CN103316691B - Magnetic solid acid and preparation method thereof - Google Patents
Magnetic solid acid and preparation method thereof Download PDFInfo
- Publication number
- CN103316691B CN103316691B CN201310226222.0A CN201310226222A CN103316691B CN 103316691 B CN103316691 B CN 103316691B CN 201310226222 A CN201310226222 A CN 201310226222A CN 103316691 B CN103316691 B CN 103316691B
- Authority
- CN
- China
- Prior art keywords
- magnetic
- acid
- solid acid
- porous carbon
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses a magnetic solid acid and a preparation method thereof. The preparation method comprises the steps that: iron ions are absorbed on lignocellulose biomass, such that iron-loading biomass is obtained; the iron-loading biomass is subjected to pyrolysis under an inert atmosphere, such that a magnetic porous carbon precursor is obtained; the magnetic porous carbon precursor is subjected to sulfonation, such that magnetic solid acid is obtained. According to the invention, waste biomass material is adopted as a raw material. The magnetic porous carbon precursor is prepared through iron ion absorption and pyrolysis, and the precursor is sulfonated, such that the magnetic solid acid is prepared. According to the magnetic solid acid preparation method, the raw material cost is low, the raw material source is wide, large-scale production can easily be carried out, and the method is environment-friendly. The prepared magnetic solid acid has good catalytic effect, and is easy to separate. The acid and the method have good application prospect.
Description
Technical field
The present invention relates to field of material preparation, particularly a kind of magnetic solid acid and preparation method thereof.
Background technology
Solid acid is the novel acid of one of Recent study and exploitation, it is a kind of powder formulation, liquid mineral acid (example hydrochloric acid, sulfuric acid, phosphoric acid etc.) can be substituted for the common acid catalyzed reaction of catalysis some hydrolysis, esterification, dehydrations etc., there is prospects for commercial application widely.But when the viscosity of reactant mixture is very high, or during wherein containing solid reactant or product, solid acid is not very high from the usual efficiency of the separation process reactant mixture, and this can cause the catalysis reuse efficiency of solid acid significantly to reduce.
For common solid acid, the separating property of magnetic solid acid improves greatly, and it is separated from high viscosity or solid reaction mixture by external magnet.The common method preparing magnetic solid acid is mainly passed through having magnetic kernel (Fe
3o
4) porous material carry out sulfonic acid funtionalized.The ferriferrous oxide nano sphere that Feyen etc. are wrapped up by p-poly-phenyl ethene carries out sulfonation, has prepared one and has had very high acid strength (2.2-2.5H
+/ g) magnetic solid acid material (Feyen et al., 2010.Synthesis of StructurallyStable Colloidal Composites as Magnetically Recyclable Acid Catalysts.Chemistryof Materials22, (9), 2955-2961); Zillillah etc. are by carrying out sulfonation to the multiple polymers containing nano-magnetic core, synthesize a series of magnetic solid acid material (Zillillah et al., 2012.Highly Active, Stable, and Recyclable Magnetic Nano-size Solid Acid Catalysts:EfficientEsterification of Free Fatty Acid in Grease to Produce Biodiesel.GreenChemistry), these magnetic solid acid materials all show higher catalytic performance and good separating power.But need very complicated chemical reaction process during preparation, and use raw material costly, cause being difficult to large-scale production and commercial applications.
Simultaneously, as an agricultural production and consumption big country, the annual discarded lignocellulose-like biomass (as paddy rice, wheat stalk etc.) producing nearly 1,000,000,000 tons of China, among them, quite a few processes by directly burning in the fields, and this processing method will bring serious environmental problem.Therefore be how a current problem in the urgent need to address with environmental friendliness, economically viable method process lignocellulose-like biomass discarded object.
Summary of the invention
In view of this, the invention provides a kind of cost low, magnetic solid acid of easy large-scale production and preparation method thereof, to process the commercial applications of discarded living beings and popularization magnetic solid acid.
For achieving the above object, the invention provides a kind of preparation method of magnetic solid acid, it comprises the steps:
(1) on lignocellulose-like biomass, adsorb iron ion, obtain iron load living beings;
(2) the iron load living beings obtained in step (1) are carried out pyrolysis under an inert atmosphere, obtain magnetic porous carbon precursor;
(3) the magnetic porous carbon precursor obtained in step (2) is carried out sulfonation, namely obtain magnetic solid acid.
Preferably, described step (1) is specially:
Lignocellulose-like biomass is added in the solution containing iron ion, heat and be uniformly mixed solution, then Separation of Solid and Liquid process is carried out to mixed solution and the dry solid obtained, namely obtain iron load living beings.
More preferably, described is 0.05 ~ 0.15mol/L containing the concentration of iron ion in the solution of iron ion, the solid-to-liquid ratio of described lignocellulose-like biomass and the described solution containing iron ion is 5:100 ~ 20:100, the unit of the quality of wherein said lignocellulose-like biomass is gram, and the unit of the volume of the described solution containing iron ion is milliliter.
More preferably, in described step (1), the temperature of heating is 30 ~ 50 DEG C, and the time of heating is 180 ~ 300min, and the speed of stirring is 200 ~ 400r/min.
Preferably, in described step (2), the temperature of pyrolysis is 500 ~ 700 DEG C, and the time of pyrolysis is 1 ~ 3h.
More preferably, in described step (2), inert atmosphere is nitrogen.
Preferably, described step (3) is specially:
Add the concentrated sulfuric acid in the magnetic porous carbon precursor obtained in step (2), filter after adding thermal response a period of time, wash and drying, namely obtain magnetic solid acid.
More preferably, the solid-to-liquid ratio of described magnetic porous carbon precursor and the described concentrated sulfuric acid is 1:10 ~ 1:20, and the unit of the quality of wherein said magnetic porous carbon precursor is gram, and the unit of the volume of the described concentrated sulfuric acid is milliliter.
More preferably, in described step (3), the temperature of heating is 120 ~ 150 DEG C, and the time of reaction is 12 ~ 18h.
Present invention also offers a kind of magnetic solid acid prepared by above-mentioned any one method, its acid strength is 2 ~ 3mmol H
+/ g, specific area is 200 ~ 400m
2/ g.
The present invention for raw material with discarded biological material, by absorption iron ion, then prepares magnetic porous carbon precursor through pyrolysis, and then carries out sulfonation to this precursor, thus prepare magnetic solid acid.Low and the wide material sources of magnetic solid acid preparation method cost of material provided by the invention, easy large-scale production, and have environment friendly, obtained magnetic solid acid excellent catalytic effect and being easily separated, has broad application prospects.
Accompanying drawing explanation
Fig. 1 is the flow chart of the preparation method of magnetic solid acid of the present invention;
Fig. 2 is MPC-SO
3h(B) and the magnetic porous carbon precursor (A) of correspondence XRD figure;
Fig. 3 is MPC-SO
3the TGA figure of H;
Fig. 4 is MPC-SO
3h and PC-SO
3the nitrogen adsorption desorption figure of H;
Fig. 5 is MPC-SO
3h, PC-SO
3h, H
2sO
4and the catalytic performance comparison diagram that catalyst-free adds.
Detailed description of the invention
For enabling above-mentioned purpose, the feature and advantage of invention more become apparent, below the specific embodiment of the present invention is described in detail.
Set forth a lot of detail in the following description so that fully understand the present invention, but the present invention can also adopt other to be different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar popularization when intension of the present invention, therefore the present invention is by the restriction of following public specific embodiment.
The invention provides a kind of preparation method of magnetic solid acid, as shown in Figure 1, comprise the following steps:
The first step: adsorb iron ion on lignocellulose-like biomass, obtains iron load living beings, and wherein iron ion can be ferrous iron or ferric iron, and lignocellulose-like biomass can have stalk or trees or the multiple choices such as wood chip or sawdust.The method of absorption can adopt method well known to those skilled in the art, preferably as follows: lignocellulose-like biomass is added in the solution containing iron ion, heat and be uniformly mixed solution, again Separation of Solid and Liquid process is carried out to mixed solution and the dry solid obtained, namely iron load living beings are obtained, wherein carrying out the Separation of Solid and Liquid process solid that also drying obtains to mixed solution is carry out in order to follow-up pyrolytic process is more convenient, also can ensure also to obtain bio oil in pyrolytic process.In addition, Separation of Solid and Liquid process can have filtration or the selection such as rotary evaporation, and rotary evaporation dewaters when being conducive to avoiding suitability for industrialized production and produces a large amount of reluctant waste water, and those skilled in the art can select according to the actual requirements flexibly.
Those skilled in the art can easily know, proportionate relationship between lignocellulose-like biomass and iron ion can be selected by adsorption effect according to the actual requirements, in adsorption process, heating and stirring are also the speed in order to accelerate iron ion absorption, preferably, be 0.05 ~ 0.15mol/L containing the concentration of iron ion in the solution of iron ion, lignocellulose-like biomass and the solid-to-liquid ratio containing the solution of iron ion are 5:100 ~ 20:100, wherein the unit of the quality of lignocellulose-like biomass is gram, and the unit of the volume of the described solution containing iron ion is milliliter; The temperature of heating is 30 ~ 50 DEG C, and the time of heating is 180 ~ 300min, and the speed of stirring is 200 ~ 400r/min.
Second step: the iron load living beings obtained in the first step are carried out pyrolysis under an inert atmosphere, obtain magnetic porous carbon precursor, wherein the temperature and time of pyrolysis all can be selected according to the actual requirements, inert atmosphere can have the selection such as nitrogen or argon gas, preferably, the temperature of pyrolysis is 500 ~ 700 DEG C, and the time of pyrolysis is 1 ~ 3h, and selects nitrogen atmosphere.In this step, except magnetic porous carbon precursor can be obtained, bio oil resource can also be obtained.
In order to allow magnetic kernel in pyrolytic process formation clearly, be that source of iron provides corresponding reaction equation: 1. FeCl below with ferric trichloride
3+ 3H
2o → Fe (OH)
3+ 3HCl ↑; 2. Fe (OH)
3→ FeO (OH)+H
2o; 3. 6FeO (OH)+4H
2→ 2Fe
3o
4+ 4H
2o ↑; 4. 6FeO (OH)+4C → 2Fe
3o
4+ 2CO ↑ 5. 6FeO (OH)+4CO → 2Fe
3o
4+ 4CO
2↑.
3rd step: the magnetic porous carbon precursor obtained in second step is carried out sulfonation, namely obtains magnetic solid acid.Technological means well known in the art can be adopted to carry out the sulfonation process of magnetic porous carbon precursor, use liquid phase sulfonation method or gas phase xanthation method, use which kind of sulfonating agent all can select according to the actual requirements, preferably as follows: in the magnetic porous carbon precursor obtained in second step, add the concentrated sulfuric acid, filter after adding thermal response a period of time, wash and drying, namely obtain magnetic solid acid.In order to allow sulfonation better effects if, can be 1:10 ~ 1:20 operation by the solid-to-liquid ratio of magnetic porous carbon precursor and the concentrated sulfuric acid in practical operation, wherein the unit of the quality of magnetic porous carbon precursor is gram, the unit of the volume of the concentrated sulfuric acid is milliliter, and the temperature controlling heating is 120 ~ 150 DEG C, and the time of reaction is 12 ~ 18h.
Those skilled in the art easily know, in order to allow the concentrated sulfuric acid better filter, can add a certain amount of water before filtration in reaction solution; In order to allow, material is more effective carries out drying, also can use low boiling-point and polarity organic solvent washing again when washing after deionized water rinsing.
Magnetic solid acid provided by the invention is not only prepared simple fast, and cost is low, and has higher acid strength and specific area, has broad application prospects.
Iron trichloride hexahydrate, anhydrous ironic sulfate, nine water ferric nitrate and the concentrated sulfuric acids that the Shanghai Reagent Company of traditional Chinese medicines group used in an embodiment produces;
The Rotary Evaporators of the RE-3000A adopting Shanghai Ya Rong biochemical instrument company to produce carries out distillation and dewaters, Japanese MXPAHF Rigaku type x-ray diffractometer (XRD) thing to magnetic solid acid is adopted to analyze mutually, adopt the thermogravimetric analyzer (TGA) of Japanese Shimadzu Co. to analyze the structure of magnetic solid acid and composition, the nitrogen adsorption desorption instrument adopting Micromeritics company of the U.S. to produce carries out the experiment of nitrogen adsorption desorption.
Embodiment 1
(1) 2.70g Iron trichloride hexahydrate (FeCl is taken
36H
2o) be dissolved in 100mL deionized water, obtain the ferric chloride solution of 0.1mol/L, take 10g waste saw dust living beings again, join in the ferric chloride solution prepared, being placed in water-bath magnetic stirring apparatus, bath temperature being risen to 50 DEG C, stirring after 180min by Rotary Evaporators decompression distillation except anhydrating with the speed of 300r/min, gained solid is put in baking oven and dries, obtain iron load living beings;
(2) by the iron load living beings that obtain in step (2) at 500 DEG C, carry out pyrolysis under the condition of nitrogen atmosphere, pyrolysis time is 1h, obtains magnetic porous carbon precursor, meanwhile, can also obtain bio oil resource;
(3) the magnetic porous carbon precursor taking 3 grams is placed in kieldahl flask, add the 30mL concentrated sulfuric acid, 12h is reacted under 150 DEG C of conditions, then reactant mixture is poured in 1000mL water, filter subsequently and carry out Separation of Solid and Liquid, gained solid deionized water is rinsed repeatedly, rinse with absolute ethyl alcohol again, finally solid is placed in baking oven to dry, namely obtains magnetic solid acid material, be designated as MPC-SO
3h.
In this embodiment, the productive rate obtaining magnetic porous carbon precursor in step (2) is about 40%, and bio oil productive rate is about 35%.The MPC-SO of final acquisition
3the acid strength of H is 2.57mmol H
+/ g, specific area is 296m
2/ g.
Shown in Fig. 2, the principal crystalline phase in the XRD diffraction maximum display magnetic solid acid in figure is Fe
3o
4, this is also that it shows the main cause of magnetic, and Fe
3o
4still preserved through concentrated sulfuric acid high-temperature process crystal formation, demonstrated higher stability.
As shown in Figure 3, before the first time Weight lose of magnetic solid acid appears at 400K, this losing mainly due to moisture; Second time Weight lose appears at 430 to 590K, and this process is mainly concerned with sulfonic decomposable process and produces SO
2and H
2o, and TGA curve confirms mutually, inhales visible two endothermic peaks in exotherm, relates separately to the volatilization of moisture and the decomposable process of sulfonate radical.
Contrast experiment
(1) by 10g waste saw dust living beings at 500 DEG C, carry out pyrolysis under the condition of nitrogen atmosphere, pyrolysis temperature is pyrolysis time is 1h, obtains porous carbon precursor;
(2) the porous carbon precursor taking 3g is placed in kieldahl flask, add the 30mL concentrated sulfuric acid, 12h is reacted under 150 DEG C of conditions, then reactant mixture is poured in 1000mL water, filter subsequently and carry out Separation of Solid and Liquid, gained solid deionized water is rinsed repeatedly, rinse with absolute ethyl alcohol again, finally gained solid is placed in baking oven to dry, namely obtains non-magnetic solids acid, be designated as PC-SO
3h.
As shown in Figure 4, according to data in figure, calculated by BET method, MPC-SO
3the specific area of H is 296m
2/ g, is significantly higher than PC-SO
3h(only has 6m
2/ g), can show that iron ion can the pore forming process of catalysed promoted material with carbon element in pyrolytic process, make the magnetic solid acid obtained have higher specific area and pore volume.
As shown in Figure 5, the esterification process for catalysis acetic acid and phenmethylol characterizes its catalytic performance, therefrom known MPC-SO
3h has excellent catalytic performance, and its catalytic esterification productive rate reaches more than 95%, is much higher than and uses PC-SO
3the productive rate (being less than 70%) of H catalysis, and with the productive rate (about 89%) of sulphuric acid catalysis.And MPC-SO
3h has good separable performance, and through repeatedly using, its catalytic efficiency there is no significant decline, and through 5 reuses, its magnetic is not also decreased significantly, and still can be separated easily by external magnetic field.Except for catalyst for esterification reaction, this magnetic solid acid can also be used for the hydrolysis of catalyzed carbon hydrate, the reactions such as the dehydration of monose, all shows good effect.
Although the present invention is described in conjunction with above embodiment, but the present invention is not defined to above-described embodiment, and only by the restriction of claims, those of ordinary skill in the art can easily modify to it and change, but do not leave essential idea of the present invention and scope.
Claims (2)
1. a preparation method for magnetic solid acid, is characterized in that, comprises the steps:
(1) sawdust living beings are added in the ferric chloride solution of 0.1mol/L, stir 180min with the speed of 300r/min at 50 DEG C after, again Separation of Solid and Liquid process is carried out to mixed solution and the dry solid obtained, obtain iron load living beings, the solid-to-liquid ratio of described sawdust living beings and the described solution containing iron ion is 1:10, the unit of the quality of wherein said sawdust living beings is gram, and the unit of the volume of described ferric chloride solution is milliliter;
(2) the iron load living beings obtained in step (1) are carried out pyrolysis in a nitrogen atmosphere, obtain magnetic porous carbon precursor, the temperature of wherein pyrolysis is 500 DEG C, and the time of pyrolysis is 1h;
(3) concentrated sulfuric acid is added by the magnetic porous carbon precursor obtained in step (2), filter after reacting 12h at 150 DEG C, wash and drying, namely magnetic solid acid is obtained, the solid-to-liquid ratio of described magnetic porous carbon precursor and the described concentrated sulfuric acid is 1:10, the unit of the quality of wherein said magnetic porous carbon precursor is gram, and the unit of the volume of the described concentrated sulfuric acid is milliliter.
2. the magnetic solid acid prepared by the method for claim 1, is characterized in that, acid strength is 2.57mmol H
+/ g, specific area is 296m
2/ g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310226222.0A CN103316691B (en) | 2013-06-07 | 2013-06-07 | Magnetic solid acid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310226222.0A CN103316691B (en) | 2013-06-07 | 2013-06-07 | Magnetic solid acid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103316691A CN103316691A (en) | 2013-09-25 |
| CN103316691B true CN103316691B (en) | 2015-03-04 |
Family
ID=49185905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310226222.0A Expired - Fee Related CN103316691B (en) | 2013-06-07 | 2013-06-07 | Magnetic solid acid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103316691B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103551151B (en) * | 2013-11-06 | 2015-07-08 | 中国矿业大学 | Method for preparing recyclable magnetic solid acid catalyst |
| CN103657652B (en) * | 2013-12-10 | 2016-11-16 | 华北电力大学 | A kind of solid acid catalyst Fe3o4@C/MWCNTs and the method for catalyzing cellulose hydrolysis thereof |
| CN104096562B (en) * | 2014-06-12 | 2016-11-09 | 陕西师范大学 | A kind of preparation method of magnetic carbonaceous solid acid catalyst |
| CN105149007A (en) * | 2015-09-21 | 2015-12-16 | 淮阴师范学院 | Preparation method of magnetic biomimetic carbon-based solid acid catalyst |
| CN105396552B (en) * | 2015-12-18 | 2018-08-03 | 中国科学技术大学 | A kind of molding biological carbon and preparation method thereof |
| CN111303220B (en) * | 2020-03-27 | 2022-03-11 | 安徽银创生物科技股份有限公司 | Preparation method of D-glucosamine sulfate |
| CN112121818B (en) * | 2020-09-30 | 2024-01-05 | 江苏大学 | Magnetic carbon-based catalyst, preparation method and application |
| CN114957002A (en) * | 2022-06-30 | 2022-08-30 | 蚌埠学院 | Green synthesis method of diisobutyl malonate |
| CN115805085A (en) * | 2022-11-28 | 2023-03-17 | 淮阴工学院 | Method for synthesizing magnetic sulfonated carbon-based solid acid by using red mud as carrier |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101670299B (en) * | 2009-10-16 | 2012-01-11 | 青岛生物能源与过程研究所 | Preparation method of nanometer carbon-based solid acid |
-
2013
- 2013-06-07 CN CN201310226222.0A patent/CN103316691B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103316691A (en) | 2013-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103316691B (en) | Magnetic solid acid and preparation method thereof | |
| CN108097255B (en) | Porous carbon frame nickel-based catalyst for carbon dioxide reforming reaction and preparation method and use method thereof | |
| CN105344380B (en) | A kind of metal organic frame/graphene-supported palladium nano-composite catalyst and its preparation method and application | |
| CN105521801B (en) | Application of catalyst in synthesis of vinyl chloride by hydrochlorination of acetylene | |
| CN101805002B (en) | Preparation method of surface modification calcium oxide | |
| CN102786094B (en) | Preparation method and application of mesoporous manganese oxide material | |
| CN105271203A (en) | Porous co-doped graphene and preparation method thereof | |
| CN105148990B (en) | A kind of preparation method and applications of sulfonic acid carbon nano tube/graphene oxide composite catalyst | |
| CN105195188A (en) | Nickel-tungsten carbide/porous carbon nano-fiber composite catalyst, intermediate and preparation | |
| CN105713017A (en) | High selectivity metal organic skeleton material and preparation method thereof | |
| CN104944458B (en) | A kind of water solublity cerium precursor prepares porous cerium base oxide method | |
| CN104891580A (en) | Preparation method of nickel hydroxide ultrathin nanosheet assemblies | |
| Zhang et al. | Magnetic N-containing carbon spheres derived from sustainable chitin for the selective oxidation of C–H bonds | |
| CN101289474B (en) | Process for preparing humic acid from residue after extraction of coal humic acid | |
| CN108722488B (en) | Bimetal center metal-organic framework material for enhancing Lewis acidity and preparation method thereof | |
| CN101428239A (en) | Absorbent charcoal based catalyst carrier, catalyst, preparation and uses thereof | |
| CN103657653B (en) | A kind of solid acid catalyst C/Fe3O4The method of MWCNTs and catalyzing cellulose hydrolysis thereof | |
| CN101406842B (en) | Al-pillared paligorskite modified solid acid catalyst and preparation and application thereof | |
| CN108855158B (en) | Preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst | |
| CN102942548B (en) | Delta-dodecalactone synthesis method | |
| CN113717391B (en) | Boron-containing zirconium-based metal organic framework material and preparation method and application thereof | |
| CN109250763B (en) | Method for preparing hydrogen by reforming hydrogen sulfide and methane | |
| CN109908962A (en) | The ionic liquid loaded amination magnetic composite of jujube cake type structure heteropoly acid, preparation method and application | |
| CN103962142B (en) | Nucleocapsid perovskite type catalyst preparation method for methane methyl alcohol | |
| CN108586202B (en) | Synthesis method of intermediate 4-phenylbutanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150304 Termination date: 20210607 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |