 500m for porous material
2/ g and pore volume are 0.8cm
3/ g) immerse wherein, after stirring 5 hours under the room temperature, 50 ℃ of following evaporates to dryness obtain solid sample.After solid sample fully ground, under nitrogen protection, rise to 150 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 6 hours, obtain load type solid body base catalyst with 5 ℃/min programming rate.
In the there-necked flask of 250ml; With rapeseed oil, methyl alcohol is raw material, and molar ratio of methanol to oil is 20: 1, is heated to temperature when being 60 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 1.0wt% of rapeseed oil weight; Speed with greater than 400 rev/mins stirs, and reacts after 3 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 95.0%.
Embodiment 16:
Take by weighing 1.26g RbNO
3With 0.57g BeNO
3Be dissolved in the 10ml deionized water, then with 1g through 5 hours SiO of 100 ℃ of dryings
2(it is mesoporous mesoporous with 25nm to have 2nm simultaneously, and specific area is 1100m for porous material
2/ g and pore volume are 2.8cm
3/ g) immerse wherein, after stirring 5 hours under the room temperature, 40 ℃ of following evaporates to dryness obtain solid sample.After solid sample fully ground, under nitrogen protection, rise to 600 ℃, and constant temperature puts into drier rapidly and naturally cool to room temperature and airtight preservation after 3 hours, obtain load type solid body base catalyst with 5 ℃/min programming rate.
In the there-necked flask of 250ml; With waste cooking oil, methyl alcohol is raw material, and molar ratio of methanol to oil is 10: 1, is heated to temperature when being 57 ℃; Adding weight ratio is the above-mentioned solid base catalyst of the 2.0wt% of waste cooking oil weight; Speed with greater than 400 rev/mins stirs, and reacts after 3 hours, stops to stir and heating.Reaction finishes rear catalyst and falls to the bottom, then with the liquefied mixture standing demix, obtains biodiesel, and its yield is 90.0%.
Claims (2)
1. one kind with porous SiO
2Material is the solid base catalyst preparation method of carrier, it is characterized in that this method may further comprise the steps:
(1) with porous SiO
2Material naturally cooled to room temperature in drier after 100-150 ℃ of dry 3-5 hour, and airtight preservation;
Described porous SiO
2Material is meant the SiO of two meso-hole structures of the second hole of the one-level hole that has 2-5nm simultaneously and 10-30nm
2Material, its specific area are 500-1500m
2/ g, pore volume are 0.8-3.5cm
3/ g;
(2) source that will contain the compound of basic component is dissolved in the deionized water, is made into the solution that concentration is 10-40wt%;
The described compound that contains basic component is meant alkali metal, and one or both in the alkaline earth oxide derive from their nitrate, carbonate or acetate;
(3) the porous SiO that step (1) is obtained
2Material joins in the solution that step (2) obtains and floods, and continues down to stir 1-12 hour at 25 ℃, and reaction finishes the back and under 25-80 ℃, carries out the solvent evaporation, obtains solid product;
(4) solid product that step (3) is obtained is under nitrogen atmosphere; Programming rate with 5-10 ℃/min rises to certain temperature between 150-600 ℃ from room temperature; And after constant temperature 3-6 under this temperature hour, cooling naturally obtains solid base catalyst under nitrogen atmosphere;
The described compound that contains basic component accounts for the 1.0wt%-10.0wt% that is of solid base catalyst quality.
2. catalyst applications according to claim 1 is in the preparation biodiesel; It is characterized in that feedstock oil, methyl alcohol and prepared solid base catalyst are mixed, stirring reaction under 57-67 ℃ of temperature, the reaction time is 2-6 hour; Reaction finishes the back standing demix, obtains biodiesel after the separation; Wherein catalyst amount is the 1.0wt%-5.0wt% of feedstock oil, and the mol ratio of methyl alcohol and feedstock oil is 5-20: 1; Described feedstock oil is vegetable oil, animal fat or waste cooking oil or waste oil.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107032477A (en) * | 2017-06-22 | 2017-08-11 | 杭州诚洁环保有限公司 | The application of acetic acid in a kind of CaO/AC catalysis of solid catalyst ozone oxidation waste water |
| CN110813270A (en) * | 2018-08-09 | 2020-02-21 | 南京大学 | Hierarchical pore solid alkali material and synthetic method thereof |
| CN112452317A (en) * | 2020-11-24 | 2021-03-09 | 南京工业大学 | Surface-modified silicon dioxide microsphere catalyst, preparation method and application |
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| US5700754A (en) * | 1994-10-18 | 1997-12-23 | Chisso Corporation | Barium/calcium catalyst and a process for producing the same |
| CN1836772A (en) * | 2005-03-23 | 2006-09-27 | 中国石油化工股份有限公司 | Load type calcium oxide catalyst, its preparation method and uses |
| CN101294094A (en) * | 2007-04-29 | 2008-10-29 | 华中农业大学 | Method for preparing biological diesel oil by using nano-solid heteropoly acid, heteropolybase catalyst |
| CN101130163A (en) * | 2007-08-14 | 2008-02-27 | 西北农林科技大学 | Supported fly ash solid base catalyst for preparing biodiesel and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107032477A (en) * | 2017-06-22 | 2017-08-11 | 杭州诚洁环保有限公司 | The application of acetic acid in a kind of CaO/AC catalysis of solid catalyst ozone oxidation waste water |
| CN110813270A (en) * | 2018-08-09 | 2020-02-21 | 南京大学 | Hierarchical pore solid alkali material and synthetic method thereof |
| CN110813270B (en) * | 2018-08-09 | 2021-06-01 | 南京大学 | Hierarchical pore solid alkali material and synthetic method thereof |
| CN112452317A (en) * | 2020-11-24 | 2021-03-09 | 南京工业大学 | Surface-modified silicon dioxide microsphere catalyst, preparation method and application |
| CN112452317B (en) * | 2020-11-24 | 2023-06-30 | 南京工业大学 | Surface modified silicon dioxide microsphere catalyst, preparation method and application |
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