CN1132688C - Magnetic solid super strong acid catalyst and its preparing method - Google Patents
Magnetic solid super strong acid catalyst and its preparing method Download PDFInfo
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- CN1132688C CN1132688C CN 00133474 CN00133474A CN1132688C CN 1132688 C CN1132688 C CN 1132688C CN 00133474 CN00133474 CN 00133474 CN 00133474 A CN00133474 A CN 00133474A CN 1132688 C CN1132688 C CN 1132688C
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Abstract
The present invention relates to a super acidic catalyst of a magnetic solid, which is prepared from a magnetic material with superparamagnetism of Fe3O4, or Ni-Fe3O4, or Co-Fe3O4, or Mn-Fe3O4 and solid acid by the combination of an improved chemical coprecipitation technology and a homogenizing technology. The present invention has the main process flow: magnetic fluid preparation, ultrasonic dispersion treatment, colloidal sol-gel solution formation, magnetic separation wash, and drying and roasting treatment for separated products. As the catalyst has the magnetic performance, the catalyst and reacting substances can be conveniently separated and recovered, the catalyst has higher acid strength and higher porosity, the catalyst has high efficiency in the reactions of hydrocarbon alkylation, hydrocarbon isomerization, hydrocarbon esterification, etc., is friendly to environment, and has wide application prospects.
Description
Technical field
The present invention relates to a kind of new solid acid---magnetic solid super acidic catalyst.The invention still further relates to this Preparation of catalysts method.
Background technology
The solid super-strong acid of domestic and international application in reactions such as hydro carbons alkylation, isomerization, esterification mainly contains SO at present
4 2-The Ni that promotes; Zr, oxide super acids such as Sn, the researcher is in order to improve the catalytic activity of solid super acid catalyst; and improve its acid strength as far as possible, as the MCM-41 load SO that in August, 2000, the 1240th～1243 page of China SCI Vol21 delivered by author's thunderclap etc.
4 2-/ ZrO
2The super acids performance is studied a literary composition, and the author adopts impregnation technology to prepare MCM-41 load SO
4 2-/ ZrO
2The type solid super-strong acid, but the solid super acid catalyst of above-mentioned preparation its shortcoming on using is, the separation difficulty of catalyst and product, reaction interface is little and resistance to mass tranfer is big.Current in the preparation method of existing solid super acid catalyst, the most frequently used i.e. two step synthetic method and one-step synthesis, these two kinds of methods have all adopted impregnation technology in preparation process, its shortcoming is that waste of raw materials is big in preparation process, cost is high, when the catalytic liquid phase reaction, reactant and catalyst separation are also quite difficult.
Summary of the invention
The objective of the invention is, in order to overcome the shortcoming on existing solid super acid catalyst and preparation method thereof, provide a kind of magnetic solid super acidic catalyst and a kind of new synthetic this Preparation of catalysts method thereof that superparamagnetism has higher acid strength again that promptly have.The advantage of this magnetic solid super acidic catalyst is owing to have superparamagnetism, can utilize magnetic separation technique to make catalyst and separating of product become easy on using; This catalyst is a porous honeycomb, so have bigger specific surface and porosity, the surface of this porous helps the generation of the high-ratio surface and the high-ratio surface free energy of catalyst, all very favourable for improving reactivity and reducing reaction activity, externally-applied magnetic field drives catalyst and moves in reaction system, make reaction interface increase, resistance to mass tranfer diminishes.Because this magnetic solid super acidic catalyst of preparation has adopted improved chemical coprecipitation and homogenization process, give solid super-strong acid a kind of superparamagnetism, its advantage is can realize multiple oxide compound, strengthened the acid strength of magnetic solid super acidic catalyst, activity of such catalysts is improved greatly, and saved raw material and reduced cost.
Magnetic solid superacid of the present invention is by the magnetic species Fe with superparamagnetism
3O
4Or Ni-Fe
3O
4, Co-Fe
3O
4, Mn-Fe
3O
4Combine by adopting improved chemical coprecipitation and homogenization process Deng with solid acid, because this catalyst has magnetic species, in application, pass through externally-applied magnetic field, driving magnetic catalyst moves in reaction system, catalyst is evenly disperseed and rotation in system, played stirring action, avoided the gathering between particulate, increased the contact area between catalyst and reactant, reaction utilizes magnetic separation technique can realize being separated from each other and reclaiming of catalyst and product very easily after finishing.Can not ignore the influence of chemical reaction in magnetic field in addition, drive the superparamagnetism that externally-applied magnetic field that magnetic solid super acidic catalyst moves and magnetic solid superacid have and to bring into play co with solid acid in system, so this magnetic solid super acidic catalyst is a kind of environmentally friendly, efficiently and the solid super acid catalyst of extensive application prospect in reactions such as hydro carbons alkylation, isomerization, esterification.
In order to obtain magnetic solid super acidic catalyst, the technical scheme that realizes this invention is: make the magnetic responsiveness height by adopting improved chemical coprecipitation, suspensible magnetic fluid, adopt homogenization process, magnetic fluid is carried out ultrasonic dispersion, with magnetic fluid as reaction medium, under alkali condition, realize the precipitation of slaine, form so-gel solution, utilize the magnetic separation technique sediment separate out, wash sediment repeatedly with distilled water, to till other foreign ion of nothing, the sediment drying, calcination process just can obtain the magnetic solid super acidic catalyst that porous honeycomb has superparamagnetism.Its concrete preparation method in detail comprises that the following experimental technique step is poly-:
1. but the preparation of stable suspersion magnetic fluid
Utilize improved chemical coprecipitation, the adding mol ratio is 1: 2 Fe in the four-necked bottle of being furnished with agitator, reflux condensing tube, nitrogen capsule
2+Salt or Fe
3+Salt is warming up to 55 ℃ in oil bath, splash into ammoniacal liquor and regulate between pH value to 11～13, and reaction 30min is cooled to room temperature.Wash magnetic separate and subside thing repeatedly to neutral with distilled water, promptly get the iron-based magnetic fluid.Other condition is constant, if the adding mol ratio is 1: 1: 4 Co
2+(Mn
2+, Ni
2+), Fe
2+And Fe
3+Salt can make cobalt-based magnetic fluid (Co-Fe respectively
3O
4), manganese base magnetic fluid (Mn-Fe
3O
4) and nickel radical magnetic fluid (Ni-Fe
3O
4).
2. magnetic fluid anticipates
The magnetic fluid for preparing is got in right amount, ultrasonic dispersion treatment 30min, the ultrasonic vibration frequency is 20-50KHz, magnetic fluid is uniformly dispersed, then it is transferred in the three-necked bottle, in oil bath, be warmed up to 65 ℃, mechanical agitation 4h, mixing speed is 600-800rpm.
3. magnetic solid superacid is synthetic
Take by weighing an amount of ZrOCl
2, joining after the dissolving in the above-mentioned three-necked bottle of being furnished with in the separatory funnel, ammoniacal liquor places another separatory funnel, by control experiment reaction condition, splashes into ZrOCl simultaneously
2With ammoniacal liquor to ZrOCl
2All drip off, during regulator solution pH=13, stop dropping ammonia, sediment is transferred in the beaker after stirring ageing, utilizes magnetic separation technique to make it sedimentation, the supernatant that inclines, and adding distil water, cyclic washing is to solution neutral and do not have Cl
-, change over to behind the suction filtration in the small beaker, put in the baking oven and dry down in 80～90 ℃, take out porphyrize, get light brown powder, this powder is put into crucible, place muffle furnace interior in 600 ℃～700 ℃ roastings 4～6 hours, take out and be the magnetic solid super acidic catalyst that makes.
4. the magnetic solid super acidic catalyst of pickling
The catalyst that makes is dipped in the H of 0.5mol/L
2SO
4In, can make the magnetic solid super acidic catalyst of pickling.
Preparation method from the above-mentioned magnetic solid super acidic catalyst of designing for the present invention, can realize the compound of multiple oxide, better bring into play the co of solid acid, improve the acid strength of solid super-strong acid greatly, make product have and add and more performance, give solid super-strong acid simultaneously, utilize magnetic separation technique thoroughly to separate with product easily with magnetic than component linearity, saved raw material and reduced cost, reduced pollution environment.
The specific embodiment
Below in conjunction with several embodiment the present invention is described in further detail.
Embodiment 1
Take by weighing Fe
3O
4With ZrO
2Mol ratio be 1: 80 magnetic solid superacid 1g join be furnished with thermometer, in the three-neck flask of oil water separator, condenser pipe, add the glacial acetic acid of 8ml, the n-butanol of 51ml simultaneously, under magnetic agitation, add hot reflux, make material under fluidized state, react 6h.Utilize magnetic separating device to reclaim catalyst, continue to do esterification, product is analyzed content with gas chromatograph, and the productive rate that calculates ester is 96.4%.
Embodiment 2
Get 75mL magnetic fluid (0.0lmolFe
3O
4/ L), (the ultrasonic vibration frequency is 20～50kHz) to be transferred in the three-necked bottle, is warmed up to 65 ℃ in the oil bath, mechanical agitation 30min (mixing speed 600～800rpm) to add the ultrasonic dispersion of 300mL distilled water 30min; Accurately take by weighing 19.335gZrOCl
2, to pour in the separatory funnel after adding the 50mL dissolved in distilled water, ammoniacal liquor is packed in another separatory funnel, is warming up to 75 ℃, splashes into basic zirconium chloride and ammoniacal liquor (dripping speed is 2 droplets/second) simultaneously to ZrOCl
2All drip off; During regulator solution pH=13, stop dropping ammonia; Constant temperature stirs ageing 2h; Solution is changed in the beaker of 1000mL, utilize magnetic separation technique to make it sedimentation; The supernatant that inclines adds distilled water, and cyclic washing is to solution neutral and do not have Cl
-Till; Product places dry 10 hours of the baking oven of 80C～90 ℃ behind suction filtration; Dry thing places muffle furnace in 600 ℃ of roastings 4～6 hours, can obtain Fe
3O
4With ZrO
2Mol ratio is 1: 80 a magnetic solid super acidic catalyst, is designated as Fe
3O
4/ ZrO
2
Embodiment 3
Change Fe
3O
4With ZrO
2The mole proportioning, iron-based magnetic fluid (0.01mol Fe
3O
4/ L) get 25mL, ZrOCl
2Take by weighing 8.056g, other experiment condition can make Fe with embodiment 2
3O
4With ZrO
2Mol ratio is 1: 100 a magnetic solid super acidic catalyst, is designated as Fe
3O
4/ ZrO
2
Embodiment 4
Get the cobalt-based magnetic fluid (0.01molCo-Fe of 70mL
3O
4/ L), other condition can obtain Co-Fe with embodiment 2
3O
4With ZrO
2Mol ratio is 1: 80 a magnetic solid super acidic catalyst, is designated as Co-Fe
3O
4/ ZrO
2
Embodiment 5
Get 50mL magnetic fluid (0.01mol Fe
3O
4/ L), add the ultrasonic dispersion of 300mL distilled water 30min, be transferred in the three-necked bottle, be warmed up to 65 ℃ in the oil bath, mechanical agitation 30min; Take by weighing 12.890gZrOCl
2And 2.968gAL (NO
3)
39H
2O pours in the separatory funnel after adding the 80mL dissolved in distilled water, and other experiment condition can make Al promoted type magnetic solid super acidic catalyst with embodiment 2, is designated as Fe
3O
4/ Al
2O
3-ZrO
2
Embodiment 6
Take by weighing mol ratio and be 1: 80 Co-Fe
3O
4/ ZrO
2Type magnetic solid superacid 2g joins the H of the 0.5mol/L of 20mL
2SO
4Dipping is 3 hours in the solution, adopts magnetic separation technique, the supernatant liquor that inclines, and 100 ℃ were descended dry 6 hours, and at last 600 ℃ of roastings 4～6 hours, just can make SO
4 2-/ Co-Fe
3O
4-ZrO
2The type magnetic solid super acidic catalyst.
Claims (2)
1. magnetic solid super acidic catalyst is characterized in that its magnetic species Fe by superparamagnetism
3O
4Or Ni-Fe
3O
4, Co-Fe
3O
4, Mn-Fe
3O
4Combine magnetic species Fe with solid acid
3O
4Or Ni-Fe
3O
4, Co-Fe
3O
4, Mn-Fe
3O
4With the mole proportioning of solid acid be 1: 60～100.
2. a method for preparing the described magnetic solid super acidic catalyst of claim 1 is characterized in that adopting improved chemical coprecipitation, reactant Fe
2+Salt and Fe
3+The mole proportioning of salt is 1: 2, and reaction control temperature is 55 ℃, and the pH value of solution is controlled between 11～13, and reaction time 30min promptly makes the iron-based magnetic fluid, and other condition is constant, if reactant Fe
2+Salt, Fe
3+Salt and Co
2+Salt or Mn
2+Salt or Ni
2+The mole proportioning of salt is 1: 1: 4, promptly makes cobalt-based magnetic fluid (Co-Fe
3O
4) or manganese base magnetic fluid (Mn-Fe
3O
4) or nickel radical magnetic fluid (Ni-Fe
3O
4); The condition of anticipating of magnetic fluid is that the ultrasonic vibration frequency is 20～50kHz, and temperature is controlled to be 65 ℃, and mechanical agitation speed is 600-800rpm, and mixing time is 4h; The synthetic of magnetic solid superacid is to regulate ZrOCl with ammoniacal liquor
2PH value to 13, utilize magnetic separation technique to make it sedimentation, sedimentary bake out temperature is 80～90 ℃, sintering temperature is 600 ℃～700 ℃, roasting time is 4～6h; If the magnetic solid superacid that makes is dipped in the H of 0.5mol/L
2SO
4In, can make load SO
4 2-Magnetic solid super acidic catalyst.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00133474 CN1132688C (en) | 2000-11-08 | 2000-11-08 | Magnetic solid super strong acid catalyst and its preparing method |
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|---|---|---|---|
| CN 00133474 CN1132688C (en) | 2000-11-08 | 2000-11-08 | Magnetic solid super strong acid catalyst and its preparing method |
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|---|---|
| CN1290574A CN1290574A (en) | 2001-04-11 |
| CN1132688C true CN1132688C (en) | 2003-12-31 |
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| CN1167504C (en) * | 2002-04-24 | 2004-09-22 | 北京化工大学 | Magnetic superfine solid acid catalyst in double-shell structure and its prepn process |
| CN100463718C (en) * | 2005-10-21 | 2009-02-25 | 哈尔滨工业大学 | Process of preparing magnetic solid acid catalyst in binary catalyst system for promoting esterification of ammonium lactate |
| CN100340539C (en) * | 2005-10-21 | 2007-10-03 | 哈尔滨工业大学 | Dual catalytic system for promoting ammonium lactate esterification and uses, preparation method of maganetic solid acid catalyst in the same |
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| CN101417822B (en) * | 2008-11-24 | 2010-12-08 | 中国科学院长春应用化学研究所 | Method for preparing super paramagnetic mesoporous ferriferrous oxide nano particle |
| CN101757949B (en) * | 2009-12-22 | 2011-09-14 | 华东师范大学 | Magnetic solid acid catalyst, preparation method and application tehreof |
| CN103055942A (en) * | 2011-10-19 | 2013-04-24 | 华东理工大学 | Preparation method of magnetic fluosulfonic acid resin/SiO2-Co0.5Fe2.5O4 solid acid catalyst |
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| CN104693023B (en) * | 2015-02-13 | 2017-03-15 | 湘潭大学 | A kind of method that biomass sugar prepares levulinate |
| CN109232225B (en) * | 2017-07-11 | 2021-07-23 | 万华化学集团股份有限公司 | Method for generating acrylic acid by cracking acrylic acid heavy component |
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