CN1133499C - Catalyst for preparing toluene by cracking isopropyl methybenzene and preparation thereof - Google Patents
Catalyst for preparing toluene by cracking isopropyl methybenzene and preparation thereof Download PDFInfo
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- CN1133499C CN1133499C CNB971190801A CN97119080A CN1133499C CN 1133499 C CN1133499 C CN 1133499C CN B971190801 A CNB971190801 A CN B971190801A CN 97119080 A CN97119080 A CN 97119080A CN 1133499 C CN1133499 C CN 1133499C
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Abstract
The present invention relates to a toluene catalyst made by cracking isopropenyl toluene, which is characterized in that the toluene catalyst is made by modifying zeolite; the zeolite is one or more of X zeolite, Y zeolite, ZSM-5 zeolite and Pentasil zeolite; one or more of alkaline earth metals such as Be, Mg , Ca, Sr and Ba, transition metals such as Ti, Cr , Mn, Co, Ni, Zn , Mo and Re, and rare earth metals such as La, Ce and Nd are used as modification components. The toluene catalyst can selectively eliminate isopropyl in p-isopropyl toluene molecules to prepare toluene, and has the advantages of low required temperature, high conversion rate and high catalyst activity.
Description
The present invention relates to catalyst technology, a kind of catalyst and preparation thereof that cymene is optionally removed isopropyl and produce toluene is provided especially.
It is one of important topic that people paid close attention in the petrochemical industry that the alkyl of alkylbenzene removes reaction.For example, the dialkyl benzene in alkylbenzene normally by be difficult to by rectifying with its separate 1,2-, 1,3-and 1, the mixture that three kinds of isomers of 4-dialkyl benzene are formed.Utilize alkyl to remove reaction selectivity ground, just remove this isomers easily after wherein a kind of a kind of alkyl of unwanted isomers removes.Announced that as European patent Eur.Pat.Appl.EP231569 a kind of selection removes by 1,2-, 1,3-and 1, in the mixture that three kinds of isomers such as 4-cymol are formed 1, isopropyl on the 4-cymol and method that this isomers is eliminated.In fine chemistry industry, alkyl removes the production that reaction also usually is used for certain special aromatic.Announced as U.S. Pat 4533768 a kind ofly utilize dealkylation, from 2,4-dialkyl group phenol is produced phenol and to the method for alkylphenol.The alkyl of alkylbenzene removes that reaction normally realizes in the presence of catalyst.Catalyst type is a lot, comprising: metal oxide, transition metal/oxide, zeolite etc.U.S. Pat 4533767 (1985) has reported with magnesia to be catalyst, and at 600 ℃ with have under the condition that water exists 2,4, the 6-pseudocuminol takes off the method that alkyl is produced phenol.Reaction conversion ratio is between 48.25～89.62%, and converted product is phenol, p-cresol 2, the mixture of 4-xylenol.57167931 (nineteen eighty-twos) of Japan Patent Jpn.Kokai Tokkyo Kobo JP have been reported with Ni-Zn-Cr/Al
2O
3Be catalyst, the toluene demethylation is produced the method for benzene.Reaction temperature is 600 ℃, and pressure is 6.0MPa, and selectivity reaches 98%, but conversion ratio only 38%.It is that 20% Y zeolite is the hydrodealkylation of catalyst that 57163328 (nineteen eighty-twos) of Japan Patent Jpn.Kokai TokkyoKoho JP have been reported with the hydrogen ion exchange degree, and under 600 ℃, 6.0MPa, reaction conversion ratio is 65%, selectivity reaches 90%.U.S. Pat 4654457 (1987) reported with the ZSM-5 zeolite be catalyst, optionally to the para-isomer in o-, m-, the p-isopropyl toluene mixture carry out isopropyl remove the reaction separate this isomers method.Reaction temperature is 350～450 ℃, and the toluene yield can reach 70%.
The object of the present invention is to provide a kind of catalyst and preparation thereof, this catalyst can optionally remove in the cymene molecule isopropyl and produce toluene, reacts temperature required lower, and conversion ratio is higher, and catalyst activity is higher.
The invention provides a kind of isopropyl toluene cracking preparing methylbenzene catalyst, it is characterized in that described catalyst made by Zeolite modifying:
Zeolite is a kind of or its combination in X type, Y type, ZSM-5 type and the Pentasil type zeolite;
Modified component is alkaline-earth metal Be, Mg, Ca, Sr, Ba, transition metal Ti, Cr, Mn, Co, Ni, Zn, Mo, Re, a kind of among rare-earth metal La, Ce, the Nd or several.
The wherein ZSM-5 that produces for the zeolite synthetic technology of utilizing Chinese patent ZL87105054.4 and being provided of Pentasil type and the mixed crystal type zeolite commodity of ZSM-11.
The invention provides catalyst and can use the binding agent moulding, binding agent is Al
2O
3, SiO
2In one or more.
Catalyst provided by the present invention can obtain by following two kinds of approach.
(1)--zeolite powder 350～600 ℃ of roastings 1～8 hour, is removed organic formwork agent, obtain the zeolite prototype;
Or with zeolite powder through ion-exchange, 400～600 ℃ of roastings 1～8 hour obtain h-type zeolite;
--with infusion process metallic element is supported on the zeolite;
--add or do not add the binding agent moulding, 400～600 ℃ of following roastings 1～8 hour.
(2)--zeolite powder is mixed without the direct metallizing thing of roasting, grind;
--add or do not add the binding agent moulding, 300～600 ℃ of roastings 1～8 hour.
Second kind of approach, also can be at first with zeolite powder 350～600 ℃ of roastings 1～8 hour, the metallizing thing mixes again, grinds; Perhaps at first with zeolite powder through ion-exchange, 400～600 ℃ of roastings 1～8 hour, the metallizing thing mixes again, grinds.
The catalyst of above-mentioned preparation also can utilize methods such as steam or high-temperature roasting to be for further processing, thereby obtains the catalyst of modification.
The present invention be used for isopropyl remove the reaction carry out with gas-phase catalysis.Reactive mode is a fixed bed continuous-flow form, use inert gases such as nitrogen, argon gas or helium as carrier gas, and play diluting effect.Reaction pressure is a normal pressure; Reaction temperature is between 200～500 ℃.The reaction raw materials cymene through after the gasifier gasification, enters reactor earlier again.The product gas chromatographic analysis.Gas-phase product on-line analysis, column packing are Parapok Qs; The column packing of analyzing product liquid is SE30, and column temperature is 110 ℃.
The invention will be further described for example below.
Embodiment 1 Preparation of Catalyst 1
Restrain through the ZSM-5 zeolite prototype (SiO of 500 ℃ of roastings after 4 hours 10
2/ Al
2O
3=52) immerse in 12 milliliters of aqueous solution that contain 6 gram Magnesium acetate (Mg(OAc)2) tetrahydrates, in air, dry.With its compressing tablet,, make granularity and be 0.45～0.9 millimeter particle through broken, screening.Put it into Muffle furnace, after 2 hours, make catalyst A 500 ℃ of blowing air roastings.
Embodiment 2 Preparation of Catalyst 2
Take by weighing 15 gram X type zeolite (SiO
2/ Al
2O
3=3.7),, filter out clear liquid with 200 milliliters of 0.5M aqueous ammonium nitrate solution exchanges 1 hour.Washing, filter each again carries out twice successively.Repeat again said process once after, oven dry, 450 ℃ of roastings are 2 hours in air, obtain the HX zeolite.Take by weighing 10 gram HX zeolites and 5 gram lithium nitrates, be ground to repeatedly evenly.With its compressing tablet, fragmentation, sieve out diameter and be 0.45～0.9 millimeter particle, 300 ℃ of roastings obtained catalyst B after 2 hours in air.
Embodiment 3 Preparation of Catalyst 3
With Pentasil type zeolite powder (SiO
2/ Al
2O
3=55) 540 ℃ of roastings obtained the prototype zeolite in 6 hours in air.Take by weighing 10 gram Pentasil zeolite prototypes, impregnated in 20 milliliters of aqueous solution that contain 15 gram Magnesium acetate (Mg(OAc)2) tetrahydrates.Be heated to 50 ℃, constant temperature stirred after 1 hour, heated up to be evaporated to appearance and to stop to stir after anhydrous.Again in 100 ℃ of oven dry.Then, 500 ℃ of roastings 2 hours in air.After being cooled to room temperature, compressing tablet, fragmentation are sieved out diameter and are 0.45～0.9 millimeter particle, as catalyst C.
Embodiment 4 Preparation of Catalyst 4～8
In 5 parts of 20 ml water solution that contain different amount Magnesium acetate (Mg(OAc)2) tetrahydrates, each adds prepared Pentasil zeolite prototype among the 10 gram embodiment 3, and according to the method for embodiment 3 with its evaporation, oven dry, roasting after, add γ-Al
2O
3, mix, be in harmonious proportion with diluted nitric acid aqueous solution.Then, extrusion, dry.After 500 ℃ of roastings, make granularity and be catalyst D～H of 0.45～0.9 millimeter, listed as table 1.
Table 1
Catalyst numbering D E F G H
MgO(wt％) 3.5 6 10 12 16
Al
2O
3(wt％) 35 35 35 35 35
Embodiment 5 Preparation of Catalyst 9～13
Take by weighing the Pentasil zeolite prototype of 5 part of 10 gram embodiment, 3 preparations, respectively with different slaine mixing.After grinding evenly, in air, 500 ℃ of roastings 2 hours.After being cooled to room temperature,, being prepared into granularity and being 0.45～0.9 millimeter, metal oxide content and be catalyst I～M of 15wt% through compressing tablet, fragmentation, screening, listed as table 2.
Table 2
Catalyst numbering I J K L M
Slaine magnesium acetate manganese nitrate cerous nitrate nickel nitrate zinc nitrate
Sintering temperature (℃) 450 300 300 300 450
Embodiment 6 cymene breaking tests
4 gram catalyst are packed in the quartz glass reactor, earlier logical nitrogen, be warming up to 400 ℃ and purge after 1 hour, be cooled to reaction temperature again, react.Reaction condition is: nitrogen flow 30 ml/min, 1.8 milliliters/hour of cymene inputs, 150 ℃ of gasifier temperature, normal pressure.Table 3 has been listed and has been adopted different catalysts, reaction to proceed to 2 hours reaction result.
Table 3
Catalyst reaction temperature conversion ratio selectivity (%) yield (mol.%)
The numbering degree (℃) (mol.%)
A 450 57.5 73.4 42.2
B 550 46.3 86.0 39.8
C 250 66.2 82.9 54.9
D 320 53.2 81.0 43.1
E 320 56.5 79.1 44.7
F 320 96.7 75.8 73.3
G 320 80.2 80.5 64.6
H 320 38.2 79.8 30.5
I 380 78.6 86.4 67.9
J 325 96.5 82.7 79.8
K 300 88.1 75.6 66.6
L 310 98.1 87.3 85.6
M 310 81.4 81.0 65.9
Embodiment 7 cymene breaking tests
3 gram F catalyst are packed in the quartz glass reactor, earlier logical nitrogen, be warming up to 400 ℃ and purge after 1 hour, be cooled to reaction temperature again, react.Reaction condition is: nitrogen flow 30 ml/min, 1.8 milliliters/hour of cymene inputs, 150 ℃ of gasifier temperature, normal pressure.Table 4 has gone out the reaction result under the differential responses.
Table 4
Reaction temperature (℃) reaction time (h) conversion ratio (mol.%) selectivity (%) yield (mol.%)
250 4.5 64.2 86.1 55.3
316 1 92.7 76.4 70.8
427 2.5 98.3 67.2 66.1
470 2 99.1 58.2 57.7
As fully visible, adopt the catalyst of present technique preparation, under lower reaction temperature,, can access the toluene of higher yields the cymene cracking.
Claims (6)
1. isopropyl toluene cracking preparing methylbenzene Application of Catalyst, it is characterized in that: described catalyst is made by Zeolite modifying:
Zeolite is a kind of or its combination in X type, Y type, ZSM-5 type and the Pentasil type zeolite;
Modified component is alkaline-earth metal Be, Mg, Ca, Sr, Ba, transition metal Ti, Cr, Mn, Co, Ni, Zn, Mo, Re, a kind of among rare-earth metal La, Ce, the Nd or several.
2. according to the described isopropyl toluene cracking of claim 1 preparing methylbenzene Application of Catalyst, it is characterized in that: catalyst binding agent moulding, binding agent are Al
2O
3, SiO
2In one or more.
3. by the described isopropyl toluene cracking of claim 1 preparing methylbenzene Application of Catalyst, it is characterized in that: wherein said catalyst adopts following process preparation,
--with zeolite powder 350～600 ℃ of roastings 1～8 hour;
Or with zeolite powder through ion-exchange, 400～600 ℃ of roastings 1～8 hour;
--with infusion process metallic element is supported on the zeolite;
--moulding, 400～600 ℃ of following roastings 1～8 hour.
4. by the described isopropyl toluene cracking of claim 1 preparing methylbenzene Application of Catalyst, it is characterized in that: wherein said catalyst adopts following process preparation,
--zeolite powder metallizing thing is mixed, grind;
--moulding, 300～600 ℃ of roastings 1～8 hour.
5. by the described isopropyl toluene cracking of claim 4 preparing methylbenzene Application of Catalyst, it is characterized in that: at first with zeolite powder 350～600 ℃ of roastings 1～8 hour, the metallizing thing mixes again, grinds.
6. by the described isopropyl toluene cracking of claim 4 preparing methylbenzene Application of Catalyst, it is characterized in that: at first with zeolite powder through ion-exchange, 400～600 ℃ of roastings 1～8 hour, the metallizing thing mixes again, grinds.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB971190801A CN1133499C (en) | 1997-10-22 | 1997-10-22 | Catalyst for preparing toluene by cracking isopropyl methybenzene and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB971190801A CN1133499C (en) | 1997-10-22 | 1997-10-22 | Catalyst for preparing toluene by cracking isopropyl methybenzene and preparation thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1214961A CN1214961A (en) | 1999-04-28 |
| CN1133499C true CN1133499C (en) | 2004-01-07 |
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|---|---|---|---|
| CNB971190801A Expired - Fee Related CN1133499C (en) | 1997-10-22 | 1997-10-22 | Catalyst for preparing toluene by cracking isopropyl methybenzene and preparation thereof |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329122C (en) * | 2004-07-12 | 2007-08-01 | 中国石油化工股份有限公司 | Catalyst for toluene disproportionation and alkyl transfer |
| TWI428180B (en) * | 2005-02-25 | 2014-03-01 | Grace W R & Co | Gasoline sulfur reduction catalyst for fluid catalytic cracking process |
| JP5577587B2 (en) | 2008-11-25 | 2014-08-27 | 株式会社明電舎 | Process for producing lower hydrocarbon aromatization catalyst and lower hydrocarbon aromatization catalyst |
| CN102502694A (en) * | 2011-10-11 | 2012-06-20 | 于向真 | Li-modified X molecular sieve and preparation method thereof |
| CN102773072A (en) * | 2012-07-29 | 2012-11-14 | 南京工业大学 | Cerium element modified mesoporous silica adsorbent, preparation method thereof and application thereof in gasoline desulfurization |
| CN105582975B (en) * | 2014-10-22 | 2018-03-27 | 中国科学院大连化学物理研究所 | A kind of modified zeolite catalyst and its application in isopropyl toluene cracks preparing methylbenzene |
| CN107324963B (en) * | 2017-05-19 | 2020-10-27 | 北京化工大学 | Method for preparing hexamethylbenzene by taking cardanol and methanol as raw materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654457A (en) * | 1984-08-10 | 1987-03-31 | Sumitomo Chemical Company, Limited | Method for selective dealkylation of 1,4-dialkylbenzene |
| CN1142986A (en) * | 1994-12-13 | 1997-02-19 | 大连理工大学 | Preparation of modified macro-porous zeolite catalyst and synthetic isopropyl aromatic hydrocarbon |
-
1997
- 1997-10-22 CN CNB971190801A patent/CN1133499C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654457A (en) * | 1984-08-10 | 1987-03-31 | Sumitomo Chemical Company, Limited | Method for selective dealkylation of 1,4-dialkylbenzene |
| CN1142986A (en) * | 1994-12-13 | 1997-02-19 | 大连理工大学 | Preparation of modified macro-porous zeolite catalyst and synthetic isopropyl aromatic hydrocarbon |
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|---|---|
| CN1214961A (en) | 1999-04-28 |
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