CN103691454B - A kind of preparation method and applications of mesoporous carbon based solid acid catalyst - Google Patents
A kind of preparation method and applications of mesoporous carbon based solid acid catalyst Download PDFInfo
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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
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- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The preparation method and applications of a kind of mesoporous carbon based solid acid catalyst are the present invention relates to.In acid condition, with saccharide or oligomeric phenolic resin etc. as carbon source, special nature by supercritical fluid, use supercritical carbon dioxide to dissolve carbon source as solvent and silica template is carried out casting filling, under inert atmosphere, high temperature carbonization obtains carbon-silicon compound, utilize strong acid or strong base solution removing silicon dioxide casting mold, rear acid-modified obtain mesoporous carbon based solid acid catalyst.The mesoporous carbon based solid acid catalyst that preparation method of the present invention obtains has regular orderly and that intensity is suitable mesopore orbit structure, bigger specific surface area and pore volume, and higher sour density.This catalyst is used for the reaction of catalysis biological diesel raw material esterification acid reduction, and after reaction, acid value of oil and fat is reduced to below 2mgKOH/g, shows the solid acid catalysis performance of excellence.
Description
Technical field
The present invention relates to catalysis material preparation and application field, be specifically related to the system of a kind of mesoporous carbon based solid acid catalyst
Standby and application in catalysis biological diesel raw material oils and fats deacidification is reacted.
Background technology
In the face of world food shortage and nervous situation of ploughing, the national conditions that particularly China has a large population and a few land are traditional with can
Alimentary crop resource is that the path of raw material production bio-fuel encounters bottleneck.This means that the development of following green energy resource is necessary
Set up on the basis of not striving grain with people, not striving ground and inedible materials cheap and easy to get with grain.In recent years, unedible height is utilized
Acid number oils and fats, as the preparation such as Jatropha oil, waste cooking oil biodiesel becomes widely studied focus.
Preparing biological diesel fuel by high-acid-value grease it is crucial that free fatty acid content in raw material is down to ester exchange reaction
Below base catalyst tolerance requires.The catalyst that current industrial widely used esterification acid reduction processes is concentrated sulphuric acid, its deacidification
Effect is the most notable, but there are following problems, at purification of products difficulty, catalyst concentrated sulphuric acid etching apparatus, waste liquid
Manage and improper easily cause environmental pollution, be difficult to continuous production etc..Solid acid catalyst has a good deacidification catalytic performance because of it, and easily
In separating, the little feature such as good with regenerability of corrosivity and be considered as most potential high-acid value grease deacidification catalyst.
Meso-porous carbon material has high specific surface area and mesoporous pore volume and good stability, thus at macromole
Absorption and catalytic reaction aspect have huge potential advantages.The most in recent years, ordered mesoporous carbon material technology of preparing obtains
Rapid progress, can obtain Jie of different morphologies and pore passage structure by nanometer casting method and organic-organic self-assembling method
Hole material with carbon element.Owing to meso-porous carbon material surface does not have catalysis active group, therefore functionalization based on meso-porous carbon material changes
Journal of Sex Research becomes domestic and international study hotspot.The present invention, on the basis of synthesising mesoporous material with carbon element, is had by surface acid modification
There is the mesoporous carbon based solid acid catalyst of the functionalized acidic of suitable acid density, and applied the meal in catalysis with high acid value
In the esterification acid reduction reaction of drink waste oil.
Summary of the invention
The purpose of the present invention is to propose to the preparation method of a kind of mesoporous carbon based solid acid catalyst and former in biodiesel
Material catalytic esterification deacidification reaction in application, the solution containing carbon source is imported in mesoporous silicon oxide casting mold, through pre-carbonization,
Carbonization and de-mesoporous silicon oxide casting mold obtain ordered mesopore carbon, and it at high temperature carries out acid treatment obtain Jie of functionalization
Hole carbon solid acid catalyst, this catalyst has good catalytic esterification deacidification effect to the esterification pretreatment of biodiesel raw material.
Technical scheme is as follows:
A kind of mesoporous carbon based solid acid catalyst, has orderly three-dimensional open-framework, surface acidic groups, acidity, acid
Intensity and acid amount are adjustable, and acid density is 0.2-2.5mmol/g.
The preparation method of mesoporous carbon based solid acid catalyst:
Use solvent carbon source to be completely dissolved, then carbon source solution is directed in mesoporous silicon oxide casting mold duct, will fill out
The silicon dioxide casting mold filling carbon source carries out the two pre-carbonizations of step, the pressed powder that pre-carbonization obtains under inert gas shielding, with
0.5-20 DEG C/min heating rate is warming up to 500-1100 DEG C and carries out carbonization, obtains carbon and mesoporous silicon oxide casting mold complex；
Carbon and mesoporous silicon oxide casting mold complex use high concentration alkali solution or acid solution to dissolve removing mesoporous silicon oxide casting mold, will
Acid solution is passed through to be placed with in the reactor of mesoporous carbon and carries out acid functionalization process, then filters, washs, is vacuum dried and is situated between
Hole material with carbon element.
Carbon source described in this method is glucose, fructose, sucrose, maltose, glycerol, oligomeric phenolic resin and aforementioned any two
The mixture planted.
Solvent described in this method is that supercritical carbon dioxide, acid solution or supercritical carbon dioxide mix with acid solution
Thing (arbitrary proportion) so that carbon source is fully dissolved and is filled into mesoporous silicon oxide casting mold duct, with obtain regular in order,
The mesoporous carbon structure that intensity is suitable.
Acid solution described in this method is concentrated sulphuric acid, hydrochloric acid, boric acid, phosphoric acid, nitric acid or hypochlorite solution.
Mesoporous silicon oxide casting mold described in this method is SBA-15, MCM-48, KIT-6, SBA-16 or MSU-2.
High concentration alkali solution described in this method or acid solution are that sodium hydroxide solution, potassium hydroxide solution or Fluohydric acid. are molten
Liquid.
The two pre-carbonizations of step described in this method are to be dried 6 hours at 100 DEG C with carbon source mixture by casting mold, are continuously heating to
160 DEG C of pre-carbonizations 6 hours, obtain carbon-silicon compound.
Described in this method, carbonization condition carries out carbonization for being warming up to 500-1100 DEG C with 0.5-20 DEG C/min heating rate,
To carbon and mesoporous silicon oxide casting mold complex.
Acid functionalization described in this method is processed as gained meso-porous carbon material and sulphuric acid, phosphoric acid, hypophosphorous acid, chlorosulfonic acid or right
Toluenesulfonic acid mixes in closed reactor, introduces different acid, acid strength and the acidic-group of acid amount.
Gained mesoporous carbon specific surface area of the present invention is 500-900m2/ g, pore-size distribution is 2-10nm, and pore volume is 0.5-
1.2m3/g.The mesoporous carbon based solid acid catalyst that mesoporous carbon acid functionalization obtains, acid density is 0.2-2.5mmol/g.
The mesoporous carbon based solid acid catalyst of the present invention, for the deacidification pretreatment of biodiesel raw material, by high acid value oil
Fat and methanol are mixed in proportion (mol ratio 5:1～20:1), are proportionally added into mesoporous carbon based solid acid according to oils and fats addition and urge
Agent carries out esterification.After reaction, acid value of oil and fat is reduced to below 2mg KOH/g.
Present invention have the advantage that
1. the mesoporous carbon based solid acid catalyst prepared, specific surface area is big, and pore volume is big, pore-size distribution is homogeneous and tool
Have regular in order, mesopore orbit structure that intensity is suitable.
2. the mesoporous carbon based solid acid catalyst prepared, its surface acidic groups, acidity, acid strength and acid amount can
Adjusting, acid density is controlled in the range of 0.2-2.5mmol/g.
3. the mesoporous carbon based solid acid catalyst prepared, has relatively the high-acid value grease as biodiesel raw material
High catalytic esterification deacidification activity, can meet the requirement to acid value of oil and fat of the follow-up ester exchange reaction.
Accompanying drawing explanation
Fig. 1. the little angle XRD figure of gained mesoporous carbon based solid acid catalyst in embodiment 1.
Fig. 2. the nitrogen adsorption of gained mesoporous carbon based solid acid catalyst-desorption isotherm figure in embodiment 1.
Fig. 3. the graph of pore diameter distribution of gained mesoporous carbon based solid acid catalyst in embodiment 1.
Fig. 4. the transmission electron microscope photo of gained mesoporous carbon based solid acid catalyst in embodiment 1.
Fig. 5. the little angle XRD figure of gained mesoporous carbon based solid acid catalyst in embodiment 2.
Fig. 6. the nitrogen adsorption of gained mesoporous carbon based solid acid catalyst-desorption isotherm figure in embodiment 2.
Fig. 7. the graph of pore diameter distribution of gained mesoporous carbon based solid acid catalyst in embodiment 2.
Fig. 8. the transmission electron microscope photo of gained mesoporous carbon based solid acid catalyst in embodiment 2.
Fig. 9. in embodiment 1, gained mesoporous carbon based solid acid catalyst is anti-to biodiesel raw material oils and fats catalytic esterification deacidification
Should result.
Figure 10. in embodiment 2, gained mesoporous carbon based solid acid catalyst is to biodiesel raw material oils and fats catalytic esterification deacidification
Reaction result.
Detailed description of the invention
Embodiment 1. weighs 1.6g glucose, 0.16g concentrated sulphuric acid and 30mL distilled water, is mixed and stirred for obtaining clarifying molten
Liquid, and using supercritical carbon dioxide as solvent, being conducted in 1g mesoporous silicon oxide SBA-15 casting powder, wherein two
It is 80% that carbonoxide accounts for the mass fraction of mixed liquor, maintains 2 hours.Then mixture is dried 6 hours at 100 DEG C, continues
It is warming up to 160 DEG C of pre-carbonizations 6 hours, obtains carbon-silicon compound.Then it is placed in tube furnace, 1 DEG C in a nitrogen atmosphere/
Min is warming up to 900 DEG C, roasting 5 hours, and gained solid mixes with 5g2mol/L sodium hydroxide solution, stirs 24 hours under room temperature,
Removing mesoporous silicon oxide, after filtration washing, at 100 DEG C, vacuum drying i.e. obtains meso-porous carbon material in 6 hours.Take 1g mesoporous carbon
Material and 20mL concentrated sulphuric acid, put in polytetrafluoroethyllining lining reactor, keeps 6 hours, naturally cool to room at 160 DEG C
Temperature.After filtration, distilled water wash, it is vacuum dried 6 hours at 100 DEG C, i.e. obtains mesoporous carbon based solid acid.As shown in Figure 1
The nitrogen adsorption desorption isotherm of shown material has back stagnant ring to occur, shows there is mesoporous existence；The aperture of material is divided as shown in Figure 2
Butut shows that material pore-size distribution is homogeneous；The little angle XRD figure of material has three obvious characteristic diffraction peaks to show material as shown in Figure 3
Material has two-dimentional hexagonal structure；The projection electromicroscopic photograph visible material of material has regular orderly mesopore orbit as shown in Figure 4
Structure；Its aperture is 3.4nm, and pore volume is 0.5cm3/ g, specific surface area is 610m2/ g, sulfonic acid density is 1.6mmol/g.
Embodiment 2. weighs 1.0g sucrose, 0.18g phosphoric acid and 30mL distilled water, is mixed and stirred for obtaining settled solution, and
Using supercritical carbon dioxide as solvent, it is conducted in 1g mesoporous silicon oxide MCM-48 casting powder, wherein titanium dioxide
It is 60% that carbon accounts for the mass fraction of mixed liquor, maintains 4 hours.Then mixture is dried 6 hours at 100 DEG C, continues to heat up
To 160 DEG C of pre-carbonizations 6 hours, obtain carbon-silicon compound.Then it is placed in tube furnace, in a nitrogen atmosphere 5 DEG C/min liter
Temperature is to 800 DEG C, and carbonization 8 hours, gained solid mixes with 5g2mol/L sodium hydroxide solution, stirs 24 hours under room temperature, removing
Mesoporous silicon oxide, after filtration washing, at 100 DEG C, vacuum drying i.e. obtains meso-porous carbon material in 6 hours.Take 1g meso-porous carbon material
With 20mL p-methyl benzenesulfonic acid, put in polytetrafluoroethyllining lining reactor, keep 10 hours at 180 DEG C, naturally cool to room
Temperature.After filtration, distilled water wash, it is vacuum dried 6 hours at 100 DEG C, i.e. obtains mesoporous carbon based solid acid.As shown in Figure 5
The nitrogen adsorption desorption isotherm of shown material has back stagnant ring to occur, shows there is mesoporous existence；The aperture of material is divided as shown in Figure 6
Butut shows that material pore-size distribution is homogeneous；The little angle XRD figure of material has three obvious characteristic diffraction peaks to show material as shown in Figure 7
Material has two-dimentional hexagonal structure；The projection electromicroscopic photograph visible material of material has regular orderly mesopore orbit as shown in Figure 8
Structure；Its aperture is 2.0nm, and pore volume is 0.67cm3/ g, specific surface area is 589m2/ g, sulfonic acid density is 1.2mmol/g.
Embodiment 3. weighs 2.0g glycerol, 0.12g hydrochloric acid and 30mL distilled water, is mixed and stirred for obtaining settled solution, and
Using supercritical carbon dioxide as solvent, it is conducted in 1g mesoporous silicon oxide KIT-6 casting powder, wherein carbon dioxide
The mass fraction accounting for mixed liquor is 40%, maintains 8 hours.Then mixture is dried 6 hours at 100 DEG C, is continuously heating to
160 DEG C of pre-carbonizations 6 hours, obtain carbon-silicon compound.Then being placed in tube furnace, 10 DEG C/min heats up in a nitrogen atmosphere
To 700 DEG C, carbonization 10 hours, gained solid mixes with 20mL hydrofluoric acid solution, stirs 24 hours, remove mesoporous dioxy under room temperature
SiClx, after filtration washing, at 100 DEG C, vacuum drying i.e. obtains meso-porous carbon material in 6 hours.Take 1g meso-porous carbon material and 20mL phosphorus
Acid, puts in polytetrafluoroethyllining lining reactor, keeps 4 hours, naturally cool to room temperature at 200 DEG C.Through filtration, distilled water
After washing, it is vacuum dried 6 hours at 100 DEG C, i.e. obtains mesoporous carbon based solid acid.Its aperture is 5.5nm, and pore volume is
1.13cm3/ g, specific surface area is 900m2/ g, sulfonic acid density is 2.2mmol/g.
Embodiment 4. weighs 0.8g phenolic resin and 0.21g nitric acid and 30mL distilled water, is mixed and stirred for obtaining clarifying molten
Liquid, and using supercritical carbon dioxide as solvent, being conducted in 1g mesoporous silicon oxide SBA-16 casting powder, wherein two
It is 20% that carbonoxide accounts for the mass fraction of mixed liquor, maintains 10 hours.Then mixture is dried 6 hours at 100 DEG C, continues
Continue and be warming up to 160 DEG C of pre-carbonizations 6 hours, obtain carbon-silicon compound.Then it is placed in tube furnace, in a nitrogen atmosphere 15
DEG C/min is warming up to 600 DEG C, carbonization 5 hours, gained solid mixes with 5g2mol/L potassium hydroxide solution, stirs 24 little under room temperature
Time, removing mesoporous silicon oxide, after filtration washing, at 100 DEG C, vacuum drying i.e. obtains meso-porous carbon material in 6 hours.Take 1g to be situated between
Hole material with carbon element and 20mL hypophosphorous acid, put in polytetrafluoroethyllining lining reactor, keeps 5 hours, naturally cool at 120 DEG C
Room temperature.After filtration, distilled water wash, it is vacuum dried 6 hours at 100 DEG C, i.e. obtains mesoporous carbon based solid acid.Its aperture is
8.2nm, pore volume is 0.76cm3/ g, specific surface area is 534m2/ g, sulfonic acid density is 0.2mmol/g.
Embodiment 5. weighs 1.8g maltose and 0.13g boric acid and 30mL distilled water respectively, is mixed and stirred for being clarified
Solution, and using supercritical carbon dioxide as solvent, be conducted in 1g mesoporous silicon oxide MSU-2 casting powder, wherein
It is 10% that carbon dioxide accounts for the mass fraction of mixed liquor, maintains 12 hours.Then mixture is dried 6 hours at 100 DEG C,
It is continuously heating to 160 DEG C of pre-carbonizations 6 hours, obtains carbon-silicon compound.Then it is placed in tube furnace, in a nitrogen atmosphere 20
DEG C/min is warming up to 1000 DEG C, carbonization 3 hours, gained solid mixes with 5g2mol/L potassium hydroxide solution, stirs 24 under room temperature
Hour, removing mesoporous silicon oxide, after filtration washing, at 100 DEG C, vacuum drying i.e. obtains meso-porous carbon material in 6 hours.Take 1g
Meso-porous carbon material and 20mL chlorosulfonic acid, put in polytetrafluoroethyllining lining reactor, keeps 2 hours, natural cooling at 100 DEG C
To room temperature.After filtration, distilled water wash, it is vacuum dried 6 hours at 100 DEG C, i.e. obtains mesoporous carbon based solid acid.Its aperture
For 10nm, pore volume is 1.2cm3/ g, specific surface area is 690m2/ g, sulfonic acid density is 2.5mmol/g.
Embodiment 6. weighs 2.0g fructose, 0.21g hypochlorous acid and 30mL distilled water respectively, is mixed and stirred for obtaining clarifying molten
Liquid, and using supercritical carbon dioxide as solvent, being conducted in 1g mesoporous silicon oxide SBA-15 casting powder, wherein two
It is 90% that carbonoxide accounts for the mass fraction of mixed liquor, maintains 5 hours.Then mixture is dried 8 hours at 100 DEG C, continues
It is warming up to 160 DEG C of pre-carbonizations 8 hours, obtains carbon-silicon compound.Then it is placed in tube furnace, 0.5 DEG C in a nitrogen atmosphere/
Min is warming up to 500 DEG C, carbonization 12 hours, and gained solid mixes with 5g2mol/L potassium hydroxide solution, stirs 24 little under room temperature
Time, removing mesoporous silicon oxide, after filtration washing, at 100 DEG C, vacuum drying i.e. obtains meso-porous carbon material in 6 hours.Take 1g to be situated between
Hole material with carbon element and 20mL nitric acid, put in polytetrafluoroethyllining lining reactor, keeps 8 hours, naturally cool to room at 140 DEG C
Temperature.After filtration, distilled water wash, it is vacuum dried 6 hours at 100 DEG C, i.e. obtains mesoporous carbon based solid acid.Its aperture is
6.6nm, pore volume is 0.91cm3/ g, specific surface area is 500m2/ g, sulfonic acid density is 0.8mmol/g.
Embodiment 7. weighs 0.6g glucose, 1.1g maltose, 0.16g concentrated sulphuric acid respectively, and 30mL and 30mL distilled water,
It is mixed and stirred for obtaining settled solution, is conducted into 1g mesoporous silicon oxide 1g mesoporous silicon oxide SBA-16 casting powder
In, stir 5 hours.Then mixture is dried 6 hours at 100 DEG C, is continuously heating to 160 DEG C of pre-carbonizations 6 hours, obtains
Carbon-silicon compound.Then being placed in tube furnace, 8 DEG C/min is warming up to 1100 DEG C in a nitrogen atmosphere, carbonization 4 hours, institute
Obtain solid to mix with 5g2mol/L sodium hydroxide solution, stir 24 hours under room temperature, remove mesoporous silicon oxide, filtration washing
After, at 100 DEG C, vacuum drying i.e. obtains meso-porous carbon material in 6 hours.Take 1g meso-porous carbon material and 20mL chlorosulfonic acid, put into poly-four
In fluorothene liner reactor, keep 1 hour at 100 DEG C, naturally cool to room temperature.After filtration, distilled water wash,
It is vacuum dried 6 hours at 100 DEG C, i.e. obtains mesoporous carbon based solid acid.Its aperture is 4.5nm, and pore volume is 0.92cm3/ g, than
Surface area is 740m2/ g, sulfonic acid density is 1.8mmol/g.
The mensuration of embodiment 8. acid number and acidity is according to GB/T5530-2005 " animal and plant fat acid number and acidity assaying " institute
The heat ethanol methods of regulation, determination step: the 50mL ethanol solution containing 0.5mL phenolphthalein indicator is poured into equipped with 10g oils and fats
In conical flask, it is heated to boiling, when the temperature of ethanol is higher than 70 DEG C, titrates with the potassium hydroxide-ethanol solution of 0.25mol/L
To solution changes color.And keep solution 30s colour-fast, it is terminal.Acid number computing formula is:
The computing formula of acid number (AV):
Embodiment 9. weighs 50g raw oil material (waste cooking oil) and is placed in Jacketed bottle, according to oil quality 0.25%～
0.1% weighs catalyst adds reactor, 5:1～20:1 weighs absolute methanol and pour Jacketed bottle into the most in molar ratio, puts into stirring
Son, connects Jacketed bottle with thermostatic water-circulator bath, sets water bath with thermostatic control temperature 80 DEG C and mixing speed 800 revs/min；In
Between sampling time, first stop being passed through and stirring of thermostatted water, wait 1～2 minute, treat that catalyst separates with reactant, and methanol
After being layered with oils and fats, take off a layer oils and fats 0.5mL with pipet, record its acid number as the method previously described.Free fatty (FFA)
Conversion ratio is to characterize the most direct index of catalyst activity, and its computing formula is:
In formula: Y free fatty yield, %；AVorThe initial acid value of raw oil material, mg KOH/g；
AVfiAcid value of oil and fat after deacidification treatment, mg KOH/g.
By embodiment 1 gained catalyst under the above-described reaction conditions, after reacting 300 minutes, acid number drops below
2mgKOH/g。
By embodiment 2 gained catalyst under the above-described reaction conditions, after reacting 300 minutes, acid number drops below
2mgKOH/g。
Claims (2)
1. a preparation method for mesoporous carbon based solid acid catalyst, is characterized in that using solvent carbon source to be completely dissolved, then will
Carbon source solution is directed in mesoporous silicon oxide casting mold duct, and the silicon dioxide casting mold filling carbon source is carried out the two pre-carbonizations of step,
The pressed powder that pre-carbonization obtains, under inert gas shielding, is warming up to 500-1100 DEG C with 0.5-20 DEG C/min heating rate and enters
Row carbonization, obtains carbon and mesoporous silicon oxide casting mold complex；Carbon uses high concentration alkali with mesoporous silicon oxide casting mold complex
Solution or acid solution dissolve removing mesoporous silicon oxide casting mold, are passed through acid solution to be placed with in the reactor of mesoporous carbon and carry out acid
Functionalization, then filters, washs, is vacuum dried and obtains meso-porous carbon material；Described solvent is supercritical carbon dioxide, acid molten
Liquid or supercritical carbon dioxide and acid solution mixture；Acid solution in described solvent is concentrated sulphuric acid, hydrochloric acid, boric acid, phosphorus
Acid, nitric acid or hypochlorite solution；Described carbon source is glucose, fructose, sucrose, maltose, glycerol or oligomeric phenolic resin
A kind of or the mixture of any two kinds；Described mesoporous silicon oxide casting mold be SBA-15, MCM-48, KIT-6, SBA-16 or
MSU-2；The two described pre-carbonizations of step are to be dried 6 hours at 100 DEG C with carbon source mixture by casting mold, are continuously heating to 160 DEG C
Pre-carbonization 6 hours, obtains carbon-silicon compound；Described high concentration alkali solution or acid solution are sodium hydroxide solution, potassium hydroxide
Or hydrofluoric acid solution；Described acid functionalization for using sulphuric acid, phosphoric acid, hypophosphorous acid, chlorosulfonic acid or p-methyl benzenesulfonic acid by mesoporous carbon
Solution carries out acid treatment.
2. the application of the mesoporous carbon based solid acid catalyst obtained by claim 1 method, for the deacidification of biodiesel raw material
Pretreatment, by high-acid value grease and methanol mixed, mol ratio 5:1～20:1, carries out esterification at 80 DEG C.
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| CN103934027B (en) * | 2014-04-24 | 2015-12-30 | 南京德灿化学有限公司 | A kind of solid acid catalyst and its preparation method and application |
| CN105597789A (en) * | 2016-01-11 | 2016-05-25 | 黄冈师范学院 | Preparation method of mesoporous carbon-based solid acid and mesoporous carbon-based solid acid prepared through method and application |
| CN107262020A (en) * | 2017-06-26 | 2017-10-20 | 安徽安顺硅基玻璃原料有限公司 | A kind of preparation method of modified porous silica sand |
| CN108435230B (en) * | 2018-04-26 | 2020-10-13 | 陕西师范大学 | Heteroatom-doped ordered mesoporous carbon-supported ruthenium catalyst for efficiently catalyzing 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxaldehyde |
| CN110423649A (en) * | 2019-07-15 | 2019-11-08 | 西安理工大学 | The overcritical heterogeneous catalysis preparation system of biodiesel |
| CN111992251A (en) * | 2020-09-16 | 2020-11-27 | 浙江大学 | Modified silicon dioxide loaded polymer solid acid catalyst and preparation method and application thereof |
| CN112941064A (en) * | 2021-02-07 | 2021-06-11 | 河南工业大学 | Method for immobilizing modified reinforced carbon-based material and application |
| CN113522344B (en) * | 2021-07-22 | 2022-03-11 | 太原理工大学 | Ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material and preparation and application thereof |
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| CN102078823A (en) * | 2010-11-25 | 2011-06-01 | 北京大学 | Carbon-based solid acid catalyst and preparation method thereof |
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