CN113171793A - Hydrodealkylation catalyst and preparation method thereof - Google Patents
Hydrodealkylation catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 15
- 238000006900 dealkylation reaction Methods 0.000 abstract description 10
- 229910003294 NiMo Inorganic materials 0.000 abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 7
- 239000008096 xylene Substances 0.000 abstract description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 abstract description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 11
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 9
- 230000020335 dealkylation Effects 0.000 description 8
- 238000006317 isomerization reaction Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000007327 hydrogenolysis reaction Methods 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 transition metal sulfides Chemical class 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- 229910003281 Ni-Mg-Al Inorganic materials 0.000 description 1
- 229910003303 NiAl2O4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 208000031975 Yang Deficiency Diseases 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000002119 pyrolysis Fourier transform infrared spectroscopy Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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Abstract
The invention discloses a micro-mesoporous ZSM-5 loaded NiMo hydrodealkylation catalyst and a preparation method thereof. Firstly, putting HZSM-5 in an alkali liquor according to the liquid-solid ratio of 20-40 mL/g, treating for 0.5-4 h at 50-80 ℃, and obtaining an alkali treatment sample after cooling, washing, filtering and drying. And (3) placing the alkali treatment sample in an ammonium solution according to the solid-to-liquid ratio of 5-15 mL/g, treating at 50-90 ℃ for 2-6 h, and then cooling, washing, filtering, drying and roasting to obtain the primary ammonium exchanged ZSM-5. And performing ammonium exchange, cooling, washing, filtering, drying and roasting on the obtained ZSM-5 to obtain the micro-mesoporous ZSM-5. And tabletting and screening the micro-mesoporous ZSM-5 to obtain the micro-mesoporous ZSM-5 carrier. And loading a metal active component on the micro-mesoporous ZSM-5 carrier, and drying and roasting to obtain the target catalyst. The micro-mesoporous ZSM-5 loaded NiMo catalyst of the invention has higher activity and benzene, toluene and xylene (BTX) selectivity in the hydrogenation dealkylation reaction of trimethylbenzene which is a heavy aromatic hydrocarbon model compound.
Description
Technical Field
The invention relates to a catalyst for hydrodealkylation of heavy aromatics and a preparation method thereof.
Background
With the construction and energy expansion of reforming and ethylene plants, the yield of heavy aromatics is increasing. The mixture of light aromatic benzene, toluene and xylene is a basic raw material for producing rubber, fiber, polyester, detergent, medicine and the like, and the demand is huge. Therefore, the preparation of BTX from heavy aromatics by catalytic hydrodealkylation is the focus of research. Xiaohuan, Zhang Weimin, Majing hong, Li Ruifeng, Petroleum institute (Petroleum processing) 35(2019)369-375) studied the influence of 5 kinds of zeolite catalysts on the conversion performance of 1,3, 5-trimethylbenzene (1,3,5-TMB), and the results show that the pore structure of the zeolite is the main factor influencing the dealkylation performance, the disproportionation reaction of 1,3,5-TMB mainly occurs on the large pore zeolite HMOR, HY and H beta, the isomerization reaction mainly occurs on the medium pore zeolite HEU-1 and HZSM-5, and the dealkylation reaction can be catalyzed by the strong acid center on the surface of HZSM-5. Research on Xiyangyang and the like (Xiyangyang, Bu Tian Tong, Wan Li Cheng, Zhu Wan Chun, Yang xu Wei, Bao Qiang Meng, Cheng Dong, Wang Zheng Lu, chemical bulletin of higher school) (2016)2215 one-fold 2220)Ni/SiO2The result shows that the modulation of Ni particle size can inhibit the side reaction of benzene ring hydrogenation and improve BTX selectivity. Lim et al (Lim D, Jang J, Kim T, Shim S E, Baeck S-H, Journal of Molecular Catalysis A: chemical.407(2015)147-151) study of grain size vs. Pt/HZSM-5C9 +The influence of the hydrodealkylation performance of heavy aromatics shows that Pt/HZSM-5 with the grain size of 5 microns has excellent catalytic performance, and the molecular sieve with the smaller grain size has higher external specific surface area, so that the diffusion rate of macromolecules on the surface of a pore channel is improved. Gao et al (Gao S, ZHai S, Yan J, Wang Z, Wang L, Chemical Engineering)&Technology.38(2015)497-503) investigated the hydrodealkylation performance of 1,2, 4-trimethylbenzene of Ni-Mg-Al mixed oxide, and the results showed uniform distribution of Ni nanoparticles and NiO, NiAl2O4And MgAl2O4The synergistic effect of (a) is a key factor in improving BTX selectivity. Shen Qunbing et al (Shen Q, Zhu X, Dong J, Zhu Z, Catalysis letters.129(2009)170-180) studied different zeolite-loaded NiO (MoO)3) The hydrodealkylation performance of the catalyst shows that the comparative area, acidity and the interaction of the metal oxide and the carrier of the catalyst influence C9 +A key factor of the hydrodealkylation performance of heavy aromatics, HMCM-56 loads NiO (MoO)3) Has better catalytic performance. In the above research works, noble metals, non-noble metals and oxides thereof are used as active components in the catalyst to perform hydrogenation and hydrogenolysis functions, and the research on transition metal sulfides as active components is very little.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a catalyst applied to the hydrodealkylation of heavy aromatics and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hydrodealkylation catalyst comprises the following components in percentage by weight: 84-97% of micro-mesoporous ZSM-5, 2-12% of molybdenum oxide and 0.5-4% of nickel oxide.
Preferably, in the hydrodealkylation catalyst, the mesoporous ZSM-5 is prepared by a method comprising: performing alkali treatment and twice ammonium exchange on the HZSM-5 to obtain micro-mesoporous ZSM-5; the alkali treatment is to place HZSM-5 in an alkali liquor according to a liquid-solid ratio of 20-40 mL/g, treat the HZSM-5 for 0.5-4 h at 50-80 ℃, and then cool, wash, filter and dry a product to obtain an alkali treatment sample; the ammonium exchange is to place an alkali treatment sample in an ammonium solution according to a solid-to-liquid ratio of 5-15 mL/g, treat the sample at 50-90 ℃ for 2-6 h, and then obtain the ammonium exchange through cooling, washing, filtering, drying and roasting.
Preferably, in the above hydrodealkylation catalyst, the base is selected from NaOH, KOH, Na2CO3Or K2CO3The concentration of the alkali solution is 0.05-0.5 mol/L.
Preferably, in the above hydrodealkylation catalyst, the ammonium is selected from NH4NO3Or NH4And Cl, wherein the concentration of the ammonium solution is 0.2-2 mol/L, the drying temperature is 100-140 ℃, the roasting temperature is 350-650 ℃, and the roasting time is 2-7 hours.
Preferably, in the hydrodealkylation catalyst, the HZSM-5 has a silica-alumina ratio of 15 to 60.
A preparation method of a hydrodealkylation catalyst comprises the following steps: the catalyst is prepared by loading micro-mesoporous ZSM-5 with molybdenum and nickel by an impregnation method, loading the molybdenum first and then the nickel, and drying and roasting the molybdenum and the nickel.
Preferably, in the above-mentioned production method: dipping the micro-mesoporous ZSM-5 in an ammonium molybdate solution for 10-30 hours, drying at 100-140 ℃ for 2-6 hours, and roasting at 350-650 ℃ for 2-7 hours to obtain a micro-mesoporous ZSM-5 intermediate containing molybdenum oxide; and soaking the intermediate in a nickel acetate solution, drying at 100-140 ℃ for 2-6 hours, and roasting at 350-650 ℃ for 2-7 hours to obtain the hydrodealkylation catalyst.
Compared with the prior art, the invention has the following beneficial effects:
in the prior art, active components playing hydrogenation and hydrogenolysis functions in the catalyst are mostly noble metals, non-noble metals and oxides thereof, and the invention is characterized in that transition metal sulfide is used as the active component for hydrogenation and hydrogenolysis. In the invention, the alkali treatment and ammonium exchange of the HZSM-5 molecular sieve are crucial, and the appropriate alkali treatment condition can optimize the pore structure of the molecular sieve, ensure the higher crystallinity of the ZSM-5, keep the basic crystal morphology of the ZSM-5, and simultaneously form a certain amount of mesopores in the ZSM-5 molecular sieve, improve the connectivity of the pore channel of the molecular sieve, improve the accessibility of reactant molecules and NiMoS and acid sites in the catalyst, and shorten the diffusion distance of aromatic hydrocarbon molecules in the pore channel, thereby improving the hydrodealkylation performance of the catalyst. The catalyst provided by the invention can be used for hydrodealkylation of heavy aromatics, has the functions of hydrogenation, hydrogenolysis and cracking dealkylation, and has higher dealkylation activity and BTX selectivity compared with the HZSM-5 supported nickel-molybdenum catalyst which is not subjected to alkali treatment and ammonium exchange modification.
Drawings
FIG. 1 is a graph of the relative crystallinity of 4 catalyst supports as a function of time of alkaline treatment;
FIG. 2 is an XRD pattern of 4 catalyst supports and 4 NiMo/ZSM-5 catalysts prepared;
FIG. 3 is an SEM photograph of 4 NiMo/ZSM-5 catalysts;
FIG. 4 is N for 4 NiMo/ZSM-5 catalysts2Adsorption-desorption isotherms and pore size distribution curves.
Detailed Description
Raw material source and analysis method:
HZSM-5(SiO2/Al2O3molar ratio 50): southern kayak university catalyst plant;
1,3, 5-trimethylbenzene (1,3, 5-TMB): aladdin reagents, Inc.;
liquid yield: the mass of the liquid product/the mass of the raw material trimethylbenzene is multiplied by 100 percent;
SiO2/Al2O3the method for measuring the molar ratio and the metal content of the catalyst comprises the following steps: x-ray fluorescence.
The invention is further illustrated, but not limited, by the following examples.
The evaluation of the hydrodealkylation performance of the heavy aromatics of the catalyst is carried out on a miniature pressurized reaction test device, and 1,3,5-TMB is used as a raw material.
Example 1
Alkali treatment: HZSM-5 was placed in 0.2mol/L NaOH aqueous solution at a liquid-solid ratio of 30mL/g, and stirred at 65 ℃ for 1 h. Filtering, washing to be neutral, and drying at 120 ℃ for 4h to obtain an alkali-treated sample. Ammonium exchange: and (3) putting the alkali-treated sample into 1mol/L ammonium chloride solution according to the solid-to-liquid ratio of 10ml/g, stirring for 4h at 70 ℃, filtering and washing a product, drying for 4h at 120 ℃, and roasting for 4h at 550 ℃. And repeating the ammonium exchange step once to obtain the micro-mesoporous ZSM-5, tabletting the micro-mesoporous ZMS-5, and screening to obtain particles of 20-40 meshes serving as the catalyst carrier AKZ-1.
16mL of the solution contained 1.4g of MoO3The obtained solution was used as a dipping solution to dip 20g of AKZ-1, and the solution was allowed to stand at room temperature for 24 hours, dried at 120 ℃ for 4 hours, and calcined at 550 ℃ for 4 hours to obtain Mo/AKZ-1.
The catalyst was obtained by impregnating Mo/AKZ-1 with 16mL of a nickel acetate solution containing 0.33g of NiO as an impregnation solution, allowing to stand at room temperature for 24 hours, drying at 120 ℃ for 4 hours, and calcining at 550 ℃ for 4 hours, and was designated as NiMoAKZ-1. Wherein the content of the organic solvent is AKZ-192 wt%, MoO3 6.5wt％，NiO 1.5wt％。
Example 2
The preparation was carried out in the same manner as in example 1, except that the alkali treatment time was 2 hours during the alkali treatment. The obtained micro-mesoporous ZSM-5 carrier is marked as AKZ-2, and the catalyst is marked as NiMoAKZ-2. The catalyst contains AKZ-292 wt% of MoO3 6.5wt％，NiO 1.5wt％。
Example 3
The preparation was identical to example 1, except that the alkali treatment time was 3h during the alkali treatment. The obtained micro-mesoporous ZSM-5 carrier is marked as AKZ-3, and the catalyst is marked as NiMoAKZ-3. The catalyst contains AKZ-392 wt% of MoO3 6.5wt％，NiO 1.5wt％。
Comparative example 1
The preparation was the same as in example 1, except that no HZSM-5 treatment was performed. HZSM-5 without any treatment was designated as PZ and the catalyst was designated as NiMoPZ. The catalyst contains PZ 92 wt% and MoO3 6.5wt％，NiO 1.5wt％。
Example 4
This example illustrates the use of a catalyst prepared according to the invention with a comparative catalyst in the hydrodealkylation of heavy aromatics.
The catalysts of examples 1-3 and comparative example 1 were each charged into a continuous fixed bed reactor at a catalyst loading of 5.6 g. Subjecting the reactor to N2Blowing for 1h, and then pre-vulcanizing the catalyst, wherein the vulcanizing agent contains 3 wt% of CS2The vulcanization pressure of the n-heptane is 1.0MPa, and the weight hourly space velocity is 2.0h-1，H2The volume ratio of the vulcanizing agent to the vulcanizing agent is 300: 1, the vulcanizing time is 1h at 150 ℃, the vulcanizing time is 1h at 230 ℃, the vulcanizing time is 270 ℃, the vulcanizing time is 320 ℃, and the vulcanizing time is 4h at 360 ℃. The evaluation conditions of the catalyst are that the temperature is 410-530 ℃, the pressure is 1MPa, and the weight hourly space velocity is 2.4h-1，H2The volume ratio of the benzene to the trimethyl benzene is 300: 1. The evaluation results are shown in table 1. In Table 1, the conversion of 1,3,5-TMB (X)1,3,5-TMB) BTX selectivity (S)BTX) Yield of a certain component in the product (Y)i) Liquid product quality yield (Y)Liq) The calculation method of (2) is as follows:
in the formula: n isf(1,3,5-TMB) represents the mole fraction,%, of 1,3,5-TMB in the feed; n isp(1,3,5-TMB)，np(BTX)，np(i) Respectively represents the mole fraction percent of 1,3,5-TMB, BTX and i components in the liquid phase product; m isfAnd mLiqRespectively represent the mass of the starting material and the liquid product, g.
As can be seen from Table 1, the conversion of 1,3,5-TMB, the yield of BTX and the selectivity of BTX on different catalysts are gradually increased with the increase of the reaction temperature, and the increase amplitude is gradually reduced; the yield of the isomerized product is increased and then reduced along with the increase of the temperature, and the yield of the isomerized product is maximum at 440 ℃. The increase of the 1,3,5-TMB conversion rate and the BTX yield is reduced along with the increase of the temperature, on one hand, the coke generated by the condensation of the aromatic hydrocarbon covers the surface of the catalyst along with the reaction, so that the number of active sites is reduced; on the other hand, the 1,3,5-TMB hydrodealkylation reaction is exothermic, the temperature is increased, the chemical equilibrium constant of the reaction is reduced, and the hydrodealkylation reaction is limited. The yield of 1,3,5-TMB isomerization products is increased from 410 ℃ to 440 ℃, because the isomerization reaction rate is increased due to the increase of the temperature; when the temperature is higher than 440 ℃, the yield of the isomerized product is reduced because the isomerization reaction is exothermic, and the increase in the isomerization reaction rate is limited by the thermodynamics of the isomerization reaction.
On NiMo/ZSM-5 with NiMoS centers and acid centers, reactions that may occur with 1,3,5-TMB include dealkylation to produce BTX, isomerization to produce 1,2,4-TMB and 1,2,3-TMB, transalkylation and disproportionation to produce xylene and tetramethylbenzene. It can also be seen from table 1 that the yields of benzene and toluene gradually increased and the yields of xylene decreased first with increasing reaction temperature over the 4 NiMo/ZSM-5 catalysts. This is probably due to the increased reaction temperature, the further dealkylation of the xylenes from the hydrodealkylation of 1,3,5-TMB to benzene and toluene, and the further dealkylation of the toluene to benzene. The liquid product mass yield decreases with increasing reaction temperature, since the dealkylation rate increases with increasing temperature, producing more dealkylated product BTX. It is noted that gaseous products other than H2In addition, it is mainly CH4。
At the reaction temperature of 410-530 ℃, the 1,3,5-TMB conversion rate, BTX yield and selectivity of 4 catalysts are all in the following sequence from large to small: NiMoAKZ-2 > NiMoAKZ-3 > NiMoAKZ-1 > NiMoPZ. From the viewpoints of high 1,3,5-TMB conversion, high BTX yield and selectivity, the catalyst with superior hydrodealkylation performance is NiMoAKZ-2, and at a reaction temperature of 530 ℃, the 1,3,5-TMB conversion, the BTX yield and the selectivity are 91.5%, 65.3% and 71.3%, respectively.
TABLE 1 hydrodealkylation Performance of the catalyst at different temperatures for 1,3,5-TMB
XRD (figures 1 and 2) and SEM (figure 3) results show that alkali treatment on HZSM-51-3 h removes partial silicon-aluminum species, defects are formed in crystal lattices, the crystallinity is reduced, the framework of ZSM-5 is not completely damaged, and the crystal morphology of ZSM-5 is basically maintained. N is a radical of2The adsorption-desorption (fig. 4 and table 2) and Py-FTIR (table 3) results show that NiMoAKZ-2 and NiMoAKZ-3 have a larger total specific surface area, a larger mesopore specific surface area and more mesopores, while having a lower acid amount, compared to NiMoAKZ and NiMoAKZ-1. When the reaction temperature is 410-530 ℃, the hydrodealkylation performance of NiMoAKZ-2 and NiMoAKZ-3 is superior to that of NiMoPZ and NiMoAKZ-1, probably because the accessibility of 1,3,5-TMB with surface NiMoS and acid sites is improved due to the existence of mesopores in the first two catalysts, and the diffusion performance of product molecules is improved. The reason why the hydrodealkylation performance of NiMoAKZ-2 is better than that of NiMoAKZ-3 is probably that more non-framework aluminum species exist on the surface of NiMoAKZ-3 compared with NiMoAKZ-2, the penetration of the pore channel is poor, and the diffusion of 1,3,5-TMB and product molecules in the pore channel is unfavorable. Compared with NiMoPZ, the 1,3,5-TMB hydrogenation dealkylation performance of NiMoAKZ-1 is better, and the accessibility of the 1,3,5-TMB and the acid site on the surface of the catalyst is improved because amorphous silica-alumina species on the surface of the NiMoAKZ-1 are removed.
TABLE 2 pore Structure parameters for 4 NiMo/ZSM-5 catalysts
TABLE 3 acid Properties of 4 NiMo/ZSM-5 catalysts
Claims (7)
1. A hydrodealkylation catalyst is characterized by comprising the following components in percentage by weight: 84-97% of micro-mesoporous ZSM-5, 2-12% of molybdenum oxide and 0.5-4% of nickel oxide.
2. The hydrodealkylation catalyst according to claim 1, wherein the micro-mesoporous ZSM-5 is prepared by a method comprising: performing alkali treatment and twice ammonium exchange on the HZSM-5 to obtain micro-mesoporous ZSM-5; the alkali treatment is to place HZSM-5 in an alkali liquor according to a liquid-solid ratio of 20-40 mL/g, treat the HZSM-5 for 0.5-4 h at 50-80 ℃, and then cool, wash, filter and dry a product to obtain an alkali treatment sample; the ammonium exchange is to place an alkali treatment sample in an ammonium solution according to a solid-to-liquid ratio of 5-15 mL/g, treat the sample at 50-90 ℃ for 2-6 h, and then obtain the ammonium exchange through cooling, washing, filtering, drying and roasting.
3. The hydrodealkylation catalyst according to claim 1, characterized in that: the alkali is selected from NaOH, KOH and Na2CO3Or K2CO3The concentration of the alkali solution is 0.05-0.5 mol/L.
4. The hydrodealkylation catalyst according to claim 1, characterized in that: the ammonium is selected from NH4NO3Or NH4And Cl, wherein the concentration of the ammonium solution is 0.2-2 mol/L, the drying temperature is 100-140 ℃, the roasting temperature is 350-650 ℃, and the roasting time is 2-7 hours.
5. The hydrodealkylation catalyst according to claim 1, characterized in that: the silicon-aluminum ratio of the HZSM-5 is 15-60.
6. A process for the preparation of the hydrodealkylation catalyst according to claim 1, characterized by comprising the steps of: the catalyst is prepared by loading micro-mesoporous ZSM-5 with molybdenum and nickel by an impregnation method, loading the molybdenum first and then the nickel, and drying and roasting the molybdenum and the nickel.
7. The method of claim 5, wherein: dipping the micro-mesoporous ZSM-5 in an ammonium molybdate solution for 10-30 hours, drying at 100-140 ℃ for 2-6 hours, and roasting at 350-650 ℃ for 2-7 hours to obtain a micro-mesoporous ZSM-5 intermediate containing molybdenum oxide; and soaking the intermediate in a nickel acetate solution, drying at 100-140 ℃ for 2-6 hours, and roasting at 350-650 ℃ for 2-7 hours to obtain the hydrodealkylation catalyst.
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