CN105879882A - Method for preparing easily dispersed magnetic biomass carbon-based solid acid catalyst - Google Patents
Method for preparing easily dispersed magnetic biomass carbon-based solid acid catalyst Download PDFInfo
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- CN105879882A CN105879882A CN201610144338.3A CN201610144338A CN105879882A CN 105879882 A CN105879882 A CN 105879882A CN 201610144338 A CN201610144338 A CN 201610144338A CN 105879882 A CN105879882 A CN 105879882A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 239000011973 solid acid Substances 0.000 title claims abstract description 22
- 239000002028 Biomass Substances 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title abstract description 4
- 241000758789 Juglans Species 0.000 claims abstract description 46
- 235000009496 Juglans regia Nutrition 0.000 claims abstract description 46
- 235000020234 walnut Nutrition 0.000 claims abstract description 46
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 8
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000012634 fragment Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000004570 mortar (masonry) Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000001117 sulphuric acid Substances 0.000 claims description 12
- 235000011149 sulphuric acid Nutrition 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 238000000643 oven drying Methods 0.000 claims description 6
- 210000000582 semen Anatomy 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- NASVITFAUKYCPM-UHFFFAOYSA-N ethanol;tetraethyl silicate Chemical compound CCO.CCO[Si](OCC)(OCC)OCC NASVITFAUKYCPM-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 abstract description 4
- 239000006249 magnetic particle Substances 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000005389 magnetism Effects 0.000 abstract 1
- 238000006277 sulfonation reaction Methods 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000000428 dust Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
Abstract
The invention discloses a method for preparing an easily dispersed magnetic biomass carbon-based solid acid catalyst and belongs to the field of carbon-based solid acid catalysts. Walnut shells are obtained for acid and alkali modification and then ground into powder, ferrous sulfate, ferric nitrate and the walnut shell powder are mixed and react to obtain a magnetic biomass matrix, then the surface of the magnetic biomass matrix is wrapped by silicon dioxide to obtain a catalyst precursor, and then the catalyst is obtained through carbonization, sulfonation reaction, washing and drying. After the magnetic biomass matrix is wrapped by silicon dioxide, dispersity and heat stability of magnetic particles in an aqueous solution are promoted, agglomeration is not likely to happen, activity of the catalyst is improved, the catalyst cannot be oxidized easily, magnetism time is kept long, the repeated utilization rate is high, the preparation process is simple, and cost is low.
Description
Technical field
The invention discloses the preparation method of a kind of easy dispersed magnetic biomass carbon based solid acid catalyst, belong to carbon back solid
Body acid catalyst field.
Background technology
The sustainable development produced along with enhancing and the Green Chemistry of people's environmental consciousness in recent years, development environment friendly is solid
Body acid catalyst is increasingly possessed high catalytic activity, high selectivity, reaction condition temperature by the attention of vast scientific researchers
With, the solid catalyst that the advantage such as can be recycled, there is in the industry such as environment, chemistry, pharmacy more and more significantly advantage.
The most difunctional composite solid acid catalyst presents many and is different from the excellent properties of Conventional solid acid, is particularly urging
Change the activity aspect such as aspect and high-specific surface area.It also show in fields such as environment, the energy, material, chemistry, pharmacy, military affairs
Wide application prospect.Therefore, magnetic core-shell shaped material catalyst field be applied to for key areas of concern it
One.At present, magnetic solid acid catalyst is mainly used in the necks such as solid acid catalysis, phase transformation transfer catalysis, photocatalysis, living things catalysis
Territory.
Summary of the invention
The technical problem that present invention mainly solves: for the magnetic group in current magnetic green material carbon-based solid acid catalyst
Point, owing to the particle diameter of magnetic particle is little, cause its surface to have bigger specific surface area and the highest surface activity, thus easily roll into a ball
Poly-, dispersibility reduces, and chemism is the highest simultaneously, the most oxidized, causes the problem that the magnetic of system reduces, it is provided that a kind of
The easily preparation method of dispersed magnetic biomass carbon based solid acid catalyst, the present invention takes after walnut shell carries out acid, alkali modification and grinds
Cheng Fen, obtains ferrous sulfate, ferric nitrate and walnut shell powder hybrid reaction magnetic green material matrix, then is used by magnetic green material matrix
Silicon dioxide carries out Surface coating and obtains catalyst precursor, then is dried by carbonization, sulfonated reaction, washing, this
Bright by magnetic green material matrix after coated with silica, promote magnetic particle dispersibility in aqueous and heat stability,
Being not likely to produce reunion, improve the activity of catalyst simultaneously, be difficult to oxidized, keep the magnetic time long, recycling rate of waterused is high, and
And preparation technology is simple, low cost.
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:
1.(1) weigh 400～500g walnut shells and pour in 5L beaker, in beaker, add appropriate distilled water walnut shell is soaked completely
Till Mei, then beaker is moved into sonic oscillation instrument, with 100～200W power ultrasonic washings 20～30min, remove walnut shell surface
Floating dust, is finally putting into oven drying, obtains the walnut shell of cleaning；
2.(2) walnut shell after above-mentioned cleaning is put into jet mill and be first ground into the particle diameter Semen Juglandis fragment less than 5mm, by broken
Block is that 0.5mol/L sulphuric acid and 0.3mol/L Caustic soda soak 1～2h by concentration respectively, soak terminate again broken with deionized water rinsing
Block is till leacheate is neutrality, then walnut shell fragment modified for soda acid is put into corundum mortar, pulverizes；
3.(3) adding 100～200mL concentration in the there-necked flask with agitator and thermometer is 0.2mol/L ferrous sulfate
Be 0.3mol/L iron nitrate solution with 200～300mL concentration, start blender be stirred, under stirring add 10～
Walnut shell powder after the above-mentioned grinding of 15g, it is the ammonia of 10% that heating in water bath is warming up to after 45～50 DEG C add 30～50mL mass concentrations
Water, filters isolated precipitate after still aging 10～20min；
4.(4) above-mentioned precipitate is put into baking oven, at 105～110 DEG C, be dried 5～6h, continue after drying to put into agate mortar
In, addition precipitate gross mass 30～the Resina persicae of 40% and 5～the soluble starch of 15%, continue to grind 20～30min, obtain certainly
Magnetic green material matrix processed；
5.(5) weighing 8～10g above-mentioned self-control magnetic green material matrixes and joining 350～450mL mass concentrations is the ethanol of 80%
In solution, put into ultrasonic disperse instrument, to move into the 1L cone with agitator after 100～150W power ultrasonic dispersions 20～30min
In shape bottle, add 100～150mL mass concentrations be 10% tetraethyl orthosilicate ethanol solution, start agitator stirring reaction 10～
Isolated catalyst precursor is filtered after 12h；
6.(6) catalyst precursor obtained above is put in retort, under nitrogen protection with 10 DEG C/min rate program
It is warming up to 400～500 DEG C, is incubated carbonization 2～3h, the catalyst precursor after carbonization and mass concentration 90% concentrated sulphuric acid are pressed solid
Liquor ratio 1:10 is put into after mixing in 1L reactor, sulfonated reaction 1～2h at 150～200 DEG C, then by 75～85 DEG C of heat
Water washs until leacheate is neutrality, and last vacuum dried device the most i.e. obtains a kind of easy dispersed magnetic biomass carbon-based solid
Acid catalyst.
The method of the application of the present invention: the easy dispersed magnetic biomass carbon based solid acid catalyst that the present invention prepares can be answered
Be used in catalytic reaction, catalyst chemical good stability, repeatable utilization, simultaneously the most again because of have that magnetic can be quick and complete with
Reaction system separates, and post processing is simple.
The invention has the beneficial effects as follows:
(1) present invention is by magnetic green material matrix through coated with silica, can improve magnetic particle dispersibility in aqueous
And heat stability, it is not likely to produce reunion；
(2) catalyst activity that prepared by the present invention is high, is difficult to oxidized, keeps the magnetic time long, and recycling rate of waterused is high, and makes
Standby technique is simple, low cost.
Detailed description of the invention
First weigh 400～500g walnut shells and pour in 5L beaker, in beaker, add appropriate distilled water walnut shell is complete
Till full submergence, then beaker is moved into sonic oscillation instrument, with 100～200W power ultrasonic washings 20～30min, remove walnut shell
Surface floating dust, is finally putting into oven drying, obtains the walnut shell of cleaning；Walnut shell after cleaning puts into jet mill elder generation powder
Be broken into particle diameter less than the Semen Juglandis fragment of 5mm, fragment is 0.5mol/L sulphuric acid by concentration respectively and 0.3mol/L Caustic soda soak 1～
2h, soak terminate again with deionized water rinsing fragment till leacheate is neutrality, then by broken for walnut shell modified for soda acid
Block puts into corundum mortar, pulverizes；Adding 100～200mL concentration in the there-necked flask with agitator and thermometer is
0.2mol/L ferrous sulfate and 200～300mL concentration are 0.3mol/L iron nitrate solution, start blender and are stirred, are stirring
Mixing the walnut shell powder after adding 10～15g grindings under state, heating in water bath adds 30～50mL mass after being warming up to 45～50 DEG C
Concentration is the ammonia of 10%, filters isolated precipitate after still aging 10～20min；Precipitate is put into baking oven, 105
～at 110 DEG C, it is dried 5～6h, continue after drying to put in agate mortar, add precipitate gross mass 30～the Resina persicae of 40% and 5
～the soluble starch of 15%, continue to grind 20～30min, obtain making magnetic green material matrix by oneself；Weigh 8～10g self-control magnetic
Biomass matrix joins in the ethanol solution that 350～450mL mass concentrations are 80%, puts into ultrasonic disperse instrument, with 100～
Move in the 1L conical flask with agitator after 150W power ultrasonic dispersion 20～30min, add 100～150mL mass concentrations
It is 10% tetraethyl orthosilicate ethanol solution, after starting agitator stirring reaction 10～12h, filters isolated catalyst precursor；
The catalyst precursor obtained is put in retort, is warming up to 400～500 with 10 DEG C/min rate program under nitrogen protection
DEG C, it is incubated carbonization 2～3h, the catalyst precursor after carbonization and mass concentration 90% concentrated sulphuric acid are mixed by solid-to-liquid ratio 1:10
Put in 1L reactor after conjunction, sulfonated reaction 1～2h at 150～200 DEG C, then with 75～85 DEG C of hot washes until drip washing
Liquid is neutrality, and last vacuum dried device the most i.e. obtains a kind of easy dispersed magnetic biomass carbon based solid acid catalyst.
Example 1
First weigh 400g walnut shell and pour in 5L beaker, add in beaker appropriate distilled water walnut shell is totally submerged into
Only, then beaker is moved into sonic oscillation instrument, wash 20min with 100W power ultrasonic, remove walnut shell surface floating dust, be finally putting into
Oven drying, obtains the walnut shell of cleaning；Walnut shell after cleaning is put into jet mill and is first ground into particle diameter less than 5mm's
Semen Juglandis fragment, is that 0.5mol/L sulphuric acid and 0.3mol/L Caustic soda soak 1h by concentration by fragment respectively, soak terminate to spend again from
Sub-water flushing fragment is till leacheate is neutrality, then walnut shell fragment modified for soda acid is put into corundum mortar, grinds
Cheng Fen；In the there-necked flask with agitator and thermometer add 100mL concentration be 0.2mol/L ferrous sulfate and 200mL dense
Degree is 0.3mol/L iron nitrate solution, starts blender and is stirred, and adds the walnut shell after 10g grinds under stirring
Powder, it is the ammonia of 10% that heating in water bath is warming up to after 45 DEG C add 30mL mass concentration, filters and separate after still aging 10min
To precipitate；Precipitate is put into baking oven, at 105 DEG C, is dried 5h, continues after drying to put in agate mortar, add precipitate
The Resina persicae of gross mass 30% and the soluble starch of 5%, continue to grind 20min, obtains making magnetic green material matrix by oneself；Weigh 8g certainly
Magnetic green material matrix processed joins in the ethanol solution that 350mL mass concentration is 80%, puts into ultrasonic disperse instrument, with 100W merit
Moving into after rate ultrasonic disperse 20min in the 1L conical flask with agitator, adding 100mL mass concentration is 10% tetraethyl orthosilicate
Ethanol solution, filters isolated catalyst precursor after starting agitator stirring reaction 10h；The catalyst precursor that will obtain
Put in retort, be warming up to 400 DEG C with 10 DEG C/min rate program under nitrogen protection, be incubated carbonization 2h, after carbonization
Catalyst precursor and mass concentration 90% concentrated sulphuric acid are put in 1L reactor, at 150 DEG C after mixing by solid-to-liquid ratio 1:10
Sulfonated reaction 1h, then with 75 DEG C of hot washes until leacheate is neutrality, last vacuum dried device the most i.e. obtains a kind of
Easily dispersed magnetic biomass carbon based solid acid catalyst.
The easy dispersed magnetic biomass carbon based solid acid catalyst that the present invention prepares can be applied in catalytic reaction, catalysis
Agent chemical stability is good, repeatable utilization, separates with reaction system because of have that magnetic can be quick and complete the most again, post processing simultaneously
Simply.
Example 2
First weigh 450g walnut shell and pour in 5L beaker, in beaker, add appropriate distilled water walnut shell is totally submerged
Till, then beaker is moved into sonic oscillation instrument, wash 25min with 150W power ultrasonic, remove walnut shell surface floating dust, finally put
Enter oven drying, obtain the walnut shell of cleaning；Walnut shell after cleaning is put into jet mill and is first ground into particle diameter less than 5mm
Semen Juglandis fragment, be that 0.5mol/L sulphuric acid and 0.3mol/L Caustic soda soak 1.5h by concentration respectively by fragment, soak and terminate to use again
Deionized water rinsing fragment is till leacheate is neutrality, then walnut shell fragment modified for soda acid is put into corundum mortar,
Pulverize；In the there-necked flask with agitator and thermometer add 150mL concentration be 0.2mol/L ferrous sulfate and
250mL concentration is 0.3mol/L iron nitrate solution, starts blender and is stirred, after adding 13g grinding under stirring
Walnut shell powder, it is the ammonia of 10% that heating in water bath is warming up to after 48 DEG C add 40mL mass concentration, filters after still aging 15min
Isolated precipitate；Precipitate is put into baking oven, at 108 DEG C, is dried 5.5h, continues after drying to put in agate mortar, add
Enter the Resina persicae of precipitate gross mass 35% and the soluble starch of 10%, continue to grind 25min, obtain making magnetic green material base by oneself
Body；Weigh 9g self-control magnetic green material matrix to join in the ethanol solution that 400mL mass concentration is 80%, put into ultrasonic disperse
Instrument, to move in the 1L conical flask with agitator after 125W power ultrasonic dispersion 25min, adding 125mL mass concentration is 10%
Tetraethyl orthosilicate ethanol solution, filters isolated catalyst precursor after starting agitator stirring reaction 11h；By urging of obtaining
Agent presoma is put in retort, is warming up to 450 DEG C with 10 DEG C/min rate program under nitrogen protection, is incubated carbonization
2.5h, puts into 1L after the catalyst precursor after carbonization and mass concentration 90% concentrated sulphuric acid being mixed by solid-to-liquid ratio 1:10 anti-
Answer in still, sulfonated reaction 1.5h at 175 DEG C, then with 80 DEG C of hot washes until leacheate is neutrality, after do through vacuum
Dry device the most i.e. obtains a kind of easy dispersed magnetic biomass carbon based solid acid catalyst.
The easy dispersed magnetic biomass carbon based solid acid catalyst that the present invention prepares can be applied in catalytic reaction, catalysis
Agent chemical stability is good, repeatable utilization, separates with reaction system because of have that magnetic can be quick and complete the most again, post processing simultaneously
Simply.
Example 3
First 12. weigh 500g walnut shell pours in 5L beaker, adds appropriate distilled water and be totally submerged by walnut shell in beaker
Till, then beaker is moved into sonic oscillation instrument, wash 30min with 200W power ultrasonic, remove walnut shell surface floating dust, finally put
Enter oven drying, obtain the walnut shell of cleaning；Walnut shell after cleaning is put into jet mill and is first ground into particle diameter less than 5mm
Semen Juglandis fragment, be that 0.5mol/L sulphuric acid and 0.3mol/L Caustic soda soak 2h by concentration respectively by fragment, soak and terminate to spend again
Ionized water flushing fragment is till leacheate is neutrality, then walnut shell fragment modified for soda acid is put into corundum mortar, grinds
Grinds；Adding 200mL concentration in the there-necked flask with agitator and thermometer is 0.2mol/L ferrous sulfate and 300mL
Concentration is 0.3mol/L iron nitrate solution, starts blender and is stirred, and adds the walnut shell after 15g grinds under stirring
Powder, it is the ammonia of 10% that heating in water bath is warming up to after 50 DEG C add 50mL mass concentration, filters and separate after still aging 20min
To precipitate；Precipitate is put into baking oven, at 110 DEG C, is dried 6h, continues after drying to put in agate mortar, add precipitate
The Resina persicae of gross mass 40% and the soluble starch of 15%, continue to grind 30min, obtains making magnetic green material matrix by oneself；Weigh 10g
Self-control magnetic green material matrix joins in the ethanol solution that 450mL mass concentration is 80%, puts into ultrasonic disperse instrument, with 150W
Moving in the 1L conical flask with agitator after power ultrasonic dispersion 30min, adding 150mL mass concentration is 10% positive silicic acid second
Ester ethanol solution, filters isolated catalyst precursor after starting agitator stirring reaction 12h；The complex catalyst precursor that will obtain
Body is put in retort, is warming up to 500 DEG C with 10 DEG C/min rate program under nitrogen protection, is incubated carbonization 3h, after carbonization
Catalyst precursor and mass concentration 90% concentrated sulphuric acid mix by solid-to-liquid ratio 1:10 after put in 1L reactor, at 200 DEG C
Under sulfonated reaction 2h, then with 85 DEG C of hot washes until leacheate is neutrality, last vacuum dried device the most i.e. obtains one
Plant easy dispersed magnetic biomass carbon based solid acid catalyst.
The easy dispersed magnetic biomass carbon based solid acid catalyst that the present invention prepares can be applied in catalytic reaction, catalysis
Agent chemical stability is good, repeatable utilization, separates with reaction system because of have that magnetic can be quick and complete the most again, post processing simultaneously
Simply.
Claims (1)
1. the preparation method of an easy dispersed magnetic biomass carbon based solid acid catalyst, it is characterised in that concrete preparation process
For:
(1) weigh 400～500g walnut shells and pour in 5L beaker, in beaker, add appropriate distilled water walnut shell is totally submerged
Till, then beaker is moved into sonic oscillation instrument, with 100～200W power ultrasonic washings 20～30min, remove walnut shell surface and float
Dirt, is finally putting into oven drying, obtains the walnut shell of cleaning；
(2) walnut shell after above-mentioned cleaning is put into jet mill and be first ground into the particle diameter Semen Juglandis fragment less than 5mm, by fragment
It is that 0.5mol/L sulphuric acid and 0.3mol/L Caustic soda soak 1～2h by concentration respectively, soaks and terminate to use deionized water rinsing fragment again
Till leacheate is neutrality, then walnut shell fragment modified for soda acid is put into corundum mortar, pulverize；
(3) in the there-necked flask with agitator and thermometer add 100～200mL concentration be 0.2mol/L ferrous sulfate and
200～300mL concentration are 0.3mol/L iron nitrate solution, start blender and are stirred, and add 10～15g under stirring
Walnut shell powder after above-mentioned grinding, it is the ammonia of 10% that heating in water bath is warming up to after 45～50 DEG C add 30～50mL mass concentrations,
Isolated precipitate is filtered after still aging 10～20min；
(4) above-mentioned precipitate is put into baking oven, at 105～110 DEG C, is dried 5～6h, continues after drying to put in agate mortar,
Add precipitate gross mass 30～the Resina persicae of 40% and 5～the soluble starch of 15%, continue to grind 20～30min, made by oneself
Magnetic green material matrix；
(5) weighing 8～10g above-mentioned self-control magnetic green material matrixes, to join the ethanol that 350～450mL mass concentrations are 80% molten
In liquid, put into ultrasonic disperse instrument, to move into the 1L taper with agitator after 100～150W power ultrasonic dispersions 20～30min
In Ping, adding 100～150mL mass concentrations is 10% tetraethyl orthosilicate ethanol solution, starts agitator stirring reaction 10～12h
Rear filtration isolated catalyst precursor；
(6) catalyst precursor obtained above is put in retort, under nitrogen protection with 10 DEG C/min rate program liter
Temperature, to 400～500 DEG C, is incubated carbonization 2～3h, the catalyst precursor after carbonization and mass concentration 90% concentrated sulphuric acid is pressed solid-liquid
Put in 1L reactor after mixing than 1:10, sulfonated reaction 1～2h at 150～200 DEG C, then with 75～85 DEG C of hot water
Washing is until leacheate is neutrality, and last vacuum dried device the most i.e. obtains a kind of easy dispersed magnetic biomass carbon based solid acid
Catalyst.
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| CN106669833A (en) * | 2016-12-11 | 2017-05-17 | 汪逸凡 | Preparation method of high-stability solid acid catalyst |
| CN109701665A (en) * | 2018-12-26 | 2019-05-03 | 湖北丹澳药业有限公司 | The preparation method and saponin extraction technology of magnetic solid acid catalyst |
| CN110465264A (en) * | 2019-08-19 | 2019-11-19 | 四川西晨智慧农业科技有限公司 | A kind of preparation method of magnetism tartary buckwheat shell charcoal |
| CN111036298A (en) * | 2019-12-17 | 2020-04-21 | 华侨大学 | Preparation method and application of natural walnut shell powder sulfonic acid catalyst |
| CN112121764A (en) * | 2020-09-22 | 2020-12-25 | 拉萨波玛拉生物科技有限公司 | Preparation method of highland barley straw-based hydrothermal carbon reinforced by acid-base pretreatment |
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| CN110465264A (en) * | 2019-08-19 | 2019-11-19 | 四川西晨智慧农业科技有限公司 | A kind of preparation method of magnetism tartary buckwheat shell charcoal |
| CN111036298A (en) * | 2019-12-17 | 2020-04-21 | 华侨大学 | Preparation method and application of natural walnut shell powder sulfonic acid catalyst |
| CN112121764A (en) * | 2020-09-22 | 2020-12-25 | 拉萨波玛拉生物科技有限公司 | Preparation method of highland barley straw-based hydrothermal carbon reinforced by acid-base pretreatment |
| CN113181877A (en) * | 2021-05-13 | 2021-07-30 | 沈阳农业大学 | Preparation method of magnetic biochar material |
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