CN102039159B - Xylene isomerization catalyst and application thereof - Google Patents
Xylene isomerization catalyst and application thereof Download PDFInfo
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Abstract
The invention relates to a xylene isomerization catalyst. The catalyst contains a molecular sieve and at least one noble metal of the eighth series. The catalyst also contains zinc, wherein the molecular sieve of the catalyst has a EUP structure; based on the weight of the catalyst, the content of the molecular sieve is 10% to 90%, the content of the noble metal of the eighth series is 0.1% to 10% and the content of the zinc is 0.1% to 20%; and in the catalyst, the weight ratio of the zinc to the noble metal of the eighth series is 0.1 to 50. Compared with the prior art, the activity and the selectivity of the catalyst are obviously improved by adding the zinc to adjust the acid function and the hydrogenation function of the catalyst. When the catalyst is used for C8 aromatic hydrocarbon isomerization, the concentration of the p-xylene in xylene in the products reaches or approaches to the thermodynamic equilibrium value, the xylene yield is high, and a great number of ethylbenzene can be converted so as to selectively generate benzene.
Description
Technical field
The present invention relates to the catalytic converting catalyst and the application thereof of C8 aromatic hydrocarbons, particularly relate to ortho-xylene and meta-xylene and tautomerize to paraxylene catalyst and application thereof, also relate to the conversion of ethylbenzene in the C8 aromatic hydrocarbons.
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.
C8 aromatic hydrocarbons contain usually ethylbenzene and neighbour, and the paraxylene mixture of isomers.These three kinds of xylene isomers usually reach the quantity near thermodynamical equilibrium, generally 52～53wt% meta-xylene can be arranged, the paraxylene of 23～24wt% and the ortho-xylene of 23.5～24.5wt%.Because xylenes (paraxylene, meta-xylene and ortho-xylene) is important intermediate, they have wide variety of applications in chemical synthesis.And paraxylene is used as a kind of chemical intermediate especially more widely, and it is used to produce synthetic textile fibres and resin through the terephthalic acid (TPA) that oxidation can be made.Be the important chemical intermediate that a kind of increasing demand increases,
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.
So will further upgrade to the low bottom product of paraxylene content; Method is that it is carried out isomerization; In isomerization; At least a portion ethylbenzene experience hydrogenolysis and generate benzene and ethane, and a part of ortho-xylene produces a kind of mixture with the meta-xylene isomerization, this mixture again can near the neighbour, and the equilibrium concentration of paraxylene.Be used for the xylene isomerization aspect now many catalyst are arranged.But with traditional technology, like adsorption/desorption on crystallization or the zeolite, it and other isomer separation.After so separating, remaining C
8Aromatic fraction contains ethylbenzene, the meta-xylene isomers adjacent with mixing of unbalanced number, and paraxylene content is very low.And the zeolite catalyst of general one or more metals of multipurpose load of prior art, its carrier is used aluminium oxide more, and zeolite is many with modenite or ZSM series zeolite.
Like 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 mordenite catalyst of year Pt (Pd), also the composite zeolite catalyst that uses ZSM-5 and modenite simultaneously arranged; Like 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.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.
US4331822 discloses the gas phase isomerization under the hydroconversion condition; Adopt crystal silicon-aluminate zeolite; Like ZSM-5; Wherein catalyst contains platinum and two kinds of different metallic of zinc, but in the method because the generation of non-purpose acid catalysis transalkylation reaction and ring crack reaction causes xylene loss a large amount of in the isomerization reaction.
Disclosed another isomerization method of US4584423 relates to the employing zeolite 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.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of alkyl aromatic hydrocarbon isomerization catalyst, and more particularly, the present invention is that a kind of xylene isomerization that can make becomes equilibrium mixture, more effectively makes ethylbenzene take off the catalyst that ethyl generates benzene and ethane simultaneously.
Xylene isomerization catalyst of the present invention comprises a kind of molecular sieve and at least a group VIII noble metals, also contains zinc in the described catalyst, and wherein said molecular sieve is the molecular sieve of EUO structure; Weight with catalyst is benchmark, and molecular sieve content is 10%～90%, is preferably 40%～70%; Group VIII noble metals content counts 0.1%～10% with metal; Be preferably 0.2%～5.0%, zinc (in metal) content is 0.1%～20%, is preferably 0.2%～5.0%; Wherein the weight ratio of zinc (in metal) and group VIII noble metals is 0.1～50 in the catalyst, is preferably 5～20.
The physicochemical property of catalyst of the present invention is following: specific surface is 80～150m
2/ g, pore volume are 0.25～0.60ml/g (adopting ASAP2400 low temperature n2 absorption apparatus to record specific surface and pore volume).
Described group VIII noble metals is preferably platinum and/or palladium, most preferably is platinum.
Described molecular sieve 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.Directly synthetic EUO molecular sieve generally contains the cation of alkali metal or alkaline-earth metal, needs to obtain Hydrogen EUO molecular sieve through the method for roasting after the ammonium ion exchange of routine.
In order to improve the catalyst serviceability, can add proper assistant as required, be generally in phosphorus, silicon, the boron one or more, be preferably phosphorus; Auxiliary agent is 0～20wt% in the 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 and zinc 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.The soluble compound that contains zinc is one or more in zinc nitrate, zinc chloride and the zinc sulfate etc.
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.
Described catalyst applications tautomerizes to paraxylene in xylene isomerization process with meta-xylene and/or ortho-xylene.The application technology condition is generally following: reaction temperature is 350～400 ℃, and reaction pressure is that normal pressure is to 5MPa.
Before reaction, catalyst is carried out reduction activation, active noble metals is existed with simple substance form, reducing condition is following: in the presence of hydrogen, 100 ℃～500 ℃ kept 1～12 hour, and pressure is 0.5MPa～10MPa.
It is main active component that catalyst of the present invention adopts the EUO molecular sieve; Regulate catalyst surface character through adding zinc, when catalyst has desirable xylene isomerization function, reduced xylenes and taken off side reactions such as alkyl; Compare with existing catalyst, obviously reduced the loss of xylenes.Catalyst of the present invention also has higher conversion of ethylbenzene (ethylbenzene dealkylation is converted into benzene and ethane) simultaneously, so this selection of catalysts property obviously improves.
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) EUO molecular sieve, inorganic refractory 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, obtains catalyst of the present invention;
Wherein zinc can be in step (2) before, with containing the catalyst carrier that zinc aqueous solution impregnation steps (1) obtains, through drying, roasting, obtain containing the zinc catalyst carrier; Also can be dipped on the catalyst carrier together with active metal component; Also can soak reactive metal earlier, soak zinc again; Preferential one of the preceding two kinds of methods that adopt.
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 ℃ maintenance 1.0h～48h; The carrier roasting condition is 400 ℃～800 ℃ and keeps 0.5h～10h that the catalyst roasting condition is 350 ℃～600 ℃ and keeps 1.0h～8h.
Through embodiment technology of the present invention is further specified below.
Feedstock property that use in the laboratory is seen table 1, and experiment is on pilot-plant, to accomplish, and catalyst volume 100ml is packed into reactor with after the 100ml quartz sand dilution, and catalyst reduces 4h in the presence of 653K hydrogen before charging.
Table 1 feedstock property (volumn concentration)
| Ethylbenzene | 7.9％ |
| Paraxylene | 0.1％ |
| Meta-xylene | 70.2％ |
| Ortho-xylene | 21.8％ |
Comparative Examples 1
A kind of preparation method of comparative catalyst of the present invention.
(1) preparation of EUO molecular sieve.
The used EUO molecular sieve of the present invention 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.
(2) acid EUO molecular sieve, the alumina powder with step (1) gained fully mixes; The nitric acid that adds 66wt% mixes pinches into plastic paste, and being extruded into diameter is the cylinder bar of 1.5mm, through 110 ℃ of dry 8h; 550 ℃ of roasting 6h in air atmosphere then; The carrier note that makes diameter and be 1.35mm is S-1, and wherein the content of molecular sieve is 60wt% in the carrier, and surplus is an aluminium oxide.
(3) get the carrier that 200 gram steps (2) obtain, use and contain Pt (NH
3)
4Cl
2And Pd (NH
3)
4(NO
3)
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, 0.8wt%Pd, are numbered C-1 then, its physico-chemical property is seen table 3, reaction result is seen table 4.
Comparative Examples 2
The preparation of carrier is with comparative example 1.Get 200 gram above-mentioned carrier S-1, use and 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 comparative catalyst who contains 1.0wt%Pt, 1.4wt%P in air atmosphere, are numbered C-2, and its physico-chemical property is seen table 3, and reaction result is seen table 4.
Comparative Examples 3
The preparation of carrier is with comparative example 1.Get 200 gram above-mentioned carrier S-1, use and contain 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, are numbered C-3 then, its physico-chemical property is seen table 3, reaction result is seen table 4.
Embodiment 1
A kind of preparation method of catalyst of the present invention.
Get 200 gram S-1 carriers, use and contain H
2PtCl
6With the saturated dipping of solution of zinc acetate, and then 100 ℃ of dryings 8 hours, 500 ℃ of roasting 3h in air atmosphere make the catalyst of the present invention that contains 0.6wt%Pt and 2.4wt%Zn, are numbered E-1, and its physico-chemical property is seen table 3, and reaction result is seen table 4.
Embodiment 2
Get 200 gram S-1 carriers, use the solution that contains palladium nitrate and zinc chloride to carry out ion-exchange 12 hours at 60 ℃; And then 110 ℃ of dryings 6 hours; 480 ℃ of roasting 4h in air atmosphere make the catalyst of the present invention that contains 0.8wt%Pd and 0.6wt%Zn, are numbered E-2; Its physico-chemical property is seen table 3, and reaction result is seen table 4.
Embodiment 3
Get 200 gram S-1 carriers; Use contains the saturated impregnation catalyst agent carrier of solution of chloroplatinic acid, zinc nitrate and phosphoric acid, and then 150 ℃ of dryings 4 hours, 540 ℃ of roasting 2h in air atmosphere; Make the catalyst of the present invention that contains 0.3wt%Pt, 4.7wt%Zn and 2.2wt%P; Be numbered E-3, its physico-chemical property is seen table 3, and reaction result is seen table 4.
Embodiment 4
Get 200 gram S-1 carriers,,, obtain containing the zinc catalyst carrier through 250 ℃ of dryings 4 hours with the saturated impregnation catalyst agent carrier of solution that contains zinc chloride.Contain the zinc catalyst carrier with the saturated dipping of the aqueous solution that contains chloroplatinic acid and palladium bichloride again; And then through 120 ℃ of dryings 6 hours; 400 ℃ of roasting 8h in air atmosphere make the catalyst of the present invention that contains 0.2wt%Pt, 1.2wt%Zn and 0.4wt%Pd, are numbered E-4; Its physico-chemical property is seen table 3, and reaction result is seen table 4.
Embodiment 5
Get 200 gram S-1 carriers,,, obtain phosphorous catalyst carrier through 200 ℃ of dryings 2 hours with the saturated impregnation catalyst agent carrier of solution that contains ammonium dihydrogen phosphate (ADP).Again with the phosphorous catalyst carrier of the saturated dipping of the aqueous solution that contains palladium bichloride and zinc chloride; Through 110 ℃ of dryings 4 hours; 450 ℃ of roasting 3h in the air atmosphere make the catalyst of the present invention that contains 0.2wt%Zn and 1.8wt%Pd, are numbered E-5; Its physico-chemical property is seen table 3, and reaction result is seen table 4.
Embodiment 6
Get 200 gram S-1 carriers,,, obtain containing the catalyst carrier of zinc and boron through 100 ℃ of dryings 4 hours and 400 ℃ of roastings 2 hours with the saturated impregnation catalyst agent carrier of solution that contains zinc nitrate and boric acid.The catalyst carrier that contains zinc and boron again with the saturated dipping 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 0.2wt%Zn and 1.8wt%Pd, are numbered E-6; Its physico-chemical property is seen table 2, and reaction result is seen table 3.
The main physico-chemical property of table 2 catalyst
| Catalyst | Pt，wt％ | Pd，wt％ | Zn，wt％ | P 2O 5(B 2O 3)，wt％ | S，m 2/g | V，ml/g |
| C-1 | 0.4 | 0.8 | - | - | 152 | 0.25 |
| C-2 | 1.0 | - | - | 1.4 | 160 | 0.26 |
| C-3 | - | 1.2 | - | - | 168 | 0.23 |
| E-1 | 0.6 | - | 2.4 | - | 180 | 0.28 |
| E-2 | - | 0.8 | 0.6 | - | 192 | 0.27 |
| E-3 | 0.3 | - | 4.7 | 2.2 | 198 | 0.23 |
| E-4 | 0.5 | 0.4 | 1.2 | - | 202 | 0.25 |
| E-5 | 1.4 | 0.1 | 3.1 | 0.5 | 210 | 0.30 |
| E-6 | ?- | 1.8 | 0.2 | 1.0 | 220 | 0.31 |
Wherein, the S presentation surface, V representes pore volume, d representes average pore diameter.
Table 3 catalyst runs condition and result
PX representes paraxylene, and ∑ X representes the xylenes total amount.
Result by table 4 can find out, compares with the comparative catalyst, and catalyst conversion of ethylbenzene of the present invention has improved 4.8%～18.0%, and xylene loss has reduced by 33.3%～56.1%, and reactivity worth is obviously because the comparative catalyst.
Claims (10)
1. an xylene isomerization catalyst comprises a kind of molecular sieve and at least a group VIII noble metals, it is characterized in that: also contain zinc in the described catalyst, wherein said molecular sieve is the molecular sieve of EUO structure; Weight with catalyst is benchmark; Molecular sieve content is 10%～90%; Group VIII noble metals content counts 0.1%～10% with metal, is 0.1%～20% in metal zinc content, and wherein the weight ratio in metal zinc and group VIII noble metals is 0.1～50 in the catalyst.
2. according to the described catalyst of claim 1; It is characterized in that: the weight with catalyst is benchmark; Molecular sieve content is 40%～70%; Group VIII noble metals content counts 0.2%～5.0% with metal, is 0.2%～5.0% in metal zinc content, and wherein the weight ratio in metal zinc and group VIII noble metals is 5～20 in the catalyst.
3. according to the described catalyst of claim 1, it is characterized in that: group VIII noble metals is preferably platinum and/or palladium.
4. according to the described catalyst of claim 1, it is characterized in that: the molecular sieve of EUO structure is a Hydrogen EUO molecular sieve.
5. 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.
6. according to the described catalyst of claim 1, it is characterized in that: 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.
7. according to the described catalyst of claim 1, it is characterized in that: the mode that noble metal component and zinc are added in the catalyst in the catalyst adopts infusion process or ion-exchange.
8. the application of the said catalyst of the arbitrary claim of claim 1～7 in xylene isomerization process.
9. according to the described application of claim 8, it is characterized in that: xylene isomerization process is for to tautomerize to paraxylene with meta-xylene and/or ortho-xylene.
10. according to the described application of claim 9, it is characterized in that: the process conditions of xylene isomerization process are: reaction temperature is 350～400 ℃, and reaction pressure is that normal pressure is to 5MPa.
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| CN103769206B (en) * | 2012-10-25 | 2017-07-14 | 中国石油化工股份有限公司 | EUO structural molecule sieve catalysts and preparation method thereof |
| CN107952472B (en) * | 2016-10-18 | 2021-05-14 | 中国石油化工股份有限公司 | Alkyl aromatic hydrocarbon isomerization catalyst, preparation 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 |
| WO2020154134A1 (en) * | 2019-01-25 | 2020-07-30 | Exxonmobil Chemical Patents Inc. | Activation of low metal content catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6376734B1 (en) * | 1999-06-22 | 2002-04-23 | Institut Francais Du Petrole | Process for the production of at least one isomer of xylenes that comprise an adsorption stage and an isomerization stage with an euo-structural-type catalyst |
| US6528695B1 (en) * | 1999-06-22 | 2003-03-04 | Institut Francais Du Petrole | Process for the production of an isomer of xylenes in three stages: separation, isomerization in the presence of a catalyst based on an EUO zeolite and transalkylation |
| CN101134171A (en) * | 2006-08-31 | 2008-03-05 | 中国石油化工股份有限公司 | Method of producing C8 arene isomerization catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6376734B1 (en) * | 1999-06-22 | 2002-04-23 | Institut Francais Du Petrole | Process for the production of at least one isomer of xylenes that comprise an adsorption stage and an isomerization stage with an euo-structural-type catalyst |
| US6528695B1 (en) * | 1999-06-22 | 2003-03-04 | Institut Francais Du Petrole | Process for the production of an isomer of xylenes in three stages: separation, isomerization in the presence of a catalyst based on an EUO zeolite and transalkylation |
| CN101134171A (en) * | 2006-08-31 | 2008-03-05 | 中国石油化工股份有限公司 | Method of producing C8 arene isomerization catalyst |
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