CN102039161B - C8 arene isomerization catalyst and application thereof - Google Patents
C8 arene isomerization catalyst and application thereof Download PDFInfo
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Abstract
The invention relates to a C8 arene isomerization catalyst. The catalyst comprises an europium oxide (EUO) molecular sieve and a zeolite socony mobil-5 (ZSM-5) molecular sieve in a weight ratio of 1:10-10:1, 0.1 to 5.0 weight percent of at least one group VIII noble metal and 0.1 to 10.0 weight percent of antimony oxide. Compared with the prior art, the catalyst has higher activity and obviously improved selectivity through synergistic effect of different types of molecular sieves and the antimony oxide, is suitable for an ethylbenzene conversion reaction and has higher ethylbenzene conversion activity and dimethylbenzene selectivity.
Description
Technical field
The present invention relates to a kind of C8 arene isomerization catalyst and application thereof, particularly is the catalyst and the application thereof of xylenes with ethylbenzene conversion.
Background technology
In the production of petrochemical industry, the C8 aromatic hydrocarbons that obtains from the technologies such as steam thermal cracking of catalytic reforming or hydrocarbon ils except that contain to,, the ortho-xylene, also contain ethylbenzene.For satisfying the needs of synthetic fibers to paraxylene, the general appropriate method that adopt are isolated ethylbenzene more, and increase the content of paraxylene through adsorbing separation and isomerized means.But because the boiling point of ethylbenzene and xylenes is very approaching, high, uneconomical economically with the processing charges of highly efficient distilling or adsorbing separation direct separation ethylbenzene, so many in recent years employing chemical reactions are xylenes or benzene with ethylbenzene conversion.Mainly contain two kinds of ethylbenzene conversion approach at present: a kind of is to be converted into xylenes through isomerization, and this approach can improve the yield of purpose product xylenes, receives the favor in market always; Another kind is to generate benzene through taking off ethyl, because benzene cut boiling point and xylenes difference are enough big, is easy to through rectifying it separated, and the production efficiency of device is effectively improved.
Accomplish simultaneously for the reaction that makes ethylbenzene conversion and xylene isomerization, use the solid acid catalyst that contains hydrogenation component that ethylbenzene conversion is drawn attention as benzene and ethane and with the method for xylene isomerization as the thermodynamical equilibrium mixture day by day.The ethylbenzene hydro-dealkylation generates in the process of benzene and ethane, and the conversion of ethylbenzene is restricted by thermodynamical equilibrium hardly, and conversion ratio is higher; Benzene and xylenes boiling point differ bigger simultaneously, and available fractionation separates.Isolated benzene also has to utilize to be worth in synthetic fibers and synthetic resin 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 paraxylene in the product in xylenes, and selection of catalysts property then is to be weighed by the selectivity of xylenes yield and ethylbenzene generation benzene.
The patent that is used for the ethylbenzene conversion aspect now has a lot.And the molecular sieve catalyst of general one or more metals of multipurpose load of prior art, its carrier is used aluminium oxide more, and molecular sieve is used mercerising molecular sieve or ZSM series molecular sieve more.For example United States Patent (USP) 4331822 discloses the gas phase isomerization under a kind of hydroconversion condition, adopts the ZSM-5 molecular sieve, contains two kinds of different metallic in the catalyst, and a kind of is platinum, and another kind is a zinc.This method can improve the conversion ratio of ethylbenzene, but the loss of xylenes is higher.
Disclosed another isomerization method of US4584423 relates to the employing molecular sieve catalyst, like ZSM-5, its load 0.05 to 1.5wt% metal, this metal is selected from the metal group that contains zinc, chromium, iron, barium, tin and caesium.This method is promptly to be lower than under the condition of about 100 pounds/square inch gauge (689 kPas) at not hydrogenation and lower pressure to carry out, and proves that the loss of xylenes is relatively low, and greatly about 1.21-2.65%, and the conversion ratio of ethylbenzene is higher relatively.Yet this method is under hydrogen that does not use interpolation and relatively low pressure condition, to carry out, and its shortcoming is, because coke assembles, catalyst is inactivation quickly easily, thereby has shortened the service life of catalyst.
US4,482,773 have proposed the ZSM-5 catalyst of year Pt and Mg, and conversion of ethylbenzene is also less than 45%.US4,487,731 have proposed ZSM-5 catalyst, the US4 of year Pt and Bi; 939,110 have proposed ZSM-5 catalyst, the US5 of year Pt and Pb, 077; 254 proposed the mercerising molecular sieve catalyst of year Pt (Pd), also the composite molecular sieve catalyst that uses ZSM-5 and mercerising molecular sieve simultaneously arranged; Like US4,467,129 have reported ZSM-5 and the mercerising molecular sieve catalyst that is loaded with a kind of metal among Re, Mo, W, the V.The xylenes yield is 95%～98.5%, and ethylbenzene generates the selectivity of benzene less than 90%.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.
Summary of the invention
To the deficiency of prior art, the invention provides a kind of catalyst, can be ethylbenzene conversion xylenes, contain the paraxylene more than about equilibrium quantity or the equilibrium quantity in the product stream, have characteristics such as conversion of ethylbenzene and xylenes yield height.
C8 arene isomerization catalyst of the present invention; Comprise two kinds of molecular sieves of EUO and ZSM-5 and at least a group VIII noble metals; Also contain antimony oxide in the described catalyst; Wherein the ratio of EUO and ZSM-5 molecular sieve weight content is 1: 10～10: 1, and the antimony oxide weight content is 0.1%～10.0%, and VIII family weight metal content is 0.1%～5.0%.
Molecular sieve described here is the EUO structure molecular screen, and the EUO molecular sieve has one dimension micropore canals structure, and (0.58 * 0.41nm) reaches twelve-ring side pocket (0.68 * 0.58 * 0.81nm) structure of vertical UNICOM with it to contain the straight-through duct of ten-ring.
The silica alumina ratio of described EUO molecular sieve is 10～200; The silica alumina ratio of ZSM-5 molecular sieve is 20～300.The cation that directly synthetic EUO molecular sieve and ZSM-5 molecular sieve generally contain alkali metal or alkaline-earth metal needs to obtain Hydrogen EUO molecular sieve and Hydrogen ZSM-5 molecular sieve through the method for roasting after the ammonium ion exchange of routine.
The ratio of described EUO and ZSM-5 molecular sieve weight content is 10: 1～1: 10, is preferably 10: 1～1: 1, more preferably 10: 1～2: 1.The gross weight content of two kinds of molecular sieves in catalyst is 5%～95%, is preferably 10%～90%, more preferably 20%～80%.
Described group VIII noble metals is preferably platinum and/or palladium, most preferably is platinum.Its weight content in catalyst is 0.1～5.0%, is preferably 0.1%～3.0%, more preferably 0.2%～1.0%.
In order to improve the catalyst serviceability, can add proper assistant as required, auxiliary agent is generally one or more in phosphorus, silicon, the boron, is preferably phosphorus; Auxiliary agent is 0～20wt% in the weight content of oxide in catalyst, is preferably 0.1wt%～10wt%, more preferably 0.2wt%～5.0wt%.
Also can contain other porous, inorganic refractory oxide in the catalyst of the present invention,, be preferably aluminium oxide and/or silica, more preferably aluminium oxide such as in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, zirconia and the clay one or more.
Catalyst of the present invention can adopt conventional method preparation, and wherein the mode that is added in the catalyst of noble metal component can adopt infusion process or ion-exchange, is preferably infusion process.Activity component impregnation solution commonly used is the aqueous solution that contains the reactive metal soluble compound, for example platinum acid chloride solution, platinum amine complex solution, palladium amine complex solution, palladium nitrate solution, palladium chloride solution and organic coordination compound solution thereof.
Antimony oxide can adopt introduces antimony oxide powder or nitric acid antimony powder end mode direct and other solid material powder mixes.Also can use the soluble-salt that contains antimony,, introduce with the form of solution and the mode of other solid material powder mixes like nitric acid antimony.
The mode that said auxiliary agent is added in the catalyst is generally infusion process; Contain the auxiliary compound that needs add in the employed maceration extract; For example phosphoric acid, boric acid or fluosilicic acid amine etc.; The order of dipping can be before the reactive metal load, add afterwards or simultaneously, is preferably before the reactive metal load to join in the carrier.
The application of C8 arene isomerization catalyst of the present invention in the ethylbenzene conversion process.Being specially ethylbenzene conversion is the application in the xylenes process.C8 arene isomerization catalyst of the present invention is generally at the reaction condition that with ethylbenzene conversion is the xylenes process: 300 ℃～450 ℃ of reaction temperatures; Be preferably 350～420 ℃; Pressure 0.1～2.0MPa; Be preferably 0.5～1.5MPa, hydrogen/hydrocarbon mol ratio 0.2～4.0, feed volume air speed (in liquid hydrocarbon) suitable during reaction is 0.5～5.0h
-1, preferred 1～3h
-1
It is to be active component jointly with the ZSM-5 molecular sieve that catalyst of the present invention adopts the EUO molecular sieve; Regulate catalyst surface character through adding antimony oxide; When making catalyst have higher ethylbenzene conversion activity; The selectivity that makes ethylbenzene tautomerize to xylenes improves greatly, and when having solved this area congeneric elements sieve and being used for similar course of reaction, ethylbenzene such as mainly is converted into more than benzene and ethane and the xylene loss at problem.
The specific embodiment
A kind of concrete preparation method of catalyst of the present invention is provided below, but is not limited thereto method, concrete steps are:
(1) molecular sieve, inorganic refractory oxide, antimony oxide, extrusion aid, water and peptizing agent are fully mixed together pinch into plastic paste, extruded moulding through super-dry, calcination process, obtains catalyst carrier.
(2) with the aqueous solution that contains active metal component, selectivity adds the water soluble compound that contains auxiliary agent, through dry, calcination process, makes catalyst of the present invention;
In the step (1), described peptizing agent is inorganic acid or organic acid, is preferably inorganic acid, and more preferably hydrochloric acid and nitric acid most preferably are nitric acid; The weight concentration of salpeter solution is 1.0%～30%, is preferably 1.0%～5.0%; Consumption expects to be as the criterion for plastic block can make to mix to pinch.
Catalyst carrier of the present invention and catalyst are dry, the operating condition of roasting process can be identical with prior art; For example drying condition is normal temperature～300 ℃, is preferably 100 ℃～150 ℃, keeps 1.0h～48h; The carrier roasting condition is 400 ℃～800 ℃; Be preferably 500 ℃～700 ℃, roasting time can be preferably 2～8 for 0.5～24 hour.
The load of the said group VIII metal of step (2) can be adopted ion-exchange or infusion process, and described infusion process can adopt a step dipping, also can adopt step impregnation, is preferably a step dipping.Maceration extract preferably with the water soluble compound solution that contains VIII family metal, floods the used preferred chloroplatinic acid of water soluble compound that contains the group VIII metal, Gu maceration extract/than being preferably 1～5.Described baking temperature can be normal temperature～300 ℃, is preferably 100 ℃～150 ℃, and be 1～48 hour drying time; Described sintering temperature can be 400 ℃～800 ℃, is preferably 500 ℃～700 ℃, and roasting time can be preferably 2～8 for 0.5～24 hour.
Give further explanation through embodiment to technology of the present invention below.
Evaluating catalyst adopts 10 milliliters of continuous flow reactor of fixed bed, and using purity is that the ethylbenzene of 99.9% (volume) is raw material, Hydrogen Vapor Pressure 1.0MPa, and 400 ℃ of temperature, under the condition of hydrogen/hydrocarbon mol ratio 1.5, the volume space velocity of liquid hydrocarbon is 2.0h
-1, reaction is carried out sampling in 8 hours and is carried out chromatography, and the result sees table 1 (down together)
Embodiment 1
A kind of preparation method of catalyst of the present invention.
The used EUO molecular sieve of embodiment is the method preparation according to U.S. Pat 6733658 embodiment 3, and the molecular sieve silica alumina ratio that obtains is 63, specific area 449m
2/ g, pore volume 0.19mL/g.
Above-mentioned synthetic zeolite contains the cation of alkali metal or alkaline-earth metal, exchanges with ammonium cation, and subsequently through roasting in 316 ℃～540 ℃ the air 1～10 hour, it is to know in this area that this kind forms acid zeolite.
(1) preparation catalyst carrier
Get above-mentioned EUO molecular sieve, silica alumina ratio is 58 Hydrogen ZSM-5 molecular sieve, antimony oxide and alumina powder, and according to 40: 10: 5: 45 butt mass ratio fully mixed.Add the weight concentration account for powder gross mass 55% and be 2.5% aqueous solution of nitric acid and mix and pinch, extrusion is the column type bar that diameter is 1.5mm, 110 ℃ of dryings 6 hours, and roasting is 4 hours in 550 ℃ of air.
(2) preparation catalyst
Get carrier 100 grams that step (1) makes, use and contain Pt (NH
3)
4Cl
2Solution carry out saturated dipping, at 110 ℃ of following dry 6h, 380 ℃ of roasting 6h in air atmosphere make the comparative catalyst of the present invention who contains 0.4wt%Pt, are numbered E-1 then, its reaction condition and reaction result in the ethylbenzene conversion reaction is seen table 1.
Embodiment 2
Press the catalyst E-2 of the method preparation of embodiment 1, different is EUO molecular sieve in (1) step, ZSM-5 molecular sieve, antimony oxide and alumina powder, and according to 40: 20: 2: 38 butt mass ratio, its reaction condition and result in the ethylbenzene conversion reaction saw table 1.
Embodiment 3
Press the catalyst E-3 of the method preparation of embodiment 1, different is EUO molecular sieve in (1) step, ZSM-5 molecular sieve, antimony oxide and alumina powder, and according to 50: 5: 1: 44 butt mass ratio, its reaction condition and result in the ethylbenzene conversion reaction saw table 1.
Embodiment 4
Press the catalyst E-4 of the method preparation of embodiment 1, different is EUO molecular sieve in (1) step, ZSM-5 molecular sieve, antimony oxide and alumina powder, and according to 30: 30: 2: 38 butt mass ratio, its reaction condition and result in the ethylbenzene conversion reaction saw table 1.
Embodiment 5
Press the catalyst E-5 of the method preparation of embodiment 1, different is to use in (2) step to contain H
2PtCl
6Carry out saturated dipping with the solution of phosphoric acid, then at 120 ℃ of dry 12h, 480 ℃ of roasting 8h make the catalyst that contains 1.0wt%Pt, 1.4wt%P in air atmosphere.Its reaction condition and result in the ethylbenzene conversion reaction sees table 1.
Embodiment 6
Press the catalyst E-6 of the method preparation of embodiment 1, different is the saturated impregnation catalyst agent carrier of solution that maceration extract contains ammonium dihydrogen phosphate (ADP) in (2) step, through 200 ℃ of dryings 2 hours, obtains phosphorous catalyst carrier.Again with the phosphorous catalyst carrier of the saturated dipping of the aqueous solution that contains palladium bichloride; Through 110 ℃ of dryings 4 hours; 450 ℃ of roasting 3h in the air atmosphere make the catalyst of the present invention that contains 1.8wt%Pd, and its reaction condition and result in the ethylbenzene conversion reaction sees table 1.
Embodiment 7
Press the catalyst E-7 of the method preparation of embodiment 2, different is in (2) step with the saturated impregnation catalyst agent carrier of solution that contains boric acid, through 100 ℃ of dryings 4 hours and 400 ℃ of roastings 2 hours, obtains the catalyst carrier of boracic.Again with the catalyst carrier of the saturated dipping boracic of the aqueous solution that contains platinous chloride amine complex and ammonum chloropalladate complex, through 110 ℃ of dryings 4 hours, 450 ℃ of roasting 3h in the air atmosphere make the catalyst of the present invention that contains 1.0wt%B, 1.8wt%Pd.Its reaction condition and result in the ethylbenzene conversion reaction sees table 1.
Comparative Examples 1
Press the catalyst C-1 of the method preparation of embodiment 1, different is EUO molecular sieve and alumina powder in (1) step, and according to 50: 50 butt mass ratio, its reaction condition and result in the ethylbenzene conversion reaction saw table 1.
Comparative Examples 2
Press the catalyst C-1 of the method preparation of embodiment 1, different is ZSM-5 molecular sieve and alumina powder in (1) step, and according to 50: 50 butt mass ratio, its reaction condition and result in the ethylbenzene conversion reaction saw table 1.
Comparative Examples 3
Press the catalyst C-1 of the method preparation of embodiment 1.Different is EUO molecular sieve and ZSM-5 molecular sieve and alumina powder in (1) step, according to 40: 15: 45 the abundant mixing ratio of butt mass ratio, uses and contains PdCl
2Solution carried out ion-exchange 48 hours at 45 ℃, at 80 ℃ of following dry 24h, 550 ℃ of roasting 2h in air atmosphere make the comparative catalyst who contains 1.2wt%Pd then, its reaction condition and result in the ethylbenzene conversion reaction sees table 1.
Raw material is that volume content is 99.9% ethylbenzene in the table 1, and other percentage is a percentage by volume.
The good reaction result of table 1 ethylbenzene reaction condition
Result by table 1 can find out, compares with the comparative catalyst, compares with the comparative catalyst, and catalyst of the present invention has higher conversion of ethylbenzene and dimethylbenzene selective in the ethylbenzene conversion reaction.
Claims (10)
1. C8 arene isomerization catalyst; It is characterized in that: comprise two kinds of molecular sieves of EUO and ZSM-5 and at least a group VIII noble metals; Also contain antimony oxide in the described catalyst; Wherein the ratio of EUO and ZSM-5 molecular sieve weight content is 1: 10～10: 1, and the antimony oxide weight content is 0.1%～10.0%, and VIII family weight metal content is 0.1%～5.0%.
2. according to the described catalyst of claim 1, it is characterized in that: EUO molecular sieve and ZSM-5 molecular sieve are Hydrogen EUO molecular sieve and Hydrogen ZSM-5 molecular sieve.
3. according to the described catalyst of claim 1, it is characterized in that: the ratio of EUO molecular sieve and ZSM-5 molecular sieve weight content is 10: 1～1: 10, and the gross weight content of two kinds of molecular sieves in catalyst is 5%～95%.
4. according to the described catalyst of claim 1, it is characterized in that: the ratio of EUO molecular sieve and ZSM-5 molecular sieve weight content is 10: 1～1: 1, and the gross weight content of two kinds of molecular sieves in catalyst is 10%～90%.
5. according to the described catalyst of claim 1, it is characterized in that: group VIII noble metals is platinum and/or palladium, and the content in catalyst is 0.1～3.0%.
6. according to the described catalyst of claim 1, it is characterized in that: VIII family weight metal content is 0.2%～1.0%.
7. according to the described catalyst of claim 1, it is characterized in that: also contain in auxiliary agent phosphorus, silicon, the boron one or more in the catalyst, auxiliary agent is 0.1wt%～10wt% in the content of oxide in catalyst.
8. according to the described catalyst of claim 1, it is characterized in that: also contain one or more the porous, inorganic refractory oxide in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, zirconia and the clay in the catalyst.
9. the application of the said catalyst of the arbitrary claim of claim 1 to 8 in the ethylbenzene conversion process.
10. according to the described application of claim 9; It is characterized in that: the ethylbenzene conversion process is for for being the process of xylenes with ethylbenzene conversion; With ethylbenzene conversion is that the reaction condition of xylenes process is 300 ℃～450 ℃ of reaction temperatures; Pressure 0.1～2.0MPa, hydrogen/hydrocarbon mol ratio 0.2～4.0 is 0.5～5.0h in the feed volume air speed of liquid hydrocarbon
-1
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102861607A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | EU-1/ZSM-5 composite molecular sieve, preparation method of EU-1/ZSM-5 composite molecular sieve and application of EU-1/ZSM-5 composite molecular sieve |
| CN102909066B (en) * | 2011-08-01 | 2014-08-20 | 中国石油化工股份有限公司 | Catalyst of toluene disproportionation and alkyl transference, and preparation method and application thereof |
| CN102909063B (en) * | 2011-08-01 | 2014-08-20 | 中国石油化工股份有限公司 | EU-1/Beta composite molecular sieve, and catalyst for toluene disproportionation and transalkylation and application of catalyst |
| CN104353487B (en) * | 2014-11-20 | 2017-08-29 | 西北化工研究院 | A kind of C8 arene isomerization catalysts and its application |
| CN106311321B (en) * | 2015-07-03 | 2019-08-02 | 中国石油天然气股份有限公司 | Catalyst containing EU-1/ZSM-5 eutectic zeolite, preparation method and application |
| CN107297221A (en) * | 2017-07-11 | 2017-10-27 | 太原大成环能化工技术有限公司 | A kind of ethylbenzene dealkylation catalyst and preparation method thereof |
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| CN101173183A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Reforming catalyst and application in producing xylol thereof |
| CN101340976A (en) * | 2005-12-22 | 2009-01-07 | 法国石油公司 | Dual zeolite catalyst comprising a group VIII metal and a group IIIV metal and its use in isomerization of aromatic C8 compounds |
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| CN1260239A (en) * | 1998-11-02 | 2000-07-19 | 法国石油公司 | Method for preparing EUO structural zeolite and use thereof as catalyst |
| CN101340976A (en) * | 2005-12-22 | 2009-01-07 | 法国石油公司 | Dual zeolite catalyst comprising a group VIII metal and a group IIIV metal and its use in isomerization of aromatic C8 compounds |
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