CN1043740C - Alleyl aromatics isomerizating catalyzer - Google Patents
Alleyl aromatics isomerizating catalyzer Download PDFInfo
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- CN1043740C CN1043740C CN93119747A CN93119747A CN1043740C CN 1043740 C CN1043740 C CN 1043740C CN 93119747 A CN93119747 A CN 93119747A CN 93119747 A CN93119747 A CN 93119747A CN 1043740 C CN1043740 C CN 1043740C
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Abstract
The present invention relates to an alkyl aromatic isomerization catalyst which uses composite zeolite and alumina as carriers and carries noble metal in the eighth family, wherein the composite zeolite is composed of ZSM-5 zeolite and mordenite. When the catalyst is used for isomerization of C8 alkyl aromatics, the concentration of p-dimethylbenzene in xylene in products reaches or approximates to a thermodynamic equilibrium value, thereby obtaining high yield of xylene and converting a large amount of ethyl benzene to selectively generate benzene. The catalyst can also be used for C9 aromatic hydrocarbon to isomerize unstrimethylbenzene for preparing sym-mesitylene.
Description
The present invention is a kind of alkyl aromatic hydrocarbon isomerization catalyst, and more particularly, the present invention is a kind of C of being used for
8Or C
9Aromatics isomerization is the catalyzer of benzene and ethane simultaneously with ethylbenzene conversion.
In the production of petrochemical complex, the C that obtains from the technologies such as steam pyrolysis of catalytic reforming or hydrocarbon ils
8Aromatic hydrocarbons except that contain to,, the o-Xylol, also contain ethylbenzene.For satisfying the needs of synthetic fiber material p-Xylol, the general appropriate means that adopt are isolated ethylbenzene more, and increase the output of p-Xylol by fractionation by adsorption and isomerized means.But because the boiling point of ethylbenzene and dimethylbenzene is very approaching, directly separate the processing charges height of ethylbenzene with highly efficient distilling or fractionation by adsorption, uneconomical economically, so many in recent years employing chemical reactions are dimethylbenzene or benzene with ethylbenzene conversion.
For the reaction that makes ethylbenzene conversion and xylene isomerization is finished simultaneously, be benzene and ethane with ethylbenzene conversion and be that the method for thermodynamic(al)equilibrium mixture draws attention day by day xylene isomerization with the solid acid catalyst that contains hydrogenation component.The ethylbenzene hydro-dealkylation generates in the process of benzene and ethane, and the conversion of ethylbenzene is restricted by thermodynamic(al)equilibrium hardly, and transformation efficiency is higher; Benzene and dimethylbenzene boiling point differ bigger simultaneously, and available fractionation is separated.Isolated benzene also has to utilize to be worth in synthon and synthetic resins industry very much.In this method for transformation, activity of such catalysts is to be weighed by the content and the conversion of ethylbenzene of the p-Xylol in the product in dimethylbenzene, and selectivity of catalyst then is to be weighed by the selectivity of dimethylbenzene yield and ethylbenzene generation benzene.
The general many zeolite catalysts of the prior art of aforesaid method with year one or more metals, its carrier is used aluminum oxide more, and zeolite is then many with mordenite or ZSM series zeolite.As US4,482,773 have proposed ZSM-5 catalyzer, the US4 of year Pt and Mg, 874,731 have proposed ZSM-5 catalyzer, the US4 of year Pt and Bi, and 939,110 ZSM-5 catalyzer, the EP138617A2 that proposed year Pt and Pb have proposed ZSM-5 catalyzer, the US5 of year Mo, 077,254 has proposed the mordenite catalyst of year Pt (or Pd).The composite zeolite catalyst that uses ZSM-5 and mordenite is simultaneously also arranged, and as US4,467,129 have reported ZSM-5 and the mordenite catalyst that is loaded with a kind of metal among Re, Mo, W, the V.All above prior aries can both make xylene isomerization and transform ethylbenzene simultaneously is benzene, but activity of such catalysts and selectivity then are still waiting further raising.As US4,467,129 dimethylbenzene yield is 95～98.5%, and ethylbenzene generates the selectivity of benzene less than 90%.US4,482,773 conversion of ethylbenzene be also less than 45%, and the conversion of ethylbenzene of EP138671A2 less than 25% still.
Purpose of the present invention will provide a kind of ethylbenzene that can more effectively make simultaneously to take off ethyl generation benzene and ethane exactly, and makes xylene isomerization become the catalyzer of equilibrium mixture.Other purpose of the present invention and characteristics will be by hereinafter described further clear and definite.
The present invention is a kind of VIII family precious metal composite zeolite catalyst that is loaded with, and its composite zeolite is made up of ZSM-5 and mordenite.Catalyzer of the present invention is a carrier with composite zeolite and activated alumina, carries platinum or palladium precious metal.The composition of catalyzer of the present invention is: the content of composite zeolite is 20～90 heavy % in the carrier, and is better with 40～70 heavy %; The content of aluminum oxide is 80～10 heavy %, and is better with 60～30 heavy %.And in composite zeolite, the content of ZSM-5 is 1～99 heavy %, and the content of mordenite is 99～1 heavy %.In whole catalyzer, the content of active ingredient VIII family precious metal is 0.01～2 heavy %, and is better with the platinum (Pt) of 0.05～0.3 heavy %.
Preparation of catalysts method of the present invention is as follows: earlier sodium type ZSM-5 zeolite, sodium type mordenite and activated alumina are mixed by a certain percentage, add binding agent mix pinch, moulding, drying, roasting, the carrier that makes exchanges wherein na-pretreated zeolite with ammonium salt solution again, obtain containing the carrier that necessarily takes off the sodium degree, use the precious metal salt solution impregnated carrier then, promptly make catalyzer finished product of the present invention.
Above-mentioned preparation method's detailed step is:
1, ZSM-5, mordenite and aluminum oxide are mixed, mixed powder and rare nitric acid (concentration is 1～5 heavy %, and heavily % are better with 1.5～3.0) mix by the weight ratio of 100: 25～60 (better with 100: 35～45) and pinch, moulding, drying.In air, after 470～650 ℃ (better with 500～600 ℃) descend roastings 2～8 hours (with 3～6 hours better), promptly make the carrier of catalyzer of the present invention.
2, under the temperature range of room temperature to 120 ℃ (better) with 85～100 ℃, with carrier with the ammonium salt solution of 0.1～0.8N concentration (better) such as ammonium chloride, ammonium nitrate solution with 0.2～0.5N, wherein na-pretreated zeolite is exchanged, each exchange 1～6 hour (better) with 1～3 hour, the sodium degree that takes off up to zeolite is 30～90% (better with 55～85%), filters then, washs, drying.
3, with above-mentioned be under 1～3 the condition through the carrier after the ammonium exchange in room temperature, liquid-solid ratio, with 8～60 hours (better) of chloride soln dipping of precious metals such as Platinic chloride or Palladous chloride with 12～36 hours, drying more after filtration,, in air,, promptly obtain catalyzer of the present invention after the cooling in 400～600 ℃ of (better) activation 1～10 hour (better) with 3～6 hours with 450～550 ℃.
Used ZSM-5 zeolite is the high silica ZSM-5 zeolite of dying of Shanghai seven factory's suitability for industrialized production in the catalyzer of the present invention, its SiO
2/ Al
2O
3Mol ratio is greater than 90, more preferably greater than 140.Used mordenite is the product of No.3 Petroleum Factory, Fushun Petroleum Chemical Industry Co., and wherein the industrial trade mark greater than 1 μ crystal grain is STM-381, is SSM-385 less than the industrial trade mark of 1 μ crystal grain, its SiO
2/ Al
2O
3Mol ratio is 8～20.Aluminum oxide is the pure γ-Al that is made by the low-carbon alkoxy aluminium hydrolysis according to Chinese patent CN85100218.8 method
2O
3Table 1～table 3 is physico-chemical properties of ZSM-5 zeolite, mordenite and aluminum oxide.
The physico-chemical property of table 1 ZSM-5 zeolite
| SiO 2/Al 2O 3 Mol/Mol | Na 2The heavy % of O | The heavy % of N | Relative crystallinity % |
| 152.5 | 0.903 | 0.76 | 100 |
The physico-chemical property of table 2 mordenite
| Crystal grain, μ | Specific surface, m 2/g | Relative crystallinity, % | Na +, heavy % |
| ＞1 | 427 | ＞85 | 4.80 |
| ＜1 | 507 | ＞85 | 4.07 |
The physico-chemical property of table 3 aluminum oxide
| Specific surface m 2/g | Pore volume ml/g | Average pore radius, _ | Crystalline phase is formed, % | |
| α-Al 2O 3·H 2O | β-Al 2O 3·3H 2O | |||
| 227.27 | 0.5613 | 49 | ＞95 | ＜5 |
Catalyzer of the present invention is mainly used in C
8The isomerization of aromatic hydrocarbons, but also can be used for C
9Aromatic hydrocarbons.The performance test of catalyzer is on testing laboratory's small stationary bed reaction device, carries out under the condition of facing hydrogen.The Intake Quantity of catalyzer is 2～10ml, and reaction conditions is: 300～500 ℃ of temperature, with 350～450 ℃ better, pressure is 0～2.0MPa (gauge pressure), and is good with 0.2～1.2MPa, volume space velocity (LHSV) is 0.5～15h
-1, with 2～12h
-1Better, hydrogen hydrocarbon mol ratio 0.1～5, better with 0.5～3.
Catalyzer of the present invention is when being used for C
8During aromatics isomerization, at 380～420 ℃ of temperature, pressure 0.6～1.0MPa, LHSV 8～12h
-1, hydrogen hydrocarbon mol ratio 1～2 condition under, the content of p-Xylol in dimethylbenzene is 23～24% in the product, reaches thermodynamic equilibrium value; Conversion of ethylbenzene can reach 50～60%, and ethylbenzene generates the selectivity of benzene generally greater than 90%.In the test of part, the yield of dimethylbenzene can reach 99.0～99.5%.And in the prior art, as US4, the ZSM-5 catalyzer of 482,773 used years Pt and Mg, its dimethylbenzene yield is less than 98.5%, and conversion of ethylbenzene is lower than 45%; The conversion of ethylbenzene of EP138617 is less than 25% still.Stability tests in 200 hours of catalyzer of the present invention show that its activity, selectivity all stablize.
Catalyzer of the present invention is when being used for C
9During aromatics isomerization, the unsym-trimethyl benzene isomerization can be obtained sym-trimethylbenzene, the content of sym-trimethylbenzene reaches thermodynamic equilibrium value in the product.Under the condition of 400～450 ℃ and 4～10MPa, the content of sym-trimethylbenzene in trimethylbenzene reaches more than 22%, and side reaction is few, and dimethylbenzene of Sheng Chenging and durene all have bigger use value simultaneously.
Compared with prior art, the advantage of catalyzer of the present invention is:
1, when being used for C
8During aromatics isomerization, content can be up to 23～24% in the total xylene of product for p-Xylol; Dimethylbenzene yield height, general all more than 97%, discrete can reach 99.0～99.5%; Conversion of ethylbenzene can reach 50～60%; Ethylbenzene generates the selectivity of benzene greater than 90%; And above-mentioned stable performance.
2, can be used for C
9Aromatics isomerization can change into sym-trimethylbenzene with unsym-trimethyl benzene effectively, and the sym-trimethylbenzene in the product reaches thermodynamic equilibrium value in total trimethylbenzene content.
Constitute the composite zeolite of catalyst characteristics of the present invention, there are certain relation in the relative content of its ZSM-5 and mordenite and activity of such catalysts and selectivity.Description of drawings this relation.Fig. 1 is the content of ZSM-5 zeolite in composite zeolite and the relation of catalyst activity, and Fig. 2 is the content of ZSM-5 zeolite in composite zeolite and the relation of selectivity of catalyst.The catalyzer that 5 used zeolites are formed in Fig. 1 and Fig. 2 all will relate separately in following embodiment.By the trend of the curvilinear motion among two figure as can be seen, when the content of ZSM-5 zeolite in composite zeolite was 55～85wt%, the good and activity of selectivity of catalyst was also than higher.
Below further specify Preparation of catalysts process of the present invention and performance by embodiment.
Embodiment 1～5
Get ZSM-5 zeolite, mordenite, and aluminum oxide mix through after the weighing according to the part by weight in the table 4.Mixed powder is that 100: 40 weight ratio is mixed and pinched with rare nitric acid of 2% concentration with powder and acid respectively, make the partial oxidation aluminium glue molten, through extruded moulding, under the temperature of in table 4, listing after the drying as binding agent, in air,, promptly make carrier 600 ℃ of roastings 2 hours.According to zeolite weight ratios different in the table 4, successively carrier is represented with a, b, c, d, e.
Get carrier a, b, c, d, each 100g of e, use 600ml, 5%NH respectively
4The Cl aqueous solution exchanges 2 hours under 95 ℃ temperature, after filtration, deionized water washing is used AgNO to filtrate
3Till solution check sediment-free generates, promptly obtain the carrier of ammonium type after the drying.
Get ammonium type carrier a, b, c, each 50g of d, e again, at room temperature reach different liquid-solid ratioes, platinum acid chloride solution with 0.35mg/ml concentration flooded 20 hours, filtering the back spread 4 hours in 60 ℃ in baking oven, 120 ℃ of dryings 4 hours, in the tubular type furnace air, activate 4 hours again, promptly make the finished catalyst of the present invention that carries platinum 0.1 heavy %, represent with A, B, C, D, E successively.Before use should be at 500 ℃ with hydrogen reducing 4 hours.Table 4
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| Carrier component weight ratio ZSM-5: mordenite: γ-Al 2O 3 | 55∶5∶40 | 50∶10∶40 | 45∶15∶40 | 40∶20∶40 | 10∶50∶40 |
| Moulding after drying temperature, ℃ | 110 | 110 | 115 | 120 | 120 |
| The carrier code name | a | b | c | d | e |
| Liquid-solid ratio when soaking platinum (weight) | 1.2 | 1.3 | 1.4 | 1.4 | 1.5 |
| The catalyzer code name | A | B | C | D | E |
Embodiment 6～10
The catalyst A of the present invention, B, C, D, the E that prepare with the foregoing description 1～5 face hydrogen and carry out C on testing laboratory's small stationary bed reaction device
8The aromatics isomerization reaction test.Tube inner diameter is 9mm, and the catalyzer Intake Quantity is 6ml.Reaction conditions is: 400 ℃ of temperature, pressure 0.8MPa, volume space velocity 10h
-1, hydrogen hydrocarbon mol ratio 1.5, mixed C
8Aroamtic hydrocarbon raw material is formulated by the monomer aromatic component.Table 5
[notes]:
| Raw material or reactant are formed, heavy % | Mixed C 8Aroamtic hydrocarbon raw material | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| The catalyzer that uses | ||||||
| A | B | C | D | E | ||
| C 7And C 7Following component C 8Saturated hydrocarbon component benzene toluene ethylbenzene paraxylene meta-xylene ortho-xylene C9And C 9Above component | 0.02 - - 0.31 15.95 2.51 61.40 19.99 - | 3.00 0.08 6.69 1.19 6.28 19.50 43.87 18.24 1.15 | 1.98 0.02 5.93 0.96 7.40 19.59 44.62 18.42 1.08 | 1.21 - 5.68 0.77 7.90 19.90 44.93 18.63 0.98 | 0.54 - 4.83 1.10 8.91 19.57 44.98 18.52 1.55 | 0.23 0.03 2.19 2.30 11.81 18.96 42.96 18.03 3.49 |
| Reactivity worth p-Xylol/xylene xylene yield conversion of ethylbenzene p-Xylol balance delivery rate ethylbenzene generates benzene selective | 23.89 97.27 60.63 101.5 94.02 | 23.71 98.49 53.61 100.7 94.25 | 23.84 99.48 50.47 101.3 95.89 | 23.56 99.01 44.14 100.1 93.24 | 23.71 95.29 25.96 100.7 71.89 | |
Embodiment 11
Present embodiment is that catalyzer of the present invention is used for C
9Aromatics isomerization, used catalyzer are the catalyzer C by embodiment 3 preparations.Isomerization reaction is carried out under the condition of facing hydrogen on testing laboratory's small stationary bed apparatus, and raw material is the BTX aromatics for preparing still.Catalyzer Intake Quantity 6ml.Reaction conditions is: 430 ℃ of temperature, pressure 0.8MPa, volume space velocity 3.1h
-1, hydrogen hydrocarbon mol ratio 1.5.Reaction result sees Table 6.Table 6
| Form heavy % | C 9Aroamtic hydrocarbon raw material | Reaction product |
| Other C of dimethylbenzene sym-trimethylbenzene unsym-trimethyl benzene hemimellitene 9Other component of aromatic hydrocarbons durene | 0.03 0.45 99.12 - 0.37 - 0.03 | 6.10 19.69 59.03 8.42 0.21 4.90 1.65 |
The content of sym-trimethylbenzene in trimethylbenzene is 22.60% in reaction product, and the unsym-trimethyl benzene transformation efficiency is 40.45%.
Claims (6)
1, a kind of is carrier with zeolite and aluminum oxide, be loaded with the alkyl aromatic hydrocarbon isomerization catalyst of VIII family noble metal active component, it is characterized in that the composite zeolite that zeolite is made up of ZSM-5 zeolite and mordenite, the content of composite zeolite is 20～90 heavy % in support of the catalyst, the content of aluminum oxide is 80～10 heavy %, in composite zeolite, the content of ZSM-5 zeolite is 1～99 heavy %, the content of mordenite is 99～1 heavy %, in catalyzer, VIII family noble metal active components contents is 0.01～2 heavy %.
2, according to the said catalyzer of claim 1, the content that it is characterized in that composite zeolite in the carrier is 40～70 heavy %, and the content of aluminum oxide is 60～30 heavy %.
3, according to claim 1 or 2 said catalyzer, it is characterized in that γ-Al that aluminum oxide makes for the low-carbon alkoxy aluminium hydrolysis
2O
3
4,, it is characterized in that the SiO of described ZSM-5 zeolite according to the said catalyzer of claim 1
2/ Al
2O
3Mol ratio is greater than 90.
5,, it is characterized in that the SiO of described ZSM-5 zeolite according to the said catalyzer of claim 4
2/ Al
2O
3Mol ratio is greater than 140.
6, according to the said catalyzer of claim 1, it is characterized in that active ingredient VIII family precious metal is a platinum, in whole catalyzer, the content of platinum is 0.05～0.3 heavy %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93119747A CN1043740C (en) | 1993-11-05 | 1993-11-05 | Alleyl aromatics isomerizating catalyzer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93119747A CN1043740C (en) | 1993-11-05 | 1993-11-05 | Alleyl aromatics isomerizating catalyzer |
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|---|---|
| CN1102360A CN1102360A (en) | 1995-05-10 |
| CN1043740C true CN1043740C (en) | 1999-06-23 |
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Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052667C (en) * | 1995-10-06 | 2000-05-24 | 中国石油化工总公司 | Polymetal carrying alkyl aromatic hydrocarbon isomerization catalyst |
| ID18446A (en) * | 1996-05-29 | 1998-04-09 | Exxon Chemical Patents Inc | PROCESS FOR ISOMERIZATION OF ALCILAROMATIC HYDROCARBONES |
| CN1075482C (en) * | 1998-11-13 | 2001-11-28 | 中国石油化工集团公司 | Process for isomerizing mixture of meta-xylene and para-xylene |
| CN1081179C (en) * | 1999-04-06 | 2002-03-20 | 黑龙江省科学院石油化学研究分院 | Catalytic alkylating separation process of mixed C9 arene to prepare high-purity S-trimethylbenzene |
| CN100425343C (en) * | 2005-06-30 | 2008-10-15 | 中国石油化工股份有限公司 | Alkyl arene isomerizing catalyst and its usage |
| US7297830B2 (en) * | 2005-09-14 | 2007-11-20 | Uop Llc | Process for isomerizing non-equilibrium xylene-containing feed streams |
| KR101470623B1 (en) | 2006-11-17 | 2014-12-12 | 에스케이이노베이션 주식회사 | Catalyst for xylene isomerization and process for preparing the same |
| CN101898145B (en) * | 2009-05-27 | 2012-12-12 | 中国石油化工股份有限公司 | Alkyl aromatic hydrocarbon isomerization catalyst and preparation method thereof |
| CN102309979B (en) * | 2010-07-07 | 2013-05-01 | 中国石油化工股份有限公司 | Catalyst for isomerizing ethyl benzene into dimethyl benzene and preparation method and application thereof |
| CN103418423B (en) * | 2012-05-22 | 2016-06-22 | 中国石油化工股份有限公司 | Arene isomerization catalyst and preparation method |
| CN103418422B (en) * | 2012-05-22 | 2016-06-22 | 中国石油化工股份有限公司 | A kind of alkyl aromatic hydrocarbon isomerization catalyst and preparation method |
| TWI657860B (en) * | 2014-07-07 | 2019-05-01 | 荷蘭商蜆殼國際研究公司 | Isomerization catalyst |
| CN107282097B (en) * | 2016-04-12 | 2019-12-27 | 中国石油化工股份有限公司 | Hydroisomerization catalyst and preparation method and application thereof |
| CN107970989B (en) * | 2016-10-25 | 2021-02-09 | 中国石油化工股份有限公司 | Preparation method of xylene isomerization catalyst |
| CN107673946A (en) * | 2017-11-09 | 2018-02-09 | 江苏华伦化工有限公司 | The method that continuity method isomerization produces durol |
| CN115212919B (en) * | 2021-04-19 | 2024-06-25 | 中国石油天然气股份有限公司 | Catalyst containing ZSM-5/MOR eutectic zeolite and preparation method and application thereof |
| CN114602548B (en) * | 2022-01-24 | 2023-05-23 | 中国科学院上海高等研究院 | Metal monoatomic dispersed alkane isomerization catalyst and preparation method thereof |
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| US5041401A (en) * | 1990-03-28 | 1991-08-20 | Mobil Oil Corporation | Thermally stable noble metal-containing zeolite catalyst |
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