CN116789514A - Process for preparing aromatic hydrocarbons - Google Patents
Process for preparing aromatic hydrocarbons Download PDFInfo
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- CN116789514A CN116789514A CN202210251232.9A CN202210251232A CN116789514A CN 116789514 A CN116789514 A CN 116789514A CN 202210251232 A CN202210251232 A CN 202210251232A CN 116789514 A CN116789514 A CN 116789514A
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 205
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 162
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 42
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 39
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims description 47
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 239000007795 chemical reaction product Substances 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 238000000926 separation method Methods 0.000 claims description 20
- 230000008929 regeneration Effects 0.000 claims description 15
- 238000011069 regeneration method Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 9
- 230000009849 deactivation Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 238000005899 aromatization reaction Methods 0.000 abstract description 10
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 12
- 239000002808 molecular sieve Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000012492 regenerant Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000001174 ascending effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- -1 methanol and ethanol Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ISNYUQWBWALXEY-OMIQOYQYSA-N tsg6xhx09r Chemical compound O([C@@H](C)C=1[C@@]23CN(C)CCO[C@]3(C3=CC[C@H]4[C@]5(C)CC[C@@](C4)(O)O[C@@]53[C@H](O)C2)CC=1)C(=O)C=1C(C)=CNC=1C ISNYUQWBWALXEY-OMIQOYQYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing aromatic hydrocarbon from methanol, which is characterized in that methanol is converted step by step to obtain higher aromatic hydrocarbon selectivity. Firstly, the methanol is converted into light hydrocarbon rich in olefin and partial aromatic hydrocarbon in a fast bed reactor, and the light hydrocarbon rich in olefin is continuously subjected to aromatization reaction in a riser reactor. The fast bed reactor and the riser reactor are coupled in one fluidized bed reactor, the process flow is simple, the reaction conditions and the catalyst activity required by methanol conversion and light hydrocarbon aromatization are met, and the content of BTX and PX in the obtained aromatic hydrocarbon is high.
Description
Technical Field
The present invention relates to a process for the preparation of aromatic hydrocarbons, and in particular to a process for the preparation of aromatic hydrocarbons from methanol.
Background
Aromatic hydrocarbons (especially triphenyl, benzene, toluene, xylenes, BTX) are important basic organic synthesis feedstocks. Driven by downstream derivative demand, there is a continuing increase in market demand for aromatic hydrocarbons, particularly xylenes.
The catalytic reforming and steam cracking process is one main arene producing process and belongs to the field of petroleum path producing technology. The coal resources in China are relatively rich. With the development of high-efficiency and long-period methanol catalyst and large-scale technology of methanol devices in recent years, the production cost of coal-based methanol is greatly reduced, and the method provides a cheap raw material source for the production of downstream products (olefins, aromatic hydrocarbons and the like) of the methanol. Therefore, it is considered to prepare aromatic hydrocarbon and xylene from methanol.
In the process of preparing aromatic hydrocarbon by containing an oxygen-containing compound, it is generally considered that the oxygen-containing compound, such as methanol and ethanol, is dehydrated under acid catalysis to generate lower hydrocarbon, and the lower hydrocarbon undergoes further aromatization reaction to obtain aromatic hydrocarbon. The reaction temperature suitable for the low-carbon hydrocarbon aromatization reaction is higher than that of the dehydration reaction of the oxygen-containing compound, and the two reactions are difficult to be combined by adopting a single reaction temperature. The oxygen-containing compound is extremely easy to generate thermal cracking reaction to generate methane and carbon monoxide with low added value at the temperature higher than 500 ℃, and the coke content is increased. To reduce this portion of the reaction, the reaction temperature is typically below 500 ℃, whereas the reaction temperature suitable for the low carbon hydrocarbon aromatization reaction is above 500 ℃, thus resulting in the problem of lower selectivity to such prior art aromatics.
CN1880288 (different catalysts are adopted), CN101607858 (double fixed beds, different catalysts are adopted), CN102775261 (different catalysts are adopted), CN102146010 (fixed bed reactor), and CN101823929 propose to adopt two reactors, wherein part or all of gas phase products obtained by the reaction in the first reactor enter the second reactor to continue the reaction. However, they have problems of complicated process flow and high energy consumption.
CN103394312 proposes a multistage fluidized bed apparatus and method for preparing aromatic hydrocarbon by catalytic conversion of alcohol/ether, wherein the temperatures of the first catalyst loading section and the second catalyst loading section are controlled to be 450-500 ℃, and the temperatures of the third catalyst loading section and the fourth catalyst loading section are controlled to be 420-450 ℃, and the temperatures are relatively low. Meanwhile, the raw material entering the multistage fluidized bed device is only alcohol/ether raw material. The aromatic hydrocarbon selectivity of the method is not high.
CN101671226 discloses a process for preparing xylene by aromatization of methanol, which uses metal-modified molecular sieve composite material as catalyst, and uses the mixture of methanol and one or several of C1-C12 hydrocarbons to react, and the single-pass carbon-based yield of xylene can be up to 37.21% by the synergistic progress of aromatization of methanol and hydrocarbons and alkylation reaction. The yield is still low.
Disclosure of Invention
One of the technical problems to be solved by the invention is to overcome the technical defects that the aromatic hydrocarbon yield is low, particularly the high yield and the high content of BTX and PX are difficult to meet simultaneously in the prior art, and provide a reaction method for preparing aromatic hydrocarbon, which has the advantages of high aromatic hydrocarbon yield and high BTX and PX content in aromatic hydrocarbon.
To solve the above problems, the present invention provides a general method for preparing aromatic hydrocarbons, comprising:
a) The raw material containing methanol enters the fast-bed reactor through a fast-bed reactor raw material inlet at the lower part of the fast-bed reactor, and is in contact reaction with a circulating catalyst from a circulating catalyst inlet of the fast-bed reactor and a first part of regenerated catalyst from a regenerated catalyst inlet of the fast-bed reactor to obtain a reaction product I and a first to-be-regenerated agent obtained by partial deactivation of the catalyst, and both the reaction product I and the first to-be-regenerated agent go upwards through an outlet structural member of the fast-bed reactor to enter the interior of a mixed stripping zone;
b) The light hydrocarbon-containing raw material enters the riser reactor through a riser reactor raw material inlet at the bottom of the riser reactor and is in contact reaction with a second part of regenerated catalyst from a riser regenerated catalyst inlet to obtain a reaction product II and a second spent agent obtained by partial deactivation of the catalyst, and both the reaction product II and the second spent agent go upwards to enter the interior of the mixed stripping zone through a riser reactor outlet structural member; mixing the first spent agent and the second spent agent in a mixed stripping zone to form a mixed catalyst;
c) The stripping medium enters a mixed stripping zone through a stripping medium inlet to strip the mixed catalyst to obtain a stripped catalyst;
d) A first part of the steam stripping catalyst is used as a spent catalyst, and enters a regeneration system through a spent catalyst outlet of a mixed steam stripping zone to remove carbon deposit on particles so as to obtain a regenerated catalyst; a second portion of the stripped catalyst is used as the recycle catalyst; and optionally
e) The reaction product rich in aromatic hydrocarbon obtained in the reaction process enters a subsequent separation system through a reaction product outlet of a mixed stripping zone to obtain C 2 -C 6 A non-aromatic hydrocarbon mixture;
wherein the fast bed reactor, the mixed stripping zone, the riser reactor are coaxially arranged, and wherein the fast bed reactor radially surrounds the riser reactor.
In one embodiment, the regenerated catalyst resulting from the removal of carbon deposits on the particles by the regeneration system is partitioned into the first partially regenerated catalyst and the second partially regenerated catalyst.
In one embodiment, the light hydrocarbon-containing feedstock comprises C 2 -C 6 Mixtures of non-aromatic hydrocarbons, essentially consisting of C 2 -C 6 Mixtures of non-aromatic hydrocarbons or of C 2 -C 6 A non-aromatic hydrocarbon mixture.
In the present invention, the reaction products involved in the various embodiments, including, for example, reaction product I, reaction product II, and other reaction products that may be involved, respectively represent materials that are converted by reactions intended to give aromatic products, and that are capable of yielding aromatic-enriched products by separation units known in the art, although the specific composition may vary somewhat from embodiment to embodiment due to variations in the starting materials, reaction conditions, etc. within the scope of the present invention.
According to one embodiment of the present invention, a ZSM-5 catalyst is used.
Generally, methanol can be converted to aromatics over a ZSM-5 catalyst, which reaction yields an amount of light hydrocarbons, such as C, along with aromatics 2 -C 6 A non-aromatic hydrocarbon mixture. The yield of aromatic hydrocarbon carbon-based by methanol single pass conversion is 40-60 wt%, and relatively harsh reaction conditions are needed to obtain higher aromatic hydrocarbon yield. However, the process is not limited to the above-described process,the methylation reaction of the aromatic hydrocarbon is promoted while the aromatic hydrocarbon is increased, the yields of C9+ heavy aromatic hydrocarbon and coke are increased, the selectivity of BTX and PX is reduced, and the quality of the aromatic hydrocarbon is reduced; in addition, the secondary reactions such as thermal cracking, hydrogen transfer and polymerization of the low-carbon hydrocarbon are promoted, so that the alkane content in the light hydrocarbon which is a byproduct in the MTA process is increased, and particularly methane, ethane and propane are increased. The difficulty of further aromatization of the light hydrocarbon is increased, which results in low aromatic hydrocarbon yield in the prior art.
According to the technical scheme for preparing aromatic hydrocarbon from methanol, the methanol is converted step by step to obtain higher aromatic hydrocarbon selectivity. Firstly, the methanol is converted into light hydrocarbon rich in olefin and partial aromatic hydrocarbon in a fast bed reactor, and the light hydrocarbon rich in olefin is continuously subjected to aromatization reaction in a riser reactor. The fast bed reactor and the riser reactor are coupled in one fluidized bed reactor, the process flow is simple, the reaction conditions and the catalyst activity required by methanol conversion and light hydrocarbon aromatization are met, and the content of BTX and PX in the obtained aromatic hydrocarbon is high.
According to one embodiment of the invention, the total yield of carbon-based aromatics in the single-pass conversion of methanol can reach 85 weight percent, the BTX content in the aromatics can exceed 90 weight percent, and the PX content in the aromatics can exceed 50 weight percent.
Drawings
FIG. 1 is a schematic diagram of a reaction system for a process for producing aromatic hydrocarbons according to one embodiment of the invention;
fig. 2 is a schematic diagram of a riser reactor outlet structure and a fast-bed reactor outlet structure according to one embodiment of the invention.
Description of the drawings with partial reference numerals
1 is a regeneration system; 2 is a riser reactor; 3 is a fast bed reactor; 4 is a mixed stripping zone; 5 is a riser regenerated catalyst inlet; 6 is a mixed stripping zone recycle catalyst outlet; 7 is a spent catalyst outlet of the mixed stripping zone; 8 is a circulating catalyst inlet of the fast-bed reactor; 9 is a mixed stripping zone reaction product outlet; 10 is a fast bed reactor feed inlet; 11 is the riser reactor feed inlet; 12 is an internal heat collector; 13 is the riser reactor outlet structure; 14 is the exit structure of the fast bed reactor; 15 is the spent catalyst inlet of the regeneration system; reference numeral 16 denotes a first outlet of the regenerated catalyst of the first portion of the regeneration system; reference numeral 17 denotes a second outlet of the regenerated catalyst of the second portion of the regeneration system; 18 is a fast bed reactor regenerant inlet; 19 is the stripping medium inlet; 20 is the riser reactor outlet structure roof; 21 is the bottom of the riser reactor outlet structure; 22 is the riser reactor outlet structure outlet ring; 23 is the top of the exit structure of the fast bed reactor; 24 is the bottom of the outlet structural member of the fast bed reactor; and 25 is an outlet ring of the outlet structure of the fast-bed reactor.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In the description of the present invention, it should be understood that the directions or positional relationships indicated by the terms "radial," "inner," "outer," etc. are based on the directions or positional relationships shown in the drawings, only for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or element in question must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention.
In the present invention, like reference numerals generally refer to like/corresponding objects.
In the present invention, the pressures are gauge pressures unless otherwise indicated. In the present invention, the content, proportion, ratio, etc. are calculated on a weight/mass basis without particular indication.
In the present invention, the "spent (catalyst)" means a catalyst which is deactivated in the reaction system and is required to be used for the reaction system by regeneration.
In the present invention, the "regenerated (catalyst)" means a catalyst which is regenerated in a regenerating device to be used for a reaction system.
As shown in FIG. 1, the present invention provides a process for preparing aromatic hydrocarbons, the reaction system and general flow scheme of which are shown in FIG. 1.
Referring to fig. 1, in one embodiment, the present invention provides an overall process for preparing aromatic hydrocarbons comprising:
a) The raw material containing methanol enters the fast-bed reactor (3) through a fast-bed reactor raw material inlet (10) at the lower part of the fast-bed reactor (3), and is contacted and reacted with circulating catalyst from a circulating catalyst inlet (8) of the fast-bed reactor and a first part of regenerated catalyst from a regenerated catalyst inlet (18) of the fast-bed reactor to obtain a reaction product I and a first to-be-regenerated agent obtained by partial deactivation of the catalyst, and the reaction product I and the first to-be-regenerated agent both go upwards through an outlet structural member (14) of the fast-bed reactor and enter the interior of the mixed stripping zone (4);
b) The light hydrocarbon-containing raw materials enter the riser reactor (2) through a riser reactor raw material inlet (11) at the bottom of the riser reactor (2) and are in contact reaction with a second part of regenerated catalyst from a riser regenerated catalyst inlet (5) to obtain a reaction product II and a second spent agent obtained by partial deactivation of the catalyst, and both the reaction product II and the second spent agent ascend to enter the interior of the mixed stripping zone (4) through a riser reactor outlet structural member (13); mixing the first spent agent and the second spent agent in a mixed stripping zone to form a mixed catalyst;
c) The stripping medium enters a mixed stripping zone through a stripping medium inlet (19) to strip the mixed catalyst to obtain a stripped catalyst;
d) A first part of the stripped catalyst is used as a spent catalyst, and enters a regeneration system (1) through a spent catalyst outlet (7) of a mixed stripping zone to remove carbon deposit on particles so as to obtain a regenerated catalyst; a second portion of the stripped catalyst is used as the recycled catalyst and is withdrawn through a mixed stripping zone recycled catalyst outlet (6); and optionally
e) Mixing the reaction product I and the reaction product II in a mixed stripping zone, and leading the obtained reaction product rich in aromatic hydrocarbon to enter a subsequent separation system through a reaction product outlet (9) of the mixed stripping zone to obtain C 2 -C 6 A non-aromatic hydrocarbon mixture;
wherein the fast bed reactor, the mixed stripping zone, the riser reactor are coaxially arranged, and wherein the fast bed reactor radially surrounds the riser reactor.
In one embodiment, riser reactor 2, fast bed reactor 3, and mixed stripping zone 4 are coaxial, with fast bed reactor 3 surrounding riser reactor 2; the outlet of the riser reactor 2 is connected with a riser reactor outlet structural member 13, and the top of the fast-bed reactor 3 is connected with a fast-bed reactor outlet structural member 14; the riser reactor outlet structure 13 and the fast bed reactor outlet structure 14 are both located within the mixed stripping zone 4. In one embodiment, riser reactor outlet structure 13 is located above fast bed reactor outlet structure 14.
In one embodiment, the inside of the mixed stripping zone 4 is provided with an annular distributor surrounding and coaxial with the upper lifting zone of the fast-bed reactor 3, for conveying the gas (for example steam) with fluidization upwards into the inside of the mixed stripping zone 4 and acting on the first and second spent agent.
In the present invention, a cyclone separator may be provided in the mixed stripping zone 4, or any other device capable of achieving a similar function (in particular, for example, separation of catalyst from product).
Referring to the illustrated embodiment of fig. 1-2, according to one embodiment of the invention, the riser reactor outlet structure (13) consists of a riser reactor outlet structure top (20) and a riser reactor outlet structure bottom (21) and a riser reactor outlet structure outlet ring (22). The riser reactor outlet structure top (20) is located above the riser reactor outlet structure bottom (21), the riser reactor outlet structure top (20) and the riser reactor outlet structure bottom (21) having a height of 30 o ~180 o The same central angle is adopted, and the ratio of the radius of the top (20) of the outlet structural member of the riser reactor to the radius of the bottom (21) of the outlet structural member of the riser reactor is (1.2-2): 1. the included angle between the plane of the outlet ring (22) of the outlet structural member of the riser reactor and the central axis of the riser reactor (2) is beta; beta is 30 o -90 o Preferably 40 o -75 o 。
According to one embodiment of the invention, theThe fast-bed reactor outlet structure (14) consists of a fast-bed reactor outlet structure top (23) and a fast-bed reactor outlet structure bottom (24) and a fast-bed reactor outlet structure outlet ring (25). The fast-bed reactor outlet structure top (23) is located above the fast-bed reactor outlet structure bottom (24), the fast-bed reactor outlet structure top (23) and the fast-bed reactor outlet structure bottom (24) having a height of 15 o ~180 o The same central angle is adopted, and the ratio of the radius of the top (23) of the outlet structural member of the fast bed reactor to the radius of the bottom (24) of the outlet structural member of the fast bed reactor is (1.1-1.5): 1. the included angle gamma between the plane of the outlet ring (25) of the outlet structural member of the fast-bed reactor and the central shaft of the fast-bed reactor (3); gamma is 0 o -60 o Preferably 0 o -45 o 。
According to one embodiment of the invention, the included angle beta between the plane of the outlet ring (22) of the outlet structure of the riser reactor and the central axis of the riser reactor (2) is larger than the included angle gamma between the plane of the outlet ring (25) of the outlet structure of the fast-bed reactor and the central axis of the fast-bed reactor (3).
According to one embodiment of the invention, the upper part of the riser reactor 2 extends beyond the top of the lift zone of the fast-bed reactor, such that the riser reactor outlet structure 13 is located above the fast-bed reactor outlet structure 14. An embodiment which may be referred to as a "top-to-bottom arrangement" in the present invention is shown, for example, in fig. 1 and 2.
According to one embodiment of the invention, the mixed stripping zone (4) is provided with an internal heat extractor (12) to reduce the temperature of the catalyst in the mixed stripping zone (4).
According to one embodiment of the invention, the fast-bed reactor (3) is provided with an external heat extractor to reduce the temperature of the catalyst inside the fast-bed reactor (3).
It will be appreciated by those skilled in the art that in the present invention, the primary function of the external heat extractor is to effect a temperature reduction of the mixed catalyst to suit the reaction requirements in the fast bed reactor. Thus, according to one embodiment of the invention, the external heat collector may be replaced by any other device capable of performing the main function, provided that it does not significantly detract from the purpose of the invention. Accordingly, the outer heat collector may be replaced with an inner heat collector.
In one embodiment, the regenerated catalyst obtained by removing carbon deposits on the particles by the regeneration system is distributed to a ratio of 1 (3-20), preferably 1 (5-15), of the first partially regenerated catalyst to the second partially regenerated catalyst.
In one embodiment, the ratio of the first portion to the second portion of the stripped catalyst used as the spent catalyst and as the recycled catalyst, respectively, is (1-8): 1, preferably (2-5): 1.
In the invention, the mass percentage of the methanol in the raw material containing the methanol is 10-100%.
In the present invention, the light hydrocarbon-containing raw material is not particularly limited, and light hydrocarbon-containing raw materials commonly used in the art can be used in the present invention, and according to one embodiment of the present invention, the light hydrocarbon-containing raw material is C 2 -C 6 The non-aromatic hydrocarbon mixture, preferably the light hydrocarbon-containing raw material at least comprises C obtained by a separation unit 2 -C 6 Part or all of the non-aromatic hydrocarbon mixture.
According to one embodiment of the invention, the light hydrocarbon-containing raw material contains C obtained from a separation unit 2 -C 6 The proportion of non-aromatic hydrocarbon mixture is more than 20% by weight, and the rest is C 2 -C 6 The non-aromatic hydrocarbon mixture may be from a catalytic cracking and/or steam cracking unit.
According to one embodiment of the invention, C is obtained by a separation unit 2 -C 6 From 30% to 100% by weight, preferably from 50% to 100% by weight, of a non-aromatic hydrocarbon mixture is used for the light hydrocarbon-containing feedstock.
According to one embodiment of the invention, all C obtained by the separation unit 2 -C 6 A non-aromatic hydrocarbon mixture is used as all of the light hydrocarbon-containing feedstock.
In the invention, C 2 -C 6 The composition of the non-aromatic hydrocarbon mixture may be, for example, that containing isobutene, 1-butene, n-buteneOne or more of alkane, isobutane, isopentene, n-pentene, n-pentane, n-hexene, and isohexene.
According to one embodiment of the present invention, the mass ratio of the light hydrocarbon-containing raw material to the methanol-containing raw material is (0.1 to 0.4): 1, preferably (0.15 to 0.3): 1.
The type of stripping medium fed via stripping medium inlet 19 is not particularly limited in the present invention, and may be any medium that is currently available and suitable for use in a methanol-to-aromatics process, such as water or nitrogen.
In the present invention, the operation conditions in the fast bed reactor 3 are not particularly limited, and those commonly used in the art can be employed. According to one embodiment of the invention, the operation condition of the fast bed reactor (3) comprises the temperature of a catalyst bed layer of 460-530 ℃, the linear velocity of gas of the catalyst bed layer of 1-3 m/s and the density of the catalyst bed layer of 50-300 kg/m 3 . According to one embodiment of the invention, the operating conditions of the riser reactor (2) comprise an outlet catalyst temperature of 530-650 ℃, an outlet gas linear velocity of 5-10 m/s, and an outlet catalyst density of 50-150 kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The pressure of the mixed stripping zone (4) is 0-1.0 MPaG.
According to the present invention, preferably, the catalyst is a molecular sieve catalyst.
According to the present invention, preferably, the molecular sieve catalyst is at least one of a SAPO-34 molecular sieve catalyst, a ZSM-5 molecular sieve catalyst and a beta molecular sieve catalyst, more preferably a ZSM-5 molecular sieve catalyst.
According to one embodiment of the invention, the regenerated catalyst has a carbon content of not more than 1% based on the total mass of the catalyst. In one embodiment, the carbon content of the regenerated catalyst is 0.01 to 1.0%, preferably not more than 0.1% based on the total mass of the regenerated catalyst.
The invention is mainly characterized in that the process of the reaction system is changed, and other operation equipment, conditions, methods and steps which are not specifically described can be performed by adopting conventional methods, conditions and steps. In particular, the present invention is not particularly limited with respect to the specific dimensions of the equipment (including riser reactors, fast bed reactors, mixed stripping zones, regeneration systems, etc.), and may be determined in detail as appropriate according to conventional means in the art, as long as it meets the limitations and requirements that the present invention has made with respect to the entire reaction system, in particular, the operating conditions required for the riser reactor (2) and the fast bed reactor (3) according to the present invention.
In the present invention, the total yield of aromatic hydrocarbon is calculated as total yield of aromatic hydrocarbon=mass of aromatic hydrocarbon/amount of carbon substrate of methanol feed x 100%.
Carbon-based mass of methanol feed = methanol feed mass x 14/32.
Examples
The invention is further illustrated, but not limited, by the following examples. In an embodiment, reference is made primarily to fig. 1; wherein the riser reactor outlet structure, the fast bed reactor outlet structure, etc. refer to the embodiment shown in fig. 2.
Example 1
The apparatus of fig. 1 was employed. The methanol-containing raw material enters the fast-bed reactor (3) through a fast-bed reactor raw material inlet (10), is contacted and reacted with circulating catalyst from a fast-bed reactor circulating catalyst inlet (8) and a first part of regenerated catalyst from a fast-bed reactor regenerant inlet (18), and goes upward to obtain a first to-be-regenerated agent, and enters the interior of the mixed stripping zone (4) through a fast-bed reactor outlet structural member (14).
The light hydrocarbon-containing raw material enters the riser reactor (2) through a riser reactor raw material inlet (11) to be in contact reaction with a second part of regenerated catalyst from a riser regenerated catalyst inlet (5), and the second spent agent is obtained by ascending, and enters the interior of the mixed stripping zone (4) through a riser reactor outlet structural member (13).
The stripping medium enters the mixed stripping zone (4) through the stripping medium inlet (19), and the spent catalyst enters the regeneration system (1) through the mixed stripping zone spent catalyst outlet (7) to remove carbon deposit on particles to obtain the regenerated catalyst.
The reaction product rich in aromatic hydrocarbon obtained in the reaction process is produced by the reaction of a mixed stripping zoneThe material outlet (9) enters a subsequent separation system to obtain C 2 -C 6 A non-aromatic hydrocarbon mixture.
The riser reactor outlet structure (13) consists of a riser reactor outlet structure top (20) and a riser reactor outlet structure bottom (21) and two riser reactor outlet structure outlet rings (22). The riser reactor outlet structure top (20) is located above the riser reactor outlet structure bottom (21), the riser reactor outlet structure top (20) and the riser reactor outlet structure bottom (21) having the same central angle 30 o The ratio of the radii of the riser reactor outlet structure top (20) and the riser reactor outlet structure bottom (21) is 2:1. the included angle between the plane of the outlet ring (22) of the outlet structural member of the riser reactor and the central axis of the riser reactor (2) is beta; beta is 30 o And an outlet structural member.
The fast-bed reactor outlet structure (14) consists of a fast-bed reactor outlet structure top (23), a fast-bed reactor outlet structure bottom (24) and two fast-bed reactor outlet structure outlet rings (25). The fast-bed reactor outlet structure top (23) is positioned above the fast-bed reactor outlet structure bottom (24), and the fast-bed reactor outlet structure top (23) and the fast-bed reactor outlet structure bottom (24) have the same central angle 15 o The ratio of the radii of the fast bed reactor outlet structure top (23) and the fast bed reactor outlet structure bottom (24) is 1.1:1. the included angle gamma between the plane of the outlet ring (25) of the outlet structural member of the fast-bed reactor and the central shaft of the fast-bed reactor (3); gamma is 0 o 。
The fast-bed reactor (3) is provided with an external heat collector to reduce the temperature of the catalyst in the fast-bed reactor (3).
The mass percentage of the methanol in the raw material containing the methanol is 100 percent. The stripping medium is steam. The light hydrocarbon-containing raw material is C obtained by a separation system 2 -C 6 A non-aromatic hydrocarbon mixture.
The catalyst is a ZSM-5 molecular sieve-containing catalyst. The carbon content of the regenerated catalyst was 1.0% based on the total mass of the regenerated catalyst.
The ratio of the first partially regenerated catalyst to the second partially regenerated catalyst is 1:3.
The ratio of spent catalyst to recycled catalyst was 1:1.
The temperature of the catalyst bed layer of the fast bed reactor (3) is 460 ℃, the linear speed of the gas of the catalyst bed layer is 1 m/s, and the density of the catalyst bed layer is 300 kg/m 3 . The outlet catalyst temperature of the riser reactor (2) is 650 ℃, the linear velocity of outlet gas is 10 m/s, and the density of outlet catalyst is 50 kg/m 3 . The pressure in the mixed stripping zone (4) was 0MPaG.
In this example, the total yield of carbon-based aromatics in the single pass conversion of methanol can reach 83.1 wt%, the BTX content in the aromatics is 87.6 wt%, and the PX content in the aromatics is 49.3 wt%.
Example 2
The apparatus of example 1 was used except that the methanol-containing feedstock was 10% methanol by mass; the stripping medium is steam; the light hydrocarbon-containing raw material is C obtained by a separation system 2 -C 6 A non-aromatic hydrocarbon mixture.
The catalyst is a ZSM-5 molecular sieve-containing catalyst; the carbon content of the regenerated catalyst was 0.01% based on the total mass of the regenerated catalyst.
The temperature of the catalyst bed layer of the fast bed reactor (3) is 530 ℃, the linear velocity of the gas of the catalyst bed layer is 3 m/s, and the density of the catalyst bed layer is 50 kg/m 3 . The temperature of the catalyst at the outlet of the riser reactor (2) is 530 ℃, the linear velocity of the outlet gas is 5 m/s, and the density of the catalyst at the outlet is 150 kg/m 3 . The pressure in the mixed stripping zone (4) was 1.0MPaG.
In this example, the total yield of carbon-based aromatics in the single pass conversion of methanol can reach 80.8 wt.%, the BTX content in the aromatics is 85.7 wt.%, and the PX content in the aromatics is 47.6 wt.%.
Example 3
The apparatus of example 1 was used except that the methanol-containing feedstock was 95% methanol by mass. The stripping medium is steam. The light hydrocarbon-containing raw material is C obtained by a separation system 2 -C 6 A non-aromatic hydrocarbon mixture.
The catalyst is a ZSM-5 molecular sieve-containing catalyst. The carbon content of the regenerated catalyst was 0.1% based on the total mass of the regenerated catalyst.
The temperature of the catalyst bed layer of the fast bed reactor (3) is 500 ℃, the linear speed of the gas of the catalyst bed layer is 2 m/s, and the density of the catalyst bed layer is 120 kg/m 3 . The temperature of the catalyst at the outlet of the riser reactor (2) is 600 ℃, the linear velocity of the outlet gas is 8 m/s, and the density of the catalyst at the outlet is 100 kg/m 3 . The pressure in the mixed stripping zone (4) was 0.15MPaG.
In this example, the total yield of carbon-based aromatics in the single pass conversion of methanol can reach 85.5 wt%, the BTX content in the aromatics is 92.2 wt%, and the PX content in the aromatics is 51.3 wt%.
Example 4
The apparatus of fig. 1 was employed. The methanol-containing raw material enters the fast-bed reactor (3) through a fast-bed reactor raw material inlet (10), is contacted and reacted with circulating catalyst from a fast-bed reactor circulating catalyst inlet (8) and a first part of regenerated catalyst from a fast-bed reactor regenerant inlet (18), and goes upward to obtain a first to-be-regenerated agent, and enters the interior of the mixed stripping zone (4) through a fast-bed reactor outlet structural member (14).
The light hydrocarbon-containing raw material enters the riser reactor (2) through a riser reactor raw material inlet (11) to be in contact reaction with a second part of regenerated catalyst from a riser regenerated catalyst inlet (5), and the second spent agent is obtained by ascending, and enters the interior of the mixed stripping zone (4) through a riser reactor outlet structural member (13).
The stripping medium enters the mixed stripping zone (4) through the stripping medium inlet (19), and the spent catalyst enters the regeneration system (1) through the mixed stripping zone spent catalyst outlet (7) to remove carbon deposit on particles to obtain the regenerated catalyst.
The reaction product rich in aromatic hydrocarbon obtained in the reaction process enters a subsequent separation system through a reaction product outlet (9) of a mixed stripping zone to obtain C 2 -C 6 A non-aromatic hydrocarbon mixture.
The outlet structural member (13) of the riser reactor consists of a top (20) of the outlet structural member of the riser reactor and a bottom of the outlet structural member of the riser reactor21 And two riser reactor outlet structure outlet rings (22). The riser reactor outlet structure top (20) is located above the riser reactor outlet structure bottom (21), the riser reactor outlet structure top (20) and the riser reactor outlet structure bottom (21) having the same central angle 180 o The ratio of the radii of the riser reactor outlet structure top (20) and the riser reactor outlet structure bottom (21) is 1.2:1. the included angle between the plane of the outlet ring (22) of the outlet structural member of the riser reactor and the central axis of the riser reactor (2) is beta; beta is 60 o And an outlet structural member.
The fast-bed reactor outlet structure (14) consists of a fast-bed reactor outlet structure top (23), a fast-bed reactor outlet structure bottom (24) and two fast-bed reactor outlet structure outlet rings (25). The fast-bed reactor outlet structure top (23) is positioned above the fast-bed reactor outlet structure bottom (24), and the fast-bed reactor outlet structure top (23) and the fast-bed reactor outlet structure bottom (24) have the same central angle 180 o The ratio of the radii of the fast bed reactor outlet structure top (23) and the fast bed reactor outlet structure bottom (24) is 1.5:1. the included angle gamma between the plane of the outlet ring (25) of the outlet structural member of the fast-bed reactor and the central shaft of the fast-bed reactor (3); gamma is 30 o 。
The mixed stripping zone (4) is provided with an internal heat extractor (12) to reduce the temperature of the catalyst in the mixed stripping zone (4).
The mass percentage of the methanol in the raw material containing the methanol is 85 percent. The stripping medium is steam. The light hydrocarbon-containing raw material is C obtained by a separation system 2 -C 6 A non-aromatic hydrocarbon mixture.
The catalyst is a ZSM-5 molecular sieve-containing catalyst. The carbon content of the regenerated catalyst was 0.05% by mass based on the total mass of the regenerated catalyst.
The ratio of the first partially regenerated catalyst to the second partially regenerated catalyst is 1:20.
The ratio of spent catalyst to recycled catalyst was 8:1.
Fast bed reactor (3) catalyst bedThe temperature is 510 ℃, the gas linear velocity of the catalyst bed is 1.3 m/s, and the density of the catalyst bed is 200 kg/m 3 . The outlet catalyst temperature of the riser reactor (2) was 630 ℃, the outlet gas line velocity was 6 m/s, and the outlet catalyst density was 120 kg/m 3 . The pressure in the mixed stripping zone (4) was 0.3MPaG.
In this example, the total yield of carbon-based aromatics in the single pass conversion of methanol can reach 85.1 wt%, the BTX content in the aromatics is 91.8 wt%, and the PX content in the aromatics is 50.4 wt%.
Example 5
The apparatus of fig. 1 was employed. The methanol-containing raw material enters the fast-bed reactor (3) through a fast-bed reactor raw material inlet (10), is contacted and reacted with circulating catalyst from a fast-bed reactor circulating catalyst inlet (8) and a first part of regenerated catalyst from a fast-bed reactor regenerant inlet (18), and goes upward to obtain a first to-be-regenerated agent, and enters the interior of the mixed stripping zone (4) through a fast-bed reactor outlet structural member (14).
The light hydrocarbon-containing raw material enters the riser reactor (2) through a riser reactor raw material inlet (11) to be in contact reaction with a second part of regenerated catalyst from a riser regenerated catalyst inlet (5), and the second spent agent is obtained by ascending, and enters the interior of the mixed stripping zone (4) through a riser reactor outlet structural member (13).
The stripping medium enters a mixed stripping zone (4) for stripping through a stripping medium inlet (19), and the spent catalyst enters a regeneration system (1) through a mixed stripping zone spent catalyst outlet (7) for removing carbon deposit on particles to obtain the regenerated catalyst.
The reaction product rich in aromatic hydrocarbon obtained in the reaction process enters a subsequent separation system through a reaction product outlet (9) of a mixed stripping zone to obtain C 2 -C 6 A non-aromatic hydrocarbon mixture.
The riser reactor outlet structure (13) consists of a riser reactor outlet structure top (20) and a riser reactor outlet structure bottom (21) and two riser reactor outlet structure outlet rings (22). The riser reactor outlet structure roof (20) is located at the riser reactor outlet junctionAbove the component bottom (21), the riser reactor outlet component top (20) and the riser reactor outlet component bottom (21) have the same central angle 90 o The ratio of the radii of the riser reactor outlet structure top (20) and the riser reactor outlet structure bottom (21) is 1.5:1. the included angle between the plane of the outlet ring (22) of the outlet structural member of the riser reactor and the central axis of the riser reactor (2) is beta; beta is 90 o And an outlet structural member.
The fast-bed reactor outlet structure (14) consists of a fast-bed reactor outlet structure top (23), a fast-bed reactor outlet structure bottom (24) and two fast-bed reactor outlet structure outlet rings (25). The fast-bed reactor outlet structure top (23) is positioned above the fast-bed reactor outlet structure bottom (24), and the fast-bed reactor outlet structure top (23) and the fast-bed reactor outlet structure bottom (24) have the same central angle 120 o The ratio of the radii of the fast bed reactor outlet structure top (23) and the fast bed reactor outlet structure bottom (24) is 1.3:1. the included angle gamma between the plane of the outlet ring (25) of the outlet structural member of the fast-bed reactor and the central shaft of the fast-bed reactor (3); gamma is 60 o 。
The mixed stripping zone (4) is provided with an internal heat extractor (12) to reduce the temperature of the catalyst in the mixed stripping zone (4).
The mass percentage of the methanol in the raw material containing the methanol is 70 percent. The stripping medium is steam. The light hydrocarbon-containing raw material is C obtained by a separation system 2 -C 6 A non-aromatic hydrocarbon mixture.
The catalyst is a ZSM-5 molecular sieve-containing catalyst. The carbon content of the regenerated catalyst was 0.2% based on the total mass of the regenerated catalyst.
The ratio of the first partially regenerated catalyst to the second partially regenerated catalyst is 1:10.
The ratio of spent catalyst to recycled catalyst was 3:1.
The temperature of the catalyst bed layer of the fast bed reactor (3) is 490 ℃, the linear velocity of the gas of the catalyst bed layer is 1.1 m/s, and the density of the catalyst bed layer is 240 kg/m 3 . Riser reactor (2) outlet catalyst temperatureOutlet gas line velocity 7 m/s at 580 deg.c, outlet catalyst density 110 kg/m 3 . The pressure in the mixed stripping zone (4) was 0.1MPaG.
In this example, the total yield of carbon-based aromatics in the single pass conversion of methanol can reach 84.3 wt%, the BTX content in the aromatics is 90.6 wt%, and the PX content in the aromatics is 49.8 wt%.
Comparative example 1
The apparatus and process conditions of example 5 were used except that no riser reactor was used and no light hydrocarbon feedstock was converted.
In this example, the total yield of carbon-based aromatics in the single pass conversion of methanol can reach 53.3 wt%, the BTX content in the aromatics is 73.4 wt%, and the PX content in the aromatics is 38.5 wt%.
Comparative example 2
With the apparatus of example 5, only the fast-bed reactor (3) had a catalyst bed gas line velocity of 0.8 m/s and a catalyst bed density of 350 kg/m 3 。
In this example, the total yield of carbon-based aromatics in the single pass conversion of methanol can reach 75.9 wt%, the BTX content in the aromatics is 80.7 wt%, and the PX content in the aromatics is 42.8 wt%.
Comparative example 3
The apparatus of example 5 was used except that beta was 25 o 。
In this example, the total yield of carbon-based aromatics in the single pass conversion of methanol can reach 83.2 wt%, the BTX content in the aromatics is 87.1 wt%, and the PX content in the aromatics is 47.6 wt%.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of individual specific technical features in any suitable way. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition. Such simple variations and combinations are likewise to be regarded as being within the scope of the present disclosure.
Claims (15)
1. A process for preparing aromatic hydrocarbons comprising:
a) The raw material containing methanol enters the fast-bed reactor (3) through a fast-bed reactor raw material inlet (10) at the lower part of the fast-bed reactor (3), and is contacted and reacted with circulating catalyst from a circulating catalyst inlet (8) of the fast-bed reactor and a first part of regenerated catalyst from a regenerated catalyst inlet (18) of the fast-bed reactor to obtain a reaction product I and a first to-be-regenerated agent obtained by partial deactivation of the catalyst, and the reaction product I and the first to-be-regenerated agent both go upwards through an outlet structural member (14) of the fast-bed reactor and enter the interior of the mixed stripping zone (4);
b) The light hydrocarbon-containing raw materials enter the riser reactor (2) through a riser reactor raw material inlet (11) at the bottom of the riser reactor (2) and are in contact reaction with a second part of regenerated catalyst from a riser regenerated catalyst inlet (5) to obtain a reaction product II and a second spent agent obtained by partial deactivation of the catalyst, and both the reaction product II and the second spent agent ascend to enter the interior of the mixed stripping zone (4) through a riser reactor outlet structural member (13); mixing the first spent agent and the second spent agent in a mixed stripping zone to form a mixed catalyst;
c) The stripping medium enters the mixed stripping zone through a stripping medium inlet (19) of the mixed stripping zone, and the mixed catalyst is stripped to obtain a stripped catalyst;
d) A first part of the stripped catalyst is used as a spent catalyst, and enters a regeneration system (1) through a spent catalyst outlet (7) of a mixed stripping zone to remove carbon deposit on particles so as to obtain a regenerated catalyst; a second portion of the stripped catalyst is used as the recycled catalyst and is withdrawn through a mixed stripping zone recycled catalyst outlet (6); and optionally
e) Mixing the reaction product I and the reaction product II in a mixed stripping zone, and leading the obtained reaction product rich in aromatic hydrocarbon to enter a subsequent separation system through a reaction product outlet (9) of the mixed stripping zone to obtain C 2 -C 6 A non-aromatic hydrocarbon mixture;
wherein the fast bed reactor, the mixed stripping zone, the riser reactor are coaxially arranged, and wherein the fast bed reactor radially surrounds the riser reactor.
2. The method according to claim 1, wherein the riser reactor outlet structure (13) is located above a fast bed reactor outlet structure (14).
3. The method according to claim 1, characterized in that the riser reactor outlet structure (13) consists of a riser reactor outlet structure top (20) and a riser reactor outlet structure bottom (21) and a riser reactor outlet structure outlet ring (22); the riser reactor outlet structure top (20) is located above the riser reactor outlet structure bottom (21), the riser reactor outlet structure top (20) and the riser reactor outlet structure bottom (21) having a height of 30o ~180 o The same central angle between the two; the ratio of the radii of the riser reactor outlet structure top (20) and the riser reactor outlet structure bottom (21) is (1.2-2): 1.
4. a process according to claim 3, characterized in that the riser reactor outlet structure outlet ring (22) is located at an angle β to the central axis of the riser reactor (2); beta is 30 o -90 o Preferably 40 o -75 o 。
5. The method according to claim 1, characterized in that the fast-bed reactor outlet structure (14) is composed of a fast-bed reactor outlet structure top (23) and a fast-bed reactor outlet structure bottom (24) and a fast-bed reactor outlet structure outlet ring (25); the fast-bed reactor outlet structure top (23) is located above the fast-bed reactor outlet structure bottom (24), the fast-bed reactor outlet structure top (23) and the fast-bed reactor outlet structure bottom (24) having a height of 15 o ~180 o The same central angle between the two; the ratio of the radii of the fast bed reactor outlet structure top (23) and the fast bed reactor outlet structure bottom (24) is (1.1-1.5): 1.
6. the method according to claim 5, characterized in that the exit ring (25) plane of the exit structure of the fast-bed reactor and the central axis of the fast-bed reactor (3) form an angle γ; gamma is 0 o -60 o Preferably 0 o -45 o 。
7. The method according to claim 1, characterized in that the angle β between the plane of the outlet ring (22) of the outlet structure of the riser reactor and the central axis of the riser reactor (2) is larger than the angle γ between the plane of the outlet ring (25) of the outlet structure of the fast-bed reactor and the central axis of the fast-bed reactor (3).
8. A method according to claim 1, characterized in that the mixed stripping zone (4) is provided with an internal heat extractor (12) to reduce the temperature of the catalyst in the mixed stripping zone (4).
9. A method according to claim 1, characterized in that the fast-bed reactor (3) is provided with an external heat extractor to reduce the temperature of the catalyst in the fast-bed reactor (3).
10. The method according to claim 1, characterized in that the regenerated catalyst obtained by removing carbon deposits on the particles by the regeneration system is distributed in a ratio of 1 (3-20), preferably 1 (5-15), of the first partially regenerated catalyst and the second partially regenerated catalyst.
11. The process according to claim 1, characterized in that the ratio of the first fraction to the second fraction of the stripped catalyst used as the spent catalyst and as the recycled catalyst, respectively, is (1-8): 1, preferably (2-5): 1.
12. The method according to claim 1, wherein the methanol-containing raw material comprises 10-100% by mass of methanol.
13. The method according to claim 1The method is characterized in that the raw material containing light hydrocarbon is C 2 -C 6 A non-aromatic hydrocarbon mixture; preferably, the light hydrocarbon-containing material contains C derived from a separation unit 2 -C 6 The proportion of non-aromatic hydrocarbon mixture is greater than 20 wt.%; also preferred is C from the separation unit 2 -C 6 From 30% to 100% by weight, preferably from 50% to 100% by weight, of a non-aromatic hydrocarbon mixture for said light hydrocarbon-containing feedstock; for example, all C obtained by the separation unit 2 -C 6 A non-aromatic hydrocarbon mixture is used as all of the light hydrocarbon-containing feedstock.
14. The method according to claim 1, wherein the mass ratio of the light hydrocarbon-containing raw material to the methanol-containing raw material is (0.1 to 0.4): 1, preferably (0.15 to 0.3): 1.
15. The method according to claim 1, characterized in that:
the temperature of the catalyst bed layer of the fast bed reactor (3) is 460-530 ℃, the linear velocity of the gas of the catalyst bed layer is 1-3 m/s, and the density of the catalyst bed layer is 50-300 kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The temperature of the catalyst at the outlet of the riser reactor (2) is 530-650 ℃, the linear velocity of the outlet gas is 5-10 m/s, and the density of the catalyst at the outlet is 50-150 kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The pressure of the mixed stripping zone (4) is 0-1.0 MPaG.
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