CN117623841A - Method for preparing aromatic hydrocarbon from methanol and/or dimethyl ether - Google Patents
Method for preparing aromatic hydrocarbon from methanol and/or dimethyl ether Download PDFInfo
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- CN117623841A CN117623841A CN202210983002.1A CN202210983002A CN117623841A CN 117623841 A CN117623841 A CN 117623841A CN 202210983002 A CN202210983002 A CN 202210983002A CN 117623841 A CN117623841 A CN 117623841A
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- dimethyl ether
- molecular sieve
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 237
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 154
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 50
- 239000002808 molecular sieve Substances 0.000 claims description 43
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 25
- 239000001569 carbon dioxide Substances 0.000 claims description 25
- 239000012429 reaction media Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- -1 ethylene, propylene, butene Chemical class 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 44
- 239000008367 deionised water Substances 0.000 description 43
- 229910021641 deionized water Inorganic materials 0.000 description 43
- 238000010438 heat treatment Methods 0.000 description 25
- 238000011068 loading method Methods 0.000 description 23
- 238000007873 sieving Methods 0.000 description 23
- 230000003213 activating effect Effects 0.000 description 22
- 238000004817 gas chromatography Methods 0.000 description 22
- 239000002245 particle Substances 0.000 description 22
- 229910001220 stainless steel Inorganic materials 0.000 description 22
- 239000010935 stainless steel Substances 0.000 description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 5
- 238000001833 catalytic reforming Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/46—Iron group metals or copper
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing aromatic hydrocarbon from methanol and/or dimethyl ether, which comprises the following steps: contacting and reacting a material containing methanol and/or dimethyl ether with a catalyst to obtain aromatic hydrocarbon; the catalyst is a metal modified molecular sieve catalyst; the pressure of the reaction is 7-15MPa. Compared with the prior art, the method provided by the application has the advantages that the reaction for preparing the aromatic hydrocarbon from the methanol and the dimethyl ether is carried out under the high-pressure atmosphere, the selectivity of the aromatic hydrocarbon, especially BTX, can be improved and stabilized, and the single-pass service life of the catalyst is prolonged.
Description
Technical Field
The invention relates to a method for preparing aromatic hydrocarbon from methanol and/or dimethyl ether, belonging to the field of catalysis.
Background
Aromatic hydrocarbons, particularly Benzene (Benzene), toluene (tolene) and Xylene (Xylene), collectively referred to as BTX, are important organic chemical raw materials whose yield and scale are inferior to those of ethylene and propylene, and derivatives thereof are widely used for chemical products and fine chemicals such as fuels, petrochemical industry, chemical fibers, plastics and rubber.
At present, aromatic hydrocarbons are mainly produced by using petroleum as a raw material, wherein 70% of BTX aromatic hydrocarbons worldwide come from catalytic reforming process units of oil refineries. The catalytic reforming technology takes naphtha as a raw material, adopts the process types of semi-regeneration and continuous regeneration reforming, and generally adopts a platinum-containing catalyst for catalytic reforming. Typical processes for catalytic reforming are represented by the CCR platformer process from UOP and the Aromizer process from IFP. In addition, the arene producing process in petroleum route includes gasoline hydrogenating technology, arene extracting technology, heavy arene light technology and light hydrocarbon aromatizing technology.
With the continuous development of society, the world demand for aromatic hydrocarbon is increasing, however, the increasing shortage of petroleum resources results in the price of aromatic hydrocarbon, especially BTX, being high. In view of the current energy structure of China rich in coal and lean in oil, the great development of the coal chemical route for preparing aromatic hydrocarbon 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 of a coal chemical industry platform product is most widely researched, and generally adopts an acidic ZSM-5 molecular sieve catalyst modified by metal assistants such as zinc, gallium, silver and the like. However, when the catalyst is used for MTA reaction, the catalyst has the defect of easy carbon deposition and inactivation, and the application of the catalyst is greatly limited.
Disclosure of Invention
The invention provides a method for preparing aromatic hydrocarbon from methanol and/or dimethyl ether under a high-pressure environment, which is used for preparing aromatic hydrocarbon from methanol and/or dimethyl ether under a high-pressure atmosphere, can improve and stabilize the selectivity of aromatic hydrocarbon, especially BTX, and prolongs the single-pass service life of a catalyst.
In the prior art, the pressure for preparing aromatic hydrocarbon from methanol and/or dimethyl ether generally does not exceed 0.5MPa, because researchers generally consider that the MTA/DTA reaction is a reaction with increased molecular volume, and from the viewpoint of balance, the reaction is reversely carried out due to the increased pressure, so that the aromatic hydrocarbon generation is unfavorable.
However, the applicant found through creative work that in experimental operations, it was difficult to reach an ideal equilibrium state for MTA reactions first; secondly, from the balance point of view, the effect of metal is ignored, and when a metal catalyst is used, the increase of the contact time under high pressure is beneficial to promoting alkane dehydrogenation, which is beneficial to the generation of aromatic hydrocarbon; in addition, increaseThe contact time is added, so that the content of olefin in the system is reduced, excessive growth of aromatic hydrocarbon is inhibited to generate carbon deposition, and the stability of the catalyst can be improved; finally, CO at high pressure 2 On one hand, the formation of aromatic hydrocarbon is promoted, and on the other hand, carbon deposition can be eliminated, so that the stability of the catalyst and the selectivity of the aromatic hydrocarbon are improved simultaneously. In the application, the MTA/DTA reaction is creatively carried out under the high-pressure carbon dioxide atmosphere, the conversion rate of methanol and/or dimethyl ether can reach 100% at the pressure of 7-15MPa, the selectivity of aromatic hydrocarbon is almost over 80%, and the stability of the catalyst is greatly improved.
The application provides a method for preparing aromatic hydrocarbon from methanol and/or dimethyl ether, which comprises the following steps:
contacting and reacting a material containing methanol and/or dimethyl ether with a catalyst to obtain aromatic hydrocarbon;
the catalyst is a metal modified molecular sieve catalyst;
the pressure of the reaction is 7-15MPa.
Alternatively, the upper pressure limit of the reaction is independently selected from any one of 15MPa, 14MPa, 13MPa, 12MPa, 11MPa, 10MPa, 9MPa, 8 MPa; the lower limit is independently selected from 7MPa, 14MPa, 13MPa, 12MPa, 11MPa, 10MPa, 9MPa, 8MPa.
Alternatively, the conditions of the reaction are: the reaction temperature is 350-550 ℃; the mass airspeed of the methanol and/or the dimethyl ether is 0.1 to 20h -1 。
Alternatively, the upper reaction temperature limit is independently selected from 550 ℃, 500 ℃, 450 ℃, 400 ℃, and the lower reaction temperature limit is independently selected from 350 ℃, 400 ℃, 450 ℃, 500 ℃.
Alternatively, the upper mass space velocity limit of the methanol and/or dimethyl ether is independently selected from 20h -1 、18h -1 、16h -1 、14h -1 、12h -1 、10h -1 、8h -1 、6h -1 、4h -1 、2h -1 、1h -1 、0.5h -1 The lower limit is independently selected from 0.1h -1 、18h -1 、16h -1 、14h -1 、12h -1 、10h -1 、8h -1 、6h -1 、4h -1 、2h -1 、1h -1 、0.5h -1 。
Preferably, the mass space velocity of the methanol and/or the dimethyl ether is 0.3 to 3h -1 。
Optionally, the reaction is carried out in the presence of a reaction medium;
the reaction medium is carbon dioxide.
The catalyst stability and the aromatic hydrocarbon selectivity can be greatly improved by carrying out the reaction under the carbon dioxide reaction medium.
Optionally, the molar ratio of the methanol to the dimethyl ether is 0-1.
Optionally, the molar ratio of the reaction medium to the methanol and/or the dimethyl ether is more than or equal to 1:1;
the mole number of the methanol and/or the dimethyl ether is calculated by the mole number of the carbon atoms contained in the methanol and/or the dimethyl ether.
Preferably, the molar ratio of the reaction medium to the methanol and/or the dimethyl ether is 2:1-20:1, if the molar ratio is too high, the cost of raw material circulation is increased, and if the molar ratio is too low, the effect of promoting the generation of aromatic hydrocarbon is not obvious.
Alternatively, the upper limit of the molar ratio of the reaction medium to methanol and/or dimethyl ether is independently selected from 20: 1. 18: 1. 14: 1. 10:1. 8: 1. 6: 1. 4:1, the lower limit is independently selected from 2: 1. 18: 1. 14: 1. 10:1. 8: 1. 6: 1. 4:1.
optionally, the material also comprises inert atmosphere and/or circulating components;
the inert atmosphere comprises one or more of nitrogen, argon and helium;
the recycle component comprises one or more of carbon monoxide, carbon dioxide, methane, ethane, propane, ethylene, propylene, butene.
Optionally, the sum of the volumes of the inert atmosphere and/or the recycled components accounts for 0.1-80% of the reaction mass;
the reaction mass does not include a reaction medium.
Alternatively, the sum of the volumes of the inert atmosphere and/or the recycled components is independently selected from the group consisting of 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5%, 1%, 0.5% for the upper limit and 0.1%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5%, 1%, 0.5% for the lower limit of the reaction mass.
In one embodiment, the circulating component can be added before or during the reaction, the existence of the circulating component can improve the catalytic performance of the catalyst, and the raw materials can be fully utilized by controlling the inert atmosphere and/or the content of the circulating component, so that the yield of the target product of the total package reaction is improved.
Optionally, the molecular sieve catalyst is selected from at least one of a silicon aluminum molecular sieve and a phosphorus aluminum molecular sieve.
Preferably, the molecular sieve catalyst is a silica-alumina molecular sieve.
Optionally, the silica alumina molecule is selected from at least one of Beta, MOR, ZSM-5, ZSM-11, ZSM-22, MCM-49.
Optionally, the metal in the metal modified molecular sieve catalyst is selected from one or more of Zn, mn, mg, ni, fe, co, ca, ga, cu, ag.
Preferably, the metal is selected from at least one of Zn, ni, ga, fe.
In the application, the method for introducing the metal in the metal modified molecular sieve catalyst can be synthesized in situ, or metal ion exchange or impregnation and loading are carried out.
Optionally, the mass content of the metal in the molecular sieve catalyst is 0.01-15%.
Alternatively, the upper limit of the mass content of the metal in the molecular sieve catalyst is independently selected from 15%, 14%, 13%, 10%, 8%, 6%, 4%, 2%, 1%, 0.5%, 0.1%, 0.05%, and the lower limit is independently selected from 0.01%, 14%, 13%, 10%, 8%, 6%, 4%, 2%, 1%, 0.5%, 0.1%, 0.05%.
Preferably, the mass content of the metal in the molecular sieve catalyst is 0.01-10%, and by controlling the content of the metal in the molecular sieve catalyst to be 0.01-10, the generation of methane can be reduced while the selectivity of aromatic hydrocarbon can be ensured, and meanwhile, the metal consumption of the catalyst is reduced, so that the cost is saved.
Optionally, si/al=20 to 300 in the aluminosilicate molecular sieve.
Alternatively, the upper Si/Al limits in the aluminosilicate molecular sieves are independently selected from 300, 280, 240, 220, 200, 180, 160, 140, 120, 100, 80, 60, 40, 30, and the lower limits are independently selected from 20, 280, 240, 220, 200, 180, 160, 140, 120, 100, 80, 60, 40, 30.
Preferably, si/al=150 to 300 in the aluminosilicate molecular sieve, and the stability of the catalyst can be improved by using the aluminosilicate molecular sieve with a silica-alumina ratio of 150 to 300 as the catalyst.
Alternatively, the reaction is carried out in the gas phase, subcritical or supercritical state.
Optionally, the reaction is carried out in a reactor; the reactor is one or a plurality of reactors connected in series and/or 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 the reaction for preparing the aromatic hydrocarbon from the methanol and the dimethyl ether is carried out under the high-pressure atmosphere, the selectivity of the aromatic hydrocarbon, especially BTX, can be improved and stabilized, and the single-pass service life of the catalyst can be prolonged;
(2) Compared with the prior art, the method provided by the application has the advantages that the reaction of preparing the aromatic hydrocarbon from the methanol and the dimethyl ether is carried out under the high-pressure carbon dioxide atmosphere, the selectivity of the aromatic hydrocarbon, especially BTX, can be improved and stabilized, and the single-pass service life of the catalyst is prolonged.
Drawings
FIG. 1 is a schematic illustration of the reaction process in example 17 of the present application.
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.
In some embodiments of the invention, both conversion and selectivity are calculated based on moles of carbon:
methanol/dimethyl ether conversion = [ (moles of methanol/dimethyl ether in feed) - (moles of methanol/dimethyl ether in discharge) ] ≡ (moles of methanol/dimethyl ether in feed) × (100%)
Selectivity of liquid hydrocarbon (hydrocarbons containing 5 carbons or more) = (number of moles of liquid hydrocarbon in discharge)/(number of moles of carbon in all products in discharge) × (100%)
Aromatic selectivity = (moles of carbon of aromatic hydrocarbon in discharge)/(moles of carbon of all products in discharge) × (100%)
BTX selectivity = (moles of carbon BTX in the discharge)/(moles of carbon for all products 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
Preparation of the supported catalyst:
will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g of deionized water, 30g of hydrogen ZSM-5 molecular sieve of Si/Al=20 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 Zn-6% -ZSM-5 (20) is obtained after roasting for 4 hours.
Tabletting Zn-6% -ZSM-5 (20), 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) =10 MPa, methanol mass space velocity (WHSV) =1 h -1 Carbon dioxide: methanol (CO) 2 MeOH) =1:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 2
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in deionized water and added dropwise to Nankui university catalyst under stirring30g of hydrogen ZSM-5 molecular sieve with Si/Al=70 purchased by a chemical reagent factory is stood for 24 hours, then 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 a heating rate of 2 ℃/min, and the Zn-6% -ZSM-5 (70) is obtained after roasting for 4 hours.
Tabletting Zn-6% -ZSM-5 (70), 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) =10 MPa, methanol mass space velocity (WHSV) =1 h -1 Carbon dioxide: methanol (CO) 2 MeOH) =1:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 3
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g deionized water, 30g of hydrogen ZSM-5 molecular sieve of Si/Al=200 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 Zn-6% -ZSM-5 (200) is obtained after roasting for 4 hours.
Tabletting Zn-6% -ZSM-5 (200), 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) =10 MPa, methanol mass space velocity (WHSV) =1 h -1 Carbon dioxide: methanol (CO) 2 MeOH) =1:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 4
Will be 4.1gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g of deionized water, and is dropwise added to 30g of hydrogen-type ZSM-5 molecular sieve of Si/Al=200 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 and is heated to 550 ℃ at a heating rate of 2 ℃/minRoasting for 4 hours at the temperature of between 3 and 200 ℃ to obtain the Zn-3 percent ZSM-5.
Tabletting Zn-3% -ZSM-5 (200), 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) =10 MPa, methanol mass space velocity (WHSV) =1 h -1 Carbon dioxide: methanol (CO) 2 MeOH) =1:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 5
Will be 1.4gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g deionized water, 30g of hydrogen ZSM-5 molecular sieve of Si/Al=200 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 Zn-1% -ZSM-5 (200) is obtained after roasting for 4 hours.
Tabletting Zn-1% -ZSM-5 (200), 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) =10 MPa, methanol mass space velocity (WHSV) =1 h -1 Carbon dioxide: methanol (CO) 2 MeOH) =1:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 6
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g deionized water, 30g of hydrogen ZSM-5 molecular sieve of Si/Al=200 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 Zn-6% -ZSM-5 (200) is obtained after roasting for 4 hours.
Tabletting Zn-6% -ZSM-5 (200), sieving to obtain particles of 20-40 meshes, loading into a stainless steel reaction tube with an inner diameter of 16mm, activating with 100ml/min nitrogen at 550deg.C for 4 hr, and the following stepsThe following reaction: reaction temperature (T) =450 ℃, reaction pressure (P) =12 MPa, methanol mass space velocity (WHSV) =1 h -1 Carbon dioxide: methanol (CO) 2 MeOH) =1:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 7
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g deionized water, 30g of hydrogen ZSM-5 molecular sieve of Si/Al=200 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 Zn-6% -ZSM-5 (200) is obtained after roasting for 4 hours.
Tabletting Zn-6% -ZSM-5 (200), 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) =7 MPa, methanol mass space velocity (WHSV) =1 h -1 Carbon dioxide: methanol (CO) 2 MeOH) =1:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 8
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g deionized water, 30g of hydrogen ZSM-5 molecular sieve of Si/Al=200 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 Zn-6% -ZSM-5 (200) is obtained after roasting for 4 hours.
Tabletting Zn-6% -ZSM-5 (200), 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) =7 MPa, methanol mass space velocity (WHSV) =1 h -1 Carbon dioxide: methanol (CO) 2 MeOH) =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
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g deionized water, 30g of hydrogen ZSM-5 molecular sieve of Si/Al=200 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 Zn-6% -ZSM-5 (200) is obtained after roasting for 4 hours.
Tabletting Zn-6% -ZSM-5 (200), 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) =7 MPa, methanol mass space velocity (WHSV) =1 h -1 Nitrogen: methanol (N) 2 MeOH) =10:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 10
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g deionized water, 30g of hydrogen ZSM-5 molecular sieve of Si/Al=200 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 Zn-6% -ZSM-5 (200) is obtained after roasting for 4 hours.
Tabletting Zn-6% -ZSM-5 (200), 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) =7 MPa, dimethyl ether mass space velocity (WHSV) =1 h -1 Nitrogen: dimethyl ether (N) 2 DME) =10:1. 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 was dissolved in 23g deionized water and added dropwise with stirring to 30g of Si/Al=200 hydrogen ZSM-5 fraction purchased from Nanko university catalyst plantAnd (3) sub-sieving, standing for 24 hours, separating, washing with deionized water, drying the obtained sample in a baking oven at 120 ℃ for 12 hours, placing the dried sample in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and roasting for 4 hours to obtain Zn-6% -ZSM-5 (200).
Tabletting Zn-6% -ZSM-5 (200), 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) =7 MPa, dimethyl ether mass space velocity (WHSV) =1 h -1 Carbon dioxide: dimethyl ether (CO) 2 DME) =10:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 12
Will.7.8 g Ga (NO) 3 ) 2 ·3H 2 O is dissolved in 23g deionized water, 30g of hydrogen ZSM-5 molecular sieve of Si/Al=200 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 mixture is baked for 4 hours, so that Ga-6% -ZSM-5 (200) is obtained.
Tabletting Ga-6% -ZSM-5 (200), sieving into particles with 20-40 meshes, loading into a stainless steel reaction tube with the 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) =7 MPa, methanol mass space velocity (WHSV) =1 h -1 Carbon dioxide: methanol (CO) 2 MeOH) =10:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 13
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g deionized water, and is added dropwise to 30g of Si/Al=200 hydrogen type ZSM-11 molecular sieve purchased by Nanka 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, the dried sample is placed in a muffle furnace, the temperature is raised to 550 ℃ at a heating rate of 2 ℃/min, and the Zn-6% -ZSM-11 is obtained after roasting for 4 hours(200)。
Tabletting Zn-6% -ZSM-11 (200), 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) =3 MPa, dimethyl ether mass space velocity (WHSV) =1 h -1 Nitrogen: dimethyl ether (N) 2 DME) =10:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 14
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g deionized water, 30g of hydrogen ZSM-11 molecular sieve of Si/Al=200 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 Zn-6% -ZSM-11 (200) is obtained after roasting for 4 hours.
Tabletting Zn-6% -ZSM-11 (200), 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) =7 MPa, dimethyl ether mass space velocity (WHSV) =1 h -1 Carbon dioxide: dimethyl ether (CO) 2 DME) =10:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 15
12.98gFe (NO) 3 ) 3 ·9H 2 O is dissolved in 23g deionized water, 30g of hydrogen ZSM-11 molecular sieve of Si/Al=200 purchased from 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 Fe-6% -ZSM-11 (200) is obtained after roasting for 4 hours.
Tabletting Fe-6% -ZSM-11 (200), 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: reactionTemperature (T) =450 ℃, reaction pressure (P) =7 MPa, dimethyl ether mass space velocity (WHSV) =1 h -1 Carbon dioxide: dimethyl ether (CO) 2 DME) =10:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 16
Will be 8.92gNi (NO 3 ) 2 ·6H 2 O is dissolved in 23g deionized water, 30g of hydrogen ZSM-11 molecular sieve of Si/Al=200 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 baking is carried out for 4 hours, thus obtaining Ni-6% -ZSM-11 (200).
Tabletting Ni-6% -ZSM-11 (200), 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) =7 MPa, dimethyl ether mass space velocity (WHSV) =1 h -1 Carbon dioxide: dimethyl ether (CO) 2 DME) =10:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Comparative example 1
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g deionized water, 30g of hydrogen ZSM-5 molecular sieve of Si/Al=200 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 Zn-6% -ZSM-5 (200) is obtained after roasting for 4 hours.
Tabletting Zn-6% -ZSM-5 (200), 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, dimethyl ether mass space velocity (WHSV) =1 h -1 Nitrogen: dimethyl ether (N) 2 DME) =10:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Comparative example 2
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g deionized water, 30g of hydrogen ZSM-5 molecular sieve of Si/Al=200 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 Zn-6% -ZSM-5 (200) is obtained after roasting for 4 hours.
Tabletting Zn-6% -ZSM-5 (200), 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 Carbon dioxide: methanol (CO) 2 MeOH) =10:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 1.
Comparative example 3
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g of deionized water, 30g of hydrogen ZSM-5 molecular sieve of Si/Al=40 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 Zn-6% -ZSM-5 (40) is obtained after roasting for 4 hours.
Tabletting Zn-6% -ZSM-5 (40), 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 Carbon dioxide: methanol (CO) 2 MeOH) =10:1. 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 was dissolved in 23g deionized water and added dropwise with stirring to 30g of Si/Al=200 hydrogen ZSM-1 purchased from Nanka university catalyst plant1 molecular sieve, standing for 24 hours, separating, washing with deionized water, drying the obtained sample in a baking oven at 120 ℃ for 12 hours, placing the dried sample in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and roasting for 4 hours to obtain Zn-6% -ZSM-11 (200).
Tabletting Zn-6% -ZSM-11 (200), 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, dimethyl ether mass space velocity (WHSV) =1 h -1 Carbon dioxide: dimethyl ether (CO) 2 DME) =10:1. 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 1-16 and comparative examples 1-4
As can be seen from Table 1, the catalysts of comparative examples 2 and 3, which have a lower silica-alumina content than the low acid content, have higher aromatic hydrocarbon selectivity and are deactivated within 20 to 30 hours at normal pressure; in contrast to normal pressure, the molecular sieves of examples 1-3, which are high in silica-alumina ratio, have longer life and higher aromatic hydrocarbon selectivity; examples 3-5 illustrate the effect of Zn content on aromatics selectivity, with higher Zn content providing higher aromatics selectivity; examples 3,6 and 7 illustrate the effect of reaction pressure on the reaction, and increasing the pressure increases the selectivity to aromaticsThe stability of the catalyst can be improved. Examples 7 and 8 illustrate CO 2 The higher the content, the higher the aromatic selectivity; examples 8 and 9, comparative examples 1 and 2 illustrate CO 2 Can promote aromatic hydrocarbon generation, and CO under high pressure 2 The amplitude of promotion is far greater than normal pressure; examples 8,9, 10, 11 compare the differences between DME and methanol feeds, which are somewhat more aromatic in selectivity but less stable than DME feeds; examples 8, 11, 12, 15, 16 compare the reactivity of different metal modifications. In conclusion, the traditional MTA reaction is carried out under normal pressure, and the reaction is carried out by using a molecular sieve with low silicon-aluminum ratio; in the present invention, at high pressure CO 2 The reaction is carried out in the atmosphere, and instead, the molecular sieve with high silicon-aluminum ratio is adopted, so that the stability of the catalyst and the selectivity of aromatic hydrocarbon are improved by prolonging the contact time (increasing the pressure).
Example 17
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g deionized water, 30g of hydrogen ZSM-5 molecular sieve of Si/Al=200 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 Zn-6% -ZSM-5 (200) is obtained after roasting for 4 hours.
Tabletting Zn-6% -ZSM-5 (200), 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) =10 MPa, methanol mass space velocity (WHSV) =20 h -1 Carbon dioxide: methanol (CO) 2 MeOH) =10:1. After the aromatic hydrocarbons are separated from the effluent, it is then passed into the reactor. The schematic diagram is shown in fig. 1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 2.
Example 18
Will be 8.2gZn (NO 3 ) 2 ·6H 2 O is dissolved in 23g deionized water, and is added dropwise to 30g of hydrogen ZSM-5 molecular sieve of Si/Al=200 purchased by Nanko university catalyst factory while stirring, and is left stand for 24 hours, and then separated and deionizedWashing with water, drying the obtained sample in a baking oven at 120 ℃ for 12 hours, placing the dried sample in a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, and roasting for 4 hours to obtain Zn-6% -ZSM-5 (200).
Tabletting Zn-6% -ZSM-5 (200), 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) =10 MPa, methanol mass space velocity (WHSV) =20 h -1 Carbon dioxide: methanol (CO) 2 MeOH) =10:1. After the reaction was stabilized, the product was analyzed by gas chromatography, and the reaction results are shown in Table 2.
TABLE 2
It can be seen that the effluent contains unreacted methanol, dimethyl ether, CO when not recycled 2 Also part of the light olefins and light alkanes; after recycling, the methanol of the total package reaction is completely converted, and simultaneously, the selectivity of aromatic hydrocarbon and BTX is greatly increased; medium CO 2 Also contributes to cost savings, since this operation may not require reintroduction of CO 2 。
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 process for the preparation of aromatic hydrocarbons from methanol and/or dimethyl ether, the process comprising:
contacting and reacting a material containing methanol and/or dimethyl ether with a catalyst to obtain aromatic hydrocarbon;
the catalyst is a metal modified molecular sieve catalyst;
the pressure of the reaction is 7-15MPa.
2. The method of claim 1, wherein the reaction conditions are: the reaction temperature is 350-550 ℃; the mass airspeed of the methanol and/or the dimethyl ether is 0.1 to 20h -1 。
3. The process of claim 1, wherein the reaction is carried out in the presence of a reaction medium;
the reaction medium is carbon dioxide.
4. A process according to claim 3, wherein the molar ratio of the reaction medium to methanol and/or dimethyl ether is ≡1:1;
the mole number of the methanol and/or the dimethyl ether is calculated by the mole number of the carbon atoms contained in the methanol and/or the dimethyl ether.
5. The method according to any one of claims 1 to 4, wherein the material further comprises inert atmosphere and/or recycle components;
the inert atmosphere comprises one or more of nitrogen, argon and helium;
the recycle component comprises one or more of carbon monoxide, carbon dioxide, methane, ethane, propane, ethylene, propylene, butene.
6. The method according to claim 5, wherein the sum of the volumes of the inert atmosphere and/or the recycle components is 0.1 to 80% of the reaction mass;
the reaction mass does not include a reaction medium.
7. The method of claim 1, wherein the molecular sieve catalyst is selected from at least one of a silicon aluminum molecular sieve, a phosphorus aluminum molecular sieve.
8. The method of claim 7, wherein the silica alumina molecule is selected from at least one of Beta, MOR, ZSM-5, ZSM-11, ZSM-22, MCM-49.
9. The method of claim 1, wherein the metal in the metal modified molecular sieve catalyst is selected from one or more of Zn, mn, mg, ni, fe, co, ca, ga, cu, ag.
10. The method according to claim 1, wherein the mass content of metal in the molecular sieve catalyst is 0.01-15%;
preferably, si/al=20 to 300 in the aluminosilicate molecular sieve;
preferably, the reaction is carried out in the gas phase, subcritical or supercritical state;
preferably, the reaction is carried out in a reactor; the reactor is one or a plurality of reactors connected in series and/or parallel.
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