CN108993606A - A kind of preparation and its application of magnetic coupling cellulose base solid acid catalyst - Google Patents
A kind of preparation and its application of magnetic coupling cellulose base solid acid catalyst Download PDFInfo
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- CN108993606A CN108993606A CN201810648588.XA CN201810648588A CN108993606A CN 108993606 A CN108993606 A CN 108993606A CN 201810648588 A CN201810648588 A CN 201810648588A CN 108993606 A CN108993606 A CN 108993606A
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- 239000001913 cellulose Substances 0.000 title claims abstract description 58
- 229920002678 cellulose Polymers 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 230000008878 coupling Effects 0.000 title claims abstract description 31
- 238000010168 coupling process Methods 0.000 title claims abstract description 31
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 31
- 239000011973 solid acid Substances 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 32
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000003225 biodiesel Substances 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 35
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 229950000244 sulfanilic acid Drugs 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000004090 dissolution Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 238000005553 drilling Methods 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 7
- 239000004519 grease Substances 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 229940096992 potassium oleate Drugs 0.000 claims description 7
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 7
- 235000010288 sodium nitrite Nutrition 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- BZFNWGMBZMZWEY-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chlorate Chemical compound [O-]Cl(=O)=O.CCCCN1C=C[N+](C)=C1 BZFNWGMBZMZWEY-UHFFFAOYSA-M 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 5
- 239000002608 ionic liquid Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 238000013517 stratification Methods 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- 238000003809 water extraction Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229960004756 ethanol Drugs 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 238000004364 calculation method Methods 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims 8
- 229920000742 Cotton Polymers 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- -1 finally Substances 0.000 claims 1
- 230000005389 magnetism Effects 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 5
- 230000002045 lasting effect Effects 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 235000013339 cereals Nutrition 0.000 description 4
- 238000009388 chemical precipitation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000002122 magnetic nanoparticle Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the preparations and its application of a kind of magnetic coupling cellulose base solid acid catalyst.The magnetic cellulose based solid acid catalyst, using the means of embedding by sulfoxidation graphene and magnetic ferroferric oxide nanometer even particulate dispersion in cellulosic matrix, again by inverse phase suspension immobilization balling-up, what is be prepared is a kind of applied to the catalyst for preparing biodiesel.Catalyst prepared by the present invention has catalytic activity high, and reaction condition is mild, magnetic strong and lasting, can be separated catalyst from reaction system by externally-applied magnetic field, can be recycled repeatedly, feature low in cost.
Description
Technical field:
It applies the present invention relates to a kind of in the catalyst for being catalyzed transesterification preparation field of biodiesel oil, in particular to a kind of magnetic
The preparation method of property compound cellulose based solid acid catalyst.
Background technique:
With the increasingly reduction of the mineral resources such as petroleum and its ball border influences over the ground, developing a kind of novel green can be again
Raw fuel resource is imperative.Biodiesel enters the sight of people as substitutability and the reproducibility energy, and synthesizes life
The key of object diesel oil is to develop efficient green catalyst.
Generally using the catalysis of the homogeneous catalysts such as highly basic (NaOH or KOH) and sulfuric acid in domestic and international biodiesel industrial production
Ester exchange reaction.Homogeneous catalyst has many advantages, such as that reaction condition is mild, high catalytic efficiency, but the disadvantage is that corrosion equipment, catalysis
Agent is difficult to recycle, be easy to produce three industrial wastes, pollutes residual soda acid in environment and the thick ester of semi-finished product and causes post-processing complexity etc.
Problem.Heterogeneous catalysis is small to equipment corrosion, is easily recycled, and can be effectively reduced environmental pollution.Therefore, it uses
Heterogeneous catalysis preparation biodiesel is a kind of production technology of green.Magnetic cellulose based solid acid is as a kind of new environment
The heterogeneous ester exchange catalyst of friendly, it possesses the high activity of homogeneous catalyst and the feature of environmental protection of heterogeneous catalysis simultaneously,
Also have many advantages, such as it is recyclable be used for multiple times, cost of material is low, prepare that simple and stability is good, and magnetic ferroferric oxide adds
Enter to make the more convenient recycling of catalyst, is efficient green catalyst truly.
Summary of the invention:
The purpose of the present invention is to provide a kind of magnetic coupling cellulose base solid acid catalysts of biodiesel synthesis
Preparation method and applications, not only have high activity, high stability and a unique Magneto separate characteristic, and preparation method it is simple,
Preparation cost is cheap, and very high catalytic performance can be shown in catalyzed transesterification.
Magnetic coupling cellulose base solid acid catalyst of the invention is by cellulose, sulfoxidation graphene and four oxidations
Three iron nano-particles are mixed with to obtain, and the specific preparation process of magnetic coupling cellulose base solid acid catalyst is as follows:
1) prepared by magnetic coupling cellulose base solid acid catalyst；
1.1) dissolution of cellulose: cellulose is put into ionic liquid 1-butyl-3-methyl imidazolium chlorate, and 85~95
Mechanical stirring 10h under the conditions of DEG C, obtains cellulose solution.
1.2) preparation of sulfoxidation graphene: graphite oxide is prepared by Hummers method, and ultrasound obtains oxidation stone
Black alkene；Anhydrous p-aminobenzene sulfonic acid is added in the sodium hydroxide solution that concentration is 2%, is allowed to dissolve in hot bath, it
After be cooled to room temperature；Sodium nitrite is added, after dissolution, under stiring instills the mixture solution equipped with ice water and concentrated hydrochloric acid
In beaker, makes temperature control at 0 DEG C, after there is the white precipitate of Diazosalt of sulfanilic acid, continue to be stirred to react
15min obtains Diazosalt of sulfanilic acid；Diazosalt of sulfanilic acid is gradually added drop-wise to the suspension of graphene oxide
In, it is washed with deionized after 2~4h is persistently stirred under condition of ice bath to neutrality, finally obtains sulfoxidation graphene,
It is sufficiently dry in 60 DEG C of vacuum ovens.
1.3) preparation of magnetic ferroferric oxide nanometer particle: with FeCl2·4H2O and FeCl3·6H2O is raw material use
Chemical precipitation method synthesizes Fe3O4Nanoparticle presses Fe first3+With Fe2+Molar ratio be 2:1 ratio weigh the molysite of calculation amount
In water with ferrous salt mixed dissolution, being then slowly added to ammonia spirit to pH value under high velocity agitation is 9~10, is washed to
Property obtains magnetic ferroferric oxide nanometer particle, dried for standby.
1.4) preparation of magnetic coupling cellulose base solid acid catalyst: next by the ferriferrous oxide nano of preparation
Abundant, mixing is added in cellulose solution in grain and sulfoxidation graphene mixture ultrasonic disperse and calcium carbonate together, will mix
Liquid be added to potassium oleate and Span 60 disperse in 300ml~400ml transformer oil of 30min from room temperature rise to 80 DEG C~90 DEG C with
High-speed mixer mechanical stirring 2.5h~3.5h forms it into the form of composite balls, then is washed repeatedly again with dehydrated alcohol and hydrochloric acid
Microballoon is closed, until hydrochloric acid drilling is complete, waste liquor PH is acidity, is then separated using magnet.Resulting composite mesopore microballoon is
Magnetic coupling cellulose base solid acid catalyst.Finally, catalyst is dried under vacuum to constant weight.
2) preparation of biodiesel:
By a certain amount of grease, methanol and magnetic coupling cellulose base solid acid catalyst are added in reaction flask, and stirring is made
With lower back flow reaction for a period of time after, catalyst is separated from reaction mixture through ethanol washing under the action of externally-applied magnetic field
Dried recovered, reaction solution, which moves in separatory funnel, is added n-hexane and water extraction, stratification.Upper layer phase biodiesel (fat
Sour methyl esters) and n-hexane, n-hexane is recycled through vacuum distillation, biodiesel is obtained and GC-MS is used to carry out yield analysis again.
Above-mentioned anhydrous p-aminobenzene sulfonic acid, sodium nitrite, graphene oxide mass ratio be 1:0.4:1.
The concentration of above-mentioned graphene oxide suspension is 10mg/ml.
Sodium hydroxide solution that above-mentioned concentration is 2%, ice water, concentrated hydrochloric acid, graphene oxide solution volume ratio be 1:2:
0.2:10.
Above-mentioned magnetic cellulose, calcium carbonate, sulfoxidation graphene, ferroferric oxide nano granules mass ratio be 1:
1.6:0.01~0.1:0.3~0.4.
Above-mentioned potassium oleate and the mass ratio of Span 60 are 1:4.
The percentage composition of above-mentioned drilling hydrochloric acid is 4%~5%.
Above-mentioned addition grease, methanol, magnetic coupling cellulose base solid acid catalyst mass ratio be 1:0.1~2:0.05
~0.2.Advantages of the present invention:
1. the magnetic coupling cellulose base solid acid catalyst activity that the present invention uses is high, cost of material is low, stability is good；
2. the present invention uses the form of doping by sulfoxidation graphene and magnetic nanoparticle packet with catalytic effect
It nuzzles cellulose, avoids conventional coprecipitation method and prepare destruction of the magnetic nanoparticle to sulfoxidation graphene-structured,
On the basis of keeping preferable catalytic activity, the form of embedding makes magnetic persistently stronger, it can be achieved that being recycled for multiple times, saving again
Resource, and greatly reduce the pollution to environment.
3. the specific surface area that this porous structure increases catalyst keeps reaction more abundant, transesterification effect is more preferable.
Detailed description of the invention
Fig. 1 is the flow chart of magnetic coupling cellulose base solid acid catalyst preparation prepared by the present invention.
Fig. 2 is the scanning electron microscope (SEM) of magnetic coupling cellulose base solid acid catalyst prepared by the present invention
Photo.
Specific embodiment
Embodiment 1
5g cellulose is put into 66g ionic liquid 1-butyl-3-methyl imidazolium chlorate, mechanical stirring under the conditions of 90 DEG C
10h obtains cellulose solution.Graphite oxide is prepared by Hummers method, and ultrasound obtains graphene oxide；By 0.5g without
Water p-aminobenzene sulfonic acid is added in the sodium hydroxide solution that 5ml concentration is 2%, is allowed to dissolve in hot bath, be cooled down later
To room temperature；0.2g sodium nitrite is added, after dissolution, under stiring instills the mixture solution dense equipped with 10ml ice water and 1ml
In the beaker of hydrochloric acid, make temperature control at 0 DEG C, after there is the white precipitate of Diazosalt of sulfanilic acid, it is anti-to continue stirring
15min is answered, Diazosalt of sulfanilic acid is obtained；Diazosalt of sulfanilic acid is gradually added drop-wise to 50ml's (10mg/ml)
In graphene oxide suspension, it is washed with deionized after 2h is persistently stirred under condition of ice bath to neutrality, finally obtains sulfonation
Graphene oxide, it is sufficiently dry in 60 DEG C of vacuum ovens.With FeCl2·4H2O and FeCl3·6H2O is raw material use
Chemical precipitation method synthesizes Fe3O4Nano particle weighs 9.75g FeCl3·6H2O and 3.81g FeCl2·4H2O mixed dissolution exists
In water, being then slowly added to ammonia spirit to pH value under high velocity agitation is 9, is washed to neutrality and obtains magnetic ferroferric oxide and receives
Rice grain, dried for standby.Next the 1.5g ferroferric oxide nano granules of preparation and 0.25g sulfoxidation graphene are mixed
Object ultrasonic disperse and 8g calcium carbonate are added in cellulose solution are sufficiently mixed together, by mixed liquor put into 0.05g potassium oleate and
Rise to 80 DEG C from room temperature in the 300ml transformer oil of the dispersion of 0.25g Span 60 30min is made with high-speed mixer mechanical stirring 2.5h
Its form for forming composite balls, then complex microsphere is washed repeatedly with dehydrated alcohol and 4% hydrochloric acid, until hydrochloric acid drilling is complete, give up
Liquid pH value is acidity, is then separated using magnet.Resulting composite mesopore hole microballoon is magnetic coupling cellulose base solid acid
Catalyst.Finally, catalyst is dried under vacuum to constant weight.By 5g grease, 5ml methanol and 0.07g catalyst are added in reaction flask,
Under stirring action back flow reaction for a period of time after, under the action of externally-applied magnetic field by catalyst from reaction mixture kind separate through second
Alcohol washs dried recovered, and reaction solution, which moves in separatory funnel, is added n-hexane and water extraction, stratification.Upper layer phase biodiesel
(fatty acid methyl ester) and n-hexane recycle n-hexane through vacuum distillation, obtain biodiesel and GC-MS is used to carry out yield point again
Analysis.
Embodiment 2
10g cellulose is put into 133g ionic liquid 1-butyl-3-methyl imidazolium chlorate, and machinery stirs under the conditions of 90 DEG C
10h is mixed, cellulose solution is obtained.Graphite oxide is prepared by Hummers method, and ultrasound obtains graphene oxide；By 1g without
Water p-aminobenzene sulfonic acid is added in the sodium hydroxide solution that 10ml concentration is 2%, is allowed to dissolve in hot bath, be cooled down later
To room temperature；0.4g sodium nitrite is added, after dissolution, under stiring instills the mixture solution dense equipped with 20ml ice water and 2ml
In the beaker of hydrochloric acid, make temperature control at 0 DEG C, after there is the white precipitate of Diazosalt of sulfanilic acid, it is anti-to continue stirring
15min is answered, Diazosalt of sulfanilic acid is obtained；Diazosalt of sulfanilic acid is gradually added drop-wise to 100ml's (10mg/ml)
In graphene oxide suspension, it is washed with deionized after 4h is persistently stirred under condition of ice bath to neutrality, finally obtains sulfonation
Graphene oxide, it is sufficiently dry in 60 DEG C of vacuum ovens.With FeCl2·4H2O and FeCl3·6H2O is raw material use
Chemical precipitation method synthesizes Fe3O4Nano particle weighs 9.75g FeCl3·6H2O and 3.81g FeCl2·4H2O mixed dissolution exists
In water, being then slowly added to ammonia spirit to pH value under high velocity agitation is 9, is washed to neutrality and obtains magnetic ferroferric oxide and receives
Rice grain, dried for standby.Next by the 3g ferroferric oxide nano granules of preparation and 0.5g sulfoxidation graphene mixture
Ultrasonic disperse and 16g calcium carbonate are added in cellulose solution are sufficiently mixed together, by mixed liquor put into 0.1g potassium oleate and
Rise to 80 DEG C from room temperature in the 350ml transformer oil of the dispersion of 0.5g Span 60 30min is made with high-speed mixer mechanical stirring 3.5h
Its form for forming composite balls, then complex microsphere is washed repeatedly with dehydrated alcohol and 4% hydrochloric acid, until hydrochloric acid drilling is complete, give up
Liquid pH value is acidity, is then separated using magnet.Resulting compound microballoon with holes is that magnetic coupling cellulose base solid acid is urged
Agent.Finally, catalyst is dried under vacuum to constant weight.By 10g grease, 10ml methanol and 0.14g catalyst are added in reaction flask,
Under stirring action back flow reaction for a period of time after, under the action of externally-applied magnetic field by catalyst from reaction mixture kind separate through second
Alcohol washs dried recovered, and reaction solution, which moves in separatory funnel, is added n-hexane and water extraction, stratification.Upper layer phase biodiesel
(fatty acid methyl ester) and n-hexane recycle n-hexane through vacuum distillation, obtain biodiesel and GC-MS is used to carry out yield point again
Analysis.
Embodiment 3
20g cellulose is put into 266g ionic liquid 1-butyl-3-methyl imidazolium chlorate, and machinery stirs under the conditions of 90 DEG C
10h is mixed, cellulose solution is obtained.Graphite oxide is prepared by Hummers method, and ultrasound obtains graphene oxide；By 2g without
Water p-aminobenzene sulfonic acid is added in the sodium hydroxide solution that 20ml concentration is 2%, is allowed to dissolve in hot bath, be cooled down later
To room temperature；0.8g sodium nitrite is added, after dissolution, under stiring instills the mixture solution dense equipped with 40ml ice water and 4ml
In the beaker of hydrochloric acid, make temperature control at 0 DEG C, after there is the white precipitate of Diazosalt of sulfanilic acid, it is anti-to continue stirring
15min is answered, Diazosalt of sulfanilic acid is obtained；Diazosalt of sulfanilic acid is gradually added drop-wise to 200ml's (10mg/ml)
In graphene oxide suspension, it is washed with deionized after 2h is persistently stirred under condition of ice bath to neutrality, finally obtains sulfonation
Graphene oxide, it is sufficiently dry in 60 DEG C of vacuum ovens.With FeCl2·4H2O and FeCl3·6H2O is raw material use
Chemical precipitation method synthesizes Fe3O4Nano particle weighs 19.5g FeCl3·6H2O and 7.62g FeCl2·4H2O mixed dissolution exists
In water, being then slowly added to ammonia spirit to pH value under high velocity agitation is 9, is washed to neutrality and obtains magnetic ferroferric oxide and receives
Rice grain, dried for standby.Next the 6g ferroferric oxide nano granules of preparation and 1g sulfoxidation graphene mixture are surpassed
Sound dispersion and 32g calcium carbonate are added in cellulose solution are sufficiently mixed together, and mixed liquor is put into 0.1g potassium oleate and 0.5g
Rising to 80 DEG C from room temperature in the 400ml transformer oil of the dispersion of Span 60 30min makes its shape with high-speed mixer mechanical stirring 3.5h
Complex microsphere is washed repeatedly at the form of composite balls, then with dehydrated alcohol and 4% hydrochloric acid, until hydrochloric acid drilling is complete, waste liquor PH
Value is acidity, is then separated using magnet.Resulting composite mesopore microballoon is magnetic coupling cellulose base solid acid catalyst.
Finally, catalyst is dried under vacuum to constant weight.By 20g grease, 20ml methanol and 1g catalyst are added in reaction flask, stirring action
Lower back flow reaction for a period of time after, catalyst is separated from reaction mixture kind under the action of externally-applied magnetic field and is done through ethanol washing
Dry recycling, reaction solution, which moves in separatory funnel, is added n-hexane and water extraction, stratification.Upper layer phase biodiesel (fatty acid
Methyl esters) and n-hexane, n-hexane is recycled through vacuum distillation, biodiesel is obtained and GC-MS is used to carry out yield analysis again.
Claims (9)
1. a kind of preparation method of magnetic coupling cellulose base solid acid catalyst, which is characterized in that first prepare cellulose solution,
Then sulfoxidation graphene and ferroferric oxide nano granules uniformly mix three kinds of substances through inverse suspension method, fixed
It is melted into ball, finally prepares a kind of magnetic coupling cellulose base solid acid catalyst；Specific preparation process is as follows:
1) prepared by magnetic coupling cellulose base solid acid catalyst；
1.1) dissolution of cellulose: cellulose is put into ionic liquid 1-butyl-3-methyl imidazolium chlorate, 85~95 DEG C of items
Mechanical stirring 10h under part, obtains cellulose solution；
1.2) preparation of sulfoxidation graphene: graphite oxide is prepared by Hummers method, and ultrasound obtains graphite oxide
Alkene；Anhydrous p-aminobenzene sulfonic acid is added in the sodium hydroxide solution that concentration is 2%, is allowed to dissolve in hot bath, later
It is cooled to room temperature；Sodium nitrite is added, after dissolution, which is instilled to the burning that ice water and concentrated hydrochloric acid are housed under stiring
In cup, makes temperature control at 0 DEG C, after there is the white precipitate of Diazosalt of sulfanilic acid, continues to be stirred to react 15min,
Obtain Diazosalt of sulfanilic acid；Diazosalt of sulfanilic acid is gradually added drop-wise in the suspension of graphene oxide,
It is washed with deionized after persistently stirring 2~4h under condition of ice bath to neutrality, finally obtains sulfoxidation graphene, it is true at 60 DEG C
It is sufficiently dry in empty drying box；
1.3) preparation of magnetic ferroferric oxide nanometer particle: with FeCl2·4H2O and FeCl3·6H2O is that raw material is heavy using chemistry
Shallow lake method synthesizes Fe3O4Nanoparticle presses Fe first3+With Fe2+Molar ratio be 2:1 ratio weigh the molysite and ferrous iron of calculation amount
In water, be then slowly added to ammonia spirit to pH value under high velocity agitation is 9~10 to salt mixed dissolution, is washed to neutrality and obtains
Magnetic ferroferric oxide nanometer particle, dried for standby；
1.4) preparation of magnetic coupling cellulose base solid acid catalyst: next by the ferroferric oxide nano granules of preparation and
Sulfoxidation graphene mixture ultrasonic disperse and calcium carbonate are added in cellulose solution are sufficiently mixed together, by mixed liquor plus
Enter to potassium oleate and Span 60 and disperses in 300ml~400ml transformer oil of 30min to rise to 80 DEG C~90 DEG C with high speed from room temperature
Blender mechanical stirring 2.5h~3.5h forms it into the form of composite balls, then compound micro- with dehydrated alcohol and hydrochloric acid repeated washing
Ball, until hydrochloric acid drilling is complete, waste liquor PH is acidity, is then separated using magnet, and resulting composite mesopore microballoon is magnetism
Compound cellulose based solid acid catalyst, finally, catalyst is dried under vacuum to constant weight；
2) preparation of biodiesel:
By a certain amount of grease, methanol and magnetic coupling cellulose base solid acid catalyst are added in reaction flask, under stirring action
Back flow reaction for a period of time after, catalyst separated from reaction mixture kind under the action of externally-applied magnetic field dry through ethanol washing
Recycling, reaction solution, which moves in separatory funnel, is added n-hexane and water extraction, stratification, upper layer phase biodiesel (fatty acid methyl
Ester) and n-hexane, n-hexane is recycled through vacuum distillation, biodiesel is obtained and GC-MS is used to carry out yield analysis again.
2. the preparation and its application of a kind of magnetic coupling cellulose base solid catalyst described in accordance with the claim 1, feature
Be: wherein cellulose origin described in step 1.1) is cotton.
3. the preparation and its application of a kind of magnetic coupling cellulose base solid catalyst described in accordance with the claim 1, feature
Be: wherein anhydrous p-aminobenzene sulfonic acid described in step 1.2), sodium nitrite, graphene oxide mass ratio be 1:0.4:
1。
4. the preparation and its application of a kind of magnetic coupling cellulose base solid catalyst described in accordance with the claim 1, feature
Be: wherein the concentration of graphene oxide suspension described in step 1.2) is 10mg/ml.
5. the preparation and its application of a kind of magnetic coupling cellulose base solid catalyst described in accordance with the claim 1, feature
Be: wherein concentration described in step 1.2) be 2% sodium hydroxide solution, ice water, concentrated hydrochloric acid, graphene oxide solution body
Product is than being 1:2:0.2:10.
6. the preparation and its application of a kind of magnetic coupling cellulose base solid catalyst described in accordance with the claim 1, feature
It is: wherein magnetic cellulose described in step 1.4), calcium carbonate, sulfoxidation graphene, ferroferric oxide nano granules
Mass ratio be 1:1.6:0.01~0.1:0.3~0.4.
7. the preparation and its application of a kind of magnetic coupling cellulose base solid catalyst described in accordance with the claim 1, feature
Be: wherein potassium oleate described in step 1.4) and the mass ratio of Span 60 are 1:4.
8. the preparation and its application of a kind of magnetic coupling cellulose base solid catalyst described in accordance with the claim 1, feature
Be: wherein the percentage composition of drilling hydrochloric acid described in step 1.4) is 4%~5%.
9. the preparation and its application of a kind of magnetic coupling cellulose base solid catalyst described in accordance with the claim 1, feature
Be: wherein described in step 2) addition grease, methanol, magnetic coupling cellulose base solid acid catalyst mass ratio be 1:
0.1~2:0.05~0.2.
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