CN105772079A - Preparation method for immobilized dimethyl biguanide catalyst - Google Patents

Preparation method for immobilized dimethyl biguanide catalyst Download PDF

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Publication number
CN105772079A
CN105772079A CN201610205390.5A CN201610205390A CN105772079A CN 105772079 A CN105772079 A CN 105772079A CN 201610205390 A CN201610205390 A CN 201610205390A CN 105772079 A CN105772079 A CN 105772079A
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catalyst
carrier
dimethylbiguanide
preparation
sba
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谢文磊
韩玉香
王宏雁
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Henan University of Technology
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Henan University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange

Abstract

The invention discloses a preparation method for an immobilized dimethyl biguanide catalyst. The preparation method comprises the following steps: firstly, soaking carrier SiO2 in acetone, separating and drying for pre-treating or mixing with polyoxyethylene-polyoxypropylene-polyoxyethylene, deionized water and hydrochloric acid; dropwise adding tetraethoxysilane and then stirring; crystallizing and drying; calcining to obtain a mesoporous SBA-15 molecular sieve carrier; adding SiO2 or SBA-15 molecular sieve into xylene; uniformly stirring and then dropwise adding 3-gamma-chloropropyl trimethoxysilane for completely reacting; separating solid from liquid and extracting with methylbenzene, thereby acquiring a chloropropyl group functionalized carrier; adding the chloropropyl group functionalized carrier, potassium iodide, dimethyl biguanide hydrochloride and NaOH into a reaction kettle; adding an acetonitrile solvent; stirring for reacting; performing solid-liquid separation; drying to obtain the end product of immobilized dimethyl biguanide catalyst with the capacity of dimethyl biguanide being 0.01-0.022 mmol/g. The preparation method is simple in technique; the end product of the catalyst still can keep higher catalytic activity after being reused for several times and can be reused; the production cost is lowered.

Description

A kind of preparation method of immobilized dimethylbiguanide catalyst
Technical field
The present invention relates to oil and fat chemical and Application in Chemical Engineering field, especially relate to a kind of for preparing the immobilized of biodiesel The preparation method of dimethylbiguanide catalyst.
Background technology
Along with petroleum resources peter out, automobile exhaust pollution day by day seriously with the continuous aggravation of greenhouse effect, Ren Menkai Begin to find the renewable green energy resource substituting fossil energy.Biodiesel is to be former with renewable biological source such as animal and plant fats The clean biometric fuel that can be used for compression ignition engine that material is transformed, because it has the feature of environmental protection and recyclability, causes World Developed Countries, particularly the great attention of natural resources shortage country, becomes the alternative fuel of preferable petrifaction diesel.Send out energetically Exhibition biodiesel, for sustainable development, advances energy substitution and diversification, alleviates environmental pollution pressure etc. and have important war Slightly meaning.
Industrial in the presence of base catalyst, carry out the ester exchange biological bavin of preparation frequently with animal and plant fat and excessive methanol Oil.In the prior art, conventional catalyst is that alkali metal hydroxide or Feldalat NM etc. that in methanol, dissolubility is bigger are equal Phase catalyst, its catalysis activity is relevant with basicity.But, these homogeneous catalysts are complicated, in needs with the separation process of product With separating steps such as, washings, produce a large amount of waste water simultaneously, and isolated homogeneous catalyst can not recycling.
The problems such as the catalyst difficulty separation caused to solve homogeneous catalysis stearic to exchange, develop easily separated and recyclable The heterogeneous catalyst utilized just becomes one of study hotspot.Heterogeneous catalysis neutralizes after avoiding reaction and the process such as washing, does not produces Raw a large amount of waste water, free from environmental pollution, and also catalyst can reuse.It is presently used for heterogeneous catalysis method and prepares biodiesel Solid base catalyst to be mainly supported complex oxide with alkali and alkaline earth metal ions oxide as active component heterogeneous Catalyst.
During preparation biodiesel, bio-oil and methanol ester exchange are reversible reaction.In order to obtain higher yields, methanol needs More excess, this just makes ester exchange carry out under the conditions of highly polar, thus creates heterogeneous catalyst stability in this system With problems such as reusabilities.Research shows, urges the multiphase solid alkali of most of carrying alkali metals and alkaline earth oxide From the point of view of agent, although there is catalysis activity high, the advantages such as reaction condition is gentle, but there is active component dissolution in polar system Make the problems such as bad stability, and dissolution component also affects the product quality of biodiesel.
Biguanide Organic substance belongs to Lewis highly basic, can dissolve in organic reaction system, belongs to homogenous alkali catalyst, instead It is difficult to after should separate with product, it is impossible to recycling.In recent years, the porous such as solid carrier material develops quickly, such as SBA-15 The application that carrier material prepares aspect at catalyst gets more and more.If Lewis organic alkali is fixed on height by chemical bond On specific surface carrier, catalyst performance can be improved by cooperative effect, it would be possible to find that novel stearic exchange is heterogeneous Catalyst.Such as, organic alkali is loaded to SBA-15 surface, while SBA-15 molecular sieve is carried out alkalescence modification, also Maintain order mesoporous regular texture and higher specific surface area, improve the dispersion of active site, thus increase Catalytic efficiency.
Therefore, in order to improve heterogeneous catalyst activity in this reaction system and stability, these biguanide can be had Machine highly basic loads on porous carrier, thus prepares novel hybrid inorganic-organic materials catalyst.Will by chemical bond force Organic base binds strongly on porous carrier materials, can effectively prevent loss of active component, improve catalyst Stability.The catalyst prepared can use simple filtration method to separate from product, more excellent than homogeneous reaction technique has Gesture, improves production efficiency.Catalyst remains to keep higher catalytic activity after being used repeatedly, and recyclable reuses, Reduce production cost.
Summary of the invention
It is an object of the invention to provide when a kind of heterogeneous catalysis method prepares biodiesel as bio-oil and methanol ester Exchange base catalyst---the preparation method of-immobilized dimethylbiguanide catalyst.
For achieving the above object, the present invention can take following technical proposals:
The preparation method of immobilized dimethylbiguanide catalyst of the present invention comprises the steps:
The first step, carrier S iO2Pretreatment or the preparation of SBA-15
Carrier S iO2Pretreatment: by commodity SiO2Soak 24h, solid-liquid separation in acetone, then solid is put into 110 DEG C of baking oven The most standby；
The preparation of carrier S BA-15: by 5g polyoxyethylene-poly-oxypropylene polyoxyethylene, 38ml deionized water, the hydrochloric acid of 2mol/L 500ml adds in beaker together, stirs 6h at a temperature of 40 DEG C；Then it is added dropwise over 10.5g tetraethyl orthosilicate, continues stirring 24h, then mixed solution is forwarded in rustless steel still, put into crystallization 48h under the conditions of 100 DEG C of baking oven；Question response still cools down, sucking filtration, After fully washing with deionized water, product is dried at room temperature for, then 550 DEG C of calcining 6h in Muffle furnace, obtains mesoporous SBA-15 Molecular sieve is standby；When industrialized production, material used can amplify in proportion；
Second step, SiO2Or the functional modification of SBA-15 molecular sieve
By a certain amount of pretreated carrier S iO2Or SBA-15 molecular sieve, dimethylbenzene add in reactor, under room temperature, stirring is all Even, then in reactor, it is slowly added dropwise 3-r-chloropropyl trimethoxyl silane, then mixture being stirred at 80 DEG C, question response is tied Bundle, is cooled to room temperature by reactor, and solid-liquid separation removes xylene solution, and solid matter toluene extracts 24h, obtains after drying Chloropropyl functionalised supports；
3rd step, dimethylbiguanide immobilized
Chloropropyl functionalised supports, potassium iodide, hydrochloride base biguanide and NaOH are put into reactor, then adds in reactor Acetonitrile solvent, then reacts at acetonitrile stirred under reflux temperature, and reaction is cooled to room temperature, solid-liquid separation after terminating, then spend from Solid matter is washed for several times by sub-water and ethanol respectively, at a temperature of being placed in 80 DEG C after vacuum drying, obtains dimethylbiguanide load Amount is the immobilized dimethylbiguanide finished catalyst of 0.01 ~ 0.022mmol/g.
Wherein in second step the inventory of each material by following weight:
Carrier: dimethylbenzene: 3-r-chloropropyl trimethoxyl silane=1:40 ~ 100:1 ~ 7；Wherein the weight portion of dimethylbenzene is preferably 50 ~ 80, most preferably 70；The weight portion of 3-r-chloropropyl trimethoxyl silane is preferably 2 ~ 5.
In 3rd step, the inventory of each material is by following weight:
Carrier: potassium iodide: hydrochloride base biguanide: NaOH: acetonitrile=1:0.71:0.17 ~ 0.25:0.8:40 ~ 60；Wherein hydrochloric acid The weight portion of dimethylbiguanide is preferably 0.20 ~ 0.22.
The present invention, will in order to improve heterogeneous catalyst activity in oils and fats and methanol ester exchange reaction system and stability Biguanide organic alkali is firmly loaded on porous carrier materials by chemical bond force, effectively prevent loss of active component, Improve the stability of catalyst, the method for simple filtration can be used to separate from product, ratio homogeneous reaction technique simultaneously There is greater advantage, improve production efficiency.Catalyst remains to keep higher catalytic activity after being used repeatedly, recyclable heavy Multiple use, reduces production cost.
The advantage of immobilized dimethylbiguanide finished catalyst prepared by the present invention be mainly reflected in following some:
1, inorganic material SiO containing surface hydroxyl is used2Or the immobilized dimethylbiguanide of SBA-15, ultimate load up to 0.022mmol/g, i.e. this porous carrier can the most immobilized dimethylbiguanide.
2, the present invention carrier is carried out modified by chloropropyl by and to dimethylbiguanide immobilized time, remain the mesoporous hole of carrier The specific surface area of road structure or higher, is conducive to increasing the dispersion of active catalyst sites, thus improves catalytic efficiency.
3, the active site of catalyst of the present invention and the connection of carrier are first with chloropropyl silylating reagent pair Carrier surface is chemically modified, and then by chemical bond, dimethylbiguanide is anchored on carrier surface, thus generates stable The solid base catalyst that property is good, can reclaim and reuse.
4, catalyst of the present invention and intermediate product can realize solid-liquid separation by conventional method, and preparation process is simple, catalysis Activity is high.
5, catalyst of the present invention does not has corrosivity, environmentally safe to reaction vessel.
Accompanying drawing explanation
Fig. 1 is the preparation method flow chart of the present invention.
Fig. 2 is used carrier of the present invention and the infrared absorpting light spectra of the immobilized dimethylbiguanide of carrier.
Detailed description of the invention
Preparation method flow process of the present invention is as shown in Figure 1.
Below by specific embodiment, the present invention done more detailed explanation, but the invention is not limited in following enforcement Example.Unless otherwise indicated, the present invention uses reagent and equipment are that the art routine is commercial.
Embodiment 1
(1)SiO2The pretreatment of carrier
By commercially available for 10g SiO2Silica gel is put in the beaker of 100mL, adds 60mL acetone, makes SiO2It is totally submerged in acetone, puts Put 24h, filter, then with washing with acetone 3 times, put in baking oven dry 5h under the conditions of 110 DEG C.
(2) SiO2The functional modification of carrier
Take the treated dry SiO of 5g2Pour in 500mL round-bottomed flask, add 250g dimethylbenzene, after stirring 15min, then In flask, it is slowly added dropwise the 3-r-chloropropyl trimethoxyl silane of 7.54g, at 80 DEG C, then stirs 6h.After being cooled to room temperature, Filter, product is used the method for soxhlet type with toluene for solvent extraction 24h, then 80 DEG C of dry 12h under vacuum, can Prepare chloropropyl functionalization SiO2Carrier (Cl-pr-SiO2).
(3) immobilization of dimethylbiguanide
Support C l-pr-SiO by 10g chloropropyl functionalization2, 7.1gKI, 1.7g hydrochloride base biguanide, 8g NaOH puts into In round-bottomed flask, add 500g acetonitrile, at acetonitrile stirred under reflux temperature 5h.Reaction is cooled to room temperature after terminating, and filters, then uses Deionized water and ethanol wash 3 times respectively, are placed in the vacuum drying oven of 80 DEG C and are dried 6h, can prepare catalyst 1#.Experiment is surveyed Obtaining the load capacity of dimethylbiguanide in this catalyst is 0.013 mmol/g.
In Fig. 2, a, b are respectively SiO2(a) and solid catalyst 1#(b) infrared absorpting light spectra.It is seen that At SiO2Infrared spectrogram (a) in, at 3650cm-1Near and 3460cm-1Near occur in that wider absworption peak, can return respectively The stretching vibration belonging to OH absorbs.1635cm-1Neighbouring absworption peak is attributed to the vibration absorption peak of water.950cm-1Neighbouring suction Receiving peak is caused by Si-OH group vibration.Additionally, 465cm-1、770cm-1And 1100cm-1The neighbouring IR absworption peak occurred is returned respectively Belong to symmetrical stretching vibration and the asymmetrical stretching vibration of Si-O-Si group.With carrier S iO2Compare, SiO2Immobilized dimethyl is double Guanidine sample is at 465cm-1、770cm-1And 1100cm-1Neighbouring Si-O-Si absworption peak substantially weakens, 3650cm-1Neighbouring absorption Peak and 950cm-1Neighbouring Si-OH group vibration absworption peak disappears, and illustrates that Si-OH group and functionalized reagent there occurs instead Should.Additionally, at 1350cm-1The neighbouring new absworption peak occurred, owing to the absorption of vibrations of C-N；At 2850cm-1And 2930cm-1Attached Near there is new absworption peak, is due to-CH respectively2-symmetrical stretching vibration and asymmetrical stretching vibration absorb.The most infrared figure Analysis of spectrum result shows, dimethylbiguanide is the most successfully covalently bonded to SiO2Surface.
Embodiment 2
(1)SiO2The pretreatment of carrier is with embodiment 1.
(2) SiO2The functional modification of carrier
Take the treated dry SiO of 5g2Pour in the round-bottomed flask of 500mL, add 250g dimethylbenzene, after stirring 15min, In flask, it is slowly added dropwise the 3-r-chloropropyl trimethoxyl silane of 8.60g again, at 80 DEG C, then stirs 6h.It is cooled to room temperature After, filter, product is used the method for soxhlet type with toluene for solvent extraction 24h, more under vacuum 80 DEG C of temperature Under be dried 12h, chloropropyl functionalization SiO can be prepared2Carrier (Cl-pr-SiO2).
(3) immobilization of dimethylbiguanide
Take support C l-pr-SiO of 10g chloropropyl functionalization2, 7.1gKI, 1.9g hydrochloride base biguanide, 0.8g NaOH puts into In round-bottomed flask, add the acetonitrile of 500g, at acetonitrile stirred under reflux temperature 5h.Reaction is cooled to room temperature after terminating, and filters, then Wash respectively 3 times with deionized water and ethanol, be placed in 80 DEG C of vacuum drying ovens and be dried 6h, catalyst 2# can be prepared.Experiment is surveyed Obtaining the load capacity of dimethylbiguanide in this catalyst is 0.016mmol/g.
Embodiment 3
(1) SiO2The pretreatment of carrier is with embodiment 1.
(2) SiO2The functional modification of carrier
Take the treated dry SiO of 5g2Pour in the round-bottomed flask of 500mL, add 250g dimethylbenzene, after stirring 15min, In flask, it is slowly added dropwise the 3-r-chloropropyl trimethoxyl silane of 9.69g again, at 80 DEG C, then stirs 6h.It is cooled to room temperature After, filter, product is used the method for soxhlet type with toluene for solvent extraction 24h, more under vacuum 80 DEG C be dried 12h, can prepare chloropropyl functionalization SiO2Carrier (Cl-pr-SiO2).
(3) immobilization of dimethylbiguanide
Support C l-pr-SiO by 10g chloropropyl functionalization2, 7.1gKI, 2.1g hydrochloride base biguanide, 8g NaOH puts into In round-bottomed flask, add 500g acetonitrile, at acetonitrile stirred under reflux temperature 5h.Reaction is cooled to room temperature after terminating, and filters, then uses Deionized water and ethanol wash 3 times respectively, are placed in the vacuum drying oven of 80 DEG C and are dried 6h, can prepare catalyst 3#.Experiment is surveyed Obtaining the load capacity of dimethylbiguanide in this catalyst is 0.017mmol/g.
Embodiment 4
(1)SiO2The pretreatment of carrier is with embodiment 1.
(2)SiO2The functional modification of carrier
Take the treated dry SiO of 5g2Pour in the round-bottomed flask of 500mL, add 250g dimethylbenzene, after stirring 15min, In flask, it is slowly added dropwise the 3-r-chloropropyl trimethoxyl silane of 10.77g again, at 80 DEG C, then stirs 6h.It is cooled to room temperature After, filter, product is used the method for soxhlet type with toluene for solvent extraction 24h, more under vacuum at a temperature of 80 DEG C It is dried 12h, chloropropyl functionalization SiO can be prepared2Carrier (Cl-pr-SiO2).
(3) immobilization of dimethylbiguanide
Support C l-pr-SiO by 10g chloropropyl functionalization2, 7.1gKI, 2.3g hydrochloride base biguanide, 8g NaOH puts into In round-bottomed flask, add 500g acetonitrile, at acetonitrile stirred under reflux temperature 5h.Reaction is cooled to room temperature after terminating, and filters, then uses Deionized water and ethanol wash 3 times respectively, are placed in the vacuum drying oven of 80 DEG C and are dried 6h, can prepare catalyst 4#.Experiment is surveyed Obtaining the load capacity of dimethylbiguanide in this catalyst is 0.019mmol/g.
Embodiment 5
(1)SiO2The pretreatment of carrier is with embodiment 1.
(2)SiO2The functional modification of carrier
Take the treated dry SiO of 5g2Pour in the round-bottomed flask of 500mL, add 250g dimethylbenzene, after stirring 15min, In flask, it is slowly added dropwise the 3-r-chloropropyl trimethoxyl silane of 11.84g again, at 80 DEG C, then stirs 6h.It is cooled to room temperature After, filter, product uses the method for soxhlet type with toluene for solvent extraction 24h drier at 80 DEG C under vacuum 12h, can prepare chloropropyl functionalization SiO2Carrier (Cl-pr-SiO2).
(3) immobilization of dimethylbiguanide
Support C l-pr-SiO by 10g chloropropyl functionalization2, 7.1gKI, 2.5g hydrochloride base biguanide, 8g NaOH puts into circle In end flask, add 500g acetonitrile, at acetonitrile stirred under reflux temperature 5h.Reaction is cooled to room temperature after terminating, and filters, then spends Ionized water and ethanol wash 3 times respectively, are placed in the vacuum drying oven of 80 DEG C and are dried 6h, can prepare catalyst 5#.Experiment records In this catalyst, the load capacity of dimethylbiguanide is 0.020mmol/g.
Embodiment 6
(1) preparation of SBA-15 carrier
By 5g polyoxyethylene-poly-oxypropylene polyoxyethylene (P123), 38mL deionized water, the hydrochloric acid 150mL of 2mol/L joins In beaker, at 40 DEG C, stir 6 h, then be added dropwise over 10.5g tetraethyl orthosilicate (TEOS), continue stirring 24h, mixing.So After, solution is forwarded in the rustless steel still with politef as liner, put into baking oven crystallization 48h under the conditions of 100 DEG C, treat anti- Answer still to cool down, filter, be washed with deionized 6 times, be dried at room temperature for, then 550 DEG C of temperature lower calcination 6h in Muffle furnace, Activation SBA-15 mesopore molecular sieve can be prepared.
(2) functionalized modification of SBA-15 carrier
Take 4g SBA-15 to pour in 500mL round-bottomed flask, then in flask, add 200g dimethylbenzene, be stirred at room temperature 15min, then it is added thereto to 15.08g 3-r-chloropropyl trimethoxyl silane, continue mixed solution at 80 DEG C to stir 6h.Official After energyization is modified, reactant mixture is cooled to room temperature, filters, then extracts 24h with toluene for solvent apparatus,Soxhlet's.Product exists It is dried at a temperature of 80 DEG C in vacuum drying oven, chloropropylation mesoporous molecular sieve SBA-15 can be prepared.
(3) immobilization of dimethylbiguanide
By the Cl-pr-SBA-15 carrier after 1g modified by chloropropyl by, 0.71gKI, 0.17g hydrochloride base biguanide, 0.8gNaOH Add in 250mL round-bottomed flask, add 50g acetonitrile, at acetonitrile stirred under reflux temperature 5h.After reaction terminates, it is cooled to room Temperature, washs 3 times with deionized water and ethanol after filtration more respectively, and then 80 DEG C of vacuum drying 6h, can prepare catalyst 6#.Experiment Recording the load capacity of dimethylbiguanide in this catalyst is 0.014mmol/g.
In Fig. 2, c, d are respectively SBA-15(c) and solid catalyst 6#(d) infrared absorpting light spectra.It can be seen that In the infrared absorpting light spectra (c) of SBA-15,465cm-1、770cm-1And 1100cm-1The neighbouring absworption peak occurred, belongs to respectively Symmetrical stretching vibration and asymmetrical stretching vibration in Si-O-Si group absorb, and are positioned at 950cm-1Absworption peak belong to Si-OH Vibration peak.Additionally, at 3460cm-1Near occur in that wider absworption peak, attribution is the stretching vibration peak of-OH group.SBA- 15 immobilized dimethylbiguanide samples are at 2850cm-1And 2930cm-1Near occur in that new absworption peak, be respectively-CH2-symmetry stretch Contracting vibration and asymmetrical stretching vibration peak.1350cm-1The neighbouring new absworption peak occurred belongs to the vibration of C-N, 675cm-1Near The bending vibration peak of new absworption peak correspondence N-H group.Additionally, compared with carrier S BA-15,465cm-1、770cm-1With 1100cm-1Neighbouring Si-O-Si absworption peak substantially weakens, 3640cm-1Neighbouring-OH stretching vibration absworption peak the most substantially weakens, 950cm-1The vibration absorption peak of Si-OH group disappear, illustrate that Si-OH group and functionalized reagent there occurs reaction.Above The results of FT-IR shows, dimethylbiguanide the most successfully loads to mesoporous SBA-15 molecular sieve surface.
Embodiment 7
(1) preparation of SBA-15 carrier is with embodiment 6.
(2) functional modification of SBA-15 carrier
Take 4g SBA-15 to pour in 500mL round-bottomed flask, then in flask, add 200g dimethylbenzene, be stirred at room temperature 15min, then it is added thereto to 16.16g 3-r-chloropropyl trimethoxyl silane, continue mixed solution at 80 DEG C to stir 6h.Official After energyization is modified, reactant mixture is cooled to room temperature, filters, then extracts 24h with toluene for solvent apparatus,Soxhlet's.Product exists It is dried at a temperature of 80 DEG C in vacuum drying oven, chloropropylation mesoporous molecular sieve SBA-15 can be prepared.
(3) immobilization of dimethylbiguanide
By the Cl-pr-SBA-15 carrier after 1g modified by chloropropyl by, 0.71gKI, 0.19g hydrochloride base biguanide, 0.8gNaOH Add in 250mL round-bottomed flask, add 50g acetonitrile, at acetonitrile stirred under reflux temperature 5h.After reaction terminates, it is cooled to room Temperature, washs respectively 3 times with deionized water and ethanol after filtration again, is then vacuum dried 6h at 80 DEG C, can prepare catalyst 7#. It is 0.017mmol/g that experiment records the load capacity of dimethylbiguanide in this catalyst.
Embodiment 8
(1) preparation of SBA-15 carrier is with embodiment 6.
(2) functional modification of SBA-15 carrier
Take 4g SBA-15 to pour in 500mL round-bottomed flask, then in flask, add 200g dimethylbenzene, be stirred at room temperature 15min, then it is added thereto to 17.23g3-r-chloropropyl trimethoxyl silane, continue mixed solution at 80 DEG C to stir 6h.Official After energyization is modified, reactant mixture is cooled to room temperature, filters, then extracts 24h with toluene for solvent apparatus,Soxhlet's.Product exists In vacuum drying oven, 80 DEG C are dried, and can prepare chloropropylation mesoporous molecular sieve SBA-15.
(3) immobilization of dimethylbiguanide
By the Cl-pr-SBA-15 carrier after 1g modified by chloropropyl by, 0.71gKI, 0.21g hydrochloride base biguanide, 0.8gNaOH Add in 250mL round-bottomed flask, add 50g acetonitrile, at acetonitrile stirred under reflux temperature 5h.After reaction terminates, it is cooled to room Temperature, washs respectively 3 times with deionized water and ethanol after filtration again, is then dried 6h at 80 DEG C in vacuum drying, can prepare Catalyst 8#.It is 0.018mmol/g that experiment records the load capacity of dimethylbiguanide in this catalyst.
Embodiment 9
(1) preparation of SBA-15 carrier is with embodiment 6.
(2) functional modification of SBA-15 carrier
Taking 4g SBA-15 to pour in 500mL round-bottomed flask, then add 200g in flask, dimethylbenzene is stirred at room temperature 15min, then it is added thereto to 18.31g3-r-chloropropyl trimethoxyl silane, continue mixed solution at 80 DEG C to stir 6h.Official After energyization is modified, reactant mixture is cooled to room temperature, filters, then extracts 24h with toluene for solvent apparatus,Soxhlet's.Product exists It is dried at a temperature of 80 DEG C in vacuum drying oven, chloropropylation mesoporous molecular sieve SBA-15 can be prepared.
(3) immobilization of dimethylbiguanide
By the Cl-pr-SBA-15 carrier after 1g modified by chloropropyl by, 0.71gKI, 0.23g hydrochloride base biguanide, 0.8gNaOH Add in 250mL round-bottomed flask, add 50g acetonitrile, at acetonitrile stirred under reflux temperature 5h.After reaction terminates, it is cooled to room Temperature, washs respectively 3 times with deionized water and ethanol after filtration again, is then dried 6h at 80 DEG C in vacuum drying, can prepare Catalyst 9#.It is 0.020mmol/g that experiment records the load capacity of dimethylbiguanide in this catalyst.
Embodiment 10
(1) preparation of SBA-15 carrier is with embodiment 6.
(2) functional modification of SBA-15 carrier
Take 4g SBA-15 to pour in 500mL round-bottomed flask, then in flask, add 200g dimethylbenzene, be stirred at room temperature 15min, then it is added thereto to 19.38g3-r-chloropropyl trimethoxyl silane, continue mixed solution at 80 DEG C to stir 6h.Official After energyization is modified, reactant mixture is cooled to room temperature, filters, then extracts 24h with toluene for solvent apparatus,Soxhlet's.Product exists In vacuum drying oven, 80 DEG C are dried, and can prepare chloropropylation mesoporous molecular sieve SBA-15.
(3) immobilization of dimethylbiguanide
By the Cl-pr-SBA-15 carrier after 1g modified by chloropropyl by, 0.71gKI, 0.25g hydrochloride base biguanide, 0.8gNaOH Add in 250mL round-bottomed flask, add 50g acetonitrile, at acetonitrile stirred under reflux temperature 5h.After reaction terminates, it is cooled to room Temperature, washs respectively 3 times with deionized water and ethanol after filtration again, is then dried 6h at 80 DEG C in vacuum drying, can prepare Catalyst 10#.It is 0.022mmol/g that experiment records the load capacity of dimethylbiguanide in this catalyst.
Embodiment 11
Catalyst activity test (soybean oil and the ester exchange reaction of methanol)
Use immobilized dimethylbiguanide catalyst prepared by the present invention, use batch reactor with soybean oil and methanol for raw material Preparation biodiesel: 50g soybean oil and 55g methanol are added reactor, adds the immobilized dimethylbiguanide of soybean oil 5wt.% Catalyst, (65 DEG C) atmospheric agitation reaction 6h under methanolic reflux temperature, mixing speed is 460rpm.Reaction is cooled to after terminating Room temperature, filtering catalyst, methanol is steamed by decompression, and the methanol steamed is applied mechanically.Then, by centrifugal method, glycerol is separated, produce The thing conversion ratio of gas chromatography detection fatty acid methyl ester.The catalyst that table 1 is prepared for embodiment 1-10 is applied to soybean oil With conversion ratio during methanol ester exchange reaction.
Table 1
。
As can be seen from Table 1, with SiO2Catalyst activity for carrier does not has the catalyst with SBA-15 as carrier to live Property high, this is owing to the specific surface area of SBA-15 compares SiO2Height, such that it is able to load more dimethylbiguanide active center, It is made to be catalyzed increased activity.
Embodiment 12
The recycling of catalyst
50g soybean oil and 55g methanol are added reactor, adds the solid catalyst 3# of soybean oil 5wt.%, at methanol eddy At a temperature of (65 DEG C) atmospheric agitation reaction 6h, mixing speed is 460rpm.Reaction is cooled to room temperature, solid catalyst warp after terminating Filter after separating, wash respectively 3 times with normal hexane and ether, at 80 DEG C, be vacuum dried after 5h once reaction (reaction on being used for Condition is identical with when using first) so this catalyst is reused 5 times (when catalytic amount deficiency, return with parallel test Receive catalyst make-up).Product post-processing approach and fatty acid methyl ester conversion rate assay method are with embodiment 11.Catalyst 3# Recycling test result see table 2
Table 2:
。
Embodiment 13
The recycling of catalyst
50g soybean oil and 55g methanol are added reactor, adds the solid catalyst 8# of soybean oil 5wt.%, at methanol eddy At a temperature of (65 DEG C) atmospheric agitation reaction 6h, mixing speed is 460rpm.Reaction is cooled to room temperature, solid catalyst warp after terminating Filter after separating, wash respectively 3 times with normal hexane and ether, at 80 DEG C, be vacuum dried after 5h once reaction (reaction on being used for Condition is identical with when using first) so this catalyst is reused 5 times (when catalytic amount deficiency, return with parallel test Receive catalyst make-up).Product post-processing approach and fatty acid methyl ester conversion rate assay method are with embodiment 11.Catalyst 8# Recycling test result is shown in Table 3.
Table 3:
。
From table 2, table 3 it can be seen that catalyst 3# and 8# is after reusing 5 times, fatty acid methyl ester conversion rate only from 86.5% and 89.5% is down to 76.2% and 76.3%, and its catalysis activity is the highest, can use continuously, fall in intermittent reaction device Low production cost.

Claims (3)

1. the preparation method of an immobilized dimethylbiguanide catalyst, it is characterised in that: comprise the steps:
The first step, carrier S iO2Pretreatment or the preparation of SBA-15
Carrier S iO2Pretreatment: by commodity SiO2Soak 24h, solid-liquid separation in acetone, then solid is put into 110 DEG C of baking oven The most standby；
The preparation of carrier S BA-15: by 5g polyoxyethylene-poly-oxypropylene polyoxyethylene, 38mL deionized water, the hydrochloric acid of 2mol/L 500mL adds in beaker together, stirs 6h at a temperature of 40 DEG C；Then it is added dropwise over 10.5g tetraethyl orthosilicate, continues stirring 24h, then mixed solution is forwarded in rustless steel still, put into crystallization 48h under the conditions of 100 DEG C of baking oven；Question response still cools down, sucking filtration, After fully washing with deionized water, product is dried at room temperature for, then 550 DEG C of calcining 6h in Muffle furnace, obtains mesoporous SBA-15 Molecular sieve is standby；
Second step, SiO2Or the functional modification of SBA-15 molecular sieve
By a certain amount of pretreated carrier S iO2Or SBA-15 molecular sieve, dimethylbenzene add in reactor, under room temperature, stirring is all Even, then in reactor, it is slowly added dropwise 3-r-chloropropyl trimethoxyl silane, then mixture being stirred at 80 DEG C, question response is tied Bundle, is cooled to room temperature by reactor, and solid-liquid separation removes xylene solution, and solid matter toluene extracts 24h, obtains after drying Chloropropyl functionalised supports；
3rd step, dimethylbiguanide immobilized
Chloropropyl functionalised supports, potassium iodide, hydrochloride base biguanide and NaOH are put into reactor, then adds in reactor Acetonitrile solvent, then reacts at acetonitrile stirred under reflux temperature, and reaction is cooled to room temperature, solid-liquid separation after terminating, then spend from Solid matter is washed for several times by sub-water and ethanol respectively, at a temperature of being placed in 80 DEG C after vacuum drying, obtains dimethylbiguanide load Amount is the immobilized dimethylbiguanide finished catalyst of 0.01 ~ 0.022mmol/g.
The preparation method of immobilized dimethylbiguanide catalyst the most according to claim 1, it is characterised in that: each in second step The inventory of material is by following weight:
Carrier: dimethylbenzene: 3-r-chloropropyl trimethoxyl silane=1:40 ~ 100:1 ~ 7.
The preparation method of immobilized dimethylbiguanide catalyst the most according to claim 1, it is characterised in that: each in the 3rd step The inventory of material is by following weight:
Carrier: potassium iodide: hydrochloride base biguanide: NaOH: acetonitrile=1:0.71:0.17 ~ 0.25:0.8:40 ~ 60.
CN201610205390.5A 2016-04-05 2016-04-05 Preparation method for immobilized dimethyl biguanide catalyst Pending CN105772079A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107597186A (en) * 2017-10-09 2018-01-19 湘潭大学 A kind of short mesoporous solid alkali BG/Zr SBA 15 of the water resistance of catalytically synthesizing biological diesel oil preparation method
CN117205963A (en) * 2023-11-09 2023-12-12 江苏奥克化学有限公司 Preparation method of inorganic oxide supported tetramethyl guanidine solid base catalyst

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100051561A1 (en) * 2008-08-29 2010-03-04 Kwangyeol Lee Porous membrane and method of making the same
CN103253679A (en) * 2012-02-16 2013-08-21 中国石油天然气股份有限公司 Method of synthesizing SBA-15 mesoporous molecular sieve

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100051561A1 (en) * 2008-08-29 2010-03-04 Kwangyeol Lee Porous membrane and method of making the same
CN103253679A (en) * 2012-02-16 2013-08-21 中国石油天然气股份有限公司 Method of synthesizing SBA-15 mesoporous molecular sieve

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A. ALIZADEH等: "The successful synthesis of biguanide-functionalized mesoporous silica catalysts:Excellent reactivity combined with facile catalyst recyclability", 《MICROPOROUS AND MESOPOROUS MATERIALS》 *
DONGYUAN ZHAO等: "Nonionic Triblock and Star Diblock Copolymer and Oligomeric Surfactant Syntheses of Highly Ordered, Hydrothermally Stable,Mesoporous Silica Structures", 《J. AM. CHEM. SOC》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107597186A (en) * 2017-10-09 2018-01-19 湘潭大学 A kind of short mesoporous solid alkali BG/Zr SBA 15 of the water resistance of catalytically synthesizing biological diesel oil preparation method
CN107597186B (en) * 2017-10-09 2019-12-31 湘潭大学 Preparation method of water-resistant short mesoporous solid base BG/Zr-SBA-15 for catalytic synthesis of biodiesel
CN117205963A (en) * 2023-11-09 2023-12-12 江苏奥克化学有限公司 Preparation method of inorganic oxide supported tetramethyl guanidine solid base catalyst
CN117205963B (en) * 2023-11-09 2024-02-23 江苏奥克化学有限公司 Preparation method of inorganic oxide supported tetramethyl guanidine solid base catalyst

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