CN105312089A - Method for preparing heteropolyacid-iron bentonite through mechanical activating, strengthening, steeping and adsorbing - Google Patents
Method for preparing heteropolyacid-iron bentonite through mechanical activating, strengthening, steeping and adsorbing Download PDFInfo
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- CN105312089A CN105312089A CN201510313872.8A CN201510313872A CN105312089A CN 105312089 A CN105312089 A CN 105312089A CN 201510313872 A CN201510313872 A CN 201510313872A CN 105312089 A CN105312089 A CN 105312089A
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Abstract
The invention relates to a method for mechanically activating and preprocessing iron-based bentonite and preparing a heteropolyacid-iron bentonite composite material for fenton-like catalysis through strengthening, steeping and adsorbing. The method comprises the steps that firstly, bentonite iron is modified to prepare the iron-based bentonite; secondly, the iron-based bentonite is mechanically activated and preprocessed; thirdly, the processed iron-based bentonite is steeped in heteropolyacid to adsorb the heteropolyacid. A high-energy ball-milling machine which serves as mechanical activating and preprocessing equipment adopts stainless steel grinding balls as grinding media, and the diameter of the stainless steel grinding balls is 2-8 mm. In the activating process, the medium filling rate is 10%-40%, the ratio of materials to the balls is 0.02-0.08 (material mass/ball filling volume, g.mL<-1>), the activating processing time is 20-40 min, and the frequency is 15-45 Hz. According to the method, the mechanical activating equipment needed in the mechanical activating processing and modifying process is simple and easy and convenient to operate, the mechanical activating and modifying production cycle is short, and the product performance is significantly improved.
Description
Technical field
The present invention relates to bentonite base compound catalyze material preparing technical field, be specifically related to the method that Fenton-like catalysis heteropoly acid/iron bentonite composite material prepared by a kind of mechanical activation pretreatment iron-based bentonite dipping absorption heteropoly acid.
Background technology
Heteropoly acid is that a class carries out the polyoxy bunch metal complex of Spatial Coupling by central atom (i.e. hetero atom, as P, Si, As, Ge etc.) and coordination atom (i.e. polyatom, as Mo, W etc.) by oxygen atom bridging mode.As a kind of green catalyst, the research of heteropoly acid in catalytic field has made a breakthrough sexual development, is widely used in all kinds of catalytic reactions such as oxidation, reduction, esterification, ester exchange, alkylation, etherificate.Though heteropoly acid has active high, selective good, nontoxic, the not advantage such as etching apparatus, exist specific area little, be soluble in polar solvent, poor repeatability, be difficult to the shortcomings such as separation and recovery, limit its commercial Application to a certain extent.By the solidification of heteropoly acid, can overcome the application shortcomings such as heteropoly acid specific area is little, poor repeatability, recovery difficulty, therefore in heteropoly acid catalysis application study, researcher constantly explores heteropoly acid solid support method and application thereof.
Bentonite is the natural non-metallic clay mineral based on silicate, has two panels silicon-oxy tetrahedron and presss from both sides a slice aluminium (magnesium) oxygen (hydroxyl) octahedral TOT type layer structure.Bentonite has stable physical and chemical performance, is a kind of excellent catalyst and catalytic active component carrier.The concern that bentonite base heteropoly acid composite and application and development have also been obtained researcher is prepared by bentonite solid-carrying heteropolyacid.Xu Limin, Lin Shen etc. have studied the load of the heteropoly acid such as phosphotungstic acid, phosphomolybdic acid on bentonite, and with the bentonite solid-carrying heteropolyacid of preparation for catalysis material, have investigated the catalytic applications that catalysis material reacts esterification and dehydration of alcohols ether.Luan Wenlou etc. with surfactant modified montmorillonite for carrier, choose different solvents, the method such as dipping, backflow absorption is adopted to be carried on by phosphorus heteropoly tungstic acid on surfactant modified montmorillonite, and be acid catalyzed reaction model with esterification, investigate prepared catalysis material performance in the esterification reaction.Wang Shaojun etc. are reported and are assembled by molecule, are inserted between anionic bentonite bed by heteropoly acid phosphotungstic acid, obtain the heteropoly acid/bentonite catalysis material with nanoscale, and have studied the catalytic action of this catalysis material to esterification.
Based on photocatalytic activity and the redox property of heteropoly acid, Wei Guangtao etc. with heteropoly acid and bentonite for primary raw material by flooding absorption method, chemical graft process prepared heteropoly acid/bentonite solid catalytic material, investigated the heteropoly acid/application performance of bentonite solid catalytic material in Fenton-like system of preparation.But find, part heteropoly acid/bentonite solid catalytic material institute solid-carrying heteropolyacid active component does not reach expection supported quantity yet, catalytic active component heteropoly acid supported quantity and stability unsatisfactory.Find the SEM morphology characterization of preparation process and final products, stratiform bentonite is difficult to delamination in preparation process, and lumpiness is still very obvious, this may be cause the few and unstable main cause of immobilized amount of active ingredients.Therefore, by outfield intensifying activated bentonite, bentonite partial portion reactivity is strengthened, and improves bentonitic stripping layering, the bentonite base solid catalytic material that obtained heteropoly acid supported quantity is high be can expect, thus stability and the catalytic activity of catalysis material improved further.
" mechanical activation " refers to that solid matter is under the effect of the mechanical forces such as friction, collision, impact, shearing, crystal structure and physical and chemical performance are changed, and cause some mechanical can be transformed into the interior energy of solid matter, thus cause the chemism of solid to increase, this effect is referred to as mechanical activation, is the category belonging to mechanochemistry.
The method that Zhang Jun etc. adopt heat treatment to combine with mechanochemical modification has activated bentonite, prove the method adopting mechanical force abrasive chemical surface modification, make to peel away by shearing force effect between the bentonite bed of adhesion weakness, crystallization degree reduces, and bentonite surface property is improved greatly.Their research also finds in the process of mechanical lapping, mechanism have activated bentonite Active sites effectively, and changes mechanical energy becomes the surface energy of particle, granule surface area increases, the organic agent good combination further promoting highly active bentonite clay particle Yu add.People Peng bravely waits the ball mill grinding by carrying out different condition to bentonite raw ore, have studied the change of bentonite physical and chemical performance in Jet Crushing, has inquired into the mechanism of performance change, and verified by XRD and IR structural analysis.People Peng bravely waits and finds in an experiment, the ion exchange capacity of bentonite powder, Absorbance ratio-derivative method, whiteness, colloid index, expansion doubly and rheological characteristic all exist with Ball-milling Time and maintain close ties with, and present the change of certain rule.Li Zhenxing make use of mechanical activation technology preparing in bentonite process, organobentonite has been prepared to adding softex kw while bentonite ball milling, and investigated the method and prepare the adsorption applications of bentonite to methyl orange, this preparation technology effectively reduces the use amount of modifier softex kw.
In a word, solid matter can cause the fracture of chemical bond under mechanical force, produce unsalted surface, cause distortion of lattice and local failure and form various defect, cause increasing in some component in mineral simultaneously, reactivity strengthens, and makes solid matter be in unstable upper state, solid easily mild reaction conditions bring out realize difficult carry out solid-, solid-gas and solid-liquid chemical reaction.In addition, mechanical activation bentonite can make bentonite bed from, be beneficial to the raising of the immobilized of active component and supported quantity thereof.But have no the report being prepared Fenton-like heteropoly acid/bentonite compound catalyze material by mechanical activation modification bentonite at present.
Summary of the invention
The object of the invention is to overcome not high to heteropoly acid supported quantity, the immobilized unstable defect of iron-based bentonite, provide a kind of mechanical activation iron-based bentonite to strengthen and flood the method for adsorbing heteropoly acid and preparing Fenton-like catalysis heteropoly acid/iron bentonite compound catalyze material.In described heteropoly acid/iron bentonite compound catalyze material, heteropoly acid comprises phosphotungstic acid, tungstosilicic acid, molybdophosphate and molybdenum silicic acid, and its preparation method comprises the bentonitic preparation of iron-based, mechanical activation pretreatment iron-based bentonite, dipping absorption heteropoly acid.Concrete preparation method is as follows:
(1) iron-based bentonite preparation: bentonite is stirred the slurries being made as 3% ~ 5%, then with Fe
2+in ion and slurries, bentonite cation exchange total amount 1: 2 ratio adds ferrous sulfate heptahydrate.At 75 ~ 80 DEG C after constant temperature stirring reaction 2h, stratification discards supernatant liquor, dries, pulverized after lower floor's mud washing 100 mesh sieves, and obtained iron-based bentonite for subsequent use at 100 ~ 105 DEG C;
(2) mechanical activation pretreatment iron-based bentonite: iron-based bentonite step (1) prepared loads in the ball grinder of high energy ball mill, after adding abrasive media stainless steel abrading-ball, ball grinder is placed in ball mill, starter motor runs ball mill mechanical activation process iron-based bentonite, obtains the pretreated iron-based bentonite of mechanical activation after shutdown;
(3) dipping absorption heteropoly acid: take mechanical activation pretreatment iron-based bentonite prepared by 1.5 ~ 5.0g step (2) and be placed in crucible, under normal temperature, adopt equi-volume impregnating that the heteropoly acid aqueous solution being dissolved with 0.15 ~ 0.5g is dripped in iron-based bentonite, dropping limit, limit is stirred, dropwise rear standing 50 ~ 60min, take out after roasting 2 ~ 4h at Muffle furnace 320 ~ 350 DEG C, ground 100 mesh sieves get product.
As limitation of the invention further, described high energy ball mill adopts abrasive media stainless steel ball radius to be 2 ~ 8mm, charge ratio of media is 10% ~ 40% of grinding jar volume, and material ball ratio that activating pretreatment adopts is 0.02 ~ 0.08 (material quality/ball packing volume, gmL
-1), the time 20 ~ 40min of activating pretreatment, frequency 15 ~ 45Hz.
Beneficial effect of the present invention is:
(1) the present invention carries out process modification on the basis that traditional bentonite powder absorption method prepares heteropoly acid/bentonite composite material, by the bentonitic mechanical activation preprocessing process of iron-based, make iron-based bentonite under the mechanical force such as friction, collision, impact, shearing of abrasive media stainless steel ball, make some mechanical can be transformed into the interior energy of material, thus cause iron-based bentonite chemism to increase, make the absorption of heteropoly acid immobilized more abundant.
(2) the modifying iron based bentonite of mechanical activation of function admirable can be produced by controlling the frequency of mechanical activation equipment and reaction time etc., product prepared by follow-up modifying iron based bentonite adsorption thus---the catalytic performance of heteropoly acid/iron bentonite composite material is good, the product that relative non-mechanical activation pretreatment iron-based bentonite is directly prepared, the Fenton-like catalytic performance of the inventive method preparing product is improved significantly.In iron-based bentonite pretreatment modification process of the present invention, required mechanical activation equipment is simple, and easy and simple to handle, mechanical activation modification is with short production cycle, improves obviously products application performance.
Accompanying drawing explanation
The method flow diagram of heteropoly acid/iron bentonite composite material is prepared in the absorption of Fig. 1 mechanical activation pretreatment of the present invention iron-based bentonite dipping.
Detailed description of the invention
Following examples are to better illustrate that mechanical activation of the present invention is anticipated iron-based bentonite and improved impact to the Fenton-like catalytic performance of heteropoly acid/bentonite compound catalyze material, not limiting the scope of protection of the invention.
Embodiment 1
Be placed in 0.1L grinding jar by 1.5g iron-based bentonite in the present embodiment, abrasive media adopts the stainless steel ball of diameter 6mm, and steel ball heap volume is 30mL, and namely charge ratio of media is 30%, material ball ratio is 0.05gmL
-1.Arranging mechanical activation frequency is 15Hz, and soak time is 40min, prepares the pretreated iron-based bentonite of mechanical activation.Take distilled water as solvent, by the ratio that phosphotungstic acid and iron-based bentonite are 1: 10 in mass ratio, dripped on mechanical activation iron-based bentonite by equi-volume impregnating, dropping limit, limit is stirred, dropwise rear standing 1h, at Muffle furnace with 350 DEG C of roasting 3h, taking out and pulverizing 100 orders is catalysis material finished product.
Above-mentioned for 0.4g catalysis material is added in 50mL25mg/L orange N solution, at original pH, 0.8mL3%H
2o
2, under condition, in room temperature Fenton-like catalyzing oxidizing degrading orange N reaction 1h, be 56.3% to the clearance of orange N.The catalysis material of non-mechanical activation pretreated iron bentonite identical dipping absorption preparation, in the experiment of equal Fenton-like catalyzing oxidizing degrading orange N, is 44.8% to orange N clearance.Mechanical activation pretreatment makes the Fenton-like catalytic performance of prepared composite improve 11.5%.
Embodiment 2
Be placed in 0.1L grinding jar by 1.5g iron-based bentonite in the present embodiment, abrasive media adopts the stainless steel ball of diameter 6mm, and steel ball heap volume is 30mL, and namely charge ratio of media is 30%, material ball ratio is 0.05gmL
-1.Arrange mechanical activation frequency 45HZ, soak time is 40min, prepares the pretreated iron-based bentonite of mechanical activation.Take distilled water as solvent, by the ratio that phosphotungstic acid and iron-based bentonite are 1: 10 in mass ratio, dripped on mechanical activation iron-based bentonite by equi-volume impregnating, dropping limit, limit is stirred, dropwise rear standing 1h, at Muffle furnace with 350 DEG C of roasting 3h, taking out and pulverizing 100 orders is catalysis material finished product.
Above-mentioned for 0.4g catalysis material is added in 50mL25mg/L orange N solution, at original pH, 0.8mL3%H
2o
2, under condition, in room temperature Fenton-like catalyzing oxidizing degrading orange N reaction 1h, be 66.7% to the clearance of orange N.The catalysis material of non-mechanical activation pretreated iron bentonite identical dipping absorption preparation, in the experiment of equal Fenton-like catalyzing oxidizing degrading orange N, is 44.8% to orange N clearance.Mechanical activation pretreatment makes the Fenton-like catalytic performance of prepared composite improve 21.9%.
Embodiment 3
Be placed in 0.1L grinding jar by 1.5g iron-based bentonite in the present embodiment, abrasive media adopts the stainless steel ball of diameter 6mm, and steel ball heap volume is 20mL, and namely charge ratio of media is 20%, material ball ratio is 0.075gmL
-1.Arrange mechanical activation frequency 35HZ, soak time is 40min, prepares the pretreated iron-based bentonite of mechanical activation.Take distilled water as solvent, by the ratio that phosphotungstic acid and iron-based bentonite are 1: 10 in mass ratio, dripped on mechanical activation iron-based bentonite by equi-volume impregnating, dropping limit, limit is stirred, dropwise rear standing 1h, at Muffle furnace with 350 DEG C of roasting 3h, taking out and pulverizing 100 orders is catalysis material finished product.
Above-mentioned for 0.4g catalysis material is added in 50mL25mg/L orange N solution, at original pH, 0.8mL3%H
2o
2, under condition, in room temperature Fenton-like catalyzing oxidizing degrading orange N reaction 1h, be 60.0% to the clearance of orange N.The catalysis material of non-mechanical activation pretreated iron bentonite identical dipping absorption preparation, in the experiment of equal Fenton-like catalyzing oxidizing degrading orange N, is 44.8% to orange N clearance.Mechanical activation pretreatment makes the Fenton-like catalytic performance of prepared composite improve 15.2%.
Embodiment 4
Be placed in 0.1L grinding jar by 0.6g iron-based bentonite in the present embodiment, abrasive media adopts the stainless steel ball of diameter 6mm, and steel ball heap volume is 30mL, and namely charge ratio of media is 30%, material ball ratio is about 0.02gmL
-1.Arrange mechanical activation frequency 35HZ, soak time is 40min, prepares the pretreated iron-based bentonite of mechanical activation.Take distilled water as solvent, by the ratio that phosphotungstic acid and iron-based bentonite are 1: 10 in mass ratio, dripped on mechanical activation iron-based bentonite by equi-volume impregnating, dropping limit, limit is stirred, dropwise rear standing 1h, at Muffle furnace with 350 DEG C of roasting 3h, taking out and pulverizing 100 orders is catalysis material finished product.
Above-mentioned for 0.4g catalysis material is added in 50mL25mg/L orange N solution, at original pH, 0.8mL3%H
2o
2, under condition, in room temperature Fenton-like catalyzing oxidizing degrading orange N reaction 1h, be 57.4% to the clearance of orange N.The catalysis material of non-mechanical activation pretreated iron bentonite identical dipping absorption preparation, in the experiment of equal Fenton-like catalyzing oxidizing degrading orange N, is 44.8% to orange N clearance.Mechanical activation pretreatment makes the Fenton-like catalytic performance of prepared composite to 12.6%.
Embodiment 5
Diameter 6mm stainless steel abrading-ball is adopted to be abrasive media, at charge ratio of media 30%, material ball ratio 0.05gmL
-1, pre-activated time 30min, under activation frequency 35Hz condition, prepare mechanical activation pretreatment iron-based bentonite.Take distilled water as solvent, by the ratio that phosphotungstic acid and iron-based bentonite are 1: 10 in mass ratio, dripped on mechanical activation iron-based bentonite by equi-volume impregnating, dropping limit, limit is stirred, dropwise rear standing 1h, at Muffle furnace with 350 DEG C of roasting 3h, take out and pulverized 100 orders for preparing phosphotungstic acid/iron bentonite catalysis material finished product.Above-mentioned for 1.2g catalysis material is added in 50mL100mg/L orange N solution, at original pH, 0.8mL3%H
2o
2under condition, phosphotungstic acid/iron bentonite catalysis material is reclaimed after room temperature Fenton-like catalyzing oxidizing degrading orange N reaction 1h, catalysis material is reused again under same item Fenton catalyzing oxidizing degrading orange N reaction condition, reuse for three times in experiment and 91.3%, 83.2%, 79.6% is respectively to the oxidation removal rate of orange N, show that catalyst prepared by the method has higher stability.After using for three times, to catalysis material thermal regeneration, again can reach 89.4% to the oxidation removal rate of orange N, still reusable after showing catalyst regeneration.
Claims (2)
1. a mechanical activation pretreatment iron-based bentonite, the method of heteropoly acid/iron bentonite compound catalyze material prepared by strengthening dipping absorption heteropoly acid, it is characterized in that, first iron-based bentonite is prepared in the modification of swelling unmanufactured iron, then iron-based bentonite is carried out mechanical activation process, then by the iron-based bentonite dipping absorption heteropoly acid after process.Concrete preparation method is as follows:
(1) iron-based bentonite preparation: bentonite is stirred the slurries being made as 3% ~ 5%, then with Fe
2+in ion and slurries, bentonite cation exchange total amount 1: 2 ratio adds ferrous sulfate heptahydrate.At 75 ~ 80 DEG C after constant temperature stirring reaction 2h, stratification discards supernatant liquor, dries, pulverized after lower floor's mud washing 100 mesh sieves, and obtained iron-based bentonite for subsequent use at 100 ~ 105 DEG C;
(2) mechanical activation pretreatment iron-based bentonite: iron-based bentonite step (1) prepared loads in the ball grinder of high energy ball mill, after adding abrasive media stainless steel abrading-ball, ball grinder is placed in ball mill, starter motor runs ball mill mechanical activation process iron-based bentonite, obtains the pretreated iron-based bentonite of mechanical activation after shutdown;
(3) dipping absorption heteropoly acid: take mechanical activation pretreatment iron-based bentonite prepared by 1.5 ~ 5.0g step (2) and be placed in crucible, under normal temperature, adopt equi-volume impregnating that the heteropoly acid aqueous solution being dissolved with 0.15 ~ 0.5g is dripped in iron-based bentonite, dropping limit, limit is stirred, dropwise rear standing 50 ~ 60min, take out after roasting 2 ~ 4h at Muffle furnace 320 ~ 350 DEG C, ground 100 mesh sieves get product.
2. the method for heteropoly acid/iron bentonite compound catalyze material prepared by mechanical activation pretreatment iron-based bentonite dipping absorption heteropoly acid according to claim 1, it is characterized in that, described high energy ball mill adopts abrasive media stainless steel ball radius to be 2 ~ 8mm, charge ratio of media is 10% ~ 40% of grinding jar volume, material ball ratio that activating pretreatment adopts is 0.02 ~ 0.08 (material quality/ball packing volume, g.mL
-1), the time 20 ~ 40min of activating pretreatment, frequency 15 ~ 45Hz.
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| CN107282865A (en) * | 2017-08-30 | 2017-10-24 | 马鞍山市三川机械制造有限公司 | A kind of bentonitic Automobile flywheel casting sand of bismuth-containingization |
| CN108772109A (en) * | 2018-07-06 | 2018-11-09 | 中国科学院合肥物质科学研究院 | A kind of spherical molybdenum heteropoly tungstic acid salt catalyst of nano wire and the preparation method and application thereof |
| CN108772109B (en) * | 2018-07-06 | 2020-11-24 | 中国科学院合肥物质科学研究院 | Nanowire spherical molybdenum-tungsten heteropoly acid salt catalyst and preparation method and application thereof |
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Application publication date: 20160210 |