CN101767038A - Catalyst for preparing paraxylene by methyl alcohol conversion, preparation method thereof and application - Google Patents
Catalyst for preparing paraxylene by methyl alcohol conversion, preparation method thereof and application Download PDFInfo
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- CN101767038A CN101767038A CN201010108457A CN201010108457A CN101767038A CN 101767038 A CN101767038 A CN 101767038A CN 201010108457 A CN201010108457 A CN 201010108457A CN 201010108457 A CN201010108457 A CN 201010108457A CN 101767038 A CN101767038 A CN 101767038A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a catalyst for preparing paraxylene by methyl alcohol conversion, a preparation method thereof and application. The catalyst provided by the invention is obtained by the method that the surface acidity and the pore structure of a metal modified zeolite molecular sieve are decorated by siloxy group compound; metal content is 0.1-10 wt% of total content of catalyst, and decorated zeolite molecular sieve bearing amount which is accounted by Si is 0.1-8 wt% of total content of catalyst; aromatic hydrocarbon content in obtained hydrocarbon products is more than 60 wt%, the selectivity of paraxylene in aromatic hydrocarbon is more than 85 wt%, and the selectivity of paraxylene in xylene isomers is more than 95 wt%.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and application that is used for methyl alcohol highly-selective preparation paraxylene.
Background technology
Paraxylene is the base stock of synthesizing polyester (PET).At present, toluene, C are mainly adopted in paraxylene production
9Aromatic hydrocarbons and mixed xylenes are raw material, produce by disproportionation, isomerization, adsorbing separation or cryogenic separation.Because the paraxylene content in its product is controlled by thermodynamics, paraxylene is at C
8Only account in the BTX aromatics about 20%, material circular treatment amount is big in the technical process, and equipment is huge, the operating cost height.Particularly the boiling point of three isomers of dimethylbenzene differs very little, adopts common distillation technique can not obtain the high-purity paraxylene, and must adopt expensive adsorptive separation technology.In recent years, domestic and international many patent disclosures the paraxylene new way of producing, the paraxylene that toluene methylation can the production high selectivity wherein, but this process still depends on petroleum resources-toluene.
Methyl alcohol/dimethyl ether production aromatic hydrocarbons technology is the new way that is prepared aromatic hydrocarbons by coal or natural gas, by methyl alcohol/dimethyl ether on the compound catalyst of metal and molecular sieve directly aromatisation prepare aromatic hydrocarbons.The ZSM-5 zeolite molecular sieve is that aromatic hydrocarbons has unique effect to methanol conversion.The hydrocarbons that the ZSM-5 zeolite molecular sieve can become to have the gasoline boiling range with methanol conversion effectively in preparing gasoline by methanol (MTG) reaction contains the aromatic hydrocarbons about 60% in the synthetic gasoline.On acidic molecular sieve, methyl alcohol can be converted into alkane, alkene and aromatic hydrocarbons etc., the molecular sieve type difference, proportion of products is distinguished to some extent, with alkane, alkene dehydroaromatizationof is the effective ways that improve aromatics yield, the therefore normal at present catalyst that adopts the metal-modified method of acidic molecular sieve to prepare methyl alcohol system aromatic hydrocarbons.
1977, the people such as Chang of Mobil company (Journal of Catalysis, 1977,47,249) reported that on ZSM-5 molecular sieve catalyst methyl alcohol and oxygenate thereof prepare the method for hydrocarbons such as aromatic hydrocarbons.Studies show that under the metal component effect, alkane, alkene can be converted into aromatic hydrocarbons under certain condition.Therefore, ZSM-5 is carried out the metal component modification, thereby in the methanol conversion process, generate more aromatic hydrocarbons, become the main direction of present research.At present the study on the modification to ZSM-5 mainly concentrates on Zn, Ga modification, and other metal such as Ag, Cu etc. are metal-modified also report.People such as Ono (J.Chem.Soc., FaradayTrans.1,1988,84 (4), 1091 of Japan; Microporous Materials, 1995,4,379) utilize ion-exchange that Zn and Ag are incorporated in the ZSM-5 molecular sieve, investigated the catalytic performance of methyl alcohol system aromatic hydrocarbons (MTA).After the Zn introducing, the content of aromatic hydrocarbons increases in the product, can reach about 67.4% (C%), and aromatics yield can reach about 80% behind the introducing Ag.
Chinese patent CN 101244969 discloses a kind of C
1-C
2The fluidized bed plant of hydro carbons or aromatization of methanol and catalyst regeneration utilizes this device and catalyst, can regulate the coking state of the catalyst in the aromatization reactor at any time, transforms C thereby reach continuous high-efficient
1-C
2Hydro carbons or methyl alcohol and high selectivity generate the purpose of aromatic hydrocarbons.Chinese patent CN 1880288 discloses a kind of process of methanol conversion for preparing arene, and on the modified zsm-5 zeolite catalyst, methyl alcohol is catalytically conveted to the product based on aromatic hydrocarbons, has the overall selectivity height of aromatic hydrocarbons, the flexible process operation advantage.U.S. Pat 4615995 discloses a kind of ZSM-5 molecular sieve catalyst that has supported Zn and Mn, is used for methanol conversion and prepares alkene and aromatic hydrocarbons, can change the ratio of low-carbon alkene/aromatic compound in the product by the content of Zn in the regulating catalyst and Mn.
Above-mentioned methanol conversion prepares the aromatic hydrocarbons that obtains in the technology of aromatic hydrocarbons and is BTX aromatics, the product complexity, and market value is low.
Summary of the invention
The object of the present invention is to provide a kind of catalyst of methanol conversion highly-selective preparation paraxylene.Utilize this catalyst can improve the selectivity that methyl alcohol is directly produced aromatic hydrocarbons.
For achieving the above object, catalyst provided by the present invention, be by zeolite molecular sieve earlier after metal-modified, obtain through siloxy group is compound modified again;
In the described catalyst, described tenor is the 0.1-10% of described catalyst gross mass, and described siloxy group compound is the 0.1-8% of catalyst gross mass in the loading of silicon.
Further, tenor described in the described catalyst is the 2-5% of described catalyst gross mass, and described siloxy group compound is the 3-5% of catalyst gross mass in the loading of silicon.
Described metal can be selected from following any one: iron, cobalt, nickel, copper and zinc are preferably zinc or iron.
Catalyst provided by the present invention is to be prepared according to the method that comprises the steps:
1) zeolite molecular sieve is prepared into acidic zeolite through ion-exchange, roasting;
2) acidic zeolite that step 1) is obtained flooded 0.5-12 hour in metal soluble-salt or metal dissolvable oxides solution, take out oven dry after, 450-650 ℃ roasting 2-6 hour, obtain metal-modified molecular sieve;
3) with step 2) the metal-modified molecular sieve that obtains flooded 0.5-12 hour in the siloxy group compound, took out the oven dry back at 450-650 ℃ of roasting 2-6 hour, obtained described catalyst.
Wherein, the metal step 2) in metal soluble-salt and the described metal oxide be selected from following any one: iron, cobalt, nickel, copper and zinc are preferably zinc or iron.
Zeolite molecular sieve described in the present invention is the alumino-silicate with crystallization skeleton structure, and its structure type is MFI type or MEL type; The zeolite molecular sieve of described MFI type is preferably ZSM-5, and the zeolite molecular sieve of described MEL type is preferably ZSM-11.Described molecular sieve SiO
2/ Al
2O
3Than being 10～100.
Described siloxy group structural general formula is suc as formula shown in the I:
(formula I)
Wherein, R
1, R
2, R
3And R
4All be selected from C
1-C
10Alkyl; Preferred siloxy group compound is a tetraethyl orthosilicate among the present invention.
A further object of the present invention provides above-mentioned catalyst and prepares application in the paraxylene in methanol conversion.
The method of methanol conversion highly-selective preparation paraxylene is: adopt catalyst provided by the present invention, react with methanol feedstock, obtain paraxylene; The condition of described reaction is: reaction temperature is 350-550 ℃, is preferably 400-500 ℃; Reaction pressure is 0-5MPa; The methanol feeding weight space velocity is 0.5-10h
-1Arene content is greater than 60wt% in the hydrocarbon product, and the paraxylene selectivity is greater than 85wt% in the aromatic hydrocarbons, and the paraxylene selectivity is greater than 95wt% in the xylene isomer.
The specific embodiment
Catalyst of the present invention is to be that MFI or MEL alumino-silicate are active component with the structure type with crystallization skeleton structure, through its acidity of metal-modified modulation, by silicone agent its outer surface acidity and duct are modified and be prepared into catalyst, its preparation process is as follows:
1) molecular screen primary powder is prepared into acidic molecular sieve through exchange, roasting;
2) with the molecular sieve impregnating metal, obtain metal modified molecular screen;
3) use siloxy group reagent that metal modified molecular screen is carried out finishing, regulating catalyst outer surface acidity and pore structure obtain catalyst.
In above-mentioned preparation process, use the oxide or the soluble-salt of metal that zeolite molecular sieve is carried out modification, its purpose is to improve the arenes selectivity of catalyst methanol conversion reaction.Use siloxy group reagent that the molecular sieve of modification is carried out outer surface acidity and pore structure modification, its purpose is to improve the paraxylene selectivity of catalyst methanol conversion reaction.
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to following examples.
Experimental technique described in the following embodiment if no special instructions, is conventional method; Described reagent and material if no special instructions, all can obtain from commercial channels; " wt% " expression quality percentage composition among the embodiment.
Embodiment 1, Zn-HZSM-5 zeolite molecular sieve
1) with the former powder (SiO of ZSM-5 zeolite molecular sieve
2/ Al
2O
3=61, Fushun catalyst plant) remove the template agent 550 ℃ of following roastings, exchange 4 times with 0.5 molar equivalent ammonium nitrate solution in 80 ℃ of water-baths, exchange is then dried in 120 ℃ of air, and 550 ℃ of following roastings 3 hours obtain the HZSM-5 zeolite molecular sieve.
2) get the HZSM-5 zeolite molecular sieve 50g that step 1) prepares, use 10wt% concentration Zn (NO
3)
2Aqueous solution dipping 6 hours after the oven dry, 550 ℃ of following roastings 3 hours, obtains the Zn-HZSM-5 zeolite molecular sieve, wherein Zn loading 3wt%.
Embodiment 2, Fe-HZSM-5 zeolite molecular sieve
1) with the former powder (SiO of ZSM-5 zeolite molecular sieve
2/ Al
2O
3=61, Fushun catalyst plant) remove the template agent 550 ℃ of following roastings, exchange 4 times with 0.5 molar equivalent ammonium nitrate solution in 80 ℃ of water-baths, exchange is then dried in 120 ℃ of air, and 550 ℃ of following roastings 3 hours obtain the HZSM-5 zeolite molecular sieve.
2) get the HZSM-5 zeolite molecular sieve 50g that step 1) prepares, use 10wt% concentration Fe (NO
3)
3Aqueous solution dipping 10 hours after the oven dry, 550 ℃ of following roastings 3 hours, obtains the Fe-HZSM-5 zeolite molecular sieve, wherein, and Fe loading 5wt%.
Embodiment 3, preparation catalyst
Use the silicone agent tetraethyl orthosilicate that Zn-HZSM-5, the Fe-HZSM-5 zeolite molecular sieve that embodiment 1 and embodiment 2 obtain carried out finishing:
(1) 10 gram Zn-HZSM-5 was put into 20 gram tetraethyl orthosilicate dippings 5 hours, incline liquid after, after 120 ℃ of oven dry, 550 ℃ of roastings 3 hours, obtain modifying back Zn-HZSM-5 catalyst, wherein, the mass content of Zn is 2.9%, and tetraethyl orthosilicate is 4.3% of a catalyst gross mass in the loading of silicon.Be numbered MTAC-01;
(2) 10 gram Fe-HZSM-5 were put into 20 gram tetraethyl orthosilicates dippings 8 hours, incline liquid after, after 120 ℃ of oven dry,, obtain modifying back Fe-HZSM-5 catalyst 550 ℃ of roastings 3 hours, be numbered MTAC-02; Wherein, the mass content of Fe is 4.8%, and tetraethyl orthosilicate is 4.6% of a catalyst gross mass in the loading of silicon.
Embodiment 4 fixed bed reaction evaluations
Carry out the methanol conversion reaction on fixed bed reactors, use the catalyst among the embodiment 3, reaction condition: the methyl alcohol weight space velocity is 2h
-1, temperature is 450 ℃.Adopt gas-chromatography on-line analysis product (normalization behind the removal methyl alcohol), as shown in table 1.
Table 1, product analysis table
| Catalyst | ??MTAC-01 | ??MTAC-02 |
| Reaction temperature (℃) | ??450 | ??450 |
| Feed time (min) | ??30 | ??30 |
| Methanol conversion (%) | ??85.35 | ??96.42 |
| Arenes selectivity in the hydro carbons (wt%) | ??63.69 | ??65.51 |
| Paraxylene selectivity (wt%) in the aromatic hydrocarbons | ??85.27 | ??86.83 |
| Paraxylene selectivity (wt%) in the xylene isomer | ??97.19 | ??96.62 |
| Product distribution (wt%) | ||
| ??C1-C5 | ??36.31 | ??34.49 |
| Benzene | ??0.22 | ??0.39 |
| Ethylbenzene | ??1.36 | ??1.21 |
| Paraxylene | ??54.31 | ??56.88 |
| Meta-xylene | ??0.32 | ??0.34 |
| Ortho-xylene | ??1.25 | ??1.65 |
| ??≥C 9 | ??6.23 | ??5.04 |
| Add up to | ??100.00 | ??100.00 |
Embodiment 5, preparation catalyst
With the former powder (SiO of ZSM-11 zeolite molecular sieve
2/ Al
2O
3=65, the Fushun catalyst plant) remove the template agent 550 ℃ of following roastings, the ammonium nitrate solution with 0.5 molar equivalent in 80 ℃ of water-baths exchanges 4 times, and the exchange back obtains the HZSM-11 zeolite molecular sieve 550 ℃ of following roastings 3 hours.
Get HZSM-11 zeolite molecular sieve 50g, use 10wt% concentration Fe (NO
3)
3Aqueous solution dipping 8 hours after the oven dry, 550 ℃ of following roastings 3 hours, obtains the Fe-HZSM-5 zeolite molecular sieve, wherein Fe loading 5wt%.
Use the silicone agent tetraethyl orthosilicate that the Fe-HZSM-11 zeolite molecular sieve is carried out finishing.Step is respectively: 10 gram Fe-HZSM-11 were put into 20 gram tetraethyl orthosilicate dippings 12 hours, incline liquid after, after 120 ℃ of oven dry, 550 ℃ of roastings 3 hours, obtain modifying back Fe-HZSM-11 catalyst, wherein, the mass content of Fe is 4.7%, and tetraethyl orthosilicate is 4.8% of a catalyst gross mass in the loading of silicon.Be numbered MTAC-03.
Embodiment 6, fixed bed reaction evaluation
Carry out the methanol conversion reaction on fixed bed reactors, use the catalyst among the embodiment 5, reaction condition: the methyl alcohol weight space velocity is 4h-1, and temperature is respectively 450 ℃ and 500 ℃.Adopt gas-chromatography on-line analysis product (normalization behind the removal methyl alcohol), as shown in table 2.
Table 2, product analysis
Claims (10)
1. a methanol conversion prepares the catalyst of paraxylene, be zeolite molecular sieve earlier after metal-modified, obtain through siloxy group is compound modified again; In the described catalyst, described tenor is the 0.1-10% of described catalyst gross mass, and described siloxy group compound is the 0.1-8% of catalyst gross mass in the loading of silicon.
2. catalyst according to claim 1 is characterized in that: in the described catalyst, described tenor is the 2-5% of described catalyst gross mass, and described siloxy group compound is the 3-5% of catalyst gross mass in the loading of silicon.
3. catalyst according to claim 1 and 2 is characterized in that: the structure type of described zeolite molecular sieve is MFI type or MEL type; The zeolite molecular sieve of described MFI type is preferably ZSM-5, and the zeolite molecular sieve of described MEL type is preferably ZSM-11.
4. according to arbitrary described catalyst among the claim 1-3, it is characterized in that: described metal be selected from following any one: iron, cobalt, nickel, copper and zinc are preferably zinc or iron.
5. according to arbitrary described catalyst among the claim 1-4, it is characterized in that: described siloxy group structural general formula is suc as formula shown in the I:
(formula I)
Wherein, R
1, R
2, R
3And R
4All be selected from C
1-C
10Alkyl;
Described siloxy group compound is preferably R among the formula I
1, R
2, R
3And R
4Be the siloxy group compound of ethyl.
6. a method for preparing the described catalyst of claim 1 comprises the steps:
1) zeolite molecular sieve is prepared into acidic zeolite through ion-exchange, roasting;
2) acidic zeolite that step 1) is obtained flooded 0.5-12 hour in metal soluble-salt or metal dissolvable oxides solution, after the taking-up oven dry, at 450-650 ℃ of roasting 2-6 hour, obtained metal-modified molecular sieve;
3) with step 2) the metal-modified molecular sieve that obtains flooded 0.5-12 hour in the siloxy group compound, took out the oven dry back at 450-650 ℃ of roasting 2-6 hour, obtained the described catalyst of claim 1.
7. method according to claim 6 is characterized in that: the structure type of described zeolite molecular sieve is MFI type or MEL type; The zeolite molecular sieve of described MFI type is preferably ZSM-5, and the zeolite molecular sieve of described MEL type is preferably ZSM-11.
8. according to claim 6 or 7 described methods, it is characterized in that: step 2) described in metal in metal soluble-salt and the described metal oxide be selected from following any one: iron, cobalt, nickel, copper and zinc are preferably zinc or iron.
9. according to arbitrary described method among the claim 6-8, it is characterized in that: described siloxy group structural general formula is suc as formula shown in the I:
(formula I)
Wherein, R
1, R
2, R
3And R
4All be selected from C
1-C
10Alkyl;
Described siloxy group compound is preferably R among the formula I
1, R
2, R
3And R
4Be the siloxy group compound of ethyl.
10. arbitrary described catalyst prepares application in the paraxylene in methanol conversion among the claim 1-5.
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