CN101780417A - Catalyst for preparing paraxylene and low-carbon olefin by methyl alcohol conversion, preparation method and application thereof - Google Patents
Catalyst for preparing paraxylene and low-carbon olefin by methyl alcohol conversion, preparation method and application thereof Download PDFInfo
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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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Abstract
本发明公开了一种甲醇转化制取对二甲苯和低碳烯烃的催化剂及其制备方法与应用。本发明所提供的催化剂由过渡金属和稀土金属改性后的沸石分子筛再经硅氧烷基化合物修饰表面酸性和孔结构得到；其中，过渡金属含量为催化剂总重量的0.1-10wt％；稀土金属含量为催化剂总重量的0.1-5wt％；硅氧烷基化合物修饰后以Si计的担载量为催化剂总重量的0.1-8wt％。利用该催化剂实现了在一个反应过程中由甲醇直接制取三大基础化学品乙烯、丙烯和对二甲苯的目的；反应所得的烃类产物中对二甲苯在芳烃中的选择性大于80wt％，乙烯丙烯在C1-C5中选择性大于80wt％。The invention discloses a catalyst for preparing p-xylene and light olefins by converting methanol, a preparation method and application thereof. The catalyst provided by the present invention is obtained by modifying the zeolite molecular sieve modified by transition metal and rare earth metal and modifying the surface acidity and pore structure by siloxane compound; wherein, the content of transition metal is 0.1-10wt% of the total weight of the catalyst; the rare earth metal The content is 0.1-5wt% of the total weight of the catalyst; the loading amount calculated as Si after the modification of the siloxane compound is 0.1-8wt% of the total weight of the catalyst. The catalyst is used to realize the purpose of directly producing three basic chemicals ethylene, propylene and p-xylene from methanol in one reaction process; the selectivity of p-xylene in aromatics in the hydrocarbon products obtained from the reaction is greater than 80wt%, The selectivity of ethylene propylene in C 1 -C 5 is greater than 80 wt%.
Description
Technical field
The present invention relates to a kind of technology, relate to a kind of Catalysts and its preparation method and application particularly by methyl alcohol highly-selective preparation paraxylene coproduction ethene, propylene by preparing low carbon olefinic hydrocarbon with methanol and aromatic hydrocarbons.
Background technology
Ethene, propylene and paraxylene are the base stocks of modern chemical industry.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.Ethene and propylene be with crude refining light oil (naphtha and light diesel fuel) and liquefied petroleum gas (LPG) and the natural gas processing ethane and the propane that make be that raw material is produced.In recent years, domestic and international many patent disclosures the paraxylene new way of producing, the paraxylene that alkylation of toluene can the production high selectivity wherein, but said process all depends on petroleum resources.
It is the new way that non-petroleum path is produced ethene, propylene and aromatic hydrocarbons that preparing light olefins from methanol and methyl alcohol prepare aromatic hydrocarbons.Mobil Oil company in 1976 has carried out methyl alcohol is converted into hydrocarbon on the ZSM-5 molecular sieve catalyst reaction.USP 4,035, disclose methyl alcohol transforms gasoline on the ZSM-5 molecular sieve catalyst process in 430; USP4 discloses methyl alcohol is produced low-carbon alkene on the ZSM-5 molecular sieve catalyst technology in 542,252; USP 3,911,041, and USP 4,049,573, USP 4,100,219, JP 60-126233, JP 61-97231 discloses among JP 62-70324 and the EP 6501 and has used the reaction of the ZSM-5 molecular sieve catalyst of phosphorus, magnesium, silicon or alkali metal modification by preparing low carbon olefinic hydrocarbon with methanol; USP 5,367, disclose the reaction that Dalian Chemical Physics Research Institute uses the ZSM-5 molecular sieve catalyst of phosphorus and lanthanum modification to produce low-carbon alkene by methyl alcohol or dimethyl ether in 100, its ethene and propylene overall selectivity only are about 65wt%, and ethene, propylene and butylene overall selectivity are greater than 85wt%.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 low-carbon alkene or aromatic hydrocarbons method, mainly concentrates on converting methanol to prepare low carbon olefin, methanol conversion is produced BTX aromatics, or converting methanol to prepare low carbon olefin by-product BTX aromatics.Methanol conversion principal product content is all lower in any method, as ethylene, propylene poor selectivity in the converting methanol to prepare low carbon olefin product, the BTX aromatics market value that methyl alcohol directly transforms preparation is lower, thereby makes these technical process be difficult in industrial application.
Summary of the invention
The object of the present invention is to provide the catalyst of a kind of methanol conversion highly-selective preparation paraxylene and low-carbon alkene (ethene, propylene).Utilize this catalyst to can be implemented in the purpose of directly producing three big Essential Chemistry product ethene, propylene and paraxylene in the course of reaction by methyl alcohol.
For achieving the above object, catalyst provided by the present invention, be by zeolite molecular sieve earlier after transition metal and rare earth metal bimetallic-modified, obtain through siloxy group is compound modified again;
In the described catalyst, described levels of transition metals is the 0.1-10% of described catalyst gross mass, and described rare earth metal content is the 0.1-5% 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, levels of transition metals is the 4-8% of described catalyst gross mass in the described catalyst, and rare earth metal content is the 2-5% of described catalyst gross mass, and described siloxy group compound is the 3-6% of catalyst gross mass in the loading of silicon.
Described transition metal can be selected from following any one: iron, cobalt, nickel, copper and zinc are preferably zinc or iron; Described rare earth metal can be lanthanum.
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 transition metal soluble-salt or transition metal dissolvable oxides solution, after the taking-up oven dry, at 450-650 ℃ of roasting 2-6 hour, obtained the molecular sieve of monometallic modification;
3) with step 2) molecular sieve of the monometallic modification that obtains in rare earth metal soluble-salt solution 0.5-12 hour, take out the oven dry back at 450-650 ℃ of roasting 2-6 hour, obtain the molecular sieve of bimetallic-modified;
4) molecular sieve of the bimetallic-modified that step 3) is obtained flooded 0.5-12 hour at 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 transition metal soluble-salt and the described transition metal dissolvable oxides be selected from following any one: iron, cobalt, nickel, copper and zinc are preferably zinc or iron; The soluble-salt of rare earth metal described in the step 3) is the soluble-salt of lanthanum.
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 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 paraxylene and the co-producing light olefins in methanol conversion.
The method that methanol conversion prepares paraxylene and coproduction ethylene, propylene is: adopt catalyst provided by the present invention, react with methanol feedstock, obtain paraxylene and ethene, propylene; Reactive mode can adopt any form of fixed bed or fluid bed; 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
-1
The selectivity of paraxylene in aromatic hydrocarbons is greater than 80wt% in the hydrocarbon product of product, and ethylene, propylene is at C
1-C
5Middle selectivity is greater than 80wt%.
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 transition metal or its acidity of rare earth metal bimetallic 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) molecular sieve is flooded transition metal and rare earth metal, obtain modified molecular screen.
4) use siloxy group reagent that modified molecular screen is carried out finishing, regulating catalyst outer surface acidity and pore structure obtain catalyst.
In above-mentioned preparation process, use oxide, the soluble-salt of transition metal and rare earth 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.
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.
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to following examples.
Embodiment 1, Zn-La-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 10 hours after the oven dry, 550 ℃ of following roastings 3 hours, obtains the Zn-HZSM-5 zeolite molecular sieve, wherein Zn loading 5wt%.
3) get Zn-HZSM-5 zeolite molecular sieve 20g, use the La (NO of 10wt% concentration
3)
3Aqueous solution dipping 10 hours after the oven dry, 550 ℃ of following roastings 3 hours, obtains the Zn-La-HZSM-5 zeolite molecular sieve, wherein La loading 3wt%.
Embodiment 2, Fe-La-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 12wt% concentration Fe (NO
3)
3Aqueous solution dipping 12 hours after the oven dry, 550 ℃ of following roastings 3 hours, obtains the Fe-HZSM-5 zeolite molecular sieve, wherein, and Fe loading 6wt%.
3) get Fe-HZSM-5 zeolite molecular sieve 20g, use the La (NO of 10wt% concentration
3)
3Aqueous solution dipping 10 hours after the oven dry, 550 ℃ of following roastings 3 hours, obtains the Fe-La-HZSM-5 zeolite molecular sieve, wherein La loading 3wt%.
The catalyst of embodiment 3, preparation methanol conversion highly-selective preparation paraxylene and low-carbon alkene
Use the silicone agent tetraethyl orthosilicate that Zn-La-HZSM-5, the Fe-La-HZSM-5 zeolite molecular sieve that embodiment 1 and embodiment 2 obtain carried out finishing:
(1) 10 gram Zn-La-HZSM-5 were put into 20 gram tetraethyl orthosilicates dippings 12 hours, incline liquid after, after 120 ℃ of oven dry,, obtain modifying back Zn-La-HZSM-5 zeolite molecular sieve 550 ℃ of roastings 3 hours, be numbered MTAC-11; Wherein, the mass content of Zn is 4.7%, and the mass content of La is 2.9%, and the loading of silicon is 4.2% of a catalyst gross mass.
(2) 10 gram Fe-La-HZSM-5 were put into 20 gram tetraethyl orthosilicates dippings 12 hours, incline liquid after, after 120 ℃ of oven dry,, obtain modifying back Fe-La-HZSM-5 zeolite molecular sieve 550 ℃ of roastings 3 hours, be numbered MTAC-12; Wherein, the mass content of Fe is 5.6%, and the mass content of La is 2.9%, and the loading of silicon is 4.3% of a catalyst gross mass.
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.C wherein
1-C
5Composition analysis adopts the gas-chromatography off-line analysis, and the result is as shown in table 2.
Table 1, product analysis table
| Catalyst | ??MTAC-11 | ??MTAC-12 |
| Reaction temperature (℃) | ??450 | ??450 |
| Feed time (min) | ??30 | ??30 |
| Methanol conversion (%) | ??85.23 | ??96.21 |
| Paraxylene selectivity (%) * | ??83.42 | ??83.58 |
| Product distribution (%) | ||
| ?C 1-C 5 | ??48.31 | ??47.32 |
| Benzene | ??0.06 | ??0.07 |
| Ethylbenzene | ??0.24 | ??0.3 |
| Paraxylene | ??43.12 | ??44.03 |
| Meta-xylene | ??0.89 | ??0.76 |
| Ortho-xylene | ??1.18 | ??1.09 |
| Catalyst | ??MTAC-11 | ??MTAC-12 |
| ?≥C 9 | ??6.20 | ??6.43 |
| Add up to | ??100.00 | ??100.00 |
*The selectivity of paraxylene in aromatic hydrocarbons
Table 2, product analysis table
| Catalyst | ??MTAC-11 | ??MTAC-12 |
| Reaction temperature (℃) | ??450 | ??450 |
| Feed time (min) | ??20-40 | ??20-40 |
| ??CH 4 | ??2.12 | ??2.36 |
| ??C 2H 4 | ??46.82 | ??45.56 |
| ??C 2H 6 | ??0.21 | ??0.28 |
| ??C 3H 6 | ??33.49 | ??34.59 |
| ??C 3H 8 | ??0.45 | ??0.43 |
| ??C 4 + | ??11.72 | ??12.01 |
| ??C 5 + | ??5.19 | ??4.77 |
| ??Total | ??100.00 | ??100.00 |
| ??C 2H 4+C 3H 6 | ??80.31 | ??80.15 |
The catalyst of embodiment 5, preparation methanol conversion highly-selective preparation paraxylene and low-carbon alkene
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 12wt% concentration Fe (NO
3)
3Aqueous solution dipping 12 hours after the oven dry, 550 ℃ of following roastings 3 hours, obtains the Fe-HZSM-5 zeolite molecular sieve, wherein Fe loading 8wt%.
Get Fe-HZSM-11 zeolite molecular sieve 20g, use the La (NO of 10wt% concentration
3)
3Aqueous solution dipping 12 hours after the oven dry, 550 ℃ of following roastings 3 hours, obtains the Fe-La-HZSM-11 zeolite molecular sieve, wherein La loading 5wt%.
Use the silicone agent tetraethyl orthosilicate that the Fe-La-HZSM-11 zeolite molecular sieve is carried out finishing.Step is respectively: 10 gram Fe-La-HZSM-11 are put into 20 gram tetraethyl orthosilicate dippings spend the night, incline liquid after, after 120 ℃ of oven dry, 550 ℃ of roastings 3 hours, obtain modifying back Fe-La-HZSM-11 zeolite molecular sieve, be numbered MTAC-13, wherein, the mass content of Fe is 7.6%, and the mass content of La is 4.8%, and the loading of silicon is 4.4% of a catalyst gross mass.
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, temperature is respectively 450 ℃ and 500 ℃.Adopt gas-chromatography on-line analysis product (normalization behind the removal methyl alcohol), as shown in table 3.C wherein
1-C
5Composition analysis adopts the gas-chromatography off-line analysis, and the result is as shown in table 4.
Table 3, product analysis
*The selectivity of paraxylene in aromatic hydrocarbons
Table 4, product analysis
Claims (10)
1. a methanol conversion prepares the catalyst of paraxylene and co-producing light olefins, be by zeolite molecular sieve earlier after transition metal and rare earth metal bimetallic-modified, obtain through siloxy group is compound modified again;
In the described catalyst, described levels of transition metals is the 0.1-10% of described catalyst gross mass, and described rare earth metal content is the 0.1-5% 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, it is characterized in that: in the described catalyst, described levels of transition metals is the 4-8% of described catalyst gross mass, described rare earth metal content is the 2-5% of described catalyst gross mass, and described siloxy group compound is the 3-6% of catalyst gross mass in the loading of silicon; Described low-carbon alkene is ethene and propylene.
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 transition metal be selected from following any one: iron, cobalt, nickel, copper and zinc are preferably zinc or iron; Described rare earth metal is a lanthanum.
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. according to arbitrary described catalyst among the claim 1-5, it is characterized in that: described catalyst prepares in accordance with the method for claim 7.
7. 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 transition metal soluble-salt or transition metal dissolvable oxides solution, after the taking-up oven dry, at 450-650 ℃ of roasting 2-6 hour, obtained transition metal modified molecular sieve;
3) with step 2) the transition metal modified molecular sieve that obtains flooded 0.5-12 hour in rare earth metal soluble-salt solution, took out the oven dry back at 450-650 ℃ of roasting 2-6 hour, obtained the molecular sieve of transition metal and rare earth metal bimetallic-modified;
4) molecular sieve of the bimetallic-modified that step 3) is obtained 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.
8. method according to claim 7 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.
9. according to claim 7 or 8 described methods, it is characterized in that: step 2) described in metal in transition metal soluble-salt and the described transition metal dissolvable oxides be selected from following any one: iron, cobalt, nickel, copper and zinc are preferably zinc or iron; The soluble-salt of rare earth metal described in the step 3) is the soluble-salt of lanthanum;
The structural general formula of siloxy group described in the step 4) 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 paraxylene and the co-producing light olefins in methanol conversion among the claim 1-6.
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| CN103157514A (en) * | 2011-12-19 | 2013-06-19 | 中国科学院大连化学物理研究所 | Catalyst for preparing p-xylene by mutual conversion of methanol and/or dimethyl ether and C4 liquefied gas, and its preparation method and application |
| CN103272633A (en) * | 2013-06-07 | 2013-09-04 | 清华大学 | Catalyst for converting alcohol ether into high p-xylene content aromatic hydrocarbon, preparation method and reaction process thereof |
| CN104069887A (en) * | 2013-03-29 | 2014-10-01 | 上海碧科清洁能源技术有限公司 | Method for preparing silicon modified ZSM-5 molecular sieve catalyst, catalyst prepared by using method and application of catalyst |
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| WO2015184598A1 (en) * | 2014-06-04 | 2015-12-10 | 中国科学院大连化学物理研究所 | Method for preparing paraxylene and propylene by methanol and/or dimethyl ether |
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