CN103769177A - Preparation method for attapulgite clay-based cycloaddition reaction catalyst - Google Patents
Preparation method for attapulgite clay-based cycloaddition reaction catalyst Download PDFInfo
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- CN103769177A CN103769177A CN201410046943.8A CN201410046943A CN103769177A CN 103769177 A CN103769177 A CN 103769177A CN 201410046943 A CN201410046943 A CN 201410046943A CN 103769177 A CN103769177 A CN 103769177A
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Abstract
The invention belongs to the field of catalyst preparation and in particular relates to a preparation method for an attapulgite clay-based solid catalyst for green catalytic Diels-Alder reaction (cycloaddition reaction). The preparation method comprises the steps of loading a proper amount of zinc chloride serving as a raw material into inner holes of attapulgite clay serving as a raw material by a solid-phase reaction method (a high-speed ball-grinding method), and then performing roasting activation to obtain a catalyst for synthesizing attapulgite clay-based C22-ring fat glycerol ester. The prepared solid catalyst is easily separated from a product, so that equipment corrosion and environment pollution are alleviated; in a loaded type catalyst, ZnCl2 and the surface of the attapulgite clay generate chemical bonding action to form a new amorphous substance; the activity of the amorphous substance is higher than a sum of the activity of the ZnCl2 and the activity of the attapulgite clay.
Description
Technical field
The invention belongs to catalyst preparation field, particularly a kind of preparation method of the Concave-convex clay rod base solid catalyst for green catalysis Diels-Alder reaction (cycloaddition reaction) use.
Background technology
Diels-Alder reaction is one of means of very important C―C bond formation in organic chemical synthesis reaction, is also one of reaction conventional in modern organic synthesis, has the meaning of particular importance in the synthetic field of medicine, spices and natural materials.For example, in chemical industry field, C22-cycloaliphatic three acid esters are reacted and are prepared from by Diels-Alder.C22-cycloaliphatic three acid esters be a class take various plants oil as raw material, utilize polyunsaturated fatty acid wherein, react the biological plasticizer synthesizing by Diels-Alder with maleate.Such plasticizer flash-point is high, and animal migration is little, and volatility is low, good with PVC compatibility, and PVC pliability and the durability of plasticising significantly improve.
Than phthalic ester plasticizer, (number of ways such as such as phthalic acid two (2-ethylhexyl) ester (DOP) can per os, respiratory tract, venous transfusion, skin absorption enters human body, to all toxic effects of the multiple systems of human body), C22-cycloaliphatic three acid esters are a kind of biodegradable and the nontoxic plasticizer product take living beings as raw material.
Document (stone mine etc., the catalytic action [J] of ZnCl2 to dissimilar Diels-Alder reaction. petrochemical industry, 1995,24(10): 726-728) report, be difficult to for some the Diels-Alder reaction of carrying out, use Lewis acid ZnCl
2make catalyst and can relax reaction condition, improve product yield, improve the stereoselectivity of reaction.But ZnCl
2as catalyst in use, not only difficulty and product separation, and can bring the problem such as equipment corrosion, environmental pollution.
Summary of the invention
Technical problem to be solved by this invention is: be difficult to for some the Diels-Alder reaction of carrying out, need to use Lewis acid ZnCl
2do the carrying out that catalyst promotes reaction, but ZnCl
2as catalyst in use, not only difficulty and product separation, and can bring the problem such as equipment corrosion, environmental pollution.
For solving this technical problem, the technical solution used in the present invention is: the invention provides and a kind ofly react for green catalysis Diels-Alder, Concave-convex clay rod base solid catalyst, specifically, that a kind of zinc chloride loads to the solid catalyst forming in Concave-convex clay rod, and ZnCl
2there is chemical bonding effect with the bore area of Concave-convex clay rod.
The present invention also provides a kind of preparation method of above-mentioned Concave-convex clay rod base solid catalyst, take Concave-convex clay rod (hereinafter to be referred as recessed soil), zinc chloride as raw material, adopt solid reaction process (high speed ball-milling method), zinc chloride is loaded among Concave-convex clay rod endoporus, then through calcination activation effect, obtain ZnCl
2/ recessed native loaded catalyst.
Concrete steps are:
(1) recessed soil being dried, is (5-20) in zinc chloride and recessed native mass ratio: 100 ratio, take respectively zinc chloride and recessed soil, and after mixing, add the ball grinder of ball mill, the grinding machine of kicking off carries out high speed ball milling, collects the powder after ball milling,
Here adopt planetary ball mill, the operation of high speed ball milling is specially: under argon atmospher protection and anhydrous and oxygen-free condition, and room temperature mechanical ball milling 0.5～10h, wherein, rotating speed is 580～1000rpm, and ratio of grinding media to material is 20:1～60:1, and the diameter of agate ball used is 5～20mm;
(2) after ball milling step (1) being obtained, powder moves into roasting kiln roasting, cooling, makes Concave-convex clay rod basic ring addition reaction catalyst (ZnCl
2/ recessed native loaded catalyst),
The baking operation here, refers at N
2under atmosphere, be warming up to the sintering temperature of 250-450 ℃ with the speed of 3-8 ℃/min, constant temperature calcining 2-8h.
Beneficial effect of the present invention is:
(1) use ZnCl
2/ recessed native supported solid catalyst, with directly use ZnCl
2compare as catalyst, catalyst separates with product is easy, has reduced equipment corrosion and environmental pollution;
(2) this method for preparing catalyst utilizes impact media in ball mill to carry out strong shock, grinding to raw material, play following 3 aspect effects: the one, feed particles size significantly reduces, comprise dissociation and the fracture of the brilliant bundle of attapulgite, the refinement of zinc chloride crystal grain; Two is that two kinds of raw materials are more mixing in small scale equably, thereby is conducive to the carrying out of solid phase reaction process; The 3rd, mechanical milling process causes the fracture of attapulgite surface texture Al, Mg-O-Si key, has increased plane of crystal defect, impels its surface to raise, active reinforcement.Method for preparing catalyst in the present invention, with conventional infusion process comparison, has saved the operating procedures such as dipping solution preparation and solvent evaporates, has not only saved solvent, and has reduced environmental pollution.
(3) in catalyst preparation process of the present invention, ZnCl
2loaded in the endoporus of recessed soil, and with the effect of recessed native inner surface generation chemical bonding, formed new amorphous substance (referring to accompanying drawing 1 and accompanying drawing 2), increased thus the acidic site quantity of catalyst inner surface, make ZnCl
2the activity of/recessed native loaded catalyst is greater than ZnCl
2the active simple sum of active and recessed soil.
(4) this method for preparing catalyst is simple, and production cost is low, is applicable to batch production.
Accompanying drawing explanation
Fig. 1: for the XRD spectra through the Concave-convex clay rod of 350 ℃ of activation (enters the recessed soil mud after drying in roaster, at N
2under atmosphere, be warming up to 350 ℃ with the speed of 5 ℃/min, constant temperature calcining 4h, cooling).
Fig. 2: in the embodiment of the present invention 5, (the ZnCl making
2support type) XRD spectra of Concave-convex clay rod basic ring addition reaction catalyst.
Comparison diagram 1 and Fig. 2, can find that a new spectrum peak has appearred in Fig. 2 at 2 θ=15.6 places, infers that according to document this peak is Zn (OH) Cl, checking ZnCl
2there is chemical bonding effect with recessed native inner surface, formed new amorphous substance.
The specific embodiment
Embodiment 1
1, take respectively 5 grams of after oven dry recessed native 100 grams, anhydrous zinc chloride, add the ball grinder of ball mill after mixing, the grinding machine of kicking off, moved after 0.5 hour, collected the powder after ball milling,
Here adopt planetary ball mill QM-1SP2, under argon atmospher protection and anhydrous and oxygen-free condition, carry out ball milling, rotating speed is 580rpm, and ratio of grinding media to material is 30:1, the diameter of agate ball used is the amount of the recessed soil of 10mm(and anhydrous zinc chloride mixture when larger, can carry out several times ball milling operation);
2, after ball milling step (1) being obtained, powder moves in roaster, at N
2under atmosphere, be warming up to 250 ℃ with the speed of 3 ℃/min, constant temperature calcining 2h, cooling, make ZnCl
2/ recessed native support type cycloaddition reaction catalyst.
1, take respectively 20 grams of after oven dry recessed native 100 grams, anhydrous zinc chloride, add the ball grinder of ball mill after mixing, the grinding machine of kicking off, moved after 10 hours, collected the powder after ball milling,
Here adopt planetary ball mill QM-1SP2, under argon atmospher protection and anhydrous and oxygen-free condition, carry out ball milling, rotating speed is 1000rpm, and ratio of grinding media to material is 60:1, the diameter of agate ball used is the amount of the recessed soil of 20mm(and anhydrous zinc chloride mixture when larger, can carry out several times ball milling operation);
2, after ball milling step (1) being obtained, powder moves in roaster, at N
2under atmosphere, be warming up to 250 ℃ with the speed of 8 ℃/min, constant temperature calcining 8h, cooling, make ZnCl
2/ recessed native support type cycloaddition reaction catalyst.
Embodiment 3
1, take respectively 15 grams of after oven dry recessed native 100 grams, anhydrous zinc chloride, add the ball grinder of ball mill after mixing, the grinding machine of kicking off, moved after 6 hours, collected the powder after ball milling,
Here adopt planetary ball mill QM-1SP2, under argon atmospher protection and anhydrous and oxygen-free condition, carry out ball milling, rotating speed is 840rpm, and ratio of grinding media to material is 40:1, the diameter of agate ball used is the amount of the recessed soil of 20mm(and anhydrous zinc chloride mixture when larger, can carry out several times ball milling operation);
2, after ball milling step (1) being obtained, powder moves in roaster, at N
2under atmosphere, be warming up to 250 ℃ with the speed of 5 ℃/min, constant temperature calcining 4h, cooling, make ZnCl
2/ recessed native support type cycloaddition reaction catalyst.
Embodiment 4
1, take respectively 15 grams of after oven dry recessed native 100 grams, anhydrous zinc chloride, add the ball grinder of ball mill after mixing, the grinding machine of kicking off, moved after 6 hours, collected the powder after ball milling,
Here adopt planetary ball mill QM-1SP2, under argon atmospher protection and anhydrous and oxygen-free condition, carry out ball milling, rotating speed is 900rpm, and ratio of grinding media to material is 20:1, the diameter of agate ball used is the amount of the recessed soil of 5mm(and anhydrous zinc chloride mixture when larger, can carry out several times ball milling operation);
2, after ball milling step (1) being obtained, powder moves in roaster, at N
2under atmosphere, be warming up to 450 ℃ with the speed of 5 ℃/min, constant temperature calcining 4h, cooling, make ZnCl
2/ recessed native support type cycloaddition reaction catalyst.
Embodiment 5
1, take respectively 15 grams of after oven dry recessed native 100 grams, anhydrous zinc chloride, add the ball grinder of ball mill after mixing, the grinding machine of kicking off, moved after 6 hours, collected the powder after ball milling,
Here adopt planetary ball mill QM-1SP2, under argon atmospher protection and anhydrous and oxygen-free condition, carry out ball milling, rotating speed is 720rpm, and ratio of grinding media to material is 20:1, the diameter of agate ball used is the amount of the recessed soil of 20mm(and anhydrous zinc chloride mixture when larger, can carry out several times ball milling operation);
2, after ball milling step (1) being obtained, powder moves in roaster, at N
2under atmosphere, be warming up to 350 ℃ with the speed of 5 ℃/min, constant temperature calcining 4h, cooling, make ZnCl
2/ recessed native support type cycloaddition reaction catalyst.
Comparative example 1
In comparative example 1, will in embodiment 5 steps 1, not add anhydrous zinc chloride, other operations are all identical with embodiment 5, and concrete operation step is as follows:
1, take recessed native 100 grams after oven dry, add the ball grinder of ball mill, the grinding machine of kicking off, moved after 6 hours, collected the powder after ball milling,
Here adopt planetary ball mill QM-1SP2, under argon atmospher protection and anhydrous and oxygen-free condition, carry out ball milling, rotating speed is 720rpm, and ratio of grinding media to material is 20:1, and the diameter of agate ball used is the amount of the recessed soil of 20mm(when larger, can carry out several times ball milling operation);
2, after ball milling step (1) being obtained, powder moves in roaster, at N
2under atmosphere, be warming up to 350 ℃ with the speed of 5 ℃/min, constant temperature calcining 4h, cooling, make Concave-convex clay rod basic ring addition reaction catalyst.
Comparative example 2
In comparative example 2, directly by anhydrous ZnCl
2as cycloaddition reaction catalyst.In catalyst catalytic performance test below, anhydrous ZnCl
2consumption and the ZnCl that makes of embodiment 5
2in/recessed native support type cycloaddition reaction catalyst, the ZnCl of institute's load
2amount equate.Other operations are all identical with embodiment 5.
Catalyst catalytic performance is evaluated
Below by catalytic performance test, to ZnCl
2the catalytic performance of/recessed native support type cycloaddition reaction catalyst is evaluated.Select the Diels--Alder of synthetic C22-cycloaliphatic three acid esters of biodiesel and dibutyl maleate react model reaction of this catalyst activity of (cycloaddition reaction) conduct evaluation, using the yield of C22-cycloaliphatic three acid esters as evaluation index.Result of the test is as shown in table 1:
Experimental procedure:
Take respectively 40g biodiesel, 12g dibutyl maleate and 4 grams of ZnCl
2/ recessed native support type cycloaddition reaction catalyst, adds in four neck flasks, stirs lower logical N
2the about 15min of gas deoxygenation, is warming up to 260 ℃, and back flow reaction 4h, removes heating jacket, at N
2under protection, be cooled to room temperature.Reactant liquor, after decompress filter is removed solid catalyst, can be used for analytical test.
Adopt the concentration C (g/mL) of C22-cycloaliphatic three acid esters in liquid chromatography for measuring reactant liquor, and calculate the productive rate y (%) of C22-cycloaliphatic three acid esters.
Formula is: y=(C/C
0) × 100
In above formula, C
0for methyl linoleate in reactant liquor, (methyl linoleate is the active ingredient for the synthesis of C22-cycloaliphatic three acid esters in biodiesel, its content adopts gas chromatography determination, by persons skilled in the art are known), theoretical concentration while being all converted into C22-cycloaliphatic three acid esters (
g/ mL).
Liquid-phase chromatographic analysis adopts U.S. ExFormma-600 high performance liquid chromatograph, chromatographic column XB-C8(4.6 × 250mm, and 5 μ are m); Mobile phase is acetonitrile and water, adopts gradient elution, and within initial 2 minutes, acetonitrile/water volume ratio is 65:35, starts to improve acetonitrile ratio after 2min, reaches 100% to 35min acetonitrile ratio, keeps ten minutes; 30 ℃ of column temperatures, flow velocity 1.0ml/min; Adopt UV-detector, detect wavelength 230nm; Sample size 20 μ l.
The catalytic performance experiment of comparative example 1 and comparative example 2, used catalyst is respectively the recessed soil of 3.48g and the anhydrous ZnCl2 of 0.52g, and all the other steps are the same.
As can be seen from Table 1, from embodiment 1 to embodiment 5, due to the ZnCl of catalyst
2load capacity difference and other preparation condition differences, the productive rate of C22-cycloaliphatic three acid esters that each embodiment is corresponding differs larger.The productive rate data of comparative example 5 and comparative example 1, comparative example 2, can find out ZnCl
2the activity of/recessed native loaded catalyst is greater than ZnCl
2the active simple sum of active and recessed soil, is used separately the catalyst of recessed soil as synthetic C22-cycloaliphatic three acid esters, and its activity is very low.
Table 1 Concave-convex clay rod basic ring addition reaction catalyst catalytic performance result of the test
Claims (4)
1. a preparation method for Concave-convex clay rod base solid catalyst, is characterized in that: described preparation method is, take Concave-convex clay rod, zinc chloride as raw material, adopt high speed ball-milling method, zinc chloride is loaded among Concave-convex clay rod endoporus, then, through calcination activation effect, obtain ZnCl
2/ recessed native loaded catalyst.
2. the preparation method of catalyst as claimed in claim 1, is characterized in that: described preparation method's concrete steps are,
(1) recessed soil being dried, is (5-20) in zinc chloride and recessed native mass ratio: 100 ratio, take respectively zinc chloride and recessed soil, and after mixing, add the ball grinder of ball mill, the grinding machine of kicking off carries out high speed ball milling, collects the powder after ball milling;
(2) after ball milling step (1) being obtained, powder moves into roasting kiln roasting, cooling, makes ZnCl
2/ recessed native loaded catalyst.
3. the preparation method of catalyst as claimed in claim 2; it is characterized in that: the high speed ball milling described in step (1); be specially employing planetary ball mill; under argon atmospher protection and anhydrous and oxygen-free condition; room temperature mechanical ball milling 0.5～10h, wherein, rotating speed is 580～1000rpm; ratio of grinding media to material is 20:1～60:1, and the diameter of agate ball used is 5～20mm.
4. the preparation method of catalyst as claimed in claim 2, is characterized in that: the roasting described in step (2), refers at N
2under atmosphere, be warming up to the sintering temperature of 250-450 ℃ with the speed of 3-8 ℃/min, constant temperature calcining 2-8h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569675A (en) * | 2018-11-27 | 2019-04-05 | 淮阴工学院 | A kind of recessed soil matrix loaded catalyst and the preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101444717A (en) * | 2008-12-05 | 2009-06-03 | 江苏工业学院 | Method for preparing concavo-convex rod soil/zinc oxide nanometer composite material |
| CN101816944A (en) * | 2009-03-14 | 2010-09-01 | 兰州理工大学 | Preparation method for solid acid catalyst for preparing diphenylmethane |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101444717A (en) * | 2008-12-05 | 2009-06-03 | 江苏工业学院 | Method for preparing concavo-convex rod soil/zinc oxide nanometer composite material |
| CN101816944A (en) * | 2009-03-14 | 2010-09-01 | 兰州理工大学 | Preparation method for solid acid catalyst for preparing diphenylmethane |
Non-Patent Citations (1)
| Title |
|---|
| 银董红等: "微波固相法制备ZnCl2/NaY催化剂 ZnCl2/NaY在月桂烯Diels-Alder反应中的催化性能", 《催化学报》, vol. 20, no. 4, 31 July 1999 (1999-07-31) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569675A (en) * | 2018-11-27 | 2019-04-05 | 淮阴工学院 | A kind of recessed soil matrix loaded catalyst and the preparation method and application thereof |
| CN109569675B (en) * | 2018-11-27 | 2021-11-12 | 淮阴工学院 | Attapulgite-based supported catalyst and preparation method and application thereof |
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