CN104945223A - Method for catalyzing methylbenzene to compound orthochlorotoluene through supported molecular sieves - Google Patents
Method for catalyzing methylbenzene to compound orthochlorotoluene through supported molecular sieves Download PDFInfo
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- CN104945223A CN104945223A CN201510343535.3A CN201510343535A CN104945223A CN 104945223 A CN104945223 A CN 104945223A CN 201510343535 A CN201510343535 A CN 201510343535A CN 104945223 A CN104945223 A CN 104945223A
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- molecular sieve
- chlorotolu
- ene
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Abstract
The invention relates to the preparation technical field of orthochlorotoluene, in particular to a method for catalyzing methylbenzene to compound orthochlorotoluene through aluminum chloride (AlCl3) supported HZSM-5 molecular sieves, which belongs to the technical field of methylbenzene directional chlorination. The method for catalyzing the methylbenzene to compound the orthochlorotoluene through the AlCl3 supported HZSM-5 molecular sieves uses the AlCl3 supported HZSM-5 molecular sieves as catalysts, uses Cl2 as chlorinating agents, and selectively chloridizes the methylbenzene by adopting a liquid phase chlorination process. The method for selectively chloridizing to prepare the orthochlorotoluene is simple in synthetic process, mild in reaction condition, excellent in catalytic activity of the used AlCl3 supported HZSM-5 molecular sieves, easy to separate from products, small in environment pollution and small in corrosivity, and has extremely high industrial application value.
Description
Technical field
The present invention relates to and prepare ortho-chlorotolu'ene technical field, refer in particular to a kind of AlCl
3the method of load HZSM-5 molecular sieve catalytic toluene synthesis ortho-chlorotolu'ene, belongs to oriented chlorination of toluene technical field.
Background technology
Ortho-chlorotolu'ene is a kind of important fine chemical material, be widely used in the aspects such as agricultural chemicals, medicine, dyestuff and paint, take ortho-chlorotolu'ene as raw material, can produce adjacent chlorobenzyl chloride, o-chlorobenzaldehyde, o-chlorobenzoyl chloride, 0-chloro-benzoic acid, cresols, toluene dichloride etc., they are mainly used to the raw material producing sterilant, agrochemical.
Existingly prepare in ortho-chlorotolu'ene technology, mainly adopt common Lewis acid to be catalyzer, comprise SbCl
3, FeCl
3, AlCl
3deng, though Lewis acid catalyst better catalytic activity, when being used alone, corrodibility is strong, harsh to equipment requirements, and the three wastes are many, are unfavorable for that industrialization generates.
By AlCl
3be carried on carrier, its catalytic activity changes little, and has catalyzer easily and product separation, and can reuse, environmental pollution is little, to features such as equipment corrosion are less, has good industrial prospect.
summary of the invention:
The invention provides a kind of AlCl
3the method of load HZSM-5 molecular sieve catalytic toluene synthesis ortho-chlorotolu'ene, technique is simple, reaction conditions is gentle, selectivity of product is high, is easy to industrialization.
AlCl
3the method of load HZSM-5 molecular sieve catalytic toluene synthesis ortho-chlorotolu'ene, is characterized in that carrying out in the steps below:
(1) HZSM-5 molecular sieve
1. ZSM-5 molecular sieve preparation: preparation method's reference: Chen Bingyi, Yang Xinli, Du Baoshi, etc. Synthesis of ZSM-5 with Inorganic Amine [J]. Zhengzhou University's journal, 2001,4(33): 70-72.
By 0.03 mol Al
2(SO
4)
3join 100 mL 1.5 mol/L H of preparation
2s0
4in solution, stir and make it to dissolve completely; 15 mL ammoniacal liquor (massfraction 25%) are joined in 100 mL distilled water, is uniformly mixed, this solution is slowly joined above-mentioned Al
2(SO
4)
3/ H
2s0
4in solution, stir, obtain solution A; Joined in 225 mL distilled water by 150g water glass (modulus 3.2), stir obtained solution B; Under agitation, with peristaltic pump, solution A is slowly added drop-wise in solution B, reacts at 30 DEG C, after 2 h, mixture is put into water heating kettle, crystallization 120 h at 170 DEG C, with distilled water, the washing of obtained ZSM-5 molecular sieve is extremely neutral, 2 h are dried at 120 DEG C, for subsequent use.
2. the preparation of HZSM-5 molecular sieve is by ZSM-5 molecular sieve obtained for 10 g and 100 mL NH
4nO
3(30wt%) solution joins in 250 mL there-necked flasks, stirs 3 h at 90 DEG C, after filtration washing, by obtained sample at 120 DEG C of oven drying 2 h, in 500 DEG C of roasting 2 h in retort furnace, can obtain HZSM-5 molecular sieve.
(2) AlCl
3load HZSM-5 molecular sieve
N
2under protection, by AlCl
3join in dehydrated alcohol with HZSM-5 molecular sieve, be warming up to 80 DEG C, return stirring 3 h, after reaction terminates, by sample filtering drying, grinding, calcining, after cooling, can AlCl be obtained
3load HZSM-5 molecular sieve.
Further, described AlCl
3be: 0.01-0.1: 1 that namely charge capacity is 1%-10% with the mass ratio of HZSM-5 molecular sieve.
Further, the quality volume of HZSM-5 molecular sieve and dehydrated alcohol is: 1g: 10mL.
Further, described calcining is for being warming up to 300 DEG C of calcining 2 h.
(3) toluene chlorination step adds a certain amount of catalyzer in toluene, stirring makes it be uniformly dispersed, then in system, pass into the chlorine through vitriol oil drying, under certain chlorination reaction temperature, reaction certain hour obtains ortho-chlorotolu'ene, and tail gas absorbs the unreacted Cl of removing through NaOH solution
2.
Wherein, the add-on of the catalyzer described in step (3) is 0.1% ~ 2% of toluene quality.
Wherein, step (3) chlorination reaction temperature is 50 ~ 80 DEG C.
Wherein, the chlorination reaction time described in step (3) is 2 ~ 8 h.
Wherein, the chlorine flowrate through vitriol oil drying described in step (3) is 30 mL/min.
The invention has the advantages that:
1. the present invention uses AlCl
3load HZSM-5 molecular sieve catalytic toluene chlorination, solves traditional Lewis acid for etching apparatus during catalyzer, causes the shortcomings such as the three wastes are many, be conducive to ortho-chlorotolu'ene suitability for industrialized production.
2. the AlCl for preparing of the present invention
3load HZSM-5 molecular sieve has that catalytic activity is high, good product selectivity, be easy to product separation, can the advantage such as recirculation use, be beneficial to lasting suitability for industrialized production.
Embodiment
Be below preferred embodiment of the present invention, can understand the present invention better, but embodiments of the invention be not limited thereto, shown in it, data do not represent the restriction to characteristic range of the present invention simultaneously.
Embodiment 1
(1) HZSM-5 molecular sieve
1. ZSM-5 molecular sieve preparation: by 0.03 mol Al
2(SO
4)
3join 100 mL 1.5 mol/L H of preparation
2s0
4in solution, stir and make it to dissolve completely, 15 mL ammoniacal liquor (massfraction 25%) are joined in 100 mL distilled water, is uniformly mixed, this solution is slowly joined above-mentioned Al
2(SO
4)
3/ H
2s0
4in solution, stir, obtain solution A; Joined in 225 mL distilled water by 150g water glass (modulus 3.2), stir obtained solution B; Under agitation, with peristaltic pump, solution A is slowly added drop-wise in solution B, reacts at 30 DEG C, after 2 h, mixture is put into water heating kettle, crystallization 120 h at 170 DEG C, with distilled water, the washing of obtained ZSM-5 molecular sieve is extremely neutral, 2 h are dried at 120 DEG C, for subsequent use.
2. the preparation of HZSM-5 molecular sieve: the ZSM-5 molecular sieve obtained by 10 g and 100 mL NH
4nO
3(30wt%) solution joins in 250 mL there-necked flasks, stirs 3 h at 90 DEG C, after filtration washing, by obtained sample at 120 DEG C of oven drying 2 h.In 500 DEG C of roasting 2 h in retort furnace, HZSM-5 molecular sieve can be obtained.
(2) AlCl
3the preparation of load HZSM-5 molecular sieve: N
2under protection, by 0.5 g AlCl
3join with 10.0 g HZSM-5 molecular sieves and be equipped with in 250 mL there-necked flasks of 100 mL dehydrated alcohols, be warming up to 80 DEG C, return stirring 3 h, after reaction terminates, sample filtering is dry, grinding, in retort furnace, be warming up to 300 DEG C of calcining 2 h, after cooling, can AlCl be obtained
3charge capacity is the catalyzer of 5%.
(3) toluene chlorination step: add 50 g toluene in the four-hole boiling flask of 100 mL, adds 0.25 g AlCl
3charge capacity is the molecular sieve of 5%, stirs and makes it be uniformly dispersed, then in system, pass into the chlorine of 30 mL/min through vitriol oil drying, at 65 DEG C, react 8 h and obtain ortho-chlorotolu'ene, and tail gas absorbs the unreacted Cl of removing through NaOH solution
2.
Change AlCl
3amount, preparation AlCl
3charge capacity is the catalyzer of 1%, 2%, 10%, can obtain different al Cl
3charge capacity on the impact of chlorination toluene process, as table 1:
Table 1 different al Cl
3charge capacity is on the impact of toluene chlorination
Table 1 reflects AlCl
3charge capacity is on the impact of toluene chlorination.As can be seen from Table 1, along with AlCl
3charge capacity is increased to 10% from 1%, and the transformation efficiency of toluene is increased to 100.0% from 68.3%; In product, the ratio of ortho-chlorotolu'ene and parachlorotoluene first increases rear reduction, works as AlCl
3when charge capacity is 5%, the ratio of ortho-chlorotolu'ene and parachlorotoluene reaches maximum, is 2.82.Result shows, AlCl
3charge capacity has larger impact to toluene chlorination; AlCl
3the increase of charge capacity, active ingredient increases, and is conducive to accelerating speed of reaction.Meanwhile, AlCl
3the increase of charge capacity, the ratio of ortho-chlorotolu'ene and parachlorotoluene declines, and this is mainly because the further chlorination of monochlorotoluene generates toluene dichloride.
Embodiment 2
The same method of embodiment 1 is adopted to produce AlCl
3load HZSM-5 molecular sieve, toluene chlorination step, with embodiment 1, changes AlCl
3load HZSM-5 molecular sieve consumption is 0.05 g, 0.5 g, 1.0 g, can obtain the impact of catalyst levels on toluene chlorination process, as table 2:
Table 2 catalyst levels affects toluene chlorination
Table 2 shows the impact of catalyst levels on toluene chlorination.Along with catalyst levels is increased to 2.0% from 0.1%, the transformation efficiency of toluene is increased to 100.0% from 62.5%; The ratio of ortho-chlorotolu'ene and parachlorotoluene is increased to 2.82 from 2.59, after be down to 2.60; As can be seen from Table 2, the consumption increasing catalyzer is conducive to improving toluene chlorination speed, but the ratio of ortho-chlorotolu'ene and parachlorotoluene also can be caused to decline simultaneously, and this is mainly because the further chlorination of monochlorotoluene generates toluene dichloride.
Embodiment 3
The same method of embodiment 1 is adopted to produce AlCl
3load HZSM-5 molecular sieve, toluene chlorination step is with embodiment 1, and changing temperature of reaction is 50 DEG C, 80 DEG C, can obtain the impact of differential responses temperature on chlorination toluene process, as table 3:
Table 3 differential responses temperature affects toluene chlorination
| Temperature of reaction/DEG C | Toluene conversion/% | Ortho-chlorotolu'ene/parachlorotoluene |
| 50 | 86.4 | 2.59 |
| 65 | 98.2 | 2.82 |
| 80 | 100.0 | 2.50 |
Table 3 reflects the impact of temperature of reaction on toluene chlorination; As can be seen from Table 3, the transformation efficiency of toluene increases along with the rising of temperature of reaction.When temperature of reaction is 65 DEG C, in product, the ratio of ortho-chlorotolu'ene and parachlorotoluene is the highest, is 2.82.
Result shows, high temperature is conducive to ortho-chlorotolu'ene and optionally improves.
Embodiment 4
The same method of embodiment 1 is adopted to produce AlCl
3load HZSM-5 molecular sieve, toluene chlorination step is with embodiment 1, and changing the reaction times is 2 h, 4 h, 6 h, can obtain the impact of differential responses time on chlorination toluene process, as table 4:
The table 4 differential responses time is on the impact of toluene chlorination
Table 4 reflects the impact of reaction times on toluene chlorination.As can be seen from the table, along with the reaction times extends to 8 h from 2 h, the transformation efficiency of toluene is increased to 98.2% from 20.9%; The ratio of ortho-chlorotolu'ene and parachlorotoluene drops to 2.82 from 2.90; Experimental result shows, extends the raising that the reaction times is conducive to toluene conversion, but the ratio of ortho-chlorotolu'ene and parachlorotoluene also can be caused to reduce simultaneously.
Embodiment 5
The same method of embodiment 1 is adopted to produce AlCl
3load HZSM-5 molecular sieve, toluene chlorination step with embodiment 1, by AlCl
3load HZSM-5 molecular sieve is separated with chlorizate, and use the 2nd time, the 3rd time, the 4th, the 5th, can obtain the impact of catalyzer access times on chlorination toluene process, as table 5::
Table 5 catalyzer access times are on the impact of toluene chlorination
Table 5 reflects the impact of catalyzer access times on toluene chlorination, as can be seen from Table 5, along with the increase of catalyzer access times, the transformation efficiency of toluene and the value of ortho-chlorotolu'ene/parachlorotoluene all slowly decline, when catalyzer uses for the 5th time, the transformation efficiency of toluene still remains on 94.1%, and the value of ortho-chlorotolu'ene/parachlorotoluene maintains 2.71%.This shows, AlCl
3load HZSM-5 molecular sieve catalyst stability is strong, and cycle performance is good.
Claims (8)
1. a method for load molecular sieve catalysis toluene synthesis ortho-chlorotolu'ene, is characterized in that: with AlCl
3load HZSM-5 molecular sieve is catalyzer, and catalysis Toluene selective chlorination produces ortho-chlorotolu'ene.
2. the method for a kind of load molecular sieve catalysis toluene synthesis ortho-chlorotolu'ene as claimed in claim 1, is characterized in that: in toluene, add AlCl
3load HZSM-5 molecular sieve, as catalyzer, stirs and makes it be uniformly dispersed, in system, then pass into the chlorine through vitriol oil drying, and under certain chlorination reaction temperature, reaction certain hour obtains ortho-chlorotolu'ene, and tail gas absorbs the unreacted Cl of removing through NaOH solution
2.
3. the method for a kind of load molecular sieve catalysis toluene synthesis ortho-chlorotolu'ene as claimed in claim 2, is characterized in that: the add-on of described catalyzer is 0.1% ~ 2% of toluene quality; Described chlorination reaction temperature is 50 ~ 80 DEG C; The described chlorination reaction time is 2 ~ 8 h.
4. the method for a kind of load molecular sieve catalysis toluene synthesis ortho-chlorotolu'ene as claimed in claim 2, is characterized in that: the described chlorine flowrate through vitriol oil drying is 30 mL/min.
5. the method for a kind of load molecular sieve catalysis toluene synthesis ortho-chlorotolu'ene as claimed in claim 1 or 2, is characterized in that described AlCl
3the preparation method of load HZSM-5 molecular sieve is as follows: N
2under protection, by AlCl
3join in dehydrated alcohol with HZSM-5 molecular sieve, be warming up to 80 DEG C, return stirring 3 h, after reaction terminates, by sample filtering drying, grinding, calcining, after cooling, can AlCl be obtained
3load HZSM-5 molecular sieve.
6. the method for a kind of load molecular sieve catalysis toluene synthesis ortho-chlorotolu'ene as claimed in claim 5, is characterized in that: AlCl
3be: 0.01-0.1: 1 that namely charge capacity is 1%-10% with the mass ratio of HZSM-5 molecular sieve; The quality volume of HZSM-5 molecular sieve and dehydrated alcohol is: 1g: 10mL; Described calcining is for being warming up to 300 DEG C of calcining 2 h.
7. the method for a kind of load molecular sieve catalysis toluene synthesis ortho-chlorotolu'ene as claimed in claim 6, is characterized in that: AlCl
3be: 0.05:1 that namely charge capacity is 5% with the mass ratio of HZSM-5 molecular sieve.
8. the method for a kind of load molecular sieve catalysis toluene synthesis ortho-chlorotolu'ene as claimed in claim 3, is characterized in that: the add-on of described catalyzer is 0.5% of toluene quality; Described chlorination reaction temperature is 65 DEG C; The described chlorination reaction time is 8 h.
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|---|---|---|---|
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|---|---|---|---|
| CN201510343535.3A CN104945223B (en) | 2015-06-19 | 2015-06-19 | A kind of method that load molecular sieve catalysis toluene synthesizes ortho-chlorotolu'ene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773146A (en) * | 2022-05-19 | 2022-07-22 | 常州新东化工发展有限公司 | Method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with supported catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002154995A (en) * | 2000-11-21 | 2002-05-28 | Toray Ind Inc | Method for producing chlorinated aromatic compound |
-
2015
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002154995A (en) * | 2000-11-21 | 2002-05-28 | Toray Ind Inc | Method for producing chlorinated aromatic compound |
Non-Patent Citations (2)
| Title |
|---|
| 蔡天锡: "固载化AlCl3催化剂的研制与应用", 《石油化工》 * |
| 韩雪等: "负载型Lewis酸催化剂的制备与应用进展", 《石油化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773146A (en) * | 2022-05-19 | 2022-07-22 | 常州新东化工发展有限公司 | Method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with supported catalyst |
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