CN101607864B - High yield preparation method of paraxylene by methanol/dimethyl ether conversion - Google Patents
High yield preparation method of paraxylene by methanol/dimethyl ether conversion Download PDFInfo
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Abstract
The invention relates to a high yield preparation method of paraxylene by methanol/dimethyl ether conversion and the method can increase the yield of paraxylene in the converted products of methanol/dimethyl ether by adopting molecular sieve based catalyst which is modified with metals or through silylanization and adding aromatic hydrocarbons in the raw materials. The aromatic hydrocarbons is the separated benzene and/or toluene which is generated through the methanol/dimethyl ether conversion reaction and part or whole of aromatic hydrocarbons is recycled in the reaction system; otherwise, additional benzene and/or toluene is added in the raw materials. By adopting the method, the content of aromatic hydrocarbons in the products of the methanol/dimethyl ether conversion reaction can be more than 50wt%; wherein, the content of paraxylene in aromatic hydrocarbons is more than 80wt% and the selectivity of paraxylene in xylene isomers is more than 99wt%.
Description
Technical field
The present invention relates to the technology that a kind of methanol/dimethyl ether conversion high yield prepares p-Xylol, relate to particularly by adding aromatic hydrocarbons to improve the yield of p-Xylol in the methanol/dimethyl ether conversion product in raw material.
Background technology
P-Xylol is the basic raw material of synthesizing polyester (PET).At present, toluene, C are mainly adopted in p-Xylol production
9Aromatic hydrocarbons and xylol are raw material, produce by disproportionation, isomerization, fractionation by adsorption or low temperature separation process.Because the p-Xylol content in its product is subjected to thermodynamic control, p-Xylol is at C
8Only account for 20% left and right in BTX aromatics, in technological process, the Matter Transfer treatment capacity is large, and equipment is huge, and process cost is high.Particularly the boiling point of three isomer of dimethylbenzene differs very little, adopts common distillation technique can not obtain the high purity p-Xylol, and must adopt expensive adsorptive separation technology.In recent years, domestic and international many patents disclose the new way that p-Xylol is produced, the p-Xylol that wherein toluene methylation can the production highly selective, but this process still depends on petroleum resources-toluene.
It is to be prepared the new way of aromatic hydrocarbons by coal or Sweet natural gas that methanol/dimethyl ether prepares the aromatic hydrocarbons technology, prepares aromatic hydrocarbons by methanol/dimethyl ether direct aromizing on metal and molecular sieve composite catalyst.ZSM-5 molecular sieve is that aromatic hydrocarbons has unique effect to methanol conversion, and in preparing gasoline by methanol (MTG) reaction, the hydrocarbons that ZSM-5 can become have the gasoline boiling range with methanol conversion effectively contains the aromatic hydrocarbons of 60% left and right in synthetic gasoline.On acidic molecular sieve, methyl alcohol can be converted into alkane, alkene and aromatic hydrocarbons etc., and molecular sieve type is different, and proportion of products is distinguished to some extent, is the effective ways that improve aromatics yield with alkane, alkene dehydroaromatizationof.Therefore often adopt at present the metal-modified method of acidic molecular sieve to prepare the catalyzer of Methanol aromatic hydrocarbons.
1977, the people such as Chang (Journal of Catalysis, 1977,47,249) of Mobil company reported that on the ZSM-5 molecular sieve catalyzer methyl alcohol and oxygenatedchemicals thereof transform the method for preparing the hydrocarbon polymers 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 generate more aromatic hydrocarbons in the methanol conversion process, become the main direction of present research.At present the study on the modification of ZSM-5 mainly concentrated on Zn, Ga modification, other metal such as Ag, Cu etc. are metal-modified also report.The people such as Ono (J.Chem.Soc., Faraday Trans.1,1988,84 (4), 1091 of Japan; Microporous Materials, 1995,4,379) utilize ion exchange method that Zn and Ag are incorporated in ZSM-5 molecular sieve, investigated the catalytic performance of Methanol aromatic hydrocarbons (MTA).After Zn was introduced, in product, the content of aromatic hydrocarbons increased, and can reach 67.4% left and right (C%), and after introducing Ag, aromatics yield can reach 80% left and right.
Chinese patent CN 101244969 discloses a kind of C
1-C
2The fluidizer of hydro carbons or aromatization of methanol and catalyst regeneration utilizes this device and catalyzer, can regulate at any time the coking state of the catalyzer in aromatization reactor, transforms C thereby reach continuous high-efficient
1-C
2Hydro carbons or methyl alcohol and highly selective generate the purpose of aromatic hydrocarbons.Chinese patent CN 1880288 discloses a kind of process of methanol conversion for preparing arene, and in the ZSM-5 Type Zeolites agent, methanol oxidation is converted into take aromatic hydrocarbons as main product, has the aromatic hydrocarbons overall selectivity high, and technological operation is advantage flexibly.US Patent No. 4615995 discloses a kind of ZSM-5 molecular sieve catalyzer that has supported Zn and Mn, is used for preparing olefin through methanol conversion and aromatic hydrocarbons, can change the ratio of low-carbon alkene/aromatic hydroxy compound in product by the content of Zn in regulating catalyst and Mn.
The aromatic hydrocarbons that obtains in above-mentioned preparing aromatic hydrocarbon through methanol transformation technique and method is BTX aromatics, and product is complicated, and marketable value is low.Process by the silanization to the HZSM-5 zeolite molecular sieve, can realize the methanol/dimethyl ether conversion high selectivity production of para-xylene, but, due to zeolite molecular sieve through acidity after silylation modification a little less than, in the methanol/dimethyl ether conversion product, aromaticity content is lower, so keeping under the high selectivity production of para-xylene condition, how to improve further that in product, aromatics yield will be the key that the methanol/dimethyl ether conversion high yield prepares p-Xylol.
Summary of the invention
The object of the present invention is to provide a kind of methanol/dimethyl ether conversion high yield to prepare the method for p-Xylol.More than in the methanol/dimethyl ether conversion product, aromaticity content can be brought up to 50wt%, wherein in aromatic hydrocarbons p-Xylol content greater than 80wt%, p-Xylol in xylene isomer selectivity greater than 99wt%.
For achieving the above object, the present invention is by adding aromatic hydrocarbons to improve the yield of p-Xylol in the methanol/dimethyl ether conversion product in raw material.The aromatic hydrocarbons source is divided or all is recycled to reactive system through separate rear part for benzene and/or the toluene that the methanol/dimethyl ether conversion reaction generates, or additionally adds toluene and/or benzene in reaction raw materials.
For achieving the above object, the present invention adopts metal and the combined modified zeolite [molecular sieve of silanization, this catalyzer first carries out the former powder of zeolite molecular sieve metal-modified, again through the compound-modified surface acidity of siloxanes and pore structure, thereby obtain methanol/dimethyl ether conversion high selectivity production of para-xylene catalyzer.
The catalyzer that the present invention uses, wherein zeolite molecular sieve is the silico-aluminate with crystallization skeleton structure, structure type is MFI or MEL.
The catalyzer that the present invention uses, wherein silico-aluminate is that ZSM-5 is or/and ZSM-11 zeolite molecular sieve, preferably ZSM-5.
The present invention uses the preparation method of catalyzer, and wherein metal is Mn, Co, Ni, Cu, Zn, Mo, Ga oxide compound or its soluble salt, preferred Mn, Zn, Mo oxide compound or its soluble salt.
The present invention uses the preparation method of catalyzer, and wherein metal content is the 0.1-8wt% of total catalyst weight;
The present invention uses the preparation method of catalyzer, and wherein the siloxanes compound is shown below:
R wherein
1, R
2, R
3And R
4It is the alkyl of 1-10 carbon atom.
The present invention uses the preparation method of catalyzer, and wherein, the siloxanes compound is tetraethyl silicate.
Method of the present invention, wherein, reaction mass is that methyl alcohol is or/and dme.
Methanol/dimethyl ether conversion high yield of the present invention prepares the method for p-Xylol, and reactive mode can adopt any form of fixed bed or fluidized-bed.Reaction conditions is: temperature of reaction is 350-550 ℃, is preferably 400-500 ℃; Reaction pressure is 0-2MPa, is preferably 0-1MPa; Methanol/dimethyl ether feed weight air speed is 0.1-20h
-1, be preferably 1-10h
-1When toluene in the methanol/dimethyl ether raw material or benzene content are not more than 10wt%, more than in reaction product, aromaticity content can reach 50wt%, wherein in aromatic hydrocarbons p-Xylol content greater than 80wt%, p-Xylol in xylene isomer selectivity greater than 99wt%.
Embodiment
Adopting methyl alcohol or dme and mixture both is raw material, and wherein methyl alcohol can be aqueous methanol, and methanol quality concentration is 50-100%.By adding aromatic hydrocarbons to improve the yield of p-Xylol in the methanol/dimethyl ether conversion product in raw material.The aromatic hydrocarbons source is divided or all is recycled to reactive system through separate rear part for benzene and/or the toluene that the methanol/dimethyl ether conversion reaction generates, or additionally adds toluene and/or benzene in reaction raw materials.Adopt metal and the combined modified zeolite [molecular sieve of silanization, under 400-500 ℃ of condition, will contain and pass into after the methyl alcohol of toluene or benzene or dme feed vaporization in reactor and the catalyzer contact reacts, product after insulation by the gas-chromatography on-line analysis.
The catalyzer that the present invention uses is that the silico-aluminate with crystallization skeleton structure MFI or MEL structure type is active ingredient, after adjusting and reforming property of metal, by silicone agent, its outer surface acidity and duct are modified and be prepared into the preparing p-xylene through methanol/dimethyl ether conversion catalyzer, its preparation process is as follows:
1, with the former powder of zeolite molecular sieve through NH
4 +Ion-exchange, roasting are prepared into acidic zeolite.
2, use metal soluble salt solution to flood modification to acidic zeolite, obtain metal-modified zeolite molecular sieve.
3, use siloxanes reagent to carry out finishing to metal-modified zeolite molecular sieve, regulating catalyst outer surface acidity and pore structure obtain metal and silanization combined modified catalyst.
4, will use after step 3 preparation modified catalyst compressing tablet or spray drying forming.
The catalyzer that the present invention uses is the Si-Al zeolite molecular sieve of MFI or MEL structure type, can select ZSM-5, ZSM-11 zeolite molecular sieve.
The catalyst modification metal that the present invention uses is Mn, Co, Ni, Cu, Zn, Mo, Ga oxide compound or its soluble salt, preferred Mn, Zn, Mo oxide compound or its soluble salt.
In the catalyzer that the present invention uses, metal content 0.1-8wt%.
The present invention uses the preparation method of catalyzer, and wherein the siloxanes compound is shown below:
R wherein
1, R
2, R
3And R
4It is the alkyl of 1-10 carbon atom.
The present invention uses the preparation method of catalyzer, and wherein the siloxanes compound is tetraethyl silicate.
Reactive mode of the present invention is reaction mass and catalyzer contact reacts, and temperature of reaction is 350-550 ℃, is preferably 400-500 ℃; Reaction pressure is 0-2MPa, is preferably 0-1MPa; Methanol/dimethyl ether feed weight air speed is 0.1-20h
-1, be preferably 1-10h
-1When toluene in the methanol/dimethyl ether raw material or benzene content are not more than 10wt%, more than in reaction product, aromaticity content can reach 50wt%, wherein in aromatic hydrocarbons p-Xylol content greater than 80wt%, p-Xylol in xylene isomer selectivity greater than 99wt%.
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to following examples.
Embodiment 1 fixed bed catalyst preparation
1) with 500g ZSM-5 zeolite molecular screen primary powder (Catalyst Factory, Nankai Univ) (SiO
2/ Al
2O
3=50) remove template 550 ℃ of lower roastings, the ammonium nitrate solution with 0.5 molar equivalent in 80 ℃ of water-baths exchanges 4 times, and exchange is dried in 120 ℃ of air afterwards, and 550 ℃ of lower roastings 3 hours obtain the HZSM-5 zeolite molecular sieve.
2) get step 1) preparation HZSM-5 zeolite molecular sieve 20g compression molding, obtain 40-60 order sample after crushing and screening, be 9% volume zinc nitrate [Zn (NO with mass concentration
3)
2] solution normal temperature dipping 4 hours, in 120 ℃ of rear 550 ℃ of air of oven dry, roasting is 6 hours; HZSM-5 zeolite molecular sieve after employing tetraethoxy (TEOS) normal temperature dipping zinc modification 24 hours, incline and after supernatant liquid roasting in 120 ℃ of oven dry, 550 ℃ of air and obtained zinc and the combined modified HZSM-5 catalyzer of silanization in 6 hours, in catalyzer, Zn content is about 3wt%, catalyzer called after MTA-06.
Embodiment 2 fixed bed catalyst preparations
Get step 1 in embodiment 1) preparation HZSM-5 zeolite molecular sieve 20g compression molding, obtain 40-60 order sample after crushing and screening, be 11.1% nitric acid molybdenum [Mo (NO with mass concentration
3)
3] solution normal temperature dipping HZSM-5 molecular sieve 4 hours, in 120 ℃ of rear 550 ℃ of air of oven dry, roasting is 6 hours; HZSM-5 zeolite molecular sieve after the modification of employing tetraethoxy (TEOS) normal temperature dipping molybdenum 24 hours, incline and after supernatant liquid roasting in 120 ℃ of oven dry, 550 ℃ of air and obtained molybdenum and the combined modified HZSM-5 catalyzer of silanization in 6 hours, in catalyzer, Mo content is about 3wt%, catalyzer called after MTA-07.
The preparation of embodiment 3 fluid catalysts.
1) get step 1 in embodiment 1) preparation HZSM-5 zeolite molecular sieve 200g, with the manganous nitrate [Mn (NO that with mass concentration is 9.8%
3)
2] solution normal temperature dipping 4 hours, in 120 ℃ of rear 550 ℃ of air of oven dry, roasting obtained the Mn Modified HZSM-5 Zeolite in 6 hours, and in molecular sieve, Mn content is about 3wt%.
2) HZSM-5 sample and kaolin, silicon sol, aluminium colloidal sol and the deionized water with above-mentioned Mn modification is mixed into slurry, and the butt mass ratio of molecular sieve and kaolin, silicon sol, aluminium colloidal sol is 30: 35: 25: 10, and the solid content of slurry is about 35wt%.Slurry obtains at aged at room temperature 5h and by spray shaping after the colloidal mill glued membrane microspherical catalyst that particle diameter is 20-100 μ m.
3) use the microspherical catalyst 24 hours of the above-mentioned preparation of tetraethoxy (TEOS) normal temperature dipping, incline and after supernatant liquid roasting in 120 ℃ of oven dry, 550 ℃ of air and obtained manganese and the combined modified HZSM-5 microspherical catalyst of silanization, catalyzer called after MTA-08 in 6 hours.
Comparative Examples 1 fixed bed reaction evaluation
,, processed 1 hour in 550 ℃ of air atmospheres the 5g catalyzer fixed-bed reactor of packing into as catalysts with the catalyzer MTA-06 of preparation in embodiment 1, at the nitrogen atmosphere borehole cooling to 450 ℃ of temperature of reaction.By fresh feed pump, methyl alcohol is pumped into reactor and catalyzer contact reacts.Material benzenemethanol feed weight air speed is 2h
-1, reaction product adopts the on-line analysis of Varian3800 gas-chromatography.Reaction result is as shown in table 1, and in product (remove and generate water), aromaticity content is 35.86wt%, and in aromatic hydrocarbons, p-Xylol content is 82.91wt%, and p-Xylol selectivity in xylene isomer is 99.37wt%.
Table 1
| Catalyzer | MTA-06 |
| Temperature of reaction | 450 |
| Methanol conversion (wt%) | 86.76 |
| Aromatics yield in hydrocarbon product (wt%) | 35.86 |
| P-Xylol is selectivity (wt%) in aromatic hydrocarbons | 82.91 |
| P-Xylol is selectivity (wt%) in dimethylbenzene | 99.37 |
Embodiment 4 fixed bed reaction evaluations
,, processed 1 hour in 550 ℃ of air atmospheres the 5g catalyzer fixed-bed reactor of packing into as catalysts with the MTA-06 catalyzer of preparation in embodiment 1, cool to respectively 450 ℃ of temperature of reaction, 500 ℃ under nitrogen atmosphere, pressure is 0.1MPa.The methanol feedstock that will contain 2wt% toluene by fresh feed pump pumps into reactor and catalyzer contact reacts.Material benzenemethanol feed weight air speed is 2h
-1, reaction product adopts the on-line analysis of Varian3800 gas-chromatography.Reaction result is as shown in table 2, in product (remove and generate water), aromaticity content is respectively 52.23wt%, 53.28%, in aromatic hydrocarbons, p-Xylol content is 88.39wt%, 87.99%, and p-Xylol selectivity in xylene isomer is 99.95wt%, 99.86%.
Table 2
Embodiment 5 fixed bed reaction evaluations
,, processed 1 hour in 550 ℃ of air atmospheres the 5g catalyzer fixed-bed reactor of packing into as catalysts with the MTA-07 catalyzer of preparation in embodiment 2, borehole cooling is to 400 ℃, 450 ℃ of temperature of reaction respectively at nitrogen atmosphere, and pressure is 0.15MPa.The methanol feedstock that will contain 7wt% benzene by fresh feed pump pumps into reactor and catalyzer contact reacts.Material benzenemethanol feed weight air speed is 2h
-1, reaction product adopts the on-line analysis of Varian3800 gas-chromatography.Reaction result is as shown in table 3, in product (remove generate water) aromaticity content be respectively 64.19%, 64.91wt%, in aromatic hydrocarbons p-Xylol content be respectively 81.56%, 82.56wt%, p-Xylol selectivity in xylene isomer is respectively 99.58%, 99.36wt%.
Table 3
| Catalyzer | MTA-07 MTA-07 |
| Temperature of reaction | 400 450 |
| Methanol conversion (wt%) | 87.39 88.95 |
| Aromatics yield in hydrocarbon product (wt%) | 64.19 64.91 |
| P-Xylol is selectivity (wt%) in aromatic hydrocarbons | 81.56 82.56 |
| P-Xylol is selectivity (wt%) in dimethylbenzene | 99.58 99.36 |
Embodiment 6 fluidized-bed reaction evaluations
,, processed 1 hour in 550 ℃ of air atmospheres the 10g catalyzer fixed fluidized-bed reactor of packing into as catalysts with the MTA-08 catalyzer of preparation in embodiment 3, at the nitrogen atmosphere borehole cooling to 450 ℃ of temperature of reaction.The methanol feedstock that will contain 5wt% toluene by fresh feed pump imports preheater, enters fixed fluidized-bed reactor after raw material is vaporized and contact with catalyzer in 280 ℃ of preheaters, and the feed weight air speed of material benzenemethanol is 2h
-1, reaction product adopts the on-line analysis of Varian3800 gas-chromatography.Reaction result is as shown in table 4, and in product (remove and generate water), aromaticity content is 65.21wt%, and in aromatic hydrocarbons, p-Xylol content is 87.81wt%, and p-Xylol selectivity in xylene isomer is 99.54wt%.
Table 3
| Catalyzer | MTA-08 |
| Temperature of reaction | 450 |
| Methanol conversion (wt%) | 84.47 |
| Aromatics yield in hydrocarbon product (wt%) | 65.21 |
| P-Xylol is selectivity (wt%) in aromatic hydrocarbons | 87.81 |
| P-Xylol is selectivity (wt%) in dimethylbenzene | 99.54 |
Claims (6)
1. a methanol/dimethyl ether conversion high yield prepares the method for p-Xylol, adopts the molecular sieve catalyst of metal and silanization modification, by add aromatic hydrocarbons in the methanol/dimethyl ether raw material, improves the yield of p-Xylol in the methanol/dimethyl ether conversion product; More than in product, aromaticity content can reach 50wt%, wherein in aromatic hydrocarbons p-Xylol content greater than 80wt%, p-Xylol in xylene isomer selectivity greater than 99wt%;
In the molecular sieve catalyst of described metal and silanization modification, molecular sieve is the ZSM-5 zeolite molecular sieve, and the siloxanes compound that uses in silanization is tetraethyl silicate, and metal is the soluble salt of Zn.
2. methanol/dimethyl ether conversion high yield as claimed in claim 1 prepares the method for p-Xylol, it is characterized in that: the aromatic hydrocarbons that adds refers to toluene and/or benzene, and the benzene that its source generates for methyl alcohol/methyl ether conversion reaction and/or toluene divide or all are recycled to reactive system through separate rear part.
3. methyl alcohol as claimed in claim 1/methyl ether transforms the method that high yield prepares p-Xylol, and it is characterized in that: additionally add toluene and/or benzene in reaction raw materials, its add-on is not more than 10wt% in methyl alcohol/methyl ether raw material.
4. methyl alcohol as claimed in claim 1/methyl ether transforms the method that high yield prepares p-Xylol, and it is characterized in that: reaction conditions is: temperature of reaction is 350-550 ℃; Reaction pressure is 0-2MPa; Methanol/dimethyl ether feed weight air speed is 0.1-20h
-1
5. methanol/dimethyl ether conversion high yield as claimed in claim 4 prepares the method for p-Xylol, it is characterized in that: reaction conditions is: temperature of reaction is 400-500 ℃; Reaction pressure is 0-1MPa; Methanol/dimethyl ether feed weight air speed is 1-10h
-1
6. methanol/dimethyl ether conversion high yield as claimed in claim 1 prepares the method for p-Xylol, it is characterized in that: reactive mode is any form of fixed bed or fluidized-bed.
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| EP3015445A1 (en) | 2014-10-30 | 2016-05-04 | China Petroleum & Chemical Corporation | A method for producing an aromatic hydrocarbon with an oxygenate as raw material |
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| CN103588611B (en) * | 2013-11-13 | 2015-03-25 | 上海华谊（集团）公司 | Method for preparing PX (p-xylene) |
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| CN101417236A (en) * | 2007-10-24 | 2009-04-29 | 中国科学院大连化学物理研究所 | Movable bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3015445A1 (en) | 2014-10-30 | 2016-05-04 | China Petroleum & Chemical Corporation | A method for producing an aromatic hydrocarbon with an oxygenate as raw material |
| US9783468B2 (en) | 2014-10-30 | 2017-10-10 | China Petroleum & Chemical Corporation | Method for producing an aromatic hydrocarbon with an oxygenate as raw material |
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