CN117700292A - Method for converting heavy aromatic hydrocarbon into BTX light aromatic hydrocarbon - Google Patents
Method for converting heavy aromatic hydrocarbon into BTX light aromatic hydrocarbon Download PDFInfo
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- aromatic hydrocarbon
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 132
- 239000004005 microsphere Substances 0.000 claims abstract description 89
- 239000002808 molecular sieve Substances 0.000 claims abstract description 74
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000002131 composite material Substances 0.000 claims abstract description 54
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000012084 conversion product Substances 0.000 claims abstract description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000047 product Substances 0.000 claims abstract description 24
- 230000020335 dealkylation Effects 0.000 claims abstract description 17
- 238000006900 dealkylation reaction Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 14
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000638 solvent extraction Methods 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 238000006276 transfer reaction Methods 0.000 claims abstract description 3
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 238000010555 transalkylation reaction Methods 0.000 claims description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 13
- 238000001694 spray drying Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000009718 spray deposition Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000001833 catalytic reforming Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 238000004939 coking Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000003921 oil Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 208000012839 conversion disease Diseases 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 150000003738 xylenes Chemical class 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- YQZBFMJOASEONC-UHFFFAOYSA-N 1-Methyl-2-propylbenzene Chemical compound CCCC1=CC=CC=C1C YQZBFMJOASEONC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a method for converting heavy aromatic hydrocarbon into BTX light aromatic hydrocarbon, which comprises the following steps: (1) C (C) 9 + The heavy aromatic hydrocarbon raw material and hydrogen enter a fluidized bed heavy aromatic hydrocarbon conversion reactor, and are subjected to dealkylation, alkyl transfer and disproportionation reaction on a composite molecular sieve microsphere catalyst under a certain condition to obtain a conversion product; (2) The converted product enters a solvent extraction tower for separation to obtain a BTX mixed component, and then enters a downstream rectifying unit for separation to obtain benzene, toluene and paraxylene products; the composite molecular sieve microsphere catalyst in the step (1) comprises a microsphere carrier and an active metal component; the microsphere carrier comprises a beta-ZSM-5 composite molecular sieve and alumina; the active metal component is one or more of Ni, mo or W. In the method, a fluidized bed reactor is adopted to match with a proper composite molecular sieve catalyst, so that the reaction has higher BTX selectivity, the probability of coking heavy aromatic hydrocarbon is reduced, and the service life of the catalyst can be obviously prolonged.
Description
Technical Field
The invention relates to a C 9 + Method for catalytically converting heavy aromatic hydrocarbon into benzene, toluene and xylene light aromatic hydrocarbon, and is especially suitable for high-selectivity low-value C 9 + Heavy aromatics are converted to high value benzene, toluene, and xylenes (BTX) products.
Background
Light aromatic hydrocarbons such as benzene, toluene, and xylene (BTX for short) are basic raw materials for producing rubber, fiber, polyester, detergents, medicines, etc., and are in great demand.
BTX is mainly derived from refinery reforming/aromatics complex. With increasing BTX yield, low value byproduct C 9 + Heavy aromatics are also increasing. Reforming C 9 + Heavy aromatics refer to monocyclic or polycyclic aromatic hydrocarbons of C9 and above, mainly derived from continuous reformers, and account for about 15% -20% of the capacity of the reformers. The following table shows a typical refinery reforming/aromatics complex C 9 + Composition of heavy aromatics.
Typical refinery reforming/aromatics complex C 9 + Composition of heavy aromatics
From the table it can be seen that: c (C) 9 + Aromatic hydrocarbon accounts for 70% of total aromatic hydrocarbon, and methyl ethylbenzene, propyl benzene, diethyl benzene, dimethyl ethylbenzene, butyl benzene, methyl propyl benzene and the like have C 2 The aromatic hydrocarbon of the alkyl side chain accounts for about 55.0% of the total aromatic hydrocarbon.
The main application is that the product is sold as a blended oil product component or fuel oil at low cost, but with the improvement of clean gasoline standard, aromatic hydrocarbon in the finished oil is limited, and C is limited 9 + Heavy aromatics are taken as the outlet of the oil regulating component.
The preparation of high added value BTX by aromatic hydrocarbon yield increasing technology realizes C 9 + An effective way for high-valued utilization of heavy aromatics. In particular benzene or toluene to lower the value of C 9 + The transalkylation of heavy aromatics to produce xylenes is an increasingly important process.
CN 109952152A describes a process for converting heavy aromatics to BTX and the catalyst composition used. It is characterized by comprising C 8 + Process for converting a feedstock of aromatic hydrocarbons into light aromatic products, wherein the feedstock and optionally hydrogen are in the presence of a catalyst composition in an effective dealkylation and transalkylation of said C 8 + Aromatic hydrocarbons are contacted under conversion conditions to produce the light aromatic product comprising benzene, toluene, and xylenes. The catalyst composition comprises a zeolite selected from the group consisting of zeolite beta, ZSM-4, ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, MCM-68, faujasite, mordenite, MCM-22 series of materials, and a first metal in group VI (molybdenum or tungsten) and a second metal in group VIII (cobalt or nickel), and is treated with a sulfur source and/or a steam source. However, the method adopts a zeolite mechanical mixing method to prepare the catalyst to generate benzene and paraxylene, and has poor selectivity.
CN 114436736A is used in a catalytic reaction system for heavy aromatics conversion and a method for catalyzing heavy aromatics conversion, which is carried out in the catalytic reaction system of the present invention, which isComprising the following steps: the catalytic reaction zones and the rectification separation zones are sequentially arranged at intervals, at least one rectification separation zone is respectively arranged before and after each catalytic reaction zone, and the catalytic reaction zones are used for containing C 9 + The heavy aromatic hydrocarbon component raw material is contacted with a catalyst to react to generate light aromatic hydrocarbon, and the rectifying and separating area is used for rectifying and separating to obtain a target component; the catalytic reaction zone is filled with a corresponding functional catalyst so that the catalyst contains C 9 + The heavy aromatic hydrocarbon component raw material and the catalyst are contacted and reacted to generate light aromatic hydrocarbon. The method can be used for converting and rectifying separation at the same time, so that the method can be used for the light-weight reaction of heavy aromatic hydrocarbon, separation of the conversion process of the polycyclic aromatic hydrocarbon and the conversion process of the monoaromatic hydrocarbon is realized, and meanwhile, the conversion efficiency and the selectivity of the product dimethylbenzene are greatly improved. The transalkylation and dealkylation catalyst comprises a first active component and a first molecular sieve component, wherein the first active component element is selected from one or more of VIB group, VIIB group, VIIIB group and IIB group, and preferably one or more of Mo, ir, re and Zn; and/or the first molecular sieve component is one or more of molecular sieves containing ten-membered ring and/or twelve-membered ring structures, preferably one or more of ZSM-5, beta and MOR molecular sieves; the method also has the problem of poor selectivity of high-value benzene and paraxylene.
CN 112745932B discloses a process for producing light aromatic hydrocarbons. The method adopts the mechanical mixing and spraying of the mesoporous ZSM-5 and the macroporous beta molecular sieve to form balls, and then directly loads Pt and Pd metal components or metal components such as presulfiding NiS and the like. The method adopts noble metal or presulfiding NiS component, the catalyst cost is high, and the manufacturing process is complex.
The prior art has the defect that a fixed bed process is generally adopted, so that the catalyst is easy to be deactivated by carbon deposition, and the service life of the catalyst for future industrial application is influenced.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for preparing a C-type compound 9 + The method for converting heavy aromatic hydrocarbon into benzene, toluene and xylene (BTX) light aromatic hydrocarbon adopts a fluidized bed reactor to match proper composite componentsThe sub-sieve catalyst ensures that the reaction has higher BTX selectivity, reduces the coking probability of heavy aromatic hydrocarbon and can obviously prolong the service life of the catalyst.
The method for converting heavy aromatic hydrocarbon into BTX light aromatic hydrocarbon comprises the following steps: (1) C (C) 9 + Dealkylation, transalkylation and disproportionation of heavy aromatic feedstock: c (C) 9 + The heavy aromatic hydrocarbon raw material and hydrogen enter a fluidized bed heavy aromatic hydrocarbon conversion reactor, and are subjected to dealkylation, alkyl transfer and disproportionation reaction on a composite molecular sieve microsphere catalyst under a certain condition to obtain a conversion product; (2) solvent extraction of the conversion product to obtain a BTX product: the converted product enters a solvent extraction tower for separation to obtain a BTX mixed component, and then enters a downstream rectifying unit for separation to obtain benzene, toluene and paraxylene products; the composite molecular sieve microsphere catalyst in the step (1) comprises a microsphere carrier and an active metal component; the microsphere carrier comprises a beta-ZSM-5 composite molecular sieve and alumina, wherein the beta-ZSM-5 composite molecular sieve is 70.0% -95.0%, preferably 80.0% -90.0% based on the mass of the microsphere carrier; alumina is 5.0% -30.0%, preferably 10.0% -20.0%; the active metal component is one or more of Ni, mo or W, preferably Ni; the content of the active metal component in terms of oxide is 2.0-15.0 wt%, preferably 5.0-10.0 wt%, based on the weight of the catalyst;
wherein the microsphere carrier adopts pyridine adsorption to measure the total acid amount (C L +C B ) 1.0 to 1.6mmol/g of L acid and B acid (C L /C B ) The ratio is 1.8 to 2.6.
Wherein, in the beta-ZSM-5 composite molecular sieve, the mass proportion of ZSM-5 is 40.0% -90.0%, preferably 50.0% -80.0%. In the beta-ZSM-5 composite molecular sieve, ZSM-5 zeolite particles are taken as cores, beta zeolite is taken as a shell, and the thickness of the shell layer is 150-500 nm, preferably 200-300 nm; wherein the beta-ZSM-5 composite molecular sieve is a hydrogen type molecular sieve;
the composite molecular sieve microsphere catalyst has particles with the diameter of 30-80 mu m, particularly microspheres with the diameter of 40-60 mu m account for 60-95 wt%, preferably 80-95 wt% of the total particles.
In the method of the invention, the preparation method of the composite molecular sieve microsphere catalyst comprises the following steps:
a) Spray balling: will contain beta-ZSM-5 composite molecular sieve and Al 2 O 3 Mixing, grinding uniformly, adding aqueous solution of nitric acid to form slurry, spray drying, forming and roasting to obtain microsphere particles;
b) Carrying out hydrothermal treatment on the microsphere particles to prepare a microsphere carrier;
c) And loading the active components on the microsphere carrier to obtain the composite molecular sieve microsphere catalyst.
Wherein the concentration of the nitric acid aqueous solution in the step (a) is 5.0-20.0 g/100mL, and the liquid-solid ratio of the slurry is 2:1-6:1; the spray forming process is generally carried out in spray drying equipment, such as a spray drying tower, wherein the hot air inlet pressure of the spray drying equipment is 3.0-7.0 MPa, the inlet temperature is 300-400 ℃, the outlet temperature is 120-200 ℃, and the microspheres obtained through cyclone separation are roasted for 3.0-10.0 hours at 400-600 ℃.
Wherein the hydrothermal treatment conditions in the step (b) are as follows: the temperature is 400-600 ℃, preferably 500-550 ℃; the volume ratio of the gasoline to the water is 3:1-10:1, preferably 5:1-8:1; the treatment time is 2.0 to 8.0 hours, preferably 4.0 to 5.0 hours. The hydrothermal treatment can be carried out in a fixed bed reactor, and generally, microsphere particles are put into the fixed bed reactor, and water is introduced according to a certain steam-to-agent ratio to carry out the hydrothermal treatment.
Wherein, the loading process in the step (c) generally adopts an impregnation mode, such as spray impregnation, the microsphere carrier is placed into a spray impregnation tank, a rotary pump is started, and the active component impregnation liquid is sprayed to the catalyst carrier; then drying and roasting to obtain a catalyst; the drying conditions are as follows: the drying time is 4.0-8.0 hours, and the drying temperature is 100-150 ℃; the roasting conditions are as follows: the roasting time is 3.0-6.0 hours, and the roasting temperature is 450-500 ℃.
The composite molecular sieve microsphere catalyst of the invention is subjected to reduction treatment before use, and the reduction treatment conditions are as follows: the pressure is 1.0-6.0 MPa, the temperature is 450-550 ℃, the hydrogen agent volume ratio is 50:1-500:1, and the time is 2.0-5.0 hours; the preferred conditions are as follows: the pressure is 2.0-4.0 MPa, the temperature is 480-520 ℃, the hydrogen agent volume ratio is 100:1-200:1, and the time is 3.0-4.0 hours.
In the method of the present invention, the step (1) is performed by the method of the present invention 9 + Heavy aromatic hydrocarbon raw materials and hydrogen enter from the lower part of a fluidized bed reactor, contact with a composite molecular sieve microsphere catalyst entering the reactor, carry out dealkylation, transalkylation and disproportionation reactions in a fluidized bed state, and are discharged from the top of the reactor to obtain a conversion product; the catalyst deactivated by carbon deposition discharged from the lower part of the reactor enters a regenerator through a lock hopper, and is regenerated by burning carbon with air; the regenerated catalyst enters the reactor through a lock hopper and is recycled.
In the process of the present invention, C is as described in step (1) 9 + The heavy aromatic hydrocarbon raw material comes from a catalytic reforming/aromatic hydrocarbon extraction combined device, C 9 The mass content of the components is 75.0-85.0% and C is 10 The mass content of the components is 5.0-15.0% and the balance is C 11 + The components are as follows.
In the process of the present invention, the operating conditions in the fluidized bed reactor described in step (1) are as follows: the reaction pressure is 1.0-6.0 MPa, the reaction temperature is 350-550 ℃ and the volume airspeed is 1.0-7.0 hours -1 The hydrogen oil volume ratio is 50:1-500:1; preferred operating conditions are as follows: the reaction pressure is 2.0-4.0 MPa, the reaction temperature is 400-500 ℃ and the volume airspeed is 2.0-6.0 hours -1 The volume ratio of the hydrogen oil is 200:1-300:1.
In the method, the catalyst to be regenerated discharged from the reactor in the step (1) is conveyed to the regenerator for regeneration after being stripped, and the obtained regenerated catalyst is returned to the fluidized bed reactor for recycling. The regeneration conditions are as follows: the pressure is 0.5 MPa-1.5 MPa, the volume ratio of the gas agent is 200:1-500:1, the roasting is carried out for 0.2-1.0 hour at 400-500 ℃, and the regeneration atmosphere is an oxygen-containing atmosphere, preferably air.
In the method, the process of removing heavy aromatics by solvent extraction of the conversion product in the step (2) adopts the common and mature process in industry. The solvent used in the extraction tower is at least one of sulfolane and N-formyl morpholine.
In the method, in the step (2), the conversion product is subjected to extractive distillation, and the extracting agent adopts a mixed solvent of sulfolane and N-formylmorpholine, wherein the volume content ratio of the sulfolane to the N-formylmorpholine in the mixed extracting agent is 6:1-12:1.
Compared with the prior art, the method has the following advantages:
the reduced Ni/beta-ZSM-5 composite molecular sieve catalyst takes ZSM-5 zeolite particles as cores and beta zeolite as shells to obtain more mesoporous channels, so that active metals are dispersed more uniformly on a carrier, on one hand, the dispersity of active centers on the microspherical catalyst is greatly improved, on the other hand, the contact area of reaction raw materials and the active centers is remarkably improved, the reaction rate is accelerated, the internal and external diffusion rates of reactants and products in the catalyst are improved, and the residence time is reduced.
The metal component for converting heavy aromatic hydrocarbon into light aromatic hydrocarbon in the prior art is conventionally selected to be in noble metal reduced state or non-noble metal sulfided state, and the invention adopts a reduced state Ni/beta-ZSM-5 composite microsphere catalyst, on one hand, the atomic nucleus electron arrangement of metal Ni is 3d 8 4s 2 The outermost layer 4s is far less than the stable structure of the octamer, has higher electron affinity and high electron-abstracting activity, and simultaneously matches with proper acidity of the catalyst carrier (the total acid amount and the strong acid amount are lower, catalyst C L /C B Higher) and the unique pore channel structure of the composite molecular sieve microsphere hole-mesopore penetration, greatly improves C 9 + Dealkylation, transalkylation, disproportionation capability, and selectivity to BTX of heavy aromatic feedstock. The catalyst of the invention is combined with the fluidized bed, and can avoid colloid C generated by raw materials and reaction 10 + Heavy aromatics polymerize and coke on the catalyst, and the pressure drop generated by the reactor affect the service life of the catalyst and the long-period operation of the device.
Drawings
FIG. 1 is a schematic diagram of the process flow of the present invention for converting heavy aromatics to light aromatics.
FIG. 2 is a Scanning Electron Microscope (SEM) of the beta-ZSM-5/50 composite molecular sieve of example 1.
FIG. 3 is a Scanning Electron Microscope (SEM) of the beta-Z/50 microsphere catalyst of example 1.
FIG. 4 is a Scanning Electron Microscope (SEM) of the beta-ZSM-5/30 composite molecular sieve of example 2.
FIG. 5 is a Scanning Electron Microscope (SEM) of the beta-Z/30 microsphere catalyst of example 2.
FIG. 6 is a Scanning Electron Microscope (SEM) of a beta+ZSM-5 mechanically mixed molecular sieve microsphere catalyst of comparative example 1.
Detailed Description
The method and effect of the present invention will be further described with reference to the accompanying drawings and examples, but the scope of the present invention is not limited thereto.
According to the flow diagram in fig. 1: c (C) 10 + The heavy aromatic hydrocarbon raw material 1 and hydrogen 2 enter a riser 3 from the bottom and are lifted into a fluidized bed reactor 4 to carry out dealkylation, transalkylation and disproportionation under certain conditions; the converted product 12 is discharged from the top of the reactor 4 and enters an extraction tower 13 for solvent extraction, the solvent 5 enters from the top of the extraction tower, the upper part of the tower is provided with a BTX mixed product 14 (raffinate oil), and the lower part of the tower is provided with extract oil rich in heavy aromatics; the extraction oil is regenerated to obtain a solvent and heavy aromatic hydrocarbon, and the solvent is recycled; the catalyst with deactivated carbon deposit enters a to-be-regenerated catalyst collector 5, hydrogen is replaced by nitrogen 7 and then enters a lock hopper 6, a regenerator 9 is arranged, carbon burning regeneration is carried out by oxygen-containing atmosphere (such as air) 10, and sulfur-containing flue gas 11 is discharged to recover sulfur; the regenerated catalyst enters a regenerated catalyst collector 8, enters a lock hopper 6 through a pipeline, and enters a riser 3 through a pipeline for recycling.
Using a composition containing typical C 9 + The main components of heavy aromatic hydrocarbon (methyl ethyl benzene, 1,2, 4-trimellitic benzene) are model compounds (C for short) 9 + Raw materials, by mass, were 48.0% methyl ethyl benzene and 52.0% 1,2, 4-pseudocumene, available from a company of Ara Ding Shiji).
The following examples further illustrate the aspects and effects of the present invention, but are not intended to limit the invention.
Example 1
This example prepared 6.0wt% NiO/beta-ZSM-5 composite molecular sieve microsphere catalyst.
The method of CN112110453B is adopted to prepare an hour beta-ZSM-5 composite molecular sieve (beta-ZSM-5/50 for short), the mass ratio of the beta molecular sieve to the ZSM-5 molecular sieve is 50 percent to 50 percent, and the ZSM-5 zeolite particles are taken as cores and the beta zeolite is taken as shells. Table 1 shows the main physical properties of the beta-ZSM-5/50 composite molecular sieve; FIG. 2 shows a Scanning Electron Microscope (SEM) of the beta-ZSM-5/50 composite molecular sieve.
Weighing the 80g dry basis hour beta-ZSM-5/50 composite molecular sieve and 20.0g dry basis Al 2 O 3 The powder is ground and mixed uniformly, 300mL of dilute nitric acid solution with the concentration of 10g/100mL and deionized water are added to prepare 340mL of slurry. And (3) carrying out spray drying on the slurry, wherein the spray drying pressure is 3.0MPa, the air inlet temperature of a drying tower is 350 ℃, and the air outlet temperature is 150 ℃. The microspheres obtained by cyclone separation are roasted for 8 hours at 520 ℃ to prepare microsphere particles.
Weighing 80ml of the microsphere particles, putting the microsphere particles into a 200ml fixed bed reactor, heating to 200 ℃ within 3.0 hours, and then starting a water pump to adjust the water inflow to 400ml; then heating to 520 ℃ in 2.0 hours, and keeping the temperature at 520 ℃ for 5.0 hours to prepare the microsphere carrier. Table 2 shows the acidity of the microsphere carriers.
Weighing 50g of the microsphere carrier, putting the microsphere carrier into a spray dipping tank, and starting a rotary pump. 35.0mL of nickel nitrate solution containing 3.0g of NiO was sprayed into the catalyst support over 30 minutes. Drying at room temperature, drying at 120deg.C for 6 hr, and calcining at 480 deg.C for 6 hr to obtain microsphere catalyst with NF/50 number. The NF/50 catalyst physical properties are set forth in Table 3, and FIG. 3 is a Scanning Electron Microscope (SEM) of the NF/50 catalyst.
Example 2
This example prepared 8.0wt% NiO/beta-ZSM-5 composite molecular sieve microsphere catalyst.
The method of CN112110453B is adopted to prepare an hour beta-ZSM-5 composite molecular sieve (beta-ZSM-5/30 for short), the mass ratio of the beta molecular sieve to the ZSM-5 molecular sieve is 30 percent to 70 percent, and ZSM-5 zeolite particles are taken as cores and beta zeolite is taken as shells. Table 1 shows the main physical properties of the beta-ZSM-5/30 composite molecular sieve; FIG. 4 shows a Scanning Electron Microscope (SEM) of the beta-ZSM-5/30 composite molecular sieve.
Weighing the 80g dry basis hour beta-ZSM-5/30 composite molecular sieve and 20.0g dry basis Al 2 O 3 The powder is ground and mixed uniformly, 300mL of dilute nitric acid solution with the concentration of 10g/100mL and deionized water are added to prepare 340mL of slurry. And (3) carrying out spray drying on the slurry, wherein the spray drying pressure is 3.0MPa, the air inlet temperature of a drying tower is 350 ℃, and the air outlet temperature is 150 ℃. The microspheres obtained by cyclone separation are roasted for 8 hours at 520 ℃ to prepare microsphere particles.
70ml of the microsphere particles are weighed and put into a 200ml fixed bed reactor, the temperature is raised to 200 ℃ within 3 hours, then a water pump is started, and the water inflow is adjusted to 560ml; then the temperature is raised to 550 ℃ in 2.0 hours, and the temperature is kept constant at 550 ℃ for 4.0 hours, so as to prepare the microsphere carrier. Table 2 shows the acidity of the microsphere carriers.
Weighing 50g of the microsphere carrier, putting the microsphere carrier into a spray dipping tank, and starting a rotary pump. 40.0mL of nickel nitrate solution containing 4.0g of NiO was sprayed into the catalyst support over 30 minutes. Drying at room temperature, drying at 120deg.C for 6 hr, and calcining at 480 deg.C for 6 hr to obtain microsphere catalyst with NF/30 number. The NF/30 catalyst physical properties are listed in Table 3, and FIG. 5 is a Scanning Electron Microscope (SEM) of the NF/30 catalyst.
Example 3
This example produces 2.0wt% NiO-4.0wt% Mo 2 O 3 beta-ZSM-5 composite molecular sieve microsphere catalyst.
Microsphere carriers prepared in the same manner as in example 1 were used.
Weighing 50g of the microsphere carrier, putting the microsphere carrier into a spray dipping tank, and starting a rotary pump. 35.0mL of nickel nitrate containing 1.0g of NiO, 2.0g of Mo were added over 30 minutes 2 O 3 The solution was sprayed into the catalyst support. Drying at room temperature, drying at 120deg.C for 6 hr, and calcining at 480 deg.C for 6 hr to obtain microsphere catalyst with NMF/50 number. The NMF/50 catalyst physical properties are listed in Table 3.
Comparative example 1
This example prepared 6.0wt% NiO/beta + ZSM-5 mixed molecular sieve microsphere catalyst.
The catalyst adopts ZSM-5 molecular Sieve (SiO) for industrial products and hours 2 /Al 2 O 3 The molar ratio is 28); industrial grade beta molecular Sieve (SiO) 2 /Al 2 O 3 The molar ratio was 25). Table 1 shows the main physical properties of the hour ZSM-5 and hour beta molecular sieves.
Weighing 40g of dry-basis hour ZSM-5 molecular sieve, 40g of dry-basis hour beta molecular sieve and 20.0g of dry-basis Al 2 O 3 The powder is ground and mixed uniformly, and 300mL of dilute nitric acid solution with the concentration of 10g/100mL and deionized water are added to prepare 500mL of slurry. And (3) carrying out spray drying on the slurry, wherein the spray drying pressure is 3.0MPa, the air inlet temperature of a drying tower is 350 ℃, and the air outlet temperature is 150 ℃. The microspheres obtained by cyclone separation are roasted for 5 hours at 550 ℃ to prepare the microsphere carrier. Table 2 shows the acidity of the microsphere carriers.
Weighing 50g of the microsphere carrier, putting the microsphere carrier into a spray dipping tank, and starting a rotary pump. 35.0mL of nickel nitrate solution containing 3.0g of NiO was sprayed into the catalyst support over 30 minutes. Drying at room temperature, drying at 120deg.C for 6 hr, and calcining at 500deg.C for 4 hr to obtain microsphere catalyst with number of Zbeta catalyst. Physical properties of the zβ catalyst are listed in table 3, and fig. 6 is a Scanning Electron Microscope (SEM) of the zβ microsphere catalyst.
Comparative example 2
The catalyst was prepared by the method of example 1.
Except that the microspheroidal particles were directly impregnated with Ni metal components without hydrothermal treatment to prepare microspheroidal catalysts, numbered NF/50C catalysts, having the main properties shown in Table 3.
Example 4
This example examined the catalytic performance of the NF/50 catalyst prepared in example 1.
The comparative example employs a composition containing typical C 9 + The main components of heavy aromatic hydrocarbon (methyl ethyl benzene, 1,2, 4-trimellitic benzene) are model compounds (C for short) 9 + Raw materials, by mass, were 48.0% methyl ethyl benzene, 52.0% 1,2, 4-pseudocumene, available from the company Ara Ding Shiji Co., ltd.).
20mL of fresh NF/50 catalyst was charged to the fluidized bed reactor of FIG. 1. Firstly, introducing hydrogen to boost pressure, and reducing the new NF/50 catalyst for 4 hours under the conditions that the hydrogen pressure is 3.0MPa, the temperature is 450 ℃ and the hydrogen agent volume ratio is 100:1The method comprises the steps of carrying out a first treatment on the surface of the Then the temperature is reduced to 430 ℃ and C is entered 9 + Raw materials, at a hydrogen-oil volume ratio of 300:1, a volume space velocity of 3.0h -1 Dealkylation, transalkylation and disproportionation are carried out;
and extracting the reaction conversion product by an extraction tower to remove heavy aromatic hydrocarbon, and adopting a mixed solvent of sulfolane and N-formylmorpholine, wherein the volume content ratio of the sulfolane to the N-formylmorpholine in the mixed extractant is 8:1.
The carbon deposition deactivated catalyst can be replaced by nitrogen and conveyed to a regenerator through a locking hopper, and is regenerated after being burned for 0.5 hour under the air pressure of 0.8MPa and the gas-agent volume ratio of 300:1 and 480 ℃; the regenerated catalyst is replaced by nitrogen and then is conveyed to a fluidized bed reactor through a locking funnel for cyclic reaction; and (5) product sampling analysis.
Table 4 lists NF/50 catalyst evaluation C 9 + Raw materials, conversion products results.
Example 5
This example examined the catalytic performance of the NF/30 catalyst prepared in example 2. The same C as in example 4 was used 9 + Raw materials.
20mL of fresh NF/30 catalyst was charged to the fluidized bed reactor of FIG. 1. Firstly, introducing hydrogen to boost pressure, and reducing a new NF/30 catalyst for 4 hours under the conditions that the hydrogen pressure is 3.0MPa, the temperature is 450 ℃ and the hydrogen agent volume ratio is 100:1; then the temperature is reduced to 450 ℃ to enter C 9 + Raw materials, at a hydrogen oil volume ratio of 400:1, a volume space velocity of 5.0h -1 Dealkylation, transalkylation and disproportionation are carried out;
the heavy aromatic hydrocarbon of the reaction conversion product is removed by extraction in an extraction tower, and a mixed solvent of sulfolane and N-formylmorpholine is adopted, wherein the volume content ratio of the sulfolane to the N-formylmorpholine in the mixed extractant is 6:1.
The carbon deposition deactivated catalyst can be replaced by nitrogen and conveyed to a regenerator through a locking hopper, and is regenerated after being burned for 0.5 hour under the air pressure of 0.8MPa and the gas-agent volume ratio of 300:1 and 480 ℃; the regenerated catalyst is replaced by nitrogen and then is conveyed to a fluidized bed reactor through a locking funnel for cyclic reaction; and (5) product sampling analysis.
Table 5 lists NF/30 catalyst evaluation C 9 + Raw materials, conversion products results.
Example 6
The NMF/50 catalyst prepared in example 3 was examined for its catalytic performance. The same C as in example 4 was used 9 + Raw materials.
20mL of fresh NMF/50 catalyst was charged to the fluidized bed reactor of FIG. 1. Firstly, introducing hydrogen to boost pressure, and reducing a new NF/30 catalyst for 4 hours under the conditions that the hydrogen pressure is 3.0MPa, the temperature is 450 ℃ and the hydrogen agent volume ratio is 100:1; then the temperature is reduced to 450 ℃ to enter C 9 + Raw materials, at a hydrogen oil volume ratio of 400:1, a volume space velocity of 5.0h -1 Dealkylation, transalkylation and disproportionation are carried out;
the heavy aromatic hydrocarbon of the reaction conversion product is removed by extraction in an extraction tower, and a mixed solvent of sulfolane and N-formylmorpholine is adopted, wherein the volume content ratio of the sulfolane to the N-formylmorpholine in the mixed extractant is 6:1.
The carbon deposition deactivated catalyst can be replaced by nitrogen and conveyed to a regenerator through a locking hopper, and is regenerated after being burned for 0.5 hour under the air pressure of 0.8MPa and the gas-agent volume ratio of 300:1 and 480 ℃; the regenerated catalyst is replaced by nitrogen and then is conveyed to a fluidized bed reactor through a locking funnel for cyclic reaction; and (5) product sampling analysis.
Table 6 shows NMF/50 catalyst evaluation C 9 + Raw materials, conversion products results.
Comparative example 3
The performance of the zβ catalyst in comparative example 1 was examined. The same C as in example 4 was used 9 + Raw materials.
20mL of fresh Zβ catalyst was charged to the fluidized bed reactor of FIG. 1. Firstly, introducing hydrogen to boost pressure, and reducing a new Zbeta catalyst for 4 hours under the conditions that the hydrogen pressure is 3.0MPa, the temperature is 450 ℃ and the hydrogen agent volume ratio is 100:1; then the temperature is reduced to 430 ℃ and C is entered 9 + Raw materials, at a hydrogen-oil volume ratio of 300:1, a volume space velocity of 3.0h -1 Dealkylation, transalkylation and disproportionation are carried out;
and extracting the reaction conversion product by an extraction tower to remove heavy aromatic hydrocarbon, and adopting a mixed solvent of sulfolane and N-formylmorpholine, wherein the volume content ratio of the sulfolane to the N-formylmorpholine in the mixed extractant is 8:1.
The carbon deposition deactivated catalyst can be replaced by nitrogen and conveyed to a regenerator through a locking hopper, and is regenerated after being burned for 0.5 hour under the air pressure of 0.8MPa and the gas-agent volume ratio of 300:1 and 480 ℃; the regenerated catalyst is replaced by nitrogen and then is conveyed to a fluidized bed reactor through a locking funnel for cyclic reaction; product sampling analysis, table 7 lists C 9 + Raw materials, conversion products results.
Comparative example 4
The performance of the NF/50C catalyst in comparative example 2 was examined. The same C as in example 4 was used 9 + Raw materials.
20mL of fresh NF/50C catalyst was charged to the fluidized bed reactor of FIG. 1. Firstly, introducing hydrogen to boost pressure, and reducing a new NF/50C catalyst for 4 hours under the conditions that the hydrogen pressure is 3.0MPa, the temperature is 450 ℃ and the hydrogen agent volume ratio is 100:1; then the temperature is reduced to 430 ℃ and C is entered 9 + Raw materials, at a hydrogen-oil volume ratio of 300:1, a volume space velocity of 3.0h -1 Dealkylation, transalkylation and disproportionation are carried out;
and extracting the reaction conversion product by an extraction tower to remove heavy aromatic hydrocarbon, and adopting a mixed solvent of sulfolane and N-formylmorpholine, wherein the volume content ratio of the sulfolane to the N-formylmorpholine in the mixed extractant is 8:1.
The carbon deposition deactivated catalyst can be replaced by nitrogen and conveyed to a regenerator through a locking hopper, and is regenerated after being burned for 0.5 hour under the air pressure of 0.8MPa and the gas-agent volume ratio of 300:1 and 480 ℃; the regenerated catalyst is replaced by nitrogen and then is conveyed to a fluidized bed reactor through a locking funnel for cyclic reaction; product sampling analysis, table 8 lists C 9 + Raw materials, conversion products results.
Comparative example 5
This example examined the catalytic performance of the NF/30 catalyst prepared in example 2. The same C as in example 4 was used 9 + Raw materials.
20mL of fresh NF/30 catalyst was charged to the fluidized bed reactor of FIG. 1. Firstly, introducing hydrogen to boost pressure, and introducing a new NF/30 catalyst into CS under the conditions that the hydrogen pressure is 3.0MPa, the temperature is 280 ℃ and the hydrogen agent volume ratio is 100:1 2 Straight-run gasoline with the mass content of 1.5 percent is vulcanized for 5 hours at constant temperature; then the temperature is increased to 450 ℃ to enter C 9 + Raw materials, at a hydrogen oil volume ratio of 400:1, a volume space velocity of 5.0h -1 Dealkylation, transalkylation and disproportionation are carried out;
the heavy aromatic hydrocarbon of the reaction conversion product is removed by extraction in an extraction tower, and a mixed solvent of sulfolane and N-formylmorpholine is adopted, wherein the volume content ratio of the sulfolane to the N-formylmorpholine in the mixed extractant is 6:1.
And (5) product sampling analysis. Table 9 lists C 9 + Raw materials, conversion products results.
Table 1 physical properties of molecular sieves
TABLE 2 microsphere Carrier acidity
C L 、C B And C L450℃ +C B450℃ Respectively represents the total L acid amount, the total B acid amount and the sum of the strong L acid amount and the B acid amount at 450 DEG C
TABLE 3 catalyst Properties
TABLE 4C in example 4 9 + Composition of raw materials and conversion products
TABLE 5 example 5C 9 + Composition of raw materials and conversion products
TABLE 6 example 6C 9 + Composition of raw materials and conversion products
Table 7 comparative example 3C 9 + Composition of raw materials and conversion products
Table 8 comparative example 4C 9 + Composition of raw materials and conversion products
Table 9 comparative example 5C 9 + Composition of raw materials and conversion products
From the comparison of tables 4 to 9, it can be seen that: 1) Microsphere catalyst C prepared by conventional mechanical mixing ZSM-5 and beta molecular sieves 9 + Microsphere catalyst C prepared by beta-ZSM-5 composite molecular sieve with conversion rate of 80.0 percent 9 + The conversion rate is improved to 87.0% -88.0%, so that the beta-ZSM-5 composite molecular sieve catalyst has higher activity; 2) The selectivity of the BTX of the microsphere catalyst prepared by the conventional mechanical mixing ZSM-5 and beta molecular sieve is 65.0%, and the selectivity of the BTX of the microsphere catalyst prepared by the beta-ZSM-5 composite molecular sieve is improved to 73.9% -75.9%, so that the beta-ZSM-5 composite molecular sieve catalyst has higher BTX selectivity; 3) Microsphere catalyst C prepared by conventional mechanical mixing ZSM-5 and beta molecular sieves 10 + Microsphere catalyst C prepared by beta-ZSM-5 composite molecular sieve with yield of 23.0 percent 10 + The yield is reduced to 16.5% -18.0%; 4) Microsphere catalyst prepared by beta-ZSM-5 composite molecular sieve, ni-based catalyst has higher C than NiMo-based catalyst 9 + Aromatic conversion activity and BTX selectivity; 5) Microsphere catalyst prepared by beta-ZSM-5 composite molecular sieve, and the reduction state of the microsphere catalyst is higher than the sulfuration state of the microsphere catalyst 9 + Aromatic conversion activity and BTX selectivity.
Therefore, the Ni-based beta-ZSM-5 composite molecular sieve catalyst has higher C 9 + Aromatic conversion activity and BTX selectivity, while reducing C 9 + Conversion of aromatic hydrocarbons to C 10 + The activity of the arene is larger, the coking probability of heavy arene is reduced, and the service life of the catalyst can be obviously prolonged.
Claims (12)
1. The method for converting the heavy aromatic hydrocarbon into the BTX light aromatic hydrocarbon is characterized by comprising the following steps of: (1) C (C) 9 + Dealkylation, transalkylation and disproportionation of heavy aromatic feedstock: c (C) 9 + The heavy aromatic hydrocarbon raw material and hydrogen enter a fluidized bed heavy aromatic hydrocarbon conversion reactor, and are subjected to dealkylation, alkyl transfer and disproportionation reaction on a composite molecular sieve microsphere catalyst under a certain condition to obtain a conversion product; (2) solvent extraction of the conversion product to obtain a BTX product: the converted product enters a solvent extraction tower for separation to obtain a BTX mixed component, and then enters a downstream rectifying unit for separation to obtain benzene, toluene and paraxylene products; wherein the composite molecular sieve microsphere catalyst comprises a microsphere carrier and an active metal component; the microsphere carrier comprises a beta-ZSM-5 composite molecular sieve and alumina, wherein the beta-ZSM-5 composite molecular sieve is 70.0% -95.0% based on the mass of the microsphere carrier; alumina is 5.0% -30.0%; the active metal component is one or more of Ni, mo or W, preferably Ni; the content of the active metal component in terms of oxide is 2.0-15.0 wt% based on the weight of the catalyst; the total acid amount of the microsphere carrier measured by pyridine adsorption is 1.0-1.6 mmol/g, and the ratio of L acid to B acid is 1.8-2.6.
2. The method according to claim 1, characterized in that: in the beta-ZSM-5 composite molecular sieve, the mass proportion of ZSM-5 is 40.0% -90.0%, ZSM-5 zeolite particles are taken as cores, beta zeolite is taken as a shell, and the thickness of the shell is 150-500 nm; wherein the beta-ZSM-5 composite molecular sieve is a hydrogen type molecular sieve; the composite molecular sieve microsphere catalyst has particles with diameters of 30-80 mu m, and microspheres with diameters of 40-60 mu m account for 60-95 wt% of total particles.
3. The method according to claim 1, characterized in that: the preparation method of the composite molecular sieve microsphere catalyst comprises the following steps: (a) spray balling: will contain beta-ZSM-5 composite molecular sieve and Al 2 O 3 Mixing, grinding uniformly, adding aqueous solution of nitric acid to form slurry, spray drying, forming and roasting to obtain microsphere particles; (b) Carrying out hydrothermal treatment on the microsphere particles to prepare a microsphere carrier; (c) And loading the active components on the microsphere carrier to obtain the composite molecular sieve microsphere catalyst.
4. A method according to claim 3, characterized in that: the concentration of the nitric acid aqueous solution in the step (a) is 5.0-20.0 g/100mL, and the liquid-solid mass ratio of the slurry is 2:1-6:1; the spray forming process is carried out in spray drying equipment, the hot air inlet pressure of the spray drying equipment is 3.0-7.0 MPa, the inlet temperature is 300-400 ℃, the outlet temperature is 120-200 ℃, and the microspheres obtained through cyclone separators are roasted for 3.0-10.0 hours at 400-600 ℃.
5. A method according to claim 3, characterized in that: the hydrothermal treatment conditions in the step (b) are as follows: at the temperature of 400-600 ℃, the volume ratio of the steam to the agent is 3:1-10:1, and the treatment time is 2.0-8.0 hours.
6. A method according to claim 3, characterized in that: the loading process in the step (c) adopts a spray impregnation mode, a microsphere carrier is placed into a spray impregnation tank, a rotary pump is started, and an active component impregnation liquid is sprayed to a catalyst carrier; then drying and roasting to obtain a catalyst; the drying conditions are as follows: the drying time is 4.0-8.0 hours, and the drying temperature is 100-150 ℃; the roasting conditions are as follows: the roasting time is 3.0-6.0 hours, and the roasting temperature is 450-500 ℃.
7. The method according to claim 1, characterized in that: the composite molecular sieve microsphere catalyst is subjected to reduction treatment before use, wherein the reduction treatment conditions are as follows: the pressure is 1.0-6.0 MPa, the temperature is 450-550 ℃, the hydrogen-oil volume ratio is 50:1-500:1, and the time is 2.0-5.0 hours.
8. The method according to claim 1, characterized in that: c described in the step (1) 9 + The heavy aromatic hydrocarbon raw material comes from a catalytic reforming/aromatic hydrocarbon extraction combined device, C 9 The mass content of the components is 75.0-85.0% and C is 10 The mass content of the components is 5.0-15.0% and the balance is C 11 + The components are as follows.
9. The method according to claim 1, characterized in that: the operating conditions in the fluidized bed reactor described in step (1) are as follows: the reaction pressure is 1.0-6.0 MPa, the reaction temperature is 350-550 ℃ and the volume airspeed is 1.0-7.0 hours -1 The hydrogen oil volume ratio is 50:1-500:1.
10. The method according to claim 1, characterized in that: and (2) extracting and rectifying the conversion product, wherein the extracting agent adopts a mixed solvent of sulfolane and N-formylmorpholine, and the volume content ratio of the sulfolane to the N-formylmorpholine in the mixed extracting agent is 6:1-12:1.
11. The method according to claim 1, characterized in that: the C is 9 + Heavy aromatic hydrocarbon raw materials and hydrogen enter from the lower part of a fluidized bed reactor, contact with a composite molecular sieve microsphere catalyst entering the reactor, carry out dealkylation, transalkylation and disproportionation reactions in a fluidized bed state, and are discharged from the top of the reactor to obtain a conversion product; the catalyst deactivated by carbon deposition discharged from the lower part of the reactor enters a regenerator through a lock hopper, and is regenerated by burning carbon with air; the regenerated catalyst enters the reactor through a lock hopper and is recycled.
12. The method according to claim 11, wherein: the regeneration conditions are as follows: the pressure is 0.5 MPa-1.5 MPa, the volume ratio of the gas agent is 200:1-500:1, the roasting is carried out for 0.2-1.0 hour at 400-500 ℃, and the regeneration atmosphere is an oxygen-containing atmosphere, preferably air.
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