CN117736060A - Method for preparing paraxylene from methanol - Google Patents
Method for preparing paraxylene from methanol Download PDFInfo
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- CN117736060A CN117736060A CN202211124106.3A CN202211124106A CN117736060A CN 117736060 A CN117736060 A CN 117736060A CN 202211124106 A CN202211124106 A CN 202211124106A CN 117736060 A CN117736060 A CN 117736060A
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- methanol
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- molecular sieve
- raw material
- metal promoter
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 204
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 111
- 239000002808 molecular sieve Substances 0.000 claims abstract description 39
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 230000002378 acidificating effect Effects 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 12
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 12
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 4
- 229940017219 methyl propionate Drugs 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 2-(6-amino-1h-indol-3-yl)acetonitrile Chemical compound NC1=CC=C2C(CC#N)=CNC2=C1 ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 238000005899 aromatization reaction Methods 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical group 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 238000004817 gas chromatography Methods 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 239000002245 particle Substances 0.000 description 17
- 229910001220 stainless steel Inorganic materials 0.000 description 17
- 239000010935 stainless steel Substances 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing paraxylene from methanol, which is characterized in that raw material I methanol and raw material II are reacted under certain reaction conditions through a reaction zone of a catalyst carrying an acidic molecular sieve without metal auxiliary agent to prepare paraxylene. The raw material II is at least one selected from compounds with a structural formula shown in a formula I, wherein R 1 Selected from C 1 ～C 4 One of the hydrocarbon groups; r is R 2 Selected from C 1 ～C 4 One of the hydrocarbon groups. The raw material II is added in the methanol aromatization reaction, so that the selectivity of aromatic hydrocarbon can be improved, and the proportion of paraxylene in dimethylbenzene can be improved.
Description
Technical Field
The invention relates to a method for preparing paraxylene by co-feeding methanol and alkyl ester, belonging to the field of catalysis.
Background
Para-xylene (PX) is an important basic chemical raw material, mainly used for producing terephthalic acid, which can continue to react with ethylene glycol to produce polyethylene terephthalate (PET), which can be used for producing polyester fibers, so that para-xylene is the most used aromatic hydrocarbon.
China is the largest paraxylene producing country in the world, but is also the largest paraxylene consuming country. With the rapid increase of the economy in China, the domestic p-xylene market supply and demand is low, and the external dependence of the domestic p-xylene in 2019 is still 50%.
At present, paraxylene is mainly produced through a petroleum route, and the main production mode is that toluene and C9 aromatic hydrocarbon are produced by an aromatic hydrocarbon combination device. In view of the current energy structure of China rich in coal and lean in oil, the method for preparing the paraxylene by the coal chemical industry route is greatly developed and has very important significance. Among the technology for preparing aromatic hydrocarbon in coal chemical industry, the technology (MTA) for preparing aromatic hydrocarbon by taking methanol as a raw material is most widely studied. However, in the MTA reaction, the proportion of paraxylene to xylene is only about 23%, and increasing the proportion of paraxylene in xylene is advantageous for industrial application.
Disclosure of Invention
The invention provides a method for preparing paraxylene from methanol, which comprises the steps of allowing raw material I methanol and raw material II to pass through a reaction zone of a catalyst of an acidic molecular sieve loaded with metal auxiliary agents or free of metal auxiliary agents, and reacting under certain reaction conditions to prepare paraxylene.
The application provides a method for preparing paraxylene from methanol, which comprises the steps of enabling raw material I methanol and raw material II to pass through a reaction zone loaded with a catalyst to react to prepare paraxylene;
the raw material II is at least one selected from compounds with structural formulas shown in a formula I;
wherein R is 1 、R 2 Are each independently selected from C 1 ～C 4 One of the alkyl groups of (a);
the reaction temperature is 200-340 ℃.
Optionally, the raw material II is at least one selected from methyl acetate, methyl propionate, methyl butyrate and methyl valerate.
Optionally, the catalyst is an acidic molecular sieve containing or not containing a metal promoter.
Alternatively, the reaction conditions are: the pressure is 0.1-3.0 MPa, and the methanol mass airspeed is 0.01-20 h -1 。
Optionally, the reaction temperature is 250-340 ℃.
Optionally, the reaction pressure is 0.1-1 MPa.
Optionally, the methanol mass space velocity is 0.3 to 3.0h -1 。
Alternatively, the upper limit of the reaction temperature is selected from 300 ℃, 250 ℃ or 200 ℃, and the lower limit of the reaction temperature is selected from 250 ℃, 300 ℃.
Alternatively, the upper limit of the reaction pressure is selected from 3.0Mpa, 2.5Mpa, 1.5Mpa, 1.0Mpa or 0.5Mpa, and the lower limit of the reaction pressure is selected from 0.1Mpa, 0.5Mpa, 1.5Mpa, 2.0Mpa or 2.5Mpa.
Optionally, the upper limit of the mass space velocity of the methanol is selected from 20h -1 、15h -1 、10h -1 、5h -1 Or 3h -1 The lower limit of the mass space velocity of the methanol is selected from 0.01h -1 、0.3h -1 、1h -1 、2h -1 Or 3h -1 。
Optionally, the molar ratio of the raw material I methanol to the raw material II is 20:1-3:1.
Alternatively, the molar ratio of the raw material I methanol to the raw material II is 10:1-3:1.
Alternatively, the molar ratio of the raw material I methanol to the raw material II is 10:1-3:1.
Optionally, the metal promoter-containing or metal promoter-free acidic molecular sieve is selected from at least one of acidic molecular sieves having a RHO, MEL, FER, MFI, MOR, FAU, EMT configuration.
Optionally, the metal auxiliary is selected from one of Zn, mn, mg, ni, co, ca and Ga.
Preferably, the metal auxiliary is selected from one of Zn, ni and Ca.
Alternatively, the method of introducing the metal promoter herein may be synthesized in situ, or metal ion exchanged, or impregnated supported.
Optionally, the acidic molecular sieve is selected from at least one of hydrogen-type ZSM-5 molecular sieve, hydrogen-type MCM-22 molecular sieve and hydrogen-type ZSM-11 molecular sieve.
Optionally, the atomic ratio of silicon to aluminum in the acidic molecular sieve is Si/al=3 to 200.
Alternatively, the atomic ratio of silicon to aluminum in the acidic ZSM-5, ZSM-11 molecular sieves is Si/al=3 to 200, preferably Si/al=30 to 70.
Optionally, the acidic ZSM-5 and ZSM-11 molecular sieves have one or more of a microstructure, a nanostructure, a micropore structure and a mesoporous-micropore structure.
Optionally, in the acidic molecular sieve containing the metal auxiliary agent, the metal auxiliary agent accounts for 0.01-15% of the mass of the catalyst.
Optionally, the reaction zone contains one reactor, or a plurality of reactors connected in series and/or parallel.
Alternatively, the reactor is one of a fixed bed reactor, a moving bed reactor or a fluidized bed reactor that achieves continuous reaction.
Preferably, the reactor is a fixed bed reactor.
Optionally, the reactor is one or more fixed bed reactors. In the form of a continuous reaction. The number of the fixed bed reactors may be one or more. When multiple fixed bed reactors are employed, the reactors may be in series, parallel, or a combination of series and parallel.
The beneficial effects that this application can produce include at least:
(1) Compared with the prior art, the method provided by the application has the advantages that alkyl ester is added in the methanol aromatization reaction, so that the selectivity of aromatic hydrocarbon can be improved, and meanwhile, the proportion of paraxylene in dimethylbenzene can be improved;
(2) Compared with the prior art, the method provided by the application has the advantages that the temperature of the methanol aromatization reaction is obviously reduced compared with the prior art, and the energy consumption is reduced.
Detailed Description
The analytical methods, conversions, selectivities in the examples were calculated as follows:
automated analysis was performed using an Agilent7890 gas chromatograph with a gas autosampler, TCD detector connected to TDX-1 packed column, FID detector connected to Plot-Q capillary column and FFAP capillary column.
In some embodiments of the invention, both conversion and selectivity are calculated based on moles of carbon:
methanol conversion = [ (moles of methanol in feed) - (moles of methanol in discharge) ] +.
Aromatic selectivity = (moles of carbon of aromatic hydrocarbon in discharge)/(moles of carbon of all products in discharge) × (100%)
Para-xylene selectivity = (moles of para-xylene carbon in the draw = (moles of carbon in all products in the draw) × (100%)
Para-xylene ratio = (moles of carbon para-xylene in the discharge)/(moles of carbon of all xylenes in the discharge) × (100%)
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
Catalyst Performance test
Example 1
10g of hydrogen type ZSM-5 molecular sieve with Si/Al=50, namely HZSM-5 (50) purchased by Nanka university catalyst factory, is pressed into particles with 20-40 meshes, is put into a stainless steel reaction tube with the inner diameter of 16mm, is activated for 4 hours at 550 ℃ by 100ml/min of nitrogen, and reacts under the following conditions: reaction temperature (T) =300 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 Methanol: methyl acetate (MeOH: MAc) =5:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 2
10g of hydrogen type ZSM-5 molecular sieve with Si/Al=100 purchased from Nanka university catalyst factory, namely HZSM-5 (100) for short, is pressed into particles with 20-40 meshes, is put into a stainless steel reaction tube with the inner diameter of 16mm, is activated for 4 hours at 550 ℃ by 100ml/min of nitrogen, and reacts under the following conditions: reaction temperature (T) =300 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 Methanol: methyl acetate (MeOH: MAc) =5:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 3
10g of hydrogen type ZSM-11 molecular sieve with Si/Al=100 purchased from Nanka university catalyst factory, namely HZSM-11 (100) for short, is pressed into particles with 20-40 meshes, is put into a stainless steel reaction tube with the inner diameter of 16mm, is activated for 4 hours at 550 ℃ by 100ml/min of nitrogen, and reacts under the following conditions: reaction temperature (T) =300 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 Methanol: methyl acetate (MeOH: MAc) =5:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 4
10g of hydrogen type ZSM-5 molecular sieve with Si/Al=100 purchased from Nanka university catalyst factory, namely HZSM-5 (100) for short, is pressed into particles with 20-40 meshes, is put into a stainless steel reaction tube with the inner diameter of 16mm, is activated for 4 hours at 550 ℃ by 100ml/min of nitrogen, and reacts under the following conditions: reaction temperature (T) =300 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =0.5 h -1 Methanol: methyl acetate (MeOH: MAc) =5:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 5
10g of hydrogen type ZSM-5 molecular sieve with Si/Al=100 purchased from Nanka university catalyst factory, namely HZSM-5 (100) for short, is pressed into particles with 20-40 meshes, is put into a stainless steel reaction tube with the inner diameter of 16mm, is activated for 4 hours at 550 ℃ by 100ml/min of nitrogen, and reacts under the following conditions: reaction temperature (T) =300 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =3 h -1 Methanol: methyl acetate (MeOH: MAc) =5:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 6
10g of hydrogen type ZSM-5 molecular sieve with Si/Al=100 purchased from Nanka university catalyst factory, namely HZSM-5 (100) for short, is pressed into particles with 20-40 meshes, is put into a stainless steel reaction tube with the inner diameter of 16mm, is activated for 4 hours at 550 ℃ by 100ml/min of nitrogen, and reacts under the following conditions: reaction temperature (T) =270 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 Methanol: acetic acid methyl esterEster (MeOH: MAc) =5:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 7
10g of hydrogen type ZSM-5 molecular sieve with Si/Al=100 purchased from Nanka university catalyst factory, namely HZSM-5 (100) for short, is pressed into particles with 20-40 meshes, is put into a stainless steel reaction tube with the inner diameter of 16mm, is activated for 4 hours at 550 ℃ by 100ml/min of nitrogen, and reacts under the following conditions: reaction temperature (T) =340 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 Methanol: methyl acetate (MeOH: MAc) =5:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 8
10g of hydrogen type ZSM-5 molecular sieve with Si/Al=100 purchased from Nanka university catalyst factory, namely HZSM-5 (100) for short, is pressed into particles with 20-40 meshes, is put into a stainless steel reaction tube with the inner diameter of 16mm, is activated for 4 hours at 550 ℃ by 100ml/min of nitrogen, and reacts under the following conditions: reaction temperature (T) =300 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 Methanol: methyl acetate (MeOH: MAc) =10:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 9
10g of hydrogen type ZSM-5 molecular sieve with Si/Al=100 purchased from Nanka university catalyst factory, namely HZSM-5 (100) for short, is pressed into particles with 20-40 meshes, is put into a stainless steel reaction tube with the inner diameter of 16mm, is activated for 4 hours at 550 ℃ by 100ml/min of nitrogen, and reacts under the following conditions: reaction temperature (T) =300 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 Methanol: methyl acetate (MeOH: MAc) =3:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 10
10g of hydrogen type ZSM-5 molecular sieve with Si/Al=100, called HZSM-5 (100) for short, purchased by Kao university catalyst factory, is pressed into tablets, sieved into particles with 20 to 40 meshes, put into a stainless steel reaction tube with the inner diameter of 16mm, activated for 4 hours at 550 ℃ with 100ml/min of nitrogen, and the following conditions are adoptedThe following reactions: reaction temperature (T) =300 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 Methanol: methyl propionate (MeOH: methyl Propionate) =5:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 11
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in deionized water, and is added dropwise to 30g of hydrogen ZSM-5 molecular sieve of Si/Al=50 purchased by Nanko university catalyst factory while stirring, and is kept stand for 24 hours, then is separated and washed by deionized water, the obtained sample is dried in a baking oven at 120 ℃ for 12 hours, and the dried sample is placed in a muffle furnace, is heated to 550 ℃ at a heating rate of 2 ℃/min, and is baked for 4 hours, so that Zn-6% -ZSM-5 (50) is obtained.
Tabletting Zn-6% -ZSM-5 (50), sieving to obtain particles with 20-40 meshes, loading into a stainless steel reaction tube with an inner diameter of 16mm, activating with 100ml/min nitrogen at 550 ℃ for 4 hours, and reacting under the following conditions: reaction temperature (T) =300 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 Methanol: methyl acetate (MeOH: MAc) =5:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 12
Will be 8.0gNi (NO 3 ) 2 ·6H 2 O is dissolved in deionized water, 30g of Si/Al=50 hydrogen ZSM-5 molecular sieve purchased by Nanka university catalyst factory is dropwise added while stirring, standing is carried out for 24 hours, then the obtained sample is separated and washed by deionized water, the obtained sample is dried in a baking oven at 120 ℃ for 12 hours, the dried sample is placed in a muffle furnace, the temperature is raised to 550 ℃ at the heating rate of 2 ℃/min, and the Ni-6% -ZSM-5 (50) is obtained after roasting for 4 hours.
Tabletting Ni-6% -ZSM-5 (50), sieving to obtain particles with 20-40 meshes, loading into a stainless steel reaction tube with an inner diameter of 16mm, activating with 100ml/min nitrogen at 550 ℃ for 4 hours, and reacting under the following conditions: reaction temperature (T) =300 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 Methanol: methyl acetate (MeOH: MAc) =5:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Comparative example 1
10g of hydrogen type ZSM-5 molecular sieve with Si/Al=50, namely HZSM-5 (50) purchased by Nanka university catalyst factory, is pressed into particles with 20-40 meshes, is put into a stainless steel reaction tube with the inner diameter of 16mm, is activated for 4 hours at 550 ℃ by 100ml/min of nitrogen, and reacts under the following conditions: reaction temperature (T) =300 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 . After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Comparative example 2
10g of hydrogen type ZSM-11 molecular sieve with Si/Al=100 purchased from Nanka university catalyst factory, namely HZSM-11 (100) for short, is pressed into particles with 20-40 meshes, is put into a stainless steel reaction tube with the inner diameter of 16mm, is activated for 4 hours at 550 ℃ by 100ml/min of nitrogen, and reacts under the following conditions: reaction temperature (T) =300 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 . After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Comparative example 3
10g of hydrogen type ZSM-5 molecular sieve with Si/Al=100 purchased from Nanka university catalyst factory, namely HZSM-5 (100) for short, is pressed into particles with 20-40 meshes, is put into a stainless steel reaction tube with the inner diameter of 16mm, is activated for 4 hours at 550 ℃ by 100ml/min of nitrogen, and reacts under the following conditions: reaction temperature (T) =300 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 . After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Comparative example 4
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in deionized water, and is added dropwise to 30g of hydrogen ZSM-5 molecular sieve of Si/Al=50 purchased by Nanko university catalyst factory while stirring, and is kept stand for 24 hours, then is separated and washed by deionized water, the obtained sample is dried in a baking oven at 120 ℃ for 12 hours, and the dried sample is placed in a muffle furnace, is heated to 550 ℃ at a heating rate of 2 ℃/min, and is baked for 4 hours, so that Zn-6% -ZSM-5 (50) is obtained.
Tabletting Zn-6% -ZSM-5 (50) and sieving to obtain particles with 20-40 meshesThe mixture was placed in a stainless steel reaction tube having an inner diameter of 16mm, activated with 100ml/min nitrogen gas at 550℃for 4 hours, and reacted under the following conditions: reaction temperature (T) =300 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 . After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Comparative example 5
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in deionized water, and is added dropwise to 30g of hydrogen ZSM-5 molecular sieve of Si/Al=50 purchased by Nanko university catalyst factory while stirring, and is kept stand for 24 hours, then is separated and washed by deionized water, the obtained sample is dried in a baking oven at 120 ℃ for 12 hours, and the dried sample is placed in a muffle furnace, is heated to 550 ℃ at a heating rate of 2 ℃/min, and is baked for 4 hours, so that Zn-6% -ZSM-5 (50) is obtained.
Tabletting Zn-6% -ZSM-5 (50), sieving to obtain particles with 20-40 meshes, loading into a stainless steel reaction tube with an inner diameter of 16mm, activating with 100ml/min nitrogen at 550 ℃ for 4 hours, and reacting under the following conditions: reaction temperature (T) =450 ℃, reaction pressure (P) =0.1 MPa, methanol mass space velocity (WHSV) =1 h -1 . After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
TABLE 1 catalytic reaction results in examples 1-11 and comparative examples 1-5
The invention has been described in detail above but is not limited to the specific embodiments described herein. Those skilled in the art will appreciate that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A method for preparing paraxylene from methanol is characterized in that raw material I methanol and raw material II pass through a reaction zone loaded with a catalyst to react to prepare paraxylene;
the raw material II is at least one selected from compounds with structural formulas shown in a formula I;
wherein R is 1 、R 2 Are each independently selected from C 1 ～C 4 One of the alkyl groups of (a);
the reaction temperature is 200-340 ℃.
2. The method according to claim 1, wherein the raw material II is at least one selected from methyl acetate, methyl propionate, methyl butyrate and methyl valerate.
3. The process of claim 1 wherein the catalyst is a metal promoter-containing or metal promoter-free acidic molecular sieve.
4. The method of claim 1, wherein the reaction conditions are: the pressure is 0.1-3.0 MPa, and the methanol mass airspeed is 0.01-20 h -1 。
5. The process according to claim 1, wherein the molar ratio of feed I methanol to feed II is from 20:1 to 3:1.
6. A process according to claim 3, wherein the metal promoter-containing or metal promoter-free acidic molecular sieve is selected from at least one of acidic molecular sieves having a RHO, MEL, FER, MFI, MOR, FAU, EMT configuration.
7. A method according to claim 3, wherein the metal promoter is selected from one of Zn, mn, mg, ni, co, ca, ga.
8. A process according to claim 3, wherein the acidic molecular sieve is selected from at least one of a hydrogen form of ZSM-5 molecular sieve, a hydrogen form of MCM-22 molecular sieve, and a hydrogen form of ZSM-11 molecular sieve.
9. A method according to claim 3, wherein the atomic ratio of silicon to aluminum in the acidic molecular sieve is Si/ai = 3-200.
10. A process according to claim 3, wherein in the metal promoter-containing acidic molecular sieve, the metal promoter comprises 0.01 to 15% by mass of the catalyst;
preferably, the reaction zone comprises one reactor, or a plurality of reactors connected in series and/or parallel;
preferably, the reactor is one of a fixed bed reactor, a moving bed reactor or a fluidized bed reactor that achieves continuous reaction.
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