CN103977820A - Method for preparing magnetic nano-solid acid catalyst from biomass hydrolysis and liquefaction residues - Google Patents
Method for preparing magnetic nano-solid acid catalyst from biomass hydrolysis and liquefaction residues Download PDFInfo
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Abstract
The invention discloses a method for preparing a magnetic nano-solid acid catalyst from biomass hydrolysis and liquefaction residues. The method is characterized by comprising the following steps: preparation of a carbon-based material, preparation of a magnetic nano-carbon-based precursor, oxidation of the magnetic nano-precursor, carbonization reaction and sulfonation reaction. The catalyst can be used in hydrolysis reaction, esterification reaction, olefin hydration reaction, alkylation reaction, acetalization and ketalization reaction and the like. Compared with a conventional magnetic catalyst which is prepared by taking magnetic Fe3O4 particles as cores, the catalyst has the higher stability. Compared with a conventional carbon-based catalyst, magnetic particles contained in the catalyst are distributed in internal pores, so that the catalyst has the larger surface area for loading functionalized functional groups. The catalyst has the advantages that the preparation method is simple, the catalytic efficiency is high, the magnetic nano-particles are distributed uniformly, the specific surface area is large, the catalyst is easily separated from products, and the waste of resources is reduced; the method is one of methods for recycling the biomass hydrolysis and liquefaction residues.
Description
Technical field
The present invention relates to method for preparing catalyst, is a kind of method of utilizing biomass by hydrolyzation liquefaction residue to prepare magnetic nano solid acid catalyst.
Background technology
Due to worsening shortages and the environmental problem non-renewable and that bring of petrochemical industry resource, the utilization of recyclability biomass resource is more and more subject to the common concern of countries in the world.In recent years; biomass energy is because its resource is huge; the features such as recyclability; for solving the economic growth of facing mankind and the dual-pressure of environmental protection, set up the conversion of sustainable development source system, energy resource structure, improvement that waste resource reclaimed, promoted socioeconomic development and ecological environment etc. is all of great practical significance and far-reaching historic significance, thereby more and more comes into one's own.
Living beings typically refer to taking lignin, cellulose, hemicellulose and other organic matters as main terrestrial plant and water plant etc., are a kind of stable Renewable Energy Resources.It is compared with the fossil energy such as coal and oil, not only sulphur, nitrogen content is low, ash content is low, and source is abundant, only China's agricultural crop straw output is about 700,000,000 tons every year, can be used as 300,000,000 tons of left and right of energy resources amount; The year rational exploitation amount of yule logs is about 1.58 hundred million tons, also has in addition a large amount of water plants.Therefore living beings are likened to the green energy resource of instant utilization, account at present 14% of world energy sources consumption.
Generally speaking, adopt physical method, thermochemical method and bioconversion method etc. can make main chemical compositions cellulose, hemicellulose and lignin etc. in living beings change into low molecule or the macromolecular liquid material with chemical reactivity, can be used for preparing bio-fuel, biological adhesive, moulding material, expanded material, carbon fibre and feed and organic fertilizer etc.Not only be conducive to solve irrational utilization and the problem of environmental pollution of rural energy in China's Development of China's Urbanization, improve the utilization ratio of countryside biomass energy source, and be conducive to improve the energy that China brings because of a large amount of Imported oils and economic unsteady phenomena.
Carbon-based solid acid catalyst is a kind of novel catalyst, is proposed the earliest by Japanese scholars (Nature, Vol.438,10 Nov., 2005).They are taking sugar, starch or cellulose as raw material, adopt the method for sulfonation after first charing to prepare carbon-based solid acid catalyst.For the preparation of biodiesel, the catalytic activity of carbon-based solid acid catalyst is apparently higher than other solid acid catalysts, and cheap, and recycling activity stability is good.At home, professor Zong Minhua, once taking saccharide compound as raw material, adopts identical technology path, has also prepared the higher carbon-based solid acid catalyst (publication number: 1899691A) of catalytic performance.Follow technology path and the method for the first low-temperature carbonizations of employing such as Wang Tonghua, Wu Rina, rear oxidation, sulfonation again and prepared biomass-based solid acid catalyst (application number: 200810012062.9).Along with magnetic Fe
3o
4deepening continuously of investigation of materials, magnetic solid acid catalyst has received researcher's concern.Contain magnetic Fe
3o
4solid acid catalyst there is magnetic, under the effect of externally-applied magnetic field, can realize with the efficient of other material in system and separating, solved the problem that solid acid catalyst is recycled.Magnetic Fe at present
3o
4the technology of preparing of material is relatively ripe, adopts on this basis the methods such as sol-gel, dipping, grafting can prepare magnetic solid acid catalyst.CN10154343786A provides a kind of preparation method of magnetic solid acid catalyst, its objective is a difficult problem that uses magnetic stability bed bioreactor to solve finely grained catalyst.CN1453067A provides a kind of magnetic super acidic catalyst preparation method, its objective is in order to solve finely grained catalyst and reclaims and separate difficult problem, and this catalyst has the advantages such as particle diameter is little, particle diameter is evenly distributed, magnetic is stronger.In sum, magnetic solid acid catalyst adopts coprecipitation solid acid material is directly coated on to magnetic kernel and obtains mostly, is converted into non-magnetic material and magnetic kernel is easily subject to the impact of external environment condition.Therefore, researching and developing cheap novel biomass base magnetic solid acid catalyst has important practical significance.
Summary of the invention
The object of the invention is: a kind of method of preparing biomass-based magnetic nano solid acid catalyst taking biomass by hydrolyzation liquefaction residue as raw material is provided, to improve processing and the recycling of biomass by hydrolyzation liquefaction residue, object is to solve the energy waste of existence now and short problem.
The object of the invention is to be realized by following technical scheme: a kind of method of utilizing biomass by hydrolyzation liquefaction residue to prepare magnetic nano solid acid catalyst, is characterized in that: comprise the following steps:
1) preparation of carbon back raw material
Biomass liquefying residue dissolved with mass volume ratio 4:10 with Isosorbide-5-Nitrae-dioxane and fully stir, filtering with sand core funnel afterwards, obtaining filtrate and residue, leaving and taking residue, at the temperature of 80～110 DEG C, drying as carbon back raw material for standby;
2) preparation of magnetic Nano carbon back presoma
In the biomass liquefying residue of preparing in step 1), add dichloromethane solution, the mass volume ratio of biomass liquefying residue and dichloromethane solution is 1:2～5, stirring makes it fully dissolve rear acquisition lysate, lysate is joined to the magnetic Nano Fe of superparamagnetism
3o
4in, lysate and Fe
3o
4volume ratio be 1:10, stir with the speed of 300～700r/min, obtain magnetic Nano carbon back presoma after dry at the temperature of 80～125 DEG C;
3) oxidation of magnetic Nano carbon back presoma
By step 2) the magnetic Nano carbon back presoma prepared is that mix 100:1～6 with oxidant according to mass ratio, grind 100～200 orders, transfer in tube type resistance furnace, be heated to 100～150 DEG C, insulation 3～5h, then fully wash by deionized water, make the oxygen-free agent ion of magnetic Nano carbon back presoma, the dry rear anaerobic agent magnetic ion nano carbon-base presoma that obtains at the temperature of 80～120 DEG C;
4) carburizing reagent
The anaerobic agent magnetic ion nano carbon-base presoma of being prepared by step 3) is transferred in tube type resistance furnace, with the continuous nitrogen injection of flow of 40～80L/min, is heated to 300～380 DEG C under nitrogen atmosphere, and charing 10～15h obtains magnetic nanometer carbon base matrix;
5) sulfonating reaction
In the magnetic nanometer carbon base matrix will step 4) obtaining, add sulfonating agent, sulfonating agent with the volume mass of magnetic nanometer carbon base matrix than being 10:1, sulfonation 2～4h at 40～100 DEG C, cooling, with deionized water fully wash in filtrate without SO
4 2-, after being dried, be biomass by hydrolyzation liquefaction residue base magnetic nano solid acid catalyst at the temperature of 80～120 DEG C.
Described biomass carbon sill comprises: one or more of the agriculturals such as stalk, wood chip and forestry waste, the compounds such as cellulose, microcrystalline cellulose, wood sugar, glucose, sucrose or mixture one or more.
Described oxidant is one or more in alchlor, p-methyl benzenesulfonic acid, phosphoric acid, potassium nitrate.
Described sulfonating agent is the concentrated sulfuric acid, and its mass fraction is greater than 98%.
A kind of biomass by hydrolyzation liquefaction of the present invention residue is prepared the method for magnetic nano solid acid catalyst, can be used for hydrolysis, esterification, alkene water and reaction, alkylated reaction, acetal ketal reaction etc., has the following advantages and positive effect:
(1) preparation technology is simple, and cost of material is cheap;
(2) one of method that living beings are recycled, economizes on resources;
(3) excellent catalytic effect, has very high catalytic activity to general catalytic reaction as esterification, hydrolysis etc.;
(4) this catalyst can repeatedly use.
Detailed description of the invention
Embodiment 1: step is as follows
1) preparation of carbon back raw material
Get 4g maize straw liquefied residue 10ml Isosorbide-5-Nitrae-dioxane and dissolve, fully stir, with sand core funnel filtration, obtain filtrate and residue, leave and take residue, maize straw liquefied residue is dried as carbon back raw material for standby at 80 DEG C;
2) preparation of magnetic Nano carbon back presoma
In the maize straw liquefied residue of preparing in step 1), add 8ml dichloromethane solution, stir and make it fully dissolve rear acquisition lysate, lysate is joined to the 220ml magnetic Nano Fe of superparamagnetism
3o
4in, stir with the speed of 300r/min, the dry rear magnetic Nano carbon back presoma that obtains at 80 DEG C of temperature;
3) oxidation of magnetic Nano carbon back presoma
By step 2) the magnetic Nano carbon back presoma prepared mixes with 2.2g p-methyl benzenesulfonic acid, grinds 100 orders, transfer in tube type resistance furnace, be heated to 100 DEG C, insulation 3h, then fully washs by deionized water, the dry rear anaerobic agent magnetic ion nano carbon-base presoma that obtains at 80 DEG C of temperature;
4) carburizing reagent
Anaerobic agent magnetic ion nano carbon-base presoma prepared by step 3) is transferred in tube type resistance furnace, with the continuous nitrogen injection of flow of 40L/min, is heated to 300 DEG C under nitrogen atmosphere, and charing 10h obtains magnetic nanometer carbon base matrix;
5) sulfonating reaction
In the magnetic nanometer carbon base matrix of preparing to step 4), adding mass fraction is 98% sulfuric acid 2440ml, sulfonation 2h at 40 DEG C, cooling, with deionized water wash in filtrate without SO
4 2-, after being dried, be maize straw liquefied residue base magnetic nano solid acid catalyst at 80 DEG C of temperature.
Embodiment 2, step is as follows:
1) preparation of carbon back raw material
Get 4g maize straw liquefied residue 10ml Isosorbide-5-Nitrae-dioxane and dissolve, fully stir, with sand core funnel filtration, obtain filtrate and residue, leave and take residue, maize straw liquefied residue is dried as carbon back raw material for standby at 90 DEG C;
2) preparation of magnetic Nano carbon back presoma
In the maize straw liquefied residue of preparing in step 1), add 12ml dichloromethane solution, stir and make it fully dissolve rear acquisition lysate, lysate is joined to the 260ml magnetic Nano Fe of superparamagnetism
3o
4in, stir with the speed of 400r/min, the dry rear magnetic Nano carbon back presoma that obtains at 90 DEG C of temperature;
3) oxidation of magnetic Nano carbon back presoma
By step 2) the magnetic Nano carbon back presoma prepared mixes with 3g p-methyl benzenesulfonic acid, grinds 120 orders, transfer in tube type resistance furnace, be heated to 110 DEG C, insulation 4h, then fully washs by deionized water, the dry rear anaerobic agent magnetic ion nano carbon-base presoma that obtains at 90 DEG C of temperature;
4) carburizing reagent
Anaerobic agent magnetic ion nano carbon-base presoma prepared by step 3) is transferred in tube type resistance furnace, with the continuous nitrogen injection of flow of 50L/min, is heated to 320 DEG C under nitrogen atmosphere, and charing 12h obtains magnetic nanometer carbon base matrix;
5) sulfonating reaction
In the magnetic nanometer carbon base matrix of preparing to step 4), adding mass fraction is 98% sulfuric acid 2900ml, sulfonation 2h at 60 DEG C, cooling, with deionized water wash in filtrate without SO
4 2-, after being dried at 90 DEG C of temperature, be maize straw liquefied residue base magnetic nano solid acid catalyst.
Embodiment 3: step is as follows
1) preparation of carbon back raw material
Get 4g maize straw liquefied residue 10ml Isosorbide-5-Nitrae-dioxane and dissolve, fully stir, with sand core funnel filtration, obtain filtrate and residue, leave and take residue, maize straw liquefied residue is dried as carbon back raw material for standby at 100 DEG C;
2) preparation of magnetic Nano carbon back presoma
In the maize straw liquefied residue of preparing in step 1), add 16ml dichloromethane solution, stir and make it fully dissolve rear acquisition lysate, lysate is joined to the 300ml magnetic Nano Fe of superparamagnetism
3o
4in, stir with the speed of 500r/min, the dry rear magnetic Nano carbon back presoma that obtains at 100 DEG C of temperature;
3) oxidation of magnetic Nano carbon back presoma
By step 2) the magnetic Nano carbon back presoma prepared mixes with 3.3g p-methyl benzenesulfonic acid, grind 140 orders, transfer in tube type resistance furnace, be heated to 120 DEG C, insulation 5h, then fully wash the dry rear anaerobic agent magnetic ion nano carbon-base presoma that obtains at 100 DEG C of temperature by deionized water;
4) carburizing reagent
Anaerobic agent magnetic ion nano carbon-base presoma prepared by step 3) is transferred in tube type resistance furnace, with the continuous nitrogen injection of flow of 55L/min, is heated to 340 DEG C under nitrogen atmosphere, and charing 13h obtains magnetic nanometer carbon base matrix;
5) sulfonating reaction
In the magnetic nanometer carbon base matrix of preparing to step 4), adding mass fraction is 98% sulfuric acid 3300ml, sulfonation 3h at 80 DEG C, cooling, with deionized water wash in filtrate without SO
4 2-, after being dried, be maize straw liquefied residue base magnetic nano solid acid catalyst at 100 DEG C of temperature.
Embodiment 4: step is as follows
1) preparation of carbon back raw material
Get 4g maize straw liquefied residue 10ml Isosorbide-5-Nitrae-dioxane and dissolve, fully stir, with sand core funnel filtration, obtain filtrate and residue, leave and take residue, maize straw liquefied residue is dried as carbon back raw material for standby at 105 DEG C;
2) preparation of magnetic Nano carbon back presoma
In the maize straw liquefied residue of preparing in step 1), add 20ml dichloromethane solution, stir and make it fully dissolve rear acquisition lysate, lysate is joined to the 340ml magnetic Nano Fe of superparamagnetism
3o
4in, stir with the speed of 600r/min, the dry rear magnetic Nano carbon back presoma that obtains at 110 DEG C of temperature;
3) oxidation of magnetic Nano carbon back presoma
By step 2) the magnetic Nano carbon back presoma prepared mixes with 3.8g p-methyl benzenesulfonic acid, grind 160 orders, transfer in tube type resistance furnace, be heated to 130 DEG C, insulation 5h, then fully wash the dry rear anaerobic agent magnetic ion nano carbon-base presoma that obtains at 110 DEG C of temperature by deionized water;
4) carburizing reagent
Magnetic Nano carbon back presoma prepared by step 3) is transferred in tube type resistance furnace, with the continuous nitrogen injection of flow of 60L/min, is heated to 360 DEG C under nitrogen atmosphere, and charing 14h obtains magnetic nanometer carbon base matrix;
5) sulfonating reaction
In the magnetic nanometer carbon base matrix of preparing to step 4), adding mass fraction is 98% sulfuric acid 3800ml, sulfonation 4h at 90 DEG C, cooling, with deionized water wash in filtrate without SO
4 2-, after being dried, be maize straw liquefied residue base magnetic nano solid acid catalyst at 110 DEG C of temperature.
Embodiment 5: step is as follows
1) preparation of carbon back raw material
Get 4g maize straw liquefied residue 10ml Isosorbide-5-Nitrae-dioxane and dissolve, fully stir, with sand core funnel filtration, obtain filtrate and residue, leave and take residue, maize straw liquefied residue is dried as carbon back raw material for standby at 110 DEG C;
2) preparation of magnetic Nano carbon back presoma
In the maize straw liquefied residue of preparing in step 1), add 20ml dichloromethane solution, stir and make it fully dissolve rear acquisition lysate, lysate is joined to the 340ml magnetic Nano Fe of superparamagnetism
3o
4in, stir with the speed of 700r/min, the dry rear magnetic Nano carbon back presoma that obtains at 120 DEG C of temperature;
3) oxidation of magnetic Nano carbon back presoma
By step 2) the magnetic Nano carbon back presoma prepared mixes with 3.8g p-methyl benzenesulfonic acid, grind 180 orders, transfer in tube type resistance furnace, be heated to 140 DEG C, insulation 5h, then fully wash the dry rear anaerobic agent magnetic ion nano carbon-base presoma that obtains at 120 DEG C of temperature by deionized water;
4) carburizing reagent
Anaerobic agent magnetic ion nano carbon-base presoma prepared by step 3) is transferred in tube type resistance furnace, with the continuous nitrogen injection of flow of 70L/min, is heated to 380 DEG C under nitrogen atmosphere, and charing 15h obtains magnetic nanometer carbon base matrix;
5) sulfonating reaction
In the magnetic nanometer carbon base matrix of preparing to step 4), adding mass fraction is 98% sulfuric acid 3800ml, sulfonation 4h at 100 DEG C, cooling, with deionized water wash in filtrate without SO
4 2-, after being dried, be liquefaction of corn straw residue base magnetic nano solid acid catalyst at 120 DEG C of temperature.
Embodiment 6: step is as follows
1) preparation of carbon back raw material
Get 4g maize straw liquefied residue 10ml Isosorbide-5-Nitrae-dioxane and dissolve, fully stir, with sand core funnel filtration, obtain filtrate and residue, leave and take residue, maize straw liquefied residue is dried as carbon back raw material for standby at 105 DEG C;
2) preparation of magnetic Nano carbon back presoma
In the maize straw liquefied residue of preparing in step 1), add 20ml dichloromethane solution, stir and make it fully dissolve rear acquisition lysate, lysate is joined to the 340ml magnetic Nano Fe of superparamagnetism
3o
4in, stir with the speed of 700r/min, the dry rear magnetic Nano carbon back presoma that obtains at 125 DEG C of temperature;
3) oxidation of magnetic Nano carbon back presoma
By step 2) the magnetic Nano carbon back presoma prepared mixes with 3.8g p-methyl benzenesulfonic acid, grinds 200 orders, transfer in tube type resistance furnace, be heated to 150 DEG C, insulation 5h, fully with deionized water washing, the dry rear anaerobic agent magnetic ion nano carbon-base presoma that obtains;
4) carburizing reagent
Anaerobic agent magnetic ion nano carbon-base presoma prepared by step 3) is transferred in tube type resistance furnace, with the continuous nitrogen injection of flow of 80L/min, is heated to 380 DEG C under nitrogen atmosphere, and charing 15h obtains magnetic nanometer carbon base matrix;
5) sulfonating reaction
In the magnetic nanometer carbon base matrix of preparing to step 4), adding mass fraction is 98% sulfuric acid 3800ml, sulfonation 2h at 80 DEG C, cooling, with deionized water wash in filtrate without SO
4 2-, after being dried, be liquefaction of corn straw residue base magnetic nano solid acid catalyst at 110 DEG C of temperature.
Embodiment 7:
Embodiment 7 is consistent with step and the parameter of embodiment 6, and difference is that biomass residue used is rice hull liquification residue.
Embodiment 8:
Embodiment 8 is consistent with step and the parameter of embodiment 6, and difference is that biomass residue used is wood chip liquefied residue.
Claims (3)
1. utilize biomass by hydrolyzation liquefaction residue to prepare a method for magnetic nano solid acid catalyst, it is characterized in that: comprise the following steps:
1) preparation of carbon back raw material
Biomass liquefying residue dissolved with mass volume ratio 4:10 with Isosorbide-5-Nitrae-dioxane and fully stir, filtering with sand core funnel afterwards, obtaining filtrate and residue, leaving and taking residue, at the temperature of 80～110 DEG C, drying as carbon back raw material for standby;
2) preparation of magnetic Nano carbon back presoma
In the biomass liquefying residue of preparing in step 1), add dichloromethane solution, the mass volume ratio of biomass liquefying residue and dichloromethane solution is 1:2～5, stirring makes it fully dissolve rear acquisition lysate, lysate is joined to the magnetic Nano Fe of superparamagnetism
3o
4in, lysate and Fe
3o
4volume ratio be 1:10, stir with the speed of 300～700r/min, the dry magnetic Nano carbon back presoma that obtains at the temperature of 80～125 DEG C;
3) oxidation of magnetic Nano carbon back presoma
By step 2) the magnetic Nano carbon back presoma prepared is that mix 100:1～6 with oxidant according to mass ratio, grinds
100～200 orders, transfer in tube type resistance furnace, are heated to 100～150 DEG C, insulation 3～5h, then fully wash by deionized water, make the oxygen-free agent ion of magnetic Nano carbon back presoma, the dry anaerobic agent magnetic ion nano carbon-base presoma that obtains at the temperature of 80～120 DEG C;
4) carburizing reagent
The anaerobic agent magnetic ion nano carbon-base presoma of being prepared by step 3) is transferred in tube type resistance furnace, with the continuous nitrogen injection of flow of 40～80L/min, is heated to 300～380 DEG C under nitrogen atmosphere, and charing 10～15h obtains magnetic nanometer carbon base matrix;
5) sulfonating reaction
In the magnetic nanometer carbon base matrix will step 4) obtaining, add sulfonating agent, sulfonating agent with the volume mass of magnetic nanometer carbon base matrix than being 10:1, sulfonation 2～4h at 40～100 DEG C, cooling, with deionized water wash in filtrate without SO
4 2-, dry at the temperature of 80～120 DEG C, be biomass by hydrolyzation liquefaction residue base magnetic nano solid acid catalyst.
2. a kind of method of utilizing biomass by hydrolyzation liquefaction residue to prepare magnetic nano solid acid catalyst as claimed in claim 1, is characterized in that: described oxidant is one or more in alchlor, p-methyl benzenesulfonic acid, phosphoric acid, potassium nitrate.
3. a kind of method of utilizing biomass by hydrolyzation liquefaction residue to prepare magnetic nano solid acid catalyst as claimed in claim 1, is characterized in that: described sulfonating agent is the concentrated sulfuric acid, and its mass fraction is greater than 98%.
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| CN105013538A (en) * | 2014-12-01 | 2015-11-04 | 青岛科技大学 | Preparation method for hydrophobically modified magnetic carbonaceous solid acid catalyst and application of catalyst |
| CN106492839A (en) * | 2016-08-29 | 2017-03-15 | 中国科学院西双版纳热带植物园 | A kind of magnetic catalyst prepared as carbon source carrier with Jatropha curcus shell and its application |
| CN109092370A (en) * | 2018-08-03 | 2018-12-28 | 华南农业大学 | A kind of rice silicon source magnetic solid acid catalyst and preparation method thereof and the application in reduced sugar is prepared in catalysis corncob |
| CN112844409A (en) * | 2021-01-22 | 2021-05-28 | 江苏省农业科学院 | Preparation method and application of biomass straw-based magnetic solid acid catalyst |
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| CN102321490A (en) * | 2011-08-11 | 2012-01-18 | 华南理工大学 | The high-pressure liquefaction biomass prepare the method for biological carbon |
| CN103084188A (en) * | 2012-12-20 | 2013-05-08 | 华南理工大学 | Solid acid catalyst containing catalytic active group and adsorption group and preparation and application of solid acid catalyst |
| CN103263935A (en) * | 2013-06-08 | 2013-08-28 | 宁夏大学 | Preparation method and application of magnetic core-shell carbon-based solid acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102321490A (en) * | 2011-08-11 | 2012-01-18 | 华南理工大学 | The high-pressure liquefaction biomass prepare the method for biological carbon |
| CN103084188A (en) * | 2012-12-20 | 2013-05-08 | 华南理工大学 | Solid acid catalyst containing catalytic active group and adsorption group and preparation and application of solid acid catalyst |
| CN103263935A (en) * | 2013-06-08 | 2013-08-28 | 宁夏大学 | Preparation method and application of magnetic core-shell carbon-based solid acid |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013538A (en) * | 2014-12-01 | 2015-11-04 | 青岛科技大学 | Preparation method for hydrophobically modified magnetic carbonaceous solid acid catalyst and application of catalyst |
| CN106492839A (en) * | 2016-08-29 | 2017-03-15 | 中国科学院西双版纳热带植物园 | A kind of magnetic catalyst prepared as carbon source carrier with Jatropha curcus shell and its application |
| CN109092370A (en) * | 2018-08-03 | 2018-12-28 | 华南农业大学 | A kind of rice silicon source magnetic solid acid catalyst and preparation method thereof and the application in reduced sugar is prepared in catalysis corncob |
| CN112844409A (en) * | 2021-01-22 | 2021-05-28 | 江苏省农业科学院 | Preparation method and application of biomass straw-based magnetic solid acid catalyst |
| CN112844409B (en) * | 2021-01-22 | 2023-06-23 | 江苏省农业科学院 | Preparation method and application of biomass straw-based magnetic solid acid catalyst |
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