CN117943110A - Hydrogenation catalyst, preparation method thereof and method for preparing BTX (benzene-toluene-xylene) from refined light aromatic-rich distillate oil - Google Patents
Hydrogenation catalyst, preparation method thereof and method for preparing BTX (benzene-toluene-xylene) from refined light aromatic-rich distillate oil Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 165
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 38
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- IHICGCFKGWYHSF-UHFFFAOYSA-N C1=CC=CC=C1.CC1=CC=CC=C1.CC1=CC=CC=C1C Chemical group C1=CC=CC=C1.CC1=CC=CC=C1.CC1=CC=CC=C1C IHICGCFKGWYHSF-UHFFFAOYSA-N 0.000 title description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 230000008021 deposition Effects 0.000 claims abstract description 20
- 238000000197 pyrolysis Methods 0.000 claims abstract description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010457 zeolite Substances 0.000 claims abstract description 18
- 239000000853 adhesive Substances 0.000 claims abstract description 11
- 230000001070 adhesive effect Effects 0.000 claims abstract description 11
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 11
- 238000007670 refining Methods 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 73
- 239000002131 composite material Substances 0.000 claims description 67
- 239000001257 hydrogen Substances 0.000 claims description 62
- 229910052739 hydrogen Inorganic materials 0.000 claims description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 58
- 239000000843 powder Substances 0.000 claims description 56
- 239000012298 atmosphere Substances 0.000 claims description 54
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 48
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 31
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 30
- 229910052593 corundum Inorganic materials 0.000 claims description 30
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 30
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 26
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 25
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 24
- 230000002378 acidificating effect Effects 0.000 claims description 20
- 235000010323 ascorbic acid Nutrition 0.000 claims description 19
- 229960005070 ascorbic acid Drugs 0.000 claims description 19
- 239000011668 ascorbic acid Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 15
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 15
- 238000004898 kneading Methods 0.000 claims description 15
- 229920000609 methyl cellulose Polymers 0.000 claims description 15
- 239000001923 methylcellulose Substances 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002738 chelating agent Substances 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- -1 rare earth nitrate Chemical class 0.000 claims description 6
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052773 Promethium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
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- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
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- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- IGNDJILOHLZCPF-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid;sodium Chemical compound [Na].OCC(P(O)(O)=O)P(O)(O)=O IGNDJILOHLZCPF-UHFFFAOYSA-N 0.000 claims 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 43
- 238000011156 evaluation Methods 0.000 description 29
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- 239000002808 molecular sieve Substances 0.000 description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 24
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005336 cracking Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
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- 239000005977 Ethylene Substances 0.000 description 3
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- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
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- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Catalysts (AREA)
Abstract
The invention relates to the field of hydrotreatment, in particular to a hydrogenation catalyst, a preparation method thereof and a method for preparing a BTX catalyst by refining light aromatic-rich distillate oil with high stability. The catalyst comprises the following components: a) 5.00% -20.00% Ni; b) 0.01% -5.00% rare earth metal oxide; c) 50.00% -84.99% ZSM-5; d) 5.00% -39.99% of beta zeolite; e) 5.00 to 20.00 percent of adhesive; the carbon deposition amount of the catalyst is 0.1-5% of the weight of the catalyst. The hydrogenation catalyst provided by the invention has high stability and long catalyst operation period. The hydrogenation catalyst provided by the invention is used for preparing BTX from the high-stability refined light aromatic-rich distillate oil, so that the problem that the refined light aromatic-rich pyrolysis distillate oil cannot be used with high added value is solved, and the low-added value light aromatic-rich pyrolysis distillate oil is converted into BTX with high added value efficiently.
Description
Technical Field
The invention relates to the field of hydrotreatment, in particular to a hydrogenation catalyst, a preparation method thereof and a method for preparing a BTX catalyst by refining light aromatic-rich distillate oil with high stability.
Background
The aromatic-rich pyrolysis distillate oil is a product of high-temperature condensation of raw materials and products of ethylene pyrolysis raw materials in the steam pyrolysis process, and mainly comes from a quenching oil tower kettle and a heavy fuel oil stripping tower kettle. The aromatic-rich pyrolysis distillate is a heavy distillate (higher than 205 ℃) rich in aromatic hydrocarbons (the aromatic hydrocarbon content is higher than 90%), the main components of the aromatic-rich pyrolysis distillate are monocyclic and polycyclic aromatic hydrocarbon compounds, the side chains are short, the hydrocarbon ratio is high, the heavy metal and ash content is low, and meanwhile, the oil also contains N, S, O and other heterocyclic compounds.
The aromatic-rich pyrolysis distillate oil has higher yield in each distillation section at 170-300 ℃ and is secondarily super heavy colloid asphaltene component. Meanwhile, the aromatic-rich pyrolysis distillate oil has high sulfur content, high content of polycyclic aromatic hydrocarbon and high density. The main components of the distillation section with the initial distillation point of 205 ℃ to 205 ℃ are indene and homologs thereof, the fraction with the temperature of 205 ℃ to 225 ℃ is naphthalene, the fraction with the temperature of 225 ℃ to 245 ℃ is mainly methylnaphthalene, the fraction with the temperature of 245 ℃ to 300 ℃ is mainly dimethylnaphthalene, the fraction with the temperature of 300 ℃ to 360 ℃ contains a large amount of anthracenes, acenaphthenes, phenanthrenes and the like, and the substances with the temperature of >360 ℃ are colloid and asphaltene with high hydrocarbon ratio; wherein the naphthalene and the above polycyclic aromatic hydrocarbon account for more than 60 percent.
The aromatic-rich pyrolysis distillate is mainly used as a raw material for producing carbon black. There are also many industries beginning to produce aromatic hydrocarbon solvent oils from pyrolysis fuel oils, and major manufacturers are the U.S. Exxon, netherlands Shell, japan Bolus Petroleum, and so on.
The cracking C9 fraction is also an aromatic-rich cracking distillate oil, and is mainly derived from cracking gasoline C9 fraction separated after passing through a BTX tower, wherein the aromatic hydrocarbon content is up to more than 70 percent (the aromatic hydrocarbon content is more than 90 percent after dicyclopentadiene is extracted), and the aromatic hydrocarbon content accounts for 11-22 percent of the ethylene yield.
How to use the low added value aromatic-rich pyrolysis distillate is an urgent problem to be solved by petrochemical technology workers. Benzene (B), toluene (T) and xylene (X) are important basic organic chemical raw materials, are widely used for producing products such as polyester, chemical fiber and the like, are closely related to national economic development and people's clothing and eating activities, and have strong demands and rapid increment in recent years. Considering the abundant arene resources in ethylene tar and cracking C9, how to convert low-added value aromatic-rich cracking distillate oil into BTX by a catalytic conversion technology is a great opportunity and challenge.
In the field of hydrotreating of aromatic-rich distillate, the hydrotreating technology of catalytic cracking raw materials has been industrially applied since the 70 s of the 20 th century, and has been applied to many refineries for processing sulfur-containing or high sulfur crude oil. At present, a mature catalytic cracking raw material pretreatment technology is already owned, and mainly comprises the following steps: VGO Unionfining from UOP company and APCU (partial conversion hydrocracking) technology, haldorAroshift technology from company, VGO Hydrotreating technology from Chevron company, VGO Hydrodesulfurization technology from Exxon company, T-star technology from IFP company, MAKFINGING technology from Mobil, AKZO, kellogg, etc. In order to further improve the product quality and conversion rate, the catalytic raw material hydrogenation pretreatment process is gradually changed from the traditional hydrodesulfurization refining (HDS) to the Mild Hydrocracking (MHC) to improve the denitrification, carbon residue and polycyclic aromatic hydrocarbon saturation capacity.
In summary, the prior art generally adopts the processes of hydrogenation saturation and hydrocracking, which has high hydrogen consumption for the aromatic hydrocarbon-rich pyrolysis distillate oil with the aromatic hydrocarbon content of more than 90 percent, and wastes valuable aromatic hydrocarbon resources. Some technologies, such as CN102234539A, are also used for hydrocracking after the aromatic hydrocarbon in the aromatic-rich oil is completely saturated, so that gasoline and diesel oil are produced, the production cost is high, and the economy is not realized.
Based on the technologies of distillate Hydrodesulfurization (HDS), denitrification (HDN) and the like, optimization and innovation are carried out, and benzene (B), toluene (T) and xylene (X) are produced to the maximum extent through means of hydro-upgrading, cracking, transalkylation and the like, so that the refined light aromatic-rich distillate oil can be fully utilized to prepare and improve the added value of the distillate oil.
Disclosure of Invention
Aiming at the problems of low BTX yield and low catalyst stability in the high value-added chemical utilization of refined light aromatic-rich pyrolysis distillate oil in the prior art, the invention provides a novel hydrogenation catalyst which is used for preparing BTX from the refined light aromatic-rich distillate oil with high stability and has excellent stability.
To achieve the foregoing object, according to a first aspect of the present invention, there is provided a hydrogenation catalyst comprising the following components:
a)5.00％～20.00％Ni；
b) 0.01% -5.00% rare earth metal oxide;
c)50.00％～84.99％ZSM-5；
d) 5.00% -39.99% of beta zeolite;
e) 5.00 to 20.00 percent of adhesive;
The carbon deposition characteristics of the catalyst include: the carbon deposition amount of the catalyst is 0.1-5% of the weight of the catalyst.
According to a second aspect of the present invention, there is provided a process for preparing the catalyst of the present invention, wherein the process comprises:
i) Preparing a rare earth metal oxide modified composite carrier containing ZSM-5, beta zeolite and a binder;
ii) preparing an impregnating solution containing a chelating agent, ascorbic acid and a Ni source;
iii) The impregnating solution is in impregnating contact with the composite carrier, then aged, then the solid is dried under inert atmosphere, baked under low oxygen-containing inert atmosphere, and then reduced;
the oxygen content in the low oxygen-containing inert atmosphere is less than 10% by volume, preferably less than 5% by volume.
According to a third aspect of the invention, the invention provides a method for preparing BTX from high-stability refined light aromatic-rich distillate oil, which comprises the following steps: and (3) hydrogenating the refined aromatic-rich light pyrolysis distillate oil under hydrogenation reaction conditions in the presence of a catalyst, wherein the catalyst contains the hydrogenation catalyst.
Compared with the prior art, the invention has the beneficial effects that:
The hydrogenation catalyst provided by the invention has high stability.
According to the preparation method of the hydrogenation catalyst, rare earth metal is added into the carrier, the chelating agent and the ascorbic acid are added in the impregnation process, the carrier is dried in the inert atmosphere and roasted in the low-oxygen-content inert atmosphere, meanwhile, the reduction temperature of the catalyst TPR hydrogen atmosphere is reduced, the stability of the catalyst is strong, the operation period of the catalyst is long, and the BTX yield is high.
The hydrogenation catalyst provided by the invention is used for preparing BTX from high-stability refined light aromatic-rich distillate oil, so that the problem that the refined light aromatic-rich pyrolysis distillate oil cannot be used with high added value is solved, the low-added value light aromatic-rich pyrolysis distillate oil is converted into high-added value BTX with high efficiency, for the initial distillation point of 85-170 ℃, the final distillation point of 220-280 ℃, the total aromatic hydrocarbon content is more than 90 percent, the sulfur content is less than 50ug/mL, and the nitrogen content is less than 10ug/mL; the hydrogenation reaction conditions are as follows: the inlet temperature of the reactor is 380-480 ℃, the fresh feeding airspeed is 0.6-4.0 h -1, the hydrogen-oil volume ratio is 500-2000, the yield of the total liquid phase product of the initial hydrogenation product is more than 80%, the yield of the BTX of the liquid phase product is more than 58%, the catalyst activity is reduced little in 2000 hours on line, the yield of the total liquid phase product is more than 80%, and the yield of the BTX of the liquid phase product is more than 55% under the pressure of 2-8 MPa, so that a better technical effect is obtained.
Drawings
FIG. 1 is an XRD pattern of a composite support and hydrogenation catalyst according to example 1 of the present invention;
FIG. 2 is a temperature programmed reduction TPR map of the hydrogenation catalyst of example 1 of the present invention;
FIG. 3 is a plot of distribution versus time on line for the results of evaluation of the hydrogenation catalyst of example 1 of this invention;
FIG. 4 is an XRD pattern of the composite support and hydrogenation catalyst of example 2 of the present invention;
FIG. 5 is a temperature programmed reduction TPR map of the hydrogenation catalyst of example 2 of the present invention;
FIG. 6 is a temperature programmed reduction TPR map of the catalyst of comparative example 1 of the present invention;
FIG. 7 is a graph showing the distribution of the products of the evaluation results of comparative example 1 of the present invention versus the on-line time;
FIG. 8 is a temperature programmed reduction TPR map of the catalyst of comparative example 2 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a hydrogenation catalyst, which comprises the following components:
a)5.00％～20.00％Ni；
b) 0.01% -5.00% rare earth metal oxide;
c)50.00％～84.99％ZSM-5；
d) 5.00% -39.99% of beta zeolite;
e) 5.00 to 20.00 percent of adhesive;
the carbon deposition amount of the catalyst is 0.1-5% of the weight of the catalyst. The hydrogenation catalyst provided by the invention has high stability. In the invention, the test method of the carbon deposition characteristic of the catalyst is a thermogravimetric analysis method.
According to a preferred embodiment of the invention, the dispersity of the active ingredient Ni is preferably greater than 8%, preferably between 9% and 20%.
In the present invention, rare earth metals may be used in the present invention, and preferably, the rare earth metals are one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu), preferably, one or more of cerium, lanthanum, praseodymium, europium and neodymium, according to a preferred embodiment of the present invention.
In the present invention, the optional range of the binder is wide, and common binders may be used in the present invention, and for the present invention, the binder may be selected from silica and/or alumina, for example.
According to a preferred embodiment of the present invention, the catalyst comprises, by weight, 10% to 15% of Ni, 0.01% to 3.0% of rare earth oxide, 55.00% to 75.50% of ZSM-5, 6.00% to 26.50% of zeolite beta, and 8% to 15% of binder.
According to a preferred embodiment of the present invention, the catalyst comprises, by weight, 10% to 15% Ni, 0.01% to 3.0% CeO 2, 8% to 15% binder, 55.00% to 75.50% ZSM-5, and 6.00% to 26.50% zeolite beta.
The catalyst having the aforementioned characteristics of the present invention can be used in the present invention, and there is no special requirement for the preparation method of the catalyst, and for the present invention, the preparation method of the catalyst is preferably selected to include:
i) Preparing a rare earth metal oxide modified composite carrier containing ZSM-5, beta zeolite and a binder;
ii) preparing an impregnating solution containing a chelating agent, ascorbic acid and a Ni source;
iii) The impregnating solution is in impregnating contact with the composite carrier, then aged, then the solid is dried under inert atmosphere, baked under low oxygen-containing inert atmosphere, and then reduced;
The oxygen content in the low oxygen-containing inert atmosphere is less than 10% by volume, preferably less than 5% by volume.
According to the preparation method of the hydrogenation catalyst, rare earth metal is added into the carrier, the chelating agent and the ascorbic acid are added in the impregnation process, the carrier is dried in the inert atmosphere and roasted in the low-oxygen-content inert atmosphere, meanwhile, the reduction temperature of the catalyst TPR hydrogen atmosphere is reduced, the stability of the catalyst is strong, the operation period of the catalyst is long, and the BTX yield is high.
In the present invention, the conditions of the impregnation contact are wide in optional range, and according to a preferred embodiment of the present invention, the impregnation temperature is 10 to 80 ℃.
The invention has no special requirement on the dipping contact mode, various dipping contact modes can be adopted, and the composite carrier is dipped by adopting a spraying method according to the preferred embodiment of the invention.
In the present invention, aging is a period of time after immersion contact, and according to a preferred embodiment of the present invention, the aging time is 0.5 to 24 hours.
In the present invention, the optional range of the drying conditions is wide, and the conventional drying conditions can be used in the present invention, and the drying temperature is preferably 30 to 200 ℃.
In the present invention, the conditions for firing are wide in optional range, and preferred conditions for firing for the present invention include: the temperature is 300-600 ℃, the roasting time is determined according to the requirement, and for the invention, the roasting time is preferably 0.5-24 h.
In the present invention, the conditions for reduction are wide in the optional range, and preferable conditions for reduction for the present invention include: the temperature of the reduction peak of the TPR hydrogen atmosphere of the catalyst before reduction is lower than 390 ℃.
The reduction temperature of the TPR hydrogen atmosphere is lower than 390 ℃.
In the present invention, the dry inert atmosphere may be various inert gas atmospheres, and for the present invention, it is preferable that the dry inert atmosphere is one or more of a nitrogen atmosphere and an argon atmosphere, and it is preferable that the dry inert atmosphere is a nitrogen atmosphere.
In the invention, the oxygen content in the calcined oxygen-containing inert atmosphere is preferably 0.1 to 5 volume percent, and the inert gas content is preferably 95 to 99.9 volume percent; inert gases may be used in the present invention, and for the present invention, preferably, the inert gas is one or more of nitrogen and argon.
In the present invention, the type of the chelating agent is widely selected, and for the present invention, the chelating agent is preferably selected from one or more of 1-hydroxyethylidene-1, 1-diphosphonic acid, tetrasodium hydroxyethylidene diphosphonate (HEDP tetrasodium), aminotrimethylene phosphonic acid (ATMPA), ethylenediamine tetramethylene phosphoric acid (EDTMP), preferably 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDPA) and/or tetrasodium hydroxyethylidene diphosphonate (HEDP tetrasodium).
In the present invention, the composition of the impregnating solution may be selected within a wide range, and it is preferable for the present invention that the chelating agent content be 0.01 to 5 g per 100 ml of the impregnating solution.
According to a preferred embodiment of the invention, the content of ascorbic acid is 0.2 to 5g per 100 ml of impregnation fluid.
According to a preferred embodiment of the invention, the immersion contact is an equal volume immersion contact.
In the present invention, the preparation method of the composite carrier is not particularly required, and according to the preferred embodiment of the present invention, the preparation method of the composite carrier includes:
(1) Uniformly mixing an adhesive source, ZSM-5 powder, beta zeolite powder and an auxiliary agent to obtain a mixture I;
(2) Adding the mixture I into an acidic aqueous solution, wherein the acidic aqueous solution contains rare earth nitrate; kneading, shaping, drying and calcining.
According to a preferred embodiment of the present invention, the preparation method of the composite carrier comprises: (1) Firstly, uniformly mixing an adhesive, ZSM-5 powder, beta zeolite powder and an auxiliary agent to obtain a mixture I; (2) Adding the mixture I into an acidic aqueous solution with the weight percentage of 1-6%, wherein the acidic aqueous solution contains nitrate containing rare earth, the weight ratio of the mixture I to the acidic aqueous solution is 100:5-100:75, kneading, extrusion molding, drying, and roasting at 450-650 ℃ for 0.5-24 h to obtain the catalyst composite carrier.
According to the preferred embodiment of the invention, preferably, the adhesive is added with the weight ratio of 1 of adhesive, ZSM-5 powder, beta zeolite powder and auxiliary agent in terms of alumina: (3-10): (0.4-3.5): (0.1-0.4).
According to a preferred embodiment of the present invention, the acidic aqueous solution preferably further contains an alkaline earth nitrate. The rare earth nitrate is calculated by rare earth oxide, the alkaline earth nitrate is calculated by alkaline earth oxide, and the acidic aqueous solution contains 1-6% of acidic aqueous solution, 1-5% of rare earth oxide and 1-2% of alkaline earth oxide by weight percent.
According to a preferred embodiment of the present invention, the conditions of calcination include: the temperature is 450-650 ℃ and the time is 0.5-24 h.
In the invention, ZSM-5 powder and beta zeolite powder can be used in the invention, and the preferred ZSM-5 powder is hydrogen type and the SiO 2/Al2O3 mol ratio is 50-300.
According to a preferred embodiment of the invention, the beta zeolite powder is in the hydrogen form and the SiO 2/Al2O3 molar ratio is 20-200.
In the present invention, the type of the binder source may be selected from a wide range, and a common binder source may be used in the present invention, and for the present invention, it is preferable that the binder source is at least one selected from silica sol, water glass, pseudo-boehmite, white carbon black, and alumina sol.
In the present invention, the optional range of the kinds of the auxiliary agents is wide, and common auxiliary agents can be used in the present invention, and for the present invention, it is preferable that the auxiliary agent is at least one selected from methylcellulose, sesbania powder, polyethylene glycol, calcium nitrate, potassium nitrate and hydroxymethyl cellulose.
In the present invention, the variety of the acidic aqueous solution is wide in the optional range, and the acidic aqueous solution which is commonly used can be used in the present invention, and for the present invention, it is preferable that the acidic substance in the acidic aqueous solution is at least one selected from nitric acid, phosphoric acid, acetic acid, citric acid and tartaric acid.
According to a preferred embodiment of the present invention, the ZSM-5 powder is in the hydrogen form, siO 2/Al2O3 is in the range of 50 to 300, the zeolite beta powder is in the hydrogen form, and SiO 2/Al2O3 is in the range of 20 to 200; the adhesive is at least one selected from silica sol, water glass, pseudo-boehmite, white carbon black and alumina sol; the auxiliary agent is at least one selected from methylcellulose, sesbania powder, polyethylene glycol, calcium nitrate, potassium nitrate and hydroxymethyl cellulose.
According to a preferred embodiment of the present invention, the acidic aqueous solution is selected from at least one of nitric acid, phosphoric acid, acetic acid, citric acid, tartaric acid.
According to a preferred embodiment of the present invention, an equivalent volume impregnation method is used to prepare an impregnation solution from a soluble metal salt precursor containing the desired amount of Ni, and a chelating agent and ascorbic acid are added; the chelating agent accounts for 0.01-5% of the weight of the impregnating solution, and the ascorbic acid accounts for 0.2-5% of the weight of the impregnating solution.
According to a preferred embodiment of the invention, the catalyst is prepared by adopting an isovolumetric impregnation method, the impregnation temperature is 10-80 ℃, the impregnation method is adopted to impregnate the composite carrier, the impregnation method is placed for 0.5-24 h, the impregnation method is dried at 30-200 ℃, and the roasting is carried out at 300-600 ℃ for 0.5-24 h to obtain the finished catalyst, wherein the TPR hydrogen atmosphere reduction temperature of the catalyst is lower than 390 ℃, and the dispersity of the active component Ni is more than 8.0%, preferably 9-20%.
According to a preferred embodiment of the present invention, the catalyst of the present invention is further reduced in a hydrogen atmosphere at 200-600 ℃ for 12-72 hours to obtain a reduced catalyst.
The invention provides a method for preparing BTX by refining light aromatic-rich distillate oil with high stability, which comprises the following steps: and (3) hydrogenating the refined aromatic-rich light pyrolysis distillate oil under hydrogenation reaction conditions in the presence of a catalyst, wherein the catalyst contains the hydrogenation catalyst.
According to a preferred embodiment of the present invention, preferably, the aromatic-rich light cracked distillate is refined: the initial distillation point is 85-170 ℃, the final distillation point is 220-280 ℃, the sulfur content is less than 50ug/mL, and the nitrogen content is less than 10ug/mL; the content of monocyclic aromatic hydrocarbon is more than 90wt%.
According to a preferred embodiment of the present invention, the hydrogenation reaction conditions include: the inlet temperature of the reactor is 380-480 ℃, the fresh feeding airspeed is 0.6-4.0 h -1, the hydrogen-oil volume ratio is 500-2000, and the pressure is 2-8 MPa.
According to a preferred embodiment of the invention, the aromatic-rich light cracked distillate is refined: the initial boiling point is 85-170 ℃, the final boiling point is 220-280 ℃, and the raw materials consist of: sulfur content <50ug/mL, nitrogen content <10ug/mL; the content of monocyclic aromatic hydrocarbon is more than 90wt%; the hydrogenation reaction conditions are as follows: the inlet temperature of the reactor is 380-480 ℃, the fresh feeding airspeed is 0.6-4.0 h -1, the hydrogen-oil volume ratio is 500-2000, the yield of the total liquid phase product of the initial hydrogenation product is more than 80% and the yield of the BTX of the liquid phase product is more than 58% under the pressure of 2-8 MPa.
According to a preferred embodiment of the invention, the catalyst is stable in operation, for refined light aromatic-rich pyrolysis distillate with a final distillation point of 220-280 ℃ and a total aromatic content of greater than 90%, the catalyst activity drops by less than 10% and the yield of the total liquid phase product is greater than 80% in 2000 hours on line, wherein the BTX yield of the liquid phase product is greater than 55%.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In the invention, the dispersity test method of the active component Ni is an oxyhydrogen titration method.
Wherein: dispersity of R- - - -Ni;
[ Ni ] - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -;
ni Total (S) - -total nickel atoms;
V 0 - -titration amount of hydrogen, mL;
N A - - -Avofacil constant (6.023) x 10 23;
w- -pattern mass, g;
p- -the mass fraction of nickel in the form,%;
M- -atomic weight of nickel 58.7.
In the invention, the test method of TPR hydrogen atmosphere reduction is an oxyhydrogen titration method.
In the invention, the liquid phase product yield is calculated by the following steps:
Liquid phase product yield = W Liquid product /W Raw materials ,
W Liquid product - -weight of liquid phase reaction product in line for 24 hours, g;
W Raw materials - -on-line 24 hours refining the feed of light aromatic-rich pyrolysis distillate feedstock, grams.
In the invention, the temperature of the active component Ni reduction peak is measured by adopting a TPR temperature programming reduction method, hydrogen atmosphere is adopted for reduction, the temperature rising rate is 10 ℃/min, and the temperature is increased to 900 ℃.
The carbon deposition was measured by using a MultiEA 2000 carbon sulfur instrument from Yena Germany, the catalyst was dried at a constant temperature of 50℃for 2 hours, and then tested at a combustion temperature of 900℃with a carrier gas of 99.995% purity in oxygen. The standard substance adopts spectral pure CaCO powder, and the mass fraction of carbon is 12.00%.
[ Example 1]
600 G of ZSM-5 molecular sieve powder with 130 of hydrogen type SiO 2/Al2O3, 150 g of beta molecular sieve powder with 40 of hydrogen type SiO 2/Al2O3, and 15 g of pseudo-boehmite containing 100g of alumina, and methyl cellulose and sesbania powder are uniformly mixed for standby; then adding 7 g of nitric acid and 5g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 10 g of cerium oxide and calcium nitrate containing 8g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding strips to form, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake for 5 hours at 600 ℃ to obtain the composite carrier, wherein the water absorption rate is 99.1%.
Preparing an impregnating solution containing 28 g of Ni by using a soluble metal salt precursor, controlling the volume of the solution to 170 ml, adding 1.5 g of 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDPA) and 2.0 g of ascorbic acid into the impregnating solution, stirring and dissolving uniformly, taking 172 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a pot-rotating spraying method, ageing for 16 hours at the impregnating temperature of 40 ℃, drying for 4 hours at 110 ℃ in a nitrogen atmosphere, roasting for 6 hours at 400 ℃ in a nitrogen atmosphere containing 1.0% of oxygen, and obtaining the catalyst, and reducing for 48 hours in a hydrogen atmosphere at 400 ℃ to obtain the reduction catalyst. The composite carrier, the catalyst preparation conditions and the carbon deposition amount of the catalyst are shown in tables 1, 2 and 3.
The XRD patterns of the composite carrier and the catalyst are shown in figure 1, and figure 1 shows that the carrier does not show characteristic peaks of the active components after loading the active components, so that the particle size of the active components on the carrier is small, and the dispersing effect is good; the temperature programmed reduction TPR spectrum of the catalyst is shown in figure 2, and the peak value of the reduction temperature of the active component in the hydrogen atmosphere is 365 ℃ as can be seen from figure 2. The dispersity of the Ni of the reduction catalyst is 17.6%, which indicates that the dispersion of the active component is good, the reduction is easy, and the activity of the catalyst is high.
Evaluation of raw materials: refining a light aromatic-rich cracking raw material: the distillation range is 165-255 ℃, the sulfur content is=0.8 ppm, and the nitrogen content is=0.6 ppm;
The raw materials comprise: 3.81wt% of non-aromatic; 40.57% by weight of alkylbenzene; 23.76wt% of indanes;
29.25wt% of tetrahydronaphthalene; 2.30wt% of naphthalene; benzene 0.31wt%.
Reaction conditions: the inlet temperature of the reactor is 410 ℃, the space velocity of fresh feed is 1.8h -1, the hydrogen-oil volume ratio is 800, and the pressure is 4.0MPa.
The evaluation results are shown in Table 4, the distribution-on-line time chart of the evaluation results of the hydrogenation catalyst is shown in FIG. 3, and FIG. 3 shows that the catalyst has good stability and high BTX yield.
[ Example 2]
630 G of ZSM-5 molecular sieve powder with the hydrogen type SiO 2/Al2O3 of 200 and 120 g of beta molecular sieve powder with the hydrogen type SiO 2/Al2O3 of 20 are selected, and 15 g of pseudo-boehmite containing 100g of alumina, methylcellulose and sesbania powder are uniformly mixed for standby; then adding 7g of nitric acid and 5g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 10 g of cerium oxide and calcium nitrate containing 8g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding strips to form, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake for 5 hours at 600 ℃ to obtain the composite carrier, wherein the water absorption rate is 100.3%.
Preparing an impregnating solution containing 28 g of Ni by using a soluble metal salt precursor, controlling the volume of the solution to 170 ml, adding 1.3 g of 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDPA) and 2.5 g of ascorbic acid into the impregnating solution, stirring and dissolving uniformly, taking 172 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a pot-rotating spraying method, carrying out ageing for 16 hours at the impregnating temperature of 60 ℃, drying for 4 hours at 110 ℃ in a nitrogen atmosphere, roasting for 6 hours at 400 ℃ in a nitrogen atmosphere containing 2.0% of oxygen, and obtaining the catalyst, and carrying out hydrogen atmosphere reduction for 48 hours at 400 ℃ to obtain the reduction catalyst. The composite carrier, the catalyst preparation conditions and the carbon deposition amount of the catalyst are shown in tables 1, 2 and 3.
The XRD patterns of the composite carrier and the catalyst are shown in figure 4, and figure 4 shows that the carrier does not show characteristic peaks of the active components after loading the active components, so that the particle size of the active components on the carrier is small, and the dispersing effect is good; the temperature programming reduction TPR map of the catalyst is shown in figure 5. It can be seen from fig. 5 that the peak reduction temperature of the active component under the hydrogen atmosphere is 368 ℃. The dispersity of the Ni of the reduction catalyst is 16.3%, which indicates that the dispersion of the active component is good, the reduction is easy, and the activity of the catalyst is high.
The evaluation materials and conditions were the same as in example 1, and the evaluation results are shown in Table 4.
[ Example 3]
600 G of ZSM-5 molecular sieve powder with 130 of hydrogen type SiO 2/Al2O3, 150 g of beta molecular sieve powder with 40 of hydrogen type SiO 2/Al2O3, and 15 g of pseudo-boehmite containing 100g of alumina, and methyl cellulose and sesbania powder are uniformly mixed for standby; then adding 7 g of nitric acid and 5g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 10 g of cerium oxide and calcium nitrate containing 8g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding strips to form, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake for 5 hours at 600 ℃ to obtain the composite carrier, wherein the water absorption rate is 99.1%.
Preparing an impregnating solution containing 28 g of Ni by using a soluble metal salt precursor, controlling the volume of the solution to 170 ml, adding 1.5 g of 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDPA) into the impregnating solution, stirring and dissolving uniformly, taking 172 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a pot-rotating spraying method, ageing for 16 hours at the impregnating temperature of 40 ℃, drying for 4 hours at 110 ℃ in a nitrogen atmosphere, roasting for 6 hours at 400 ℃ in a nitrogen atmosphere containing 1.0% of oxygen, and obtaining the catalyst, and reducing for 48 hours in a hydrogen atmosphere at 400 ℃ to obtain the reduction catalyst. The composite carrier, the catalyst preparation conditions and the carbon deposition amount of the catalyst are shown in tables 1, 2 and 3.
The peak reduction temperature of the active component under the hydrogen atmosphere of the catalyst is 382 ℃. The dispersity of the Ni of the reduction catalyst is 8.7%, and the dispersibility of the active component is general.
The evaluation materials and conditions were the same as in example 1, and the evaluation results are shown in Table 4.
[ Example 4]
The procedure of example 1 was followed except that the chelating agent was contained in the impregnation fluid in an amount of 0.005% by weight. 600 g of ZSM-5 molecular sieve powder with 130 of hydrogen type SiO 2/Al2O3, 150 g of beta molecular sieve powder with 40 of hydrogen type SiO 2/Al2O3, and 15 g of pseudo-boehmite containing 100 g of alumina, and methyl cellulose and sesbania powder are uniformly mixed for standby; then adding 7g of nitric acid and 5g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 10g of cerium oxide and calcium nitrate containing 8g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding strips to form, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake for 5 hours at 600 ℃ to obtain the composite carrier, wherein the water absorption rate is 99.1%.
Preparing an impregnating solution containing 28 g of Ni by using a soluble metal salt precursor, controlling the volume of the solution to 170 ml, adding 0.0085 g of 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDPA) into the impregnating solution, stirring and dissolving uniformly, taking 172 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume by adopting a pot-rotating spraying method, carrying out ageing for 16 hours at the impregnating temperature of 40 ℃, drying for 4 hours at 110 ℃ in a nitrogen atmosphere, roasting for 6 hours at 400 ℃ in a nitrogen atmosphere containing 1.0% of oxygen, and obtaining the catalyst, and carrying out hydrogen atmosphere reduction for 48 hours at 400 ℃ to obtain the reduction catalyst. The composite carrier, the catalyst preparation conditions and the carbon deposition amount of the catalyst are shown in tables 1,2 and 3.
The peak reduction temperature of the active component under the hydrogen atmosphere of the catalyst is 389 ℃. The dispersity of the Ni of the reduction catalyst is 8.9%, and the dispersibility of the active component is general.
The evaluation materials and conditions were the same as in example 1, and the evaluation results are shown in Table 4.
[ Example 5]
The procedure of example 1 was followed except that the oxygen content of the calcined oxygen-containing inert atmosphere was 8% by volume. 600 g of ZSM-5 molecular sieve powder with 130 of hydrogen type SiO 2/Al2O3, 150 g of beta molecular sieve powder with 40 of hydrogen type SiO 2/Al2O3, and 15g of pseudo-boehmite containing 100 g of alumina, and methyl cellulose and sesbania powder are uniformly mixed for standby; then adding 7 g of nitric acid and 5g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 10 g of cerium oxide and calcium nitrate containing 8g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding strips to form, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake for 5 hours at 600 ℃ to obtain the composite carrier, wherein the water absorption rate is 99.1%.
Preparing an impregnating solution containing 28 g of Ni by using a soluble metal salt precursor, controlling the volume of the solution to 170 ml, adding 1.5 g of 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDPA) and 2.0 g of ascorbic acid into the impregnating solution, stirring and dissolving uniformly, taking 172 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a pot-rotating spraying method, ageing for 16 hours at the impregnating temperature of 40 ℃, drying for 4 hours at 110 ℃ in a nitrogen atmosphere, roasting for 6 hours at 400 ℃ in a nitrogen atmosphere containing 8.0% of oxygen, and obtaining the catalyst, and reducing for 48 hours in a hydrogen atmosphere at 400 ℃ to obtain the reduction catalyst. The composite carrier, the catalyst preparation conditions and the carbon deposition amount of the catalyst are shown in tables 1, 2 and 3.
The peak reduction temperature of the active component under the hydrogen atmosphere of the catalyst is 385 ℃. The dispersity of the reduced catalyst Ni is 11.6%, and the dispersibility of the active component is general.
The evaluation materials and conditions were the same as in example 1, and the evaluation results are shown in Table 4.
[ Example 6]
600G of ZSM-5 molecular sieve powder with 130 of hydrogen type SiO 2/Al2O3, 150 g of beta molecular sieve powder with 40 of hydrogen type SiO 2/Al2O3, and 15 g of pseudo-boehmite containing 100 g of alumina, and methyl cellulose and sesbania powder are uniformly mixed for standby; then adding 7g of nitric acid and 5g of citric acid into 600g of water to dissolve uniformly, adding europium nitrate containing 8 g of europium oxide and calcium nitrate containing 8 g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding strips to form, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake for 5 hours at 600 ℃ to obtain the composite carrier, wherein the water absorption rate is 100.1%.
Preparing an impregnating solution containing 20g of Ni by using a soluble metal salt precursor, controlling the volume of the solution to 180 ml, adding 6.0 g of 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDPA) and 5.0 g of ascorbic acid into the impregnating solution, stirring and dissolving uniformly, taking 180 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a pot-rotating spraying method, ageing for 16 hours at the impregnating temperature of 40 ℃, drying for 4 hours at 110 ℃ in a nitrogen atmosphere, roasting for 6 hours at 400 ℃ in a nitrogen atmosphere containing 1.0% of oxygen, and obtaining the catalyst, and reducing for 48 hours in a hydrogen atmosphere at 400 ℃ to obtain the reduction catalyst. The composite carrier, the catalyst preparation conditions and the carbon deposition amount of the catalyst are shown in tables 1, 2 and 3.
The peak reduction temperature of the active component under the hydrogen atmosphere of the catalyst is 367 ℃. The dispersity of the Ni of the reduction catalyst is 16.8%, which indicates that the dispersion of the active component is good, the reduction is easy, and the activity of the catalyst is high.
The evaluation materials and conditions were the same as in example 1, and the evaluation results are shown in Table 4.
[ Example 7]
600 G of ZSM-5 molecular sieve powder with 130 of hydrogen type SiO 2/Al2O3, 150 g of beta molecular sieve powder with 40 of hydrogen type SiO 2/Al2O3, and 15 g of pseudo-boehmite containing 100g of alumina, and methyl cellulose and sesbania powder are uniformly mixed for standby; then adding 7 g of nitric acid and 5g of citric acid into 600 g of water to dissolve uniformly, adding lanthanum nitrate containing 10 g of lanthanum oxide and calcium nitrate containing 8g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding strips to form, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake for 5 hours at 600 ℃ to obtain the composite carrier, wherein the water absorption rate is 99.1%.
Preparing an impregnating solution containing 28 g of Ni by using a soluble metal salt precursor, controlling the volume of the solution to 170 ml, adding 2.5 g of aminotrimethylene phosphonic acid (ATMPA) and 2.0 g of ascorbic acid into the impregnating solution, stirring and dissolving uniformly, taking 172 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a pot-rotating spraying method, carrying out ageing for 16 hours at the impregnating temperature of 40 ℃, drying for 4 hours at 110 ℃ in a nitrogen atmosphere, roasting for 6 hours at 400 ℃ in a nitrogen atmosphere containing 1.0% of oxygen, and obtaining the catalyst, and reducing for 48 hours in a hydrogen atmosphere at 400 ℃ to obtain the reduction catalyst. The composite carrier, the catalyst preparation conditions and the carbon deposition amount of the catalyst are shown in tables 1,2 and 3.
The peak reduction temperature of the active component under the hydrogen atmosphere of the catalyst is 370 ℃. The dispersity of the Ni of the reduction catalyst is 15.3%, which indicates that the dispersion of the active component is good, the reduction is easy, and the activity of the catalyst is high.
The evaluation materials and conditions were the same as in example 1, and the evaluation results are shown in Table 4.
[ Example 8]
600 G of ZSM-5 molecular sieve powder with 130 of hydrogen type SiO 2/Al2O3, 150 g of beta molecular sieve powder with 40 of hydrogen type SiO 2/Al2O3, and 15 g of pseudo-boehmite containing 100g of alumina, and methyl cellulose and sesbania powder are uniformly mixed for standby; then adding 7 g of nitric acid and 5g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 10 g of cerium oxide and calcium nitrate containing 8g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding strips to form, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake for 5 hours at 600 ℃ to obtain the composite carrier, wherein the water absorption rate is 99.1%.
Preparing an impregnating solution containing 28 g of Ni by using a soluble metal salt precursor, controlling the volume of the solution to 170 ml, adding 1.5 g of ethylenediamine tetramethylene phosphoric acid (EDTMP) and 2.0 g of ascorbic acid into the impregnating solution, stirring and dissolving uniformly, taking 172 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a pot-rotating spraying method, carrying out ageing for 16 hours at the impregnating temperature of 40 ℃, drying for 4 hours at 110 ℃ in a nitrogen atmosphere, roasting for 6 hours at 400 ℃ in a nitrogen atmosphere containing 0.5% of oxygen, and obtaining the catalyst, and reducing for 48 hours in a hydrogen atmosphere at 400 ℃ to obtain the reduction catalyst. The composite carrier, the catalyst preparation conditions and the carbon deposition amount of the catalyst are shown in tables 1,2 and 3.
The peak reduction temperature of the active component under the hydrogen atmosphere of the catalyst is 369 ℃. The dispersity of the Ni of the reduction catalyst is 14.8%, which indicates that the dispersion of the active component is good, the reduction is easy, and the activity of the catalyst is high.
The evaluation materials and conditions were the same as in example 1, and the evaluation results are shown in Table 4.
[ Example 9]
600 G of ZSM-5 molecular sieve powder with 130 of hydrogen type SiO 2/Al2O3, 150 g of beta molecular sieve powder with 40 of hydrogen type SiO 2/Al2O3, and 15 g of pseudo-boehmite containing 100g of alumina, and methyl cellulose and sesbania powder are uniformly mixed for standby; then adding 7 g of nitric acid and 5g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 10 g of cerium oxide and calcium nitrate containing 8g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding strips to form, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake for 5 hours at 600 ℃ to obtain the composite carrier, wherein the water absorption rate is 99.1%.
Preparing an impregnating solution containing 28 g of Ni by using a soluble metal salt precursor, controlling the volume of the solution to 170 ml, adding 1.5 g of hydroxy ethylene tetra sodium diphosphonate (HEDP tetra sodium) and 2.0 g of ascorbic acid into the impregnating solution, stirring and dissolving uniformly, taking 172 g of composite carrier, loading the impregnating solution on the composite carrier in equal volume by adopting a pot-rotating spraying method, carrying out ageing for 16 hours at the impregnating temperature of 40 ℃, drying for 4 hours at 110 ℃ in a nitrogen atmosphere, roasting for 6 hours at 400 ℃ in a nitrogen atmosphere containing 1.0% of oxygen, and obtaining the catalyst, and reducing for 48 hours in a hydrogen atmosphere at 400 ℃ to obtain the reduced catalyst. The composite carrier, the catalyst preparation conditions and the carbon deposition amount of the catalyst are shown in tables 1,2 and 3.
The peak reduction temperature of the active component under the hydrogen atmosphere of the catalyst is 372 ℃. The dispersity of the Ni of the reduction catalyst is 12.9%, which indicates that the dispersion of the active component is good, the reduction is easy, and the activity of the catalyst is high.
The evaluation materials and conditions were the same as in example 1, and the evaluation results are shown in Table 4.
[ Example 10]
600 G of ZSM-5 molecular sieve powder with 130 of hydrogen type SiO 2/Al2O3, 150 g of beta molecular sieve powder with 40 of hydrogen type SiO 2/Al2O3, and 15 g of pseudo-boehmite containing 100g of alumina, and methyl cellulose and sesbania powder are uniformly mixed for standby; then adding 7 g of nitric acid and 5g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 10 g of cerium oxide and calcium nitrate containing 8g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding strips to form, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake for 5 hours at 600 ℃ to obtain the composite carrier, wherein the water absorption rate is 99.1%.
Preparing an impregnating solution containing 28 g of Ni by using a soluble metal salt precursor, controlling the volume of the solution to 170 ml, adding 0.75 g of 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDPA) into the impregnating solution, stirring and dissolving 0.75 g of tetrasodium hydroxyethylidene diphosphonate (tetrasodium HEDP) and 2.0 g of ascorbic acid uniformly, taking 172 g of a composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a rotary pot spraying method, ageing for 16 hours at the impregnating temperature of 40 ℃, drying for 4 hours at 110 ℃ in a nitrogen atmosphere, roasting for 6 hours at 400 ℃ in a nitrogen atmosphere containing 1.0% of oxygen, and obtaining the reduced catalyst after hydrogen reduction for 48 hours at 400 ℃. The composite carrier, the catalyst preparation conditions and the carbon deposition amount of the catalyst are shown in tables 1,2 and 3.
The peak reduction temperature of the active component under the hydrogen atmosphere of the catalyst is 366 ℃. The dispersity of the Ni of the reduction catalyst is 16.8%, which indicates that the dispersion of the active component is good, the reduction is easy, and the activity of the catalyst is high.
The evaluation materials and conditions were the same as in example 1, and the evaluation results are shown in Table 4.
[ Comparative example 1]
600 G of ZSM-5 molecular sieve powder with 130 of hydrogen type SiO 2/Al2O3, 150 g of beta molecular sieve powder with 40 of hydrogen type SiO 2/Al2O3, and 15 g of pseudo-boehmite containing 100g of alumina, and methyl cellulose and sesbania powder are uniformly mixed for standby; then adding 7 g of nitric acid and 5g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 10 g of cerium oxide and calcium nitrate containing 8g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding strips to form, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake for 5 hours at 600 ℃ to obtain the composite carrier, wherein the water absorption rate is 99.1%.
Preparing an impregnating solution containing 28 g of Ni by using a soluble metal salt precursor, controlling the volume of the solution to 170 ml, taking 172 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume by adopting a rotary pot spraying method, ageing for 16 hours at the impregnating temperature of 40 ℃, drying for 4 hours at 110 ℃ in an air atmosphere, roasting for 6 hours at 400 ℃ to obtain the catalyst, and reducing for 48 hours at 400 ℃ in a hydrogen atmosphere to obtain the reduced catalyst. The composite carrier, the catalyst preparation conditions and the carbon deposition amount of the catalyst are shown in tables 1,2 and 3.
The temperature programmed reduction TPR map of the catalyst is shown in figure 6. It can be seen from fig. 6 that the peak reduction temperature of the active component under the hydrogen atmosphere is 415 ℃. The dispersity of the Ni of the reduction catalyst is 4.8%, which indicates that the dispersibility of the active component is poor, the reduction is difficult, and the activity of the catalyst is low.
The evaluation materials and conditions were the same as in example 1, the evaluation results are shown in Table 4, the distribution of the evaluation results of the catalyst-on-line time chart is shown in FIG. 7, and FIG. 7 shows that the initial activity of the catalyst was rapidly decreased, the stability was poor, the BTX yield was 53.3% on line for 200 hours, and the BTX yield was decreased to 34.0% on line for 2000 hours.
[ Comparative example 2]
600 G of ZSM-5 molecular sieve powder with 130 of hydrogen type SiO 2/Al2O3, 150 g of beta molecular sieve powder with 40 of hydrogen type SiO 2/Al2O3, and 15 g of pseudo-boehmite containing 100g of alumina, and methyl cellulose and sesbania powder are uniformly mixed for standby; then adding 7 g of nitric acid and 5g of citric acid into 600 g of water to dissolve uniformly, adding cerium nitrate containing 10 g of cerium oxide and calcium nitrate containing 8g of calcium oxide to dissolve uniformly, pouring the solution into the mixed powder, kneading for 35 minutes, extruding strips to form, standing for 12 hours, drying at 110 ℃ for 6 hours, and then placing into a muffle furnace to bake for 5 hours at 600 ℃ to obtain the composite carrier, wherein the water absorption rate is 99.1%.
Preparing an impregnating solution containing 28 g of Ni by using a soluble metal salt precursor, controlling the volume of the solution to 170 ml, adding 1.5g of 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDPA) and 2.0 g of ascorbic acid into the impregnating solution, stirring and dissolving uniformly, taking 172 g of composite carrier, loading the impregnating solution on the composite carrier in an equal volume manner by adopting a rotary pot spraying method, carrying out ageing for 16 hours at the impregnating temperature of 40 ℃, drying for 4 hours at 110 ℃ in an air atmosphere, roasting for 6 hours at 400 ℃ to obtain the catalyst, and reducing for 48 hours in a hydrogen atmosphere at 400 ℃ to obtain the reduced catalyst. The composite carrier, the catalyst preparation conditions and the carbon deposition amount of the catalyst are shown in tables 1,2 and 3.
The temperature programming reduction TPR map of the catalyst is shown in figure 8; it can be seen from FIG. 8 that the peak reduction temperature of the active component under the hydrogen atmosphere was 399 ℃. The dispersity of the Ni of the reduction catalyst is 6.8%, which indicates that the dispersibility of the active component is poor, the reduction is difficult, and the activity of the catalyst is low.
The evaluation materials and conditions were the same as in example 1, and the evaluation results are shown in Table 4.
TABLE 1 preparation conditions of composite vectors
TABLE 2 catalyst preparation conditions, carbon deposition and Ni dispersity
As can be seen from the results of Table 2, the catalysts prepared in examples 1-2 and 6-10 have higher dispersity than those of the other examples and comparative examples, and the reduction temperature is lower than those of the other examples and comparative examples, and it is apparent that the catalysts prepared by the method of the present invention have the effects of high dispersity and low reduction temperature.
TABLE 3 catalyst chelating agent, ascorbic acid addition
Table 4 results of catalyst evaluation
As can be seen from the results in Table 4, examples 1-2 and 6-10 were on line for 200 hours, the total liquid phase product yield was greater than 80%, and the liquid phase product BTX yield was greater than 58%; the yield of the total liquid phase product is more than 80 percent in 2000 hours on line, wherein the yield of the liquid phase product BTX is more than 55 percent, and a better technical effect is obtained. Whereas comparative examples 1 and 2 had on-line 200 hours liquid phase product BTX yields of 53.3% and 54.2%, respectively; after 2000 hours on line, the liquid phase product BTX yields were only 34.0% and 40.3%, respectively. Obviously, the catalyst provided by the invention has the characteristics of good stability and high BTX yield.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A hydrogenation catalyst, characterized in that the catalyst comprises the following components:
a)5.00％～20.00％Ni；
b) 0.01% -5.00% rare earth metal oxide;
c)50.00％～84.99％ZSM-5；
d) 5.00% -39.99% of beta zeolite;
e) 5.00 to 20.00 percent of adhesive;
the carbon deposition amount of the catalyst is 0.1-5% of the weight of the catalyst.
2. The catalyst according to claim 1, wherein,
The dispersity of the active component Ni is more than 8%, preferably 9% -20%;
and/or
The rare earth metal is one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, preferably one or more of cerium, lanthanum, praseodymium, europium and neodymium;
and/or
The binder is selected from silica and/or alumina;
and/or
In the catalyst, the Ni content is 10-15% by weight, the rare earth metal oxide content is 0.01-3.0%, the ZSM-5 content is 55.00-75.50%, the beta zeolite content is 6.00-26.50%, and the binder content is 8-15%.
3. The method for preparing a catalyst according to claim 1 or 2, wherein the method comprises:
i) Preparing a rare earth metal oxide modified composite carrier containing ZSM-5, beta zeolite and a binder;
ii) preparing an impregnating solution containing a chelating agent, ascorbic acid and a Ni source;
iii) The impregnating solution is in impregnating contact with the composite carrier, then aged, then the solid is dried under inert atmosphere, baked under low oxygen-containing inert atmosphere, and then reduced;
The oxygen content in the low oxygen-containing inert atmosphere is less than 10% by volume, preferably less than 5% by volume.
4. A process according to claim 3, wherein in step iii),
The conditions of the immersion contact include:
the dipping temperature is 10-80 ℃; and/or
Dipping the composite carrier by adopting a spraying method; and/or
The aging time is 0.5-24 h.
5. The process according to claim 3 or 4, wherein step iii),
The drying conditions included: the temperature is 30-200 ℃; and/or
The roasting conditions include: the temperature is 300-600 ℃ and/or the time is 0.5-24 h; and/or
The temperature of the reduction peak of the TPR hydrogen atmosphere of the catalyst before reduction is lower than 390 ℃.
6. The process according to any one of claim 3 to 5, wherein,
The dry inert atmosphere is one or more of nitrogen atmosphere and argon atmosphere, preferably nitrogen atmosphere; and/or
The oxygen content in the roasted oxygen-containing inert atmosphere is 0.1 to 5 volume percent, and the inert gas content is 95 to 99.9 volume percent; preferably, the inert gas is one or more of nitrogen and argon.
7. The process according to any one of claim 3 to 6, wherein,
The chelating agent is selected from one or more of 1-hydroxyethylidene-1, 1-diphosphonic acid, tetra sodium hydroxyethylidene diphosphonic acid, amino trimethylene phosphonic acid and ethylenediamine tetramethylene phosphoric acid, preferably 1-hydroxyethylidene-1, 1-diphosphonic acid and/or tetra sodium hydroxyethylidene diphosphonic acid; and/or
The content of the chelating agent in each 100ml of impregnating solution is 0.01-5 g; and/or
The content of the ascorbic acid in each 100ml of impregnating solution is 0.2-5 g; and/or
The immersion contact is an equal volume immersion contact.
8. The production method according to any one of claims 3 to 7, wherein the production method of the composite carrier comprises:
(1) Uniformly mixing an adhesive source, ZSM-5 powder, beta zeolite powder and an auxiliary agent to obtain a mixture I;
(2) Adding the mixture I into an acidic aqueous solution, wherein the acidic aqueous solution contains rare earth nitrate; kneading, molding, drying and roasting;
Preferably, the method comprises the steps of,
The concentration of the acidic substance in the acidic aqueous solution is 1 to 6 weight percent; and/or
The weight ratio of the mixture I to the acidic aqueous solution is 100:5-100:75; and/or
The roasting conditions include: the temperature is 450-650 ℃ and the time is 0.5-24 h.
9. The preparation method according to claim 8, wherein,
The ZSM-5 powder is hydrogen, and the molar ratio of SiO 2/Al2O3 is 50-300; and/or
The beta zeolite powder is hydrogen type, and the SiO 2/Al2O3 mol ratio is 20-200; and/or
The adhesive source is at least one selected from silica sol, water glass, pseudo-boehmite, white carbon black and alumina sol; and/or
The auxiliary agent is at least one of methylcellulose, sesbania powder, polyethylene glycol, calcium nitrate, potassium nitrate and hydroxymethyl cellulose;
the acidic substance in the acidic aqueous solution is at least one selected from nitric acid, phosphoric acid, acetic acid, citric acid and tartaric acid.
10. A method for preparing BTX by refining light aromatic-rich distillate oil with high stability is characterized by comprising the following steps:
hydrogenating the refined aromatic-rich light cracked distillate in the presence of a catalyst under hydrogenation reaction conditions, said catalyst comprising the hydrogenation catalyst of claim 1 or 2;
Preferably, the method comprises the steps of,
Refining aromatic-rich light pyrolysis distillate oil: the initial distillation point is 85-170 ℃, the final distillation point is 220-280 ℃, the sulfur content is less than 50ug/mL, and the nitrogen content is less than 10ug/mL; the content of monocyclic aromatic hydrocarbon is more than 90wt%;
The hydrogenation reaction conditions include: the inlet temperature of the reactor is 380-480 ℃, the fresh feeding airspeed is 0.6-4.0 h -1, the hydrogen-oil volume ratio is 500-2000, and the pressure is 2-8 MPa.
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