CN102309979A - Catalyst for isomerizing ethyl benzene into dimethyl benzene and preparation method and application thereof - Google Patents
Catalyst for isomerizing ethyl benzene into dimethyl benzene and preparation method and application thereof Download PDFInfo
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- CN102309979A CN102309979A CN2010102211530A CN201010221153A CN102309979A CN 102309979 A CN102309979 A CN 102309979A CN 2010102211530 A CN2010102211530 A CN 2010102211530A CN 201010221153 A CN201010221153 A CN 201010221153A CN 102309979 A CN102309979 A CN 102309979A
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Abstract
The invention discloses a catalyst for isomerizing ethyl benzene into dimethyl benzene and a preparation method and application thereof. The catalyst comprises the following components: 5 to 95 percent of MCM-22 zeolite and mordenite, 0.1 to 10.0 percent of antimony oxide, 0.01 to 5.0 percent of VIII noble metal, and the balance of inorganic refractory oxide, wherein the weight content ratio of the MCM-22 zeolite to the mordenite is 1:10-10:1. The catalyst is particularly suitable for the isomerization process of ethyl benzene-containing C8 mixed arene, and has relatively high ethyl benzene conversion activity and dimethyl benzene selectivity and low dimethyl benzene loss.
Description
Technical field
The present invention relates to a kind of ethylbenzene isomerization is the xylenes Catalysts and its preparation method, is particularly containing the C of ethylbenzene
8In the BTX aromatics isomerization process.
Background technology
In petrochemical production process, the C that obtains from various technologies
8In the aromatic hydrocarbons, except to,, adjacent three kinds of xylenes, also contain ethylbenzene.As raw material,, can obtain the paraxylene product through joint operations such as isomerization, rectifying and adsorbing separation.Because ethylbenzene and xylenes boiling point are very approaching, separation difficulty causes ethylbenzene accumulation in the combined unit recycle stream, causes isomerization combined unit logistics internal circulating load to improve, and the operating severity of adsorbing separation increases, and but can not increase the output capacity of device.For avoiding above situation to take place, improve the production efficiency of device, just must the part ethylbenzene conversion be removed.At present, ethylbenzene conversion mainly contains two approach: a kind of is that ethylbenzene is converted into xylenes through isomerization, and this approach can improve the yield of purpose product xylenes; Another kind is that ethylbenzene takes off ethyl generation benzene, 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.
It is a lot of at present to be converted into the patent of xylenes catalyst about ethylbenzene isomerization; This catalyst mainly is to adopt ZSM series and SAPO series zeolite etc. to be acidic components; Adopting group VIII metal is the hydrogenation active metals component, like US5028573, EP0151351A, US5276236.Above-mentioned catalyst is converted in conversion of ethylbenzene and ethylbenzene isomerization can not be taken into account aspect the selectivity two of xylenes, and when conversion of ethylbenzene was higher, its selectivity was relatively poor, and vice versa.
CN1901991A discloses a kind of C
8Arene isomerization catalyst, adopting MTW type zeolite is that low silica ZSM-12 is acidic components, is active metal component with platinum and germanium, above-mentioned catalyst applications is in C
8During aromatics isomerization, though conversion of ethylbenzene is higher, the loss late of xylenes is higher, explains that side reaction is more, and selection of catalysts property is relatively poor, and paraxylene does not reach equilibrium quantity yet in the product stream.
Summary of the invention
For overcoming shortcoming of the prior art, the invention provides the good ethylbenzene isomerization of a kind of activity and selectivity is the xylenes Catalysts and its preparation method, and this catalyst is containing the C of ethylbenzene
8The application of BTX aromatics isomerization process.This catalyst is at the C that is used to contain ethylbenzene
8In the BTX aromatics isomerization process, have higher conversion of ethylbenzene and dimethylbenzene selective, can make simultaneously the paraxylene that contains in the product stream more than about equilibrium quantity or the equilibrium quantity, xylene loss is few.
Ethylbenzene isomerization of the present invention is the xylenes catalyst, is benchmark with the weight of catalyst, and form as follows: the total content of MCM-22 zeolite and modenite is 5.0%～95.0%; Be preferably 10.0%～90.0%; More preferably 20.0%～80.0%, antimony oxide content is 0.1%～10.0%, is preferably 0.5%～6.0%; VIII family bullion content is 0.01%～5.0%, and surplus is an inorganic refractory oxide; Wherein the ratio of the weight content of MCM-22 zeolite and modenite is 1: 10～10: 1, is preferably 10: 1～1: 1, more preferably 10: 1～2: 1.
The silica alumina ratio of MCM-22 zeolite of the present invention is 10～200; The silica alumina ratio of modenite is 10～50.Described MCM-22 zeolite and modenite adopt h-type zeolite.Directly synthetic molecular sieve generally contains the cation of alkali metal or alkaline-earth metal, can obtain hydrogen type molecular sieve through the method for roasting after the ammonium ion exchange of routine.
Described VIII family noble metal is platinum and/or palladium, is preferably platinum, and the weight content of described VIII family's noble metal in catalyst is preferably 0.02%～3.0%, more preferably 0.05%～1.0%.
Described inorganic refractory oxide is one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, zirconia and the clay, is preferably aluminium oxide and/or silica, more preferably aluminium oxide.
Ethylbenzene isomerization of the present invention is an xylenes Preparation of catalysts method, comprises the steps:
(1) MCM-22 zeolite, modenite, antimony oxide, inorganic refractory oxide precursor and peptizing agent are mixed, behind the kneading and compacting,, obtain catalyst carrier through drying and roasting;
(2) the catalyst carrier load regulation VIII family noble metal of step (1) gained after dry and roasting, 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/or 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.The condition of said drying and roasting is following: 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 0.5～24 hour, is preferably 2～8 hours.
Inorganic refractory oxide precursor described in the step (1) can adopt the conventional material that kneading and compacting prepares carrier that is used for, such as the corresponding hydroxide of inorganic refractory oxide, hydrous oxide etc.
The load of the said VIII of step (2) family noble metal 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 noble metal, floods the used preferred chloroplatinic acid of water soluble compound that contains VIII family noble metal, and maceration extract/solid volume ratio is 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 0.5～24 hour, is preferably 2～8 hours.
Catalyst of the present invention can be used for containing the hydrocarbon raw material of ethylbenzene, contains the C of ethylbenzene especially for processing
8Aromatic hydrocarbons mixture especially contains ethylbenzene and the poor C that contains paraxylene
8Aromatic hydrocarbons mixture, wherein the weight content of ethylbenzene is 10%～45%.Described C
8In the aromatic hydrocarbons mixture, the weight content of meta-xylene is less than 60%, and the weight content of ortho-xylene is not less than 10%.
The application of catalyst provided by the invention in xylene isomerization process comprises making raw material in the presence of hydrogen, is 0.5～5.0h in 300 ℃～450 ℃, 0.1～2.0MPa, hydrogen/hydrocarbon mol ratio 0.2～4.0 and feed volume air speed
-1Condition under contact with catalyst of the present invention and to carry out isomerization reaction; Preferred operating condition is following: 350～420 ℃ of reaction temperatures, reaction pressure 0.5～1.5MPa, hydrogen/hydrocarbon mol ratio 0.2～4.0 and feed volume air speed are 1.0～3.0h
-1
Catalyst of the present invention adopts MCM-22 and two kinds of zeolites of mercerising, and adopts kneading method that antimony is incorporated on the molecular sieve, modifies two kinds of zeolites, and adjustment hole structure and acid strength make catalyst of the present invention be used to handle the C that contains ethylbenzene
8During BTX aromatics; It is less to take off side reactions such as alkyl, transalkylation, cracking, disproportionation; Improved conversion of ethylbenzene and dimethylbenzene selective, can also make simultaneously the paraxylene that contains in the product stream more than about equilibrium quantity or the equilibrium quantity, xylene loss is few.
The specific embodiment
Through embodiment the present invention is described further below, but the present invention is not limited to this.
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.Reaction condition and reaction result that each embodiment is used are seen table 2.
Table 1 feedstock property (quality percentage composition)
| Ethylbenzene | 22.9％ |
| Paraxylene | 0.1％ |
| Meta-xylene | 55.2％ |
| Ortho-xylene | 21.8％ |
Embodiment 1
(1) preparation catalyst carrier
Get silica alumina ratio and be 32 Hydrogen MCM-22 zeolite, silica alumina ratio and be 28 h-mordenite, antimony oxide and alumina powder, according to 40: 10: 5: 45 butt mass ratio fully mixed.Add the 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, 120 ℃ of dryings 6 hours, and roasting is 4 hours in 550 ℃ of air, makes catalyst carrier.
(2) preparation catalyst
Get (1) step carrier that makes 100 grams, join in 200 milliliters of platinum acid chloride solutions that contain 0.3 gram platinum, room temperature condition dynamically kept 12 hours, collected solid, and in 100 ℃ of dryings 6 hours, 480 ℃ of roastings were 3 hours in the air, obtain catalyst, numbering E-1.The reaction result of its catalyst is seen table 2.
Embodiment 2
Method by embodiment 1 prepares catalyst E-2, and different is MCM-22 zeolite, modenite, antimony oxide and alumina powder in (1) step, and according to 10: 20: 2: 68 butt mass ratio, the reaction result of its catalyst was seen table 2.
Embodiment 3
Method by embodiment 1 prepares catalyst E-3, and different is MCM-22 zeolite, modenite, antimony oxide and alumina powder in (1) step, and according to 50: 25: 1: 24 butt mass ratio, the reaction result of its catalyst was seen table 2.
Embodiment 4
Press the catalyst E-4 of the method preparation of embodiment 1; Silica alumina ratio is that 132 MCM-22 zeolite, silica alumina ratio are 36 modenite, antimony oxide and alumina powder in different is (1) step; According to 30: 30: 2: 38 butt mass ratio, the reaction result of its catalyst was seen table 2.
Embodiment 5
Method by embodiment 1 prepares catalyst E-5, and different is that the volume of maceration extract was 300 milliliters during (2) went on foot, and wherein platiniferous 0.15 restrains, and the reaction result of its catalyst is seen table 2.
Embodiment 6
Method by embodiment 1 prepares catalyst E-6, and different is that the volume of maceration extract was 100 milliliters during (2) went on foot, and wherein contains palladium 0.35 gram, and the reaction result of its catalyst is seen table 2.
Embodiment 7
Press the catalyst E-7 of the method preparation of embodiment 1, different is that the volume of maceration extract was 200 milliliters during (2) went on foot, and wherein platiniferous 0.25 restrains, contains palladium 0.10 gram, and the reaction result of its catalyst is seen table 2.
Comparative Examples 1
Method by embodiment 1 prepares catalyst C-1, and different is not add modenite and antimony oxide, i.e. MCM-22 zeolite and alumina powder in (1) step fully mix according to 50: 50 butt mass ratioes, and the reaction result of its catalyst is seen table 2.
Comparative Examples 2
Method by embodiment 1 prepares catalyst C-2, and different is not add MCM-22 zeolite and antimony oxide, i.e. modenite and alumina powder in (1) step fully mix according to 50: 50 butt mass ratioes, and the reaction result of its catalyst is seen table 2.
Comparative Examples 3
Press the catalyst C-3 of the method preparation of embodiment 1; Different is not add antimony oxide in (1) step; MCM-22 zeolite, modenite and alumina powder fully mix according to 40: 10: 50 butt mass ratioes in i.e. (1) step, and the reaction result of its catalyst is seen table 2.
Table 2 catalyst runs condition and result
[notes]: the percentage in the table 2 is mass percent.
PX representes paraxylene, and ∑ X representes the xylenes total amount.
1. xylene loss is represented in this process for negative, and xylene content increases.
Result by from table 1 can find out that the very low even increase of the xylene loss of catalyst of the present invention explains that the ethylbenzene major part is converted into xylenes.Compare catalyst conversion of ethylbenzene of the present invention with the comparative catalyst and obviously improve, xylene loss obviously reduces.
Claims (16)
1. an ethylbenzene isomerization is the xylenes catalyst; Weight with catalyst is benchmark; Form as follows: the total content of MCM-22 zeolite and modenite is 5.0%～95.0%; Antimony oxide content is 0.1%～10.0%, and VIII family bullion content is 0.01%～5.0%, and surplus is an inorganic refractory oxide; Wherein the ratio of the weight content of MCM-22 zeolite and modenite is 1: 10～10: 1.
2. according to the described catalyst of claim 1, the ratio that it is characterized in that the weight content of described MCM-22 zeolite and modenite is 10: 1～1: 1.
3. according to the described catalyst of claim 1, the ratio that it is characterized in that the weight content of described MCM-22 zeolite and modenite is 10: 1～2: 1.
4. according to the arbitrary described catalyst of claim 1 to 3, it is characterized in that described MCM-22 zeolite and modenite are h-type zeolite, the silica alumina ratio of described MCM-22 zeolite is 10～200, and the silica alumina ratio of described modenite is 10～50.
5. according to the described catalyst of claim 1, it is characterized in that described MCM-22 zeolite and modenite gross weight content in catalyst is 20.0%～80.0%.
6. according to the described catalyst of claim 1, it is characterized in that described VIII family noble metal is platinum and/or palladium.
7. according to the described catalyst of claim 1, it is characterized in that the weight content of described VIII family's noble metal in catalyst is 0.05%～1.0%.
8. according to claim 1,5 or 7 described catalyst, it is characterized in that the weight content of described antimony oxide in catalyst is 0.5%～6.0%.
9. according to the described catalyst of claim 1, it is characterized in that described inorganic refractory oxide is one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, zirconia and the clay.
10. according to the described catalyst of claim 1, it is characterized in that described inorganic refractory oxide is an aluminium oxide.
11. the arbitrary said Preparation of catalysts method of claim 1～10 comprises:
(1) MCM-22 zeolite, modenite, antimony oxide, inorganic refractory oxide precursor and peptizing agent are mixed, behind the kneading and compacting,, obtain catalyst carrier through drying and roasting;
(2) the catalyst carrier load regulation VIII family noble metal of step (1) gained, after dry and roasting, making said ethylbenzene isomerization is the xylenes catalyst.
12. according to the described preparation method of claim 11, it is characterized in that in the step (1), described peptizing agent is a nitric acid, the weight concentration of salpeter solution is 1.0%～30.0%, consumption expects to be as the criterion for plastic block can make to mix to pinch; The condition of said drying and roasting is following: described baking temperature is normal temperature～300 ℃, and be 1～48 hour drying time; Described sintering temperature is 400 ℃～800 ℃, and roasting time is 0.5～24 hour.
13. according to the described preparation method of claim 11, it is characterized in that ion-exchange or infusion process are adopted in the load of the said VIII of step (2) family noble metal, described baking temperature is normal temperature～300 ℃, be 1～48 hour drying time; Described sintering temperature is 400 ℃～800 ℃, and roasting time is 0.5～24 hour.
14. a processing contains the C of ethylbenzene
8The method of BTX aromatics; It is characterized in that adopting the arbitrary said catalyst of claim 1～10; Process is following: raw material is in the presence of hydrogen; With described catalyst haptoreaction, reaction condition is following: 300 ℃～450 ℃, 0.1～2.0MPa, hydrogen/hydrocarbon mol ratio 0.2～4.0 and feed volume air speed are 0.5～5.0h
-1
15. according to the described method of claim 14, it is characterized in that described reaction condition is following: 350～420 ℃ of reaction temperatures, reaction pressure 0.5～1.5MPa, hydrogen/hydrocarbon mol ratio 0.2～4.0 and feed volume air speed are 1～3h
-1
16., it is characterized in that described raw material is the poor C that contains paraxylene according to the described method of claim 14
8Aromatic hydrocarbons mixture.
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| CN2010102211530A CN102309979B (en) | 2010-07-07 | 2010-07-07 | Catalyst for isomerizing ethyl benzene into dimethyl benzene and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105833900A (en) * | 2016-04-06 | 2016-08-10 | 山东成泰化工有限公司 | Isomerization catalyst and preparation method thereof |
| CN108246354A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of preparation method of catalyst, preparation method and dimethylbenzene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0151351A1 (en) * | 1984-01-11 | 1985-08-14 | Mobil Oil Corporation | Process for isomerizing alkyl aromatic hydrocarbons |
| US5240891A (en) * | 1991-12-26 | 1993-08-31 | Patton Robert L | Discrete molecular sieve and use |
| CN1076184A (en) * | 1988-10-17 | 1993-09-15 | 美国环球油品公司 | A kind of aromatics isomerization process |
| CN1102360A (en) * | 1993-11-05 | 1995-05-10 | 中国石油化工总公司 | Alleyl aromatics isomerizating catalyzer |
-
2010
- 2010-07-07 CN CN2010102211530A patent/CN102309979B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0151351A1 (en) * | 1984-01-11 | 1985-08-14 | Mobil Oil Corporation | Process for isomerizing alkyl aromatic hydrocarbons |
| CN1076184A (en) * | 1988-10-17 | 1993-09-15 | 美国环球油品公司 | A kind of aromatics isomerization process |
| US5240891A (en) * | 1991-12-26 | 1993-08-31 | Patton Robert L | Discrete molecular sieve and use |
| CN1102360A (en) * | 1993-11-05 | 1995-05-10 | 中国石油化工总公司 | Alleyl aromatics isomerizating catalyzer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105833900A (en) * | 2016-04-06 | 2016-08-10 | 山东成泰化工有限公司 | Isomerization catalyst and preparation method thereof |
| CN108246354A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of preparation method of catalyst, preparation method and dimethylbenzene |
| CN108246354B (en) * | 2016-12-28 | 2021-08-31 | 中国石油天然气股份有限公司 | Catalyst, preparation method thereof and preparation method of dimethylbenzene |
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