CN103406154A - Preparation method of efficient Fourier alkylation catalyst - Google Patents
Preparation method of efficient Fourier alkylation catalyst Download PDFInfo
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- CN103406154A CN103406154A CN2013103920928A CN201310392092A CN103406154A CN 103406154 A CN103406154 A CN 103406154A CN 2013103920928 A CN2013103920928 A CN 2013103920928A CN 201310392092 A CN201310392092 A CN 201310392092A CN 103406154 A CN103406154 A CN 103406154A
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Abstract
The invention belongs to the field of Fourier alkylation reaction and discloses a preparation method of an efficient Fourier alkylation catalyst, for solving the problems of an existing heterogeneous Fourier alkylation catalyst, such as small aperture, low efficiency and low recycling capacity. The method comprises the steps of adding FeCl3.6H2O or FeCl2.4H2O to anhydrous alcohol and uniformly mixing, wherein the anhydrous alcohol is either absolute ethyl alcohol or absolute methanol; adding MIL-101(Cr), processing by an impregnation method, drying and implementing vacuum drying. The preparation method is applied to the field of Fourier alkylation reaction. The Fourier alkylation catalyst has quite high catalysis efficiency; the Fourier alkylation catalyst containing 30wt% of Fe can catalyze mesitylene and benzyl chloride, and conversion rate of benzyl chloride is close to 100% within 5min of reaction; and the catalyst is repeatedly used for catalyzing the mesitylene and the benzyl chloride for 5 times, and conversion rate of the benzyl chloride within 5min of reaction is close to 100%.
Description
Technical field
The invention belongs to Fu Shi alkylated reaction field; Be specifically related to the preparation method of efficient Fu Shi alkylation catalyst.
Background technology
Fu Rui Deer-Kerafyrm thatch (Friedel-Crafts) alkylated reaction (being called for short the Fu Shi alkylated reaction) refers to the reaction that in benzene and aromatic derivant, the H atom on phenyl ring is replaced by alkyl.It in organic chemistry, is the very important reaction of a class.In these reactions, liquid phase reactor makes benzene with benzyl chloride and other aromatic benzyl prepares diphenyl methane and derivative is an important industrialization organic reaction, especially in field of medicaments and other friendly type chemistry industry, is widely used.
This type of reaction is mainly to carry out with Lewis acid or the bronsted acid catalyst of homogeneous phase at the beginning of finding, for example: AlCl
3, FeCl
3And H
2SO
4.This type of homogeneous catalyst exists serious environment and operational issue.With the most frequently used AlCl
3Catalyst is example, and in course of reaction, its chance water decomposes rapidly, discharges a large amount of hydrogen chloride gas, and thermal discharge is large, and forms the acid solution that is rich in aluminium, not only equipment is caused to corrosion, and contaminated environment that can be serious.And this type of catalyst efficiency is lower, in catalytic process, easily form many alkylates with and isomer.Therefore, research is used heterogeneous catalyst to replace above-mentioned homogeneous catalyst very necessary, has good environment and economy and is worth.
Summary of the invention
The present invention is that will to solve existing heterogeneous Fu Shi alkylation catalyst aperture little, and efficiency is low, reuses the problem that ability is not high, and a kind of preparation method of efficient Fu Shi alkylation catalyst is provided.
For addressing the above problem, the preparation method of efficient Fu Shi alkylation catalyst of the present invention is undertaken by following reaction: by FeCl
36H
2O or FeCl
24H
2O joins in absolute alcohol and mixes, and described absolute alcohol is absolute ethyl alcohol or absolute methanol, then adds MIL-101(Cr), then infusion process is processed, drier final vacuum drying, obtains the Fu Shi alkylation catalyst; It is to exchange at ambient temperature 2h~6h or add heat exchange 2h~6h under 30~65 ℃ of conditions that wherein said infusion process is processed.
Said method is to be 5%~40% to join MIL-101(Cr by the quality percentage composition that Fe accounts for the Fu Shi alkylation catalyst) in.
The described pure consumption of said method is extremely excessive 20 times of equivalent, and in the equivalent situation, the absolute alcohol consumption is pressed 1.2mL absolute alcohol/g Fu Shi alkylation catalyst calculating.
The described MIL-101(Cr of said method) preparation method is as follows: by Cr(NO
3)
39H
2O, terephthalic acid (TPA) (H
2BDC, PTA) and deionized water according to the mixed in molar ratio of 1:1:222, ultrasonic mixing, obtain suspension, then suspension is placed in to the inner liner polytetrafluoroethylene stainless steel autoclave, then autoclave is placed in baking oven, synthesized 18 hours under 218 ℃ of conditions, be cooled to room temperature, filter, with reusable heat ethanol after hot DMF washing, wash, then dry 8~12h under 60~100 ℃, 100~150 ℃ of drying 8~12h under vacuum condition, obtain MIL-101(Cr again).
The described drying of said method is dry 12~24h at 50~60 ℃ of temperature.
The described vacuum drying of said method is vacuum drying 8h~12h at 100~150 ℃ of temperature.
Fu Shi alkylation catalyst of the present invention aperture is large, catalytic efficiency is very high, the Fu Shi alkylation catalyst catalysis benzene that contains 30wt%Fe with the conversion ratio that reacts benzyl chloride in 30min of benzyl chloride near 100%, the Fu Shi alkylation catalyst catalysis mesitylene that contains 30wt%Fe with the conversion ratio that reacts benzyl chloride in 5min of benzyl chloride near 100%; The catalyst repeat usage is high, reuses react 5 times that catalyst carries out catalysis mesitylene and benzyl chloride, and the conversion ratio of benzyl chloride all reaches 100% in 5min, and its catalytic activity is still good.Reuse react 50 times that catalyst carries out catalysis mesitylene and benzyl chloride, the conversion ratio of its benzyl chloride reaches more than 99.8%.
The accompanying drawing explanation
Fig. 1 is the nitrogen adsorption desorption isotherm of prepared Fu Shi alkylation catalyst, in Fig. 1, curve 1 means the MIL-101 (Cr) that the specific embodiment ten obtains, curve 2 means the catalyst that the specific embodiment ten obtains, curve 3 means the catalyst that the specific embodiment 11 obtains, curve 4 means the catalyst that the specific embodiment 12 obtains, and curve 5 means the catalyst that the specific embodiment 20 obtains;
Fig. 2 is the activity figure that prepared material catalysis benzene reacts with benzyl chloride, in Fig. 2, curve 1 means the catalyst that the specific embodiment 12 obtains, curve 2 means the catalyst that the specific embodiment 20 obtains, curve 3 means the catalyst that the specific embodiment 11 obtains, curve 4 means the catalyst that the specific embodiment ten obtains, and curve 5 means the MIL-101 (Cr) that the specific embodiment ten obtains;
Fig. 3 is the activity figure that prepared material catalysis mesitylene reacts with benzyl chloride, in Fig. 3, curve 1 means the catalyst that the specific embodiment 12 obtains, curve 2 means the catalyst that the specific embodiment 20 obtains, curve 3 means the catalyst that the specific embodiment 11 obtains, curve 4 means the catalyst that the specific embodiment ten obtains, and curve 5 means the MIL-101 (Cr) that the specific embodiment ten obtains;
Fig. 4 is that the specific embodiment 12 obtains the stability diagram that the catalyst mesitylene reacts with benzyl chloride.
The specific embodiment
The specific embodiment one: in present embodiment, the preparation method of efficient Fu Shi alkylation catalyst is undertaken by following reaction: by FeCl
36H
2O or FeCl
24H
2O joins in absolute alcohol and mixes, described absolute alcohol is absolute ethyl alcohol or absolute methanol, then adds MIL-101(Cr), exchange at ambient temperature 2h~6h or exchange 2h~6h under 30-65 ℃ of heating condition, dry final vacuum drying, obtain the Fu Shi alkylation catalyst again.
The catalytic efficiency of present embodiment Fu Shi alkylation catalyst is very high, the Fu Shi alkylation catalyst catalysis benzene that contains 30wt%Fe with the conversion ratio that reacts benzyl chloride in 30min of benzyl chloride near 100%, the Fu Shi alkylation catalyst catalysis mesitylene that contains 30wt%Fe with the conversion ratio that reacts benzyl chloride in 5min of benzyl chloride near 100%; And it is high to reuse ability, reuse 5 times, the conversion ratio of benzyl chloride all in 5min near 100%, its catalytic activity is still good; Reuse react 50 times that catalyst carries out catalysis mesitylene and benzyl chloride, the conversion ratio of its benzyl chloride reaches more than 99.8%.
The specific embodiment two: what present embodiment was different from the specific embodiment one is: the quality percentage composition that accounts for the Fu Shi alkylation catalyst by Fe is 5%~40% to join MIL-101(Cr) in.Other step and parameter are identical with the specific embodiment one.
The specific embodiment three: what present embodiment was different from the specific embodiment one is: the quality percentage composition that accounts for the Fu Shi alkylation catalyst by Fe is 30% to join MIL-101(Cr) in.Other step and parameter are identical with the specific embodiment one.
The specific embodiment four: what present embodiment was different from one of specific embodiment one to three is: pure consumption is extremely excessive 20 times of equivalent, and in the equivalent situation, the absolute alcohol consumption is pressed 1.2mL absolute alcohol/g Fu Shi alkylation catalyst calculating.Other step and parameter are identical with one of specific embodiment one to three.
The specific embodiment five: what present embodiment was different from one of specific embodiment one to four is: described MIL-101(Cr) preparation method is as follows: by Cr(NO
3)
39H
2O, terephthalic acid (TPA) and deionized water are according to the mixed in molar ratio of 1:1:222, ultrasonic mixing, obtain suspension, then suspension is placed in to the inner liner polytetrafluoroethylene stainless steel autoclave, again autoclave is placed in baking oven, under 218 ℃ of conditions, synthesized 18 hours, be cooled to room temperature, filter, with reusable heat ethanol washing after hot DMF washing, then dry 8~12h under 60~100 ℃, then under vacuum condition 100~150 ℃ of drying 8~12h, obtain MIL-101(Cr).Other step and parameter are identical with one of specific embodiment one to four.
The specific embodiment six: what present embodiment was different from one of specific embodiment one to five is: with the DMF washings of 60~70 ℃ 1~2 time, wash time is 3h~12h.Other step and parameter are identical with one of specific embodiment one to five.
The specific embodiment seven: what present embodiment was different from one of specific embodiment one to six is: with the absolute ethanol washings of 60~65 ℃ 2 times, wash 3h at every turn.Other step and parameter are identical with one of specific embodiment one to six.
The specific embodiment eight: what present embodiment was different from one of specific embodiment one to seven is: described drying is dry 12~24h at 50~60 ℃ of temperature.Other step and parameter are identical with one of specific embodiment one to seven.
The specific embodiment nine: what present embodiment was different from one of specific embodiment one to eight is: described vacuum drying is vacuum drying 8h~12h at 100~150 ℃ of temperature.Other step and parameter are identical with one of specific embodiment one to eight.
The specific embodiment ten: in present embodiment, the preparation method of Fu Shi alkylation catalyst carries out in the steps below: by 0.0636gFeCl
36H
2O adds the 5mL absolute ethyl alcohol to mix, then the MIL-101(Cr that adds 0.25g to prepare), under room temperature, exchange 4h, dry 12h under 60 ℃ of conditions then, then under vacuum condition 150 ℃ of dry 12h, obtain containing 5wt%Fe Fu Shi alkylation catalyst.
MIL-101(Cr described in present embodiment) prepare as follows: by 5mmol(2.0g) Cr(NO
3)
39H
2O, 5mmol(0.83g) terephthalic acid (TPA) and the mixing of 20mL deionized water, ultrasonic mixing, obtain suspension, then suspension is placed in to the inner liner polytetrafluoroethylene stainless steel autoclave of 25mL, again autoclave is placed in baking oven, under 218 ℃ of conditions, synthesized 18 hours, be cooled to room temperature, filter, with 1 time (wash time 12h) of 60 ℃ of DMF washings, (60 ℃ of reusable heat ethanol washings, 3h, 2 times), dry 12h under 60 ℃ then, 150 ℃ of dry 12h under vacuum condition, obtain MIL-101(Cr again);
The specific embodiment 11: in present embodiment, the preparation method of Fu Shi alkylation catalyst carries out in the steps below: by 0.2130gFeCl
36H
2O adds the 5mL absolute ethyl alcohol to mix, then the MIL-101(Cr that adds 0.25g to prepare), under room temperature, exchange 4h, dry 12h under 60 ℃ of conditions then, then under vacuum condition 150 ℃ of dry 12h, obtain containing 15wt%Fe Fu Shi alkylation catalyst.
MIL-101(Cr described in present embodiment) by the preparation of the method in the specific embodiment ten.
The specific embodiment 12: in present embodiment, the preparation method of Fu Shi alkylation catalyst carries out in the steps below: by 0.5173gFeCl
36H
2O adds the 5mL absolute ethyl alcohol to mix, then the MIL-101(Cr that adds 0.25g to prepare), under room temperature, exchange 4h, dry 12h under 60 ℃ of conditions then, then under vacuum condition 150 ℃ of dry 12h, obtain containing 30wt%Fe Fu Shi alkylation catalyst.MIL-101(Cr described in present embodiment) by the preparation of the method in the specific embodiment ten.
MIL-101(Cr described in present embodiment) by the preparation of the method in the specific embodiment ten.
The specific embodiment 13: what present embodiment was different from the specific embodiment 12 is: absolute methanol is replaced absolute ethyl alcohol.Other step and parameter are identical with the specific embodiment 12.
The specific embodiment 14: what present embodiment was different from the specific embodiment 12 is: change 0.7mL absolute ethyl alcohol (equivalent alcohol dipping) into 0.7~5mL absolute ethyl alcohol (excess ethyl alcohol dipping).Other step and parameter are identical with the specific embodiment 12.
The specific embodiment 15: what present embodiment was different from the specific embodiment 12 is: change the 0.7mL absolute ethyl alcohol into 0.7~5mL absolute methanol (excessive methanol dipping).Other step and parameter are identical with the specific embodiment 12.
The specific embodiment 16: what present embodiment was different from the specific embodiment 12 is: by FeCl
36H
2O changes FeCl into
24H
2O(equivalent alcohol dipping).Other step and parameter are identical with the specific embodiment 12.
The specific embodiment 17: what present embodiment was different from the specific embodiment 12 is: change 0.7mL absolute ethyl alcohol (equivalent alcohol dipping) into 0.7~5mL absolute ethyl alcohol (excess ethyl alcohol dipping), other step and parameter are identical with the specific embodiment 12.
The specific embodiment 18: what present embodiment was different from the specific embodiment 12 is: change 0.7mL absolute ethyl alcohol (equivalent alcohol dipping) into 0.7mL absolute methanol (equivalent methyl alcohol dipping).Other step and parameter are identical with the specific embodiment 12.
The specific embodiment 19: what present embodiment was different from the specific embodiment 12 is: change 0.7mL absolute ethyl alcohol (equivalent alcohol dipping) into 0.7~5mL absolute methanol (excessive methanol dipping).Other step and parameter are identical with the specific embodiment 12.
The specific embodiment 20: in present embodiment, the preparation method of Fu Shi alkylation catalyst carries out in the steps below: by 0.8059gFeCl
36H
2O adds the 5mL absolute ethyl alcohol to mix, then the MIL-101(Cr that adds 0.25g to prepare), under room temperature, exchange 4h, dry 12h under 60 ℃ of conditions then, then under vacuum condition 150 ℃ of dry 12h, obtain containing 40wt%Fe Fu Shi alkylation catalyst.MIL-101(Cr described in present embodiment) by the preparation of the method in the specific embodiment ten.
As seen from Figure 1, MIL-101 (Cr) has large BET specific area, and along with the increase of the loading of iron, the BET specific area reduces gradually.
Utilize the Fu Shi alkylation catalyst nitrogen adsorption desorption of the specific embodiment ten, 11,12,20 preparations, result such as Fig. 1, as seen from Figure 1, MIL-101 (Cr) has large BET specific area, along with the increase of the loading of iron, the BET specific area reduces gradually.
Utilize the Fu Shi alkylation catalyst catalysis mesitylene of the specific embodiment ten, 11,12,20 preparations with benzyl chloride, to react to verify the invention effect: to react as follows:
Trimethylbenzene (or benzene) is 13:1 with the benzyl chloride volume ratio, it is the 13ml trimethylbenzene, 20mg Fu Shi alkylation catalyst is in there-necked flask under the reflux condensation mode condition, under 70 ℃, stir 30min, then add wherein the 1ml benzyl chloride, start clock reaction, take a sample after the reaction certain hour, by gas-chromatography, calculate the conversion ratio of reaction.
Result is In Figure 2-4:
As seen from Figure 2, MIL-101 (Cr) is faint to this catalytic reaction activity, MIL-101 (Cr) catalytic activity supported after iron improves greatly, contains the conversion ratio of Fu Shi alkylation catalyst benzyl chloride in 30min of 30wt% and 40wt%Fe all near 100%.
As seen from Figure 3, the catalytic effect of Fu Shi alkylation catalyst that contains 30wt%Fe is best, the conversion ratio of benzyl chloride reaches 100% in 5min, the Fu Shi alkylation catalyst that contains 40wt%Fe than the catalytic effect of the Fu Shi alkylation catalyst that contains 30wt%Fe slightly a little less than, the conversion ratio of benzyl chloride reaches 100% in 10min, contain the Fu Shi alkylation catalyst of 15wt%Fe, the conversion ratio of benzyl chloride is near 100% in 30min.
As seen from Figure 4, the stability of the MIL-101 of the iron content of preparation (Cr) material is very good, reuses 5 times in the reacting of catalysis mesitylene and benzyl chloride, and the conversion ratio of benzyl chloride all reaches 100% in 5min, and catalytic activity is still good.
The Fu Shi alkylation catalyst that contains 30wt%Fe is reused 50 times in the reacting of catalysis mesitylene and benzyl chloride, the conversion ratio of benzyl chloride reaches 99.9%.Visible, the catalyst repeat usage is high.
Claims (9)
1. the preparation method of efficient Fu Shi alkylation catalyst, is characterized in that the preparation method of efficient Fu Shi alkylation catalyst carries out as follows: by FeCl
36H
2O or FeCl
24H
2O joins in absolute alcohol and mixes, and described absolute alcohol is absolute ethyl alcohol or absolute methanol, then adds MIL-101(Cr), then infusion process is processed, drier final vacuum drying, obtains the Fu Shi alkylation catalyst.
2. the preparation method of efficient Fu Shi alkylation catalyst according to claim 1, is characterized in that it is to exchange 2h~6h under room temperature or heating condition that described infusion process is processed.
3. the preparation method of efficient Fu Shi alkylation catalyst according to claim 2, the temperature that it is characterized in that described heating is 30~65 ℃.
4. according to the preparation method of claim 1,2 or 3 described efficient Fu Shi alkylation catalysts, it is characterized in that by the quality percentage composition that Fe accounts for the Fu Shi alkylation catalyst being 5%~40% to add MIL-101(Cr).
5. according to the preparation method of claim 1,2 or 3 described efficient Fu Shi alkylation catalysts, it is characterized in that by the quality percentage composition that Fe accounts for the Fu Shi alkylation catalyst being 30% to add MIL-101(Cr).
6. the preparation method of efficient Fu Shi alkylation catalyst according to claim 4, is characterized in that pure consumption is extremely excessive 20 times of equivalent, and in the equivalent situation, the absolute alcohol consumption is pressed 1.2mL absolute alcohol/g Fu Shi alkylation catalyst calculating.
7. the preparation method of efficient Fu Shi alkylation catalyst according to claim 6, is characterized in that described MIL-101(Cr) preparation method is as follows: by Cr(NO
3)
39H
2O, terephthalic acid (TPA) and deionized water are according to the mixed in molar ratio of 1:1:222, ultrasonic mixing, obtain suspension, then suspension is placed in to the inner liner polytetrafluoroethylene stainless steel autoclave, again autoclave is placed in baking oven, under 218 ℃ of conditions, synthesized 18 hours, be cooled to room temperature, filter, with reusable heat ethanol washing after hot DMF washing, then dry 8~12h under 60~100 ℃, then under vacuum condition 100~150 ℃ of drying 8~12h, obtain MIL-101(Cr).
8. the preparation method of efficient Fu Shi alkylation catalyst according to claim 7, is characterized in that described drying is dry 12~24h at 50~60 ℃ of temperature.
9. the preparation method of efficient Fu Shi alkylation catalyst according to claim 8, is characterized in that described vacuum drying is vacuum drying 8h~12h at 100~150 ℃ of temperature.
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CN110256210A (en) * | 2019-05-28 | 2019-09-20 | 河南科技大学 | A kind of preparation method of 1,2,3- trimethoxy -4- benzyl benzene |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2958945A1 (en) * | 2010-04-16 | 2011-10-21 | Inst Francais Du Petrole | New crystalline solid hybrid having organic-inorganic matrix of three-dimensional structure, having an inorganic network of iron-based metal centers connected by organic ligands, useful as e.g. catalyst or adsorbent |
CN102744105A (en) * | 2011-04-18 | 2012-10-24 | 韩国化学研究院 | Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst |
CN102962090A (en) * | 2012-11-30 | 2013-03-13 | 哈尔滨工业大学 | Preparation method of high-activity environment-friendly low-cost Friedel-Crafts alkylation catalyst |
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FR2958945A1 (en) * | 2010-04-16 | 2011-10-21 | Inst Francais Du Petrole | New crystalline solid hybrid having organic-inorganic matrix of three-dimensional structure, having an inorganic network of iron-based metal centers connected by organic ligands, useful as e.g. catalyst or adsorbent |
CN102744105A (en) * | 2011-04-18 | 2012-10-24 | 韩国化学研究院 | Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst |
CN102962090A (en) * | 2012-11-30 | 2013-03-13 | 哈尔滨工业大学 | Preparation method of high-activity environment-friendly low-cost Friedel-Crafts alkylation catalyst |
Cited By (2)
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CN110256210A (en) * | 2019-05-28 | 2019-09-20 | 河南科技大学 | A kind of preparation method of 1,2,3- trimethoxy -4- benzyl benzene |
CN110256210B (en) * | 2019-05-28 | 2021-12-24 | 河南科技大学 | Preparation method of 1,2, 3-trimethoxy-4-benzyl benzene |
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