CN115703063A - Dehydrogenation method for hydrogenated aromatic compound - Google Patents
Dehydrogenation method for hydrogenated aromatic compound Download PDFInfo
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- CN115703063A CN115703063A CN202110945768.6A CN202110945768A CN115703063A CN 115703063 A CN115703063 A CN 115703063A CN 202110945768 A CN202110945768 A CN 202110945768A CN 115703063 A CN115703063 A CN 115703063A
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- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 47
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 127
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 4
- 238000005486 sulfidation Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 38
- 230000008569 process Effects 0.000 claims description 29
- 238000005470 impregnation Methods 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000012018 catalyst precursor Substances 0.000 claims description 3
- -1 cyclic aromatic hydrocarbon Chemical class 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 241000219793 Trifolium Species 0.000 claims 1
- 150000002390 heteroarenes Chemical class 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 26
- 239000002994 raw material Substances 0.000 abstract description 23
- 238000002360 preparation method Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 229910052736 halogen Inorganic materials 0.000 description 11
- 150000002367 halogens Chemical class 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 9
- 150000001342 alkaline earth metals Chemical class 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 238000005070 sampling Methods 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
- 238000003860 storage Methods 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000006298 dechlorination reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 238000002803 maceration Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- SBVSDAFTZIVQEI-UHFFFAOYSA-N 2,3,4,4a,4b,5,6,7,8,8a,9,9a-dodecahydro-1h-carbazole Chemical compound C1CCCC2C3CCCCC3NC21 SBVSDAFTZIVQEI-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910004349 Ti-Al Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910004692 Ti—Al Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a dehydrogenation method for hydrogenating aromatic compounds, which comprises the following steps: adding a raw material rich in hydrogenated aromatic compounds and a dehydrogenation catalyst into a dehydrogenation reactor, and reacting at a temperature: 240-420 ℃, pressure: 0.01-2 MPa, mass space velocity: 1 to 5 hours ‑1 Carrying out dehydrogenation reaction under the condition that the molar ratio of hydrogen to oil is 0-1.0; the dehydrogenation catalyst is a non-sulfidation type catalyst and comprises an active component, chloride ions and a carrier; the active component at least contains noble metal component in VIII group, which accounts for 0.1-3% of the total weight of the dehydrogenation catalyst; the chlorine ion accounts for 0.3-1.2 of the total weight of the dehydrogenation catalystPercent; the carrier is mainly gamma-Al 2 O 3 . The catalyst of the invention has the advantages of easily available raw materials, simple composition, easy preparation, and high activity and selectivity of low-temperature dehydrogenation reaction of a reaction system.
Description
Technical Field
The invention belongs to the field of hydrogen storage of liquid organic compounds and the technical field of catalytic materials, and particularly relates to a dehydrogenation method for hydrogenated aromatic compounds.
Background
Hydrogen has wide application in various industries of national economy. Hydrogen can be used as a petrochemical raw material, is a clean, efficient, safe and sustainable new energy, and technically can solve the two major problems of energy and environment faced by human beings, so that the hydrogen energy is internationally considered to be the most ideal energy and also the long-term strategic energy of human beings.
The hydrogen energy related technology comprises large-scale preparation, storage and transportation and high-efficiency utilization of hydrogen. The normal temperature and pressure storage and transportation of hydrogen are key bottlenecks that restrict the wide-range application of hydrogen. The development of efficient liquid hydrogen storage materials to realize reversible storage and release of hydrogen becomes an important link for solving the whole hydrogen industry chain.
The liquid hydrogen storage material is hydrogenated in the hydrogen-rich place to obtain hydride which is also in liquid state, and the hydrogen is released through dehydrogenation. The dehydrogenation process is a strongly endothermic heterogeneous reaction, and the reaction process is reversible, and must be performed under low-pressure and high-temperature conditions from the aspects of kinetics and thermodynamics, however, the high temperature easily causes the occurrence of catalyst carbon deposition and cracking reaction, reduces the activity of the catalyst and the selectivity of main products, and further affects the stability of the dehydrogenation process and the service life of the catalyst. Therefore, the key to the large-scale application of the organic liquid hydride hydrogen storage technology is the development of a low-temperature high-selectivity dehydrogenation catalyst.
The dehydrogenation catalyst generally used is a supported metal catalyst, and the active components are Pt, pd, rh, ni, co, and the like. Also, the dehydrogenation activity of the catalyst can be further improved by adding a second metal component such as Ni, mo, W, re, rh, pd, ir, sn, etc. The support is typically alumina or a modified component of alumina.
Most commercially available activated alumina has too many surface hydroxyl groups and too strong acidity. When the aluminum oxide is used as a carrier to prepare the dehydrogenation catalyst, the surface of the catalyst is easy to deposit carbon in the reaction process, and the rapid inactivation is caused. In addition, precursors of the active components often contain acidic chloride ions, and the competitive adsorbent adopted in the active component impregnation process also often adopts hydrochloric acid solution, so that the chloride ions are introduced, the acidity of the catalyst is increased, and the surface acid strength of the catalyst is further enhanced. The acidity in the catalyst is moderate and too strong, isomerization and even hydrocracking can occur, byproducts are generated, and the dehydrogenation selectivity is reduced. The acidity is too weak, the activity of the catalyst is reduced, and the dehydrogenation conversion rate is influenced.
Therefore, the catalyst needs to be subjected to proper acid reduction treatment according to the use requirement of the catalyst. Some materials except alumina, such as activated carbon, molecular sieve, etc., are directly used as carriers. Some precursors adopting non-chloride ion active components and some precursors adopting a chlorine washing mode wash away residual chloride ions in the catalyst. Some methods introduce alkaline or alkaline earth metals into the catalyst to weaken the acidity of the support surface. Some carriers are modified in an alkaline environment, and active components are loaded in the alkaline environment.
CN109701610A relates to a modified dehydrogenation catalyst, a preparation method and application thereof, the related catalyst comprises two active components, wherein the component (a) is one or more of platinum metals, the component (b) is one or more of In, cs, ga, ge and Sr, the carrier is one or more of alumina, molecular sieve and silica, and the related modification is that the molecular sieve carrier is modified by nitrogen. The organic liquid hydrogen storage material is one or more selected from methylcyclohexane, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole and perhydrocarbazole. The embodiment shows that the carrier is molecular sieve, the initial conversion rate of the synthesized catalyst at 320 ℃ for cyclohexane, tetrahydronaphthalene, decahydronaphthalene and methylcyclohexane is up to 82%, the conversion rate after 100h reaction is reduced to 79%, and the coking rate reaches 0.4%.
CN105582917B discloses a dechlorination method of a precious metal dehydrogenation catalyst, which comprises the steps of introducing 1-10% ammonia water solution by mass concentration into a catalyst bed layer for hydrothermal dechlorination, and introducing deionized water for hydrothermal deamination after the hydrothermal dechlorination is finished to obtain the dechlorinated precious metal dehydrogenation catalyst. The method can dehydrogenate Cl in noble metal catalyst - The content of the Pt particles is removed to be below 0.15wt%, so that the Pt particles are prevented from being aggregated and grown at high temperature, and the energy consumption is reduced.
CN110252422A discloses a method for washing chloride ions in a catalyst, which comprises washing a semi-finished catalyst loaded with active components with a washing liquid containing ammonium salt, or ammonium salt and a reducing agent for 3-20 times, drying and calcining to obtain the catalyst with the chloride ion content below 10 ppm.
CN112452340A, CN112371193A, CN112316977A and other patents disclose methods for washing chloride ions with deionized water, which are repeated washing, and washing the solution to neutrality, that is, washing all the acidic substances.
US patent No. 3531543 discloses the dehydrogenation of hydrocarbons using a catalyst consisting of platinum, tin and a neutral metal oxide support. Preferred supports are oxidic materials whose inherent acidity has been substantially neutralized by alkali metal or alkaline earth metal components. Furthermore, as the alkali metal content increases, the acidity of these aluminas decreases accordingly. The support of this patent is preferably a non-acidic lithium oxide-added alumina. The catalysts of this patent are preferably made from halogen-free compounds. However, halogen-containing compounds can also be used for the preparation of the catalyst, provided that the residual halogen can be removed effectively from the final catalyst complex.
US3745112 discloses a catalyst for reforming hydrocarbons, which comprises a platinum component, a tin component and a halogen component and a porous support material. The patent also discloses that the platinum-tin-alkali or alkaline earth metal complex is a particularly effective hydrocarbon dehydrogenation catalyst. In the dehydrogenation catalyst complexes of this patent, alkali or alkaline earth metal components are added so that the amount of halogen is minimized, if not completely excluded, in order to minimize or neutralize the acidic action of the alumina and halogen components; this acidity promotes cracking and isomerization side reactions of hydrocarbons which are undesirable in commercial dehydrogenation processes.
U.S. patent 3,892,657 discloses that indium is a good promoter for platinum group-containing catalysts when the atomic ratio of indium to platinum is from about 0.1: 1 to about 1: 1. The patent also discloses the addition of a group IVA component selected from germanium, tin and lead to an indium containing acidic catalyst which may be used in reforming applications. The acidic catalyst thus consists of a platinum group component, a group IVA component, an indium component, a halogen component and a porous support material. For reforming applications, the acidic catalyst contains up to about 3.5% by weight of halogen, while for isomerization and cracking applications, the acidic catalyst contains up to about 10% by weight of halogen. In the dehydrogenation catalysts of this patent, the halogen content is kept to the lowest possible value, approximately 0.1% by weight, despite the addition of alkali metal or alkaline earth metal components.
CN110882703A discloses a naphthene dehydrogenation catalyst containing alkaline earth metal and a preparation method thereof, wherein Pt is used as an active metal component, sn is used as an auxiliary component, and a carrier is an alumina carrier containing alkaline earth metal, sulfur and titanium. The alkaline earth metal-Ti-Al skeleton structure formed in the process of preparing the carrier in situ can obviously improve the characteristic of single acidity of the alumina on the surface of the carrier, obviously reduce the acidity of the alumina carrier, improve the carbon deposition resistance of the catalyst and improve the high-temperature activity and stability of the catalyst. Preferably for the dehydrogenation of cyclohexane to benzene or methylcyclohexaneAnd preparing toluene. The embodiment shows that the catalyst is used for dehydrogenation of cyclohexane, the reaction temperature is 430 ℃, the pressure is 1.0MPa, and the space velocity is 2h -1 The conversion was as high as 92% with a selectivity of 84%.
US patent No. 3909451 discloses a novel method for producing a dehydrogenation catalyst comprising a platinum component, a tin component and an alkali or alkaline earth metal component. This patent discloses in example V a composition of platinum, tin and potassium containing less than 0.2% by weight of chlorine in compound form.
UK patent UK1499297 discloses a dehydrogenation catalyst using alumina as a support and consisting of platinum and at least one of the elements gallium indium thallium, and an alkali metal, in particular lithium and potassium. The catalyst of this patent also contains halogen in an amount of from 0.01 to 0.1% by weight. The halogen content is deliberately reduced to such low weight percent ranges in order to increase the selectivity and stability of the catalyst.
The patent CN 111686718A treats a carrier in an alkaline solution, and loads an active component in an alkaline environment to increase the steric hindrance and the metal loading rate of a metal loading compound in an impregnation liquid, prevent metal particles from agglomerating, and improve the dispersibility and the uniformity of the active component of the catalyst. The results show that the conversion rate can reach 99.5 percent at the temperature of 430-450 ℃, and the selectivity can reach more than 99 percent.
In summary, the compounds involved in dehydrogenation include primarily lower alkanes (e.g., propane, butane) and cycloalkanes, as well as hydrides of aromatic hydrocarbons containing heteroatoms. In order to reduce the acidity of the catalyst surface and improve the stability of the dehydrogenation catalyst, researchers have employed a method of washing chloride ions or a method of doping an alkali metal or an alkaline earth metal in the preparation process of the carrier. In the course of the washing of chloride ions, chlorine is generally removed completely or is kept as low as possible, generally less than 0.1% by weight, and always less than 0.2% by weight, calculated on an elemental basis.
Disclosure of Invention
The invention aims to overcome the defects of low conversion rate and selectivity of the existing hydrogenated aromatic compound dehydrogenation, especially low conversion rate under low temperature condition. The invention provides a dehydrogenation method for hydrogenating aromatic compounds, wherein the dehydrogenation conversion rate of a reaction system in the dehydrogenation method is high, and the selectivity can reach 100%.
The technical scheme adopted by the invention is as follows:
the present invention provides a dehydrogenation method for hydrogenating an aromatic compound, comprising: adding a raw material rich in hydrogenated aromatic compounds and a dehydrogenation catalyst into a dehydrogenation reactor, and reacting at a temperature: 240-420 ℃, pressure: 0.01-2 MPa, mass space velocity: 1 to 5 hours -1 Carrying out dehydrogenation reaction under the condition that the molar ratio of hydrogen to oil is 0-1.0; the dehydrogenation catalyst is a non-sulfidation type catalyst and comprises an active component, chloride ions and a carrier; the active component at least contains a noble metal component in the VIII group, and accounts for 0.1 to 3 percent of the total weight of the dehydrogenation catalyst; the chlorine ion accounts for 0.3 to 1.2 percent of the total weight of the dehydrogenation catalyst; the carrier is mainly gamma-Al 2 O 3 。
Preferably, the active component accounts for 0.1 to 0.6 percent of the total weight of the dehydrogenation catalyst; the chloride ion accounts for 0.3-0.9% of the total weight of the dehydrogenation catalyst.
In the technical scheme, the active component comprises at least one substance of Pt, pd and Rh.
Preferably, the active component is Pt.
In the technical scheme, the carrier is mainly gamma-alumina, and gamma-Al is contained in the carrier 2 O 3 In an amount of>50wt%, preferably 100wt%, of a carrier which may also contain GrO 2 ，CeO 2 Molecular sieves, activated carbon, and the like.
The morphology and structure of the carrier required for different raw materials are different, the invention is not particularly limited, and the specific surface area of the carrier is generally 180-240 m 2 The pore volume is 0.5-2.0 mL/g, and the pore diameter is 2-20 nm.
The shape of the carrier is not particularly limited in the present invention, and the shape of the carrier may be spherical, strip-shaped, cylindrical, clover-shaped.
In the above technical solution, the raw material rich in hydrogenated aromatic compound refers to a product obtained by hydrogenating the aromatic compound rich in aromatic compound to obtain complete hydrogenation or partial hydrogenation.
In the technical scheme, the aromatic compound comprises 1-3 ring aromatic hydrocarbon and 1-3 ring heterocyclic aromatic hydrocarbon containing N heteroatom. The 1-3 cyclic aromatic hydrocarbon may contain 0-3 side chains, and the length of the side chain is 1-3 carbon numbers.
The invention does not limit the dehydrogenation reaction form, but the technical scheme adopts a fixed bed reaction form.
The dehydrogenation reaction conditions are preferably reaction temperatures: 260-320 ℃, reaction pressure: 0.01-0.5 MPa, mass space velocity: 1 to 3 hours -1 The molar ratio of hydrogen to oil is 0-0.6.
The invention also provides a preparation method of the dehydrogenation catalyst, which comprises the following steps:
s1, preparing a metal salt solution containing active components, and adjusting the pH value to 0-3 to form chlorine-containing impregnation liquid;
s2: mixing the impregnating solution and the carrier, impregnating for 3-6 h, removing residual solution, drying for 2-6 h at 120-200 ℃, transferring into a tubular furnace, roasting for 4-12 h at 400-600 ℃ to control the chloride ion at 0.3-1.2%. Cooling to obtain a precursor of the dehydrogenation catalyst;
s3: and reducing the catalyst precursor for 4-8 h in a hydrogen atmosphere at the temperature of 300-600 ℃ to obtain the dehydrogenation catalyst.
In the above technical scheme, the metal salt solution of the active component may be one or more of a chlorate solution, a nitrate solution and a sulfate solution.
In the above technical solution, the chlorine in the chlorine-containing dipping solution may be derived from a chlorate solution of an active component, or may be derived from a chlorine-containing acidic component added to the dipping solution.
The impregnated carrier is not washed and is finished in a circulating air atmosphere with the introduction of deionized water. The invention does not emphasize the heating mode in the roasting process, but the temperature programming is preferred in the technical scheme, and the heating rate is 2-5 ℃/min.
According to the invention, researches show that in the preparation process of the catalyst, the chlorine content of the catalyst is reduced, so that the surface acidity of the catalyst can be effectively reduced, and the dehydrogenation conversion rate and selectivity are improved.
Compared with the prior art, the invention has the following advantages:
(1) The catalyst has the advantages of easily obtained raw materials, simple composition, easily controlled preparation conditions, good product repeatability and easy realization of amplified preparation;
(2) The dehydrogenation raw material has wide source and can be industrially prepared in large scale;
(3) The reaction form can be a fixed bed, and the maturation is reliable;
(4) The reaction condition is mild, and the reaction system has high activity and selectivity of low-temperature dehydrogenation reaction.
Detailed Description
The present invention will be specifically described below by way of examples. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the above teachings.
Example 1
(1) Catalyst and process for preparing same
The carrier adopts a spherical agent, gamma-Al 2 O 3 The content is 98wt%, and the specific surface area is 230.4m 2 The pore volume is 1.05mL/g, and the pore diameter is 15.2nm. Pt content 0.3wt%, cl content 0.70wt%.
(2) Catalyst preparation
4mL of chloroplatinic acid salt solution with the concentration of 15mg/mL and 5mL of hydrochloric acid solution with the concentration of 80mg/mL are added into a triangular flask in sequence, 27mL of deionized water is added, and the pH value is adjusted to 1 to prepare an impregnation solution. Adding 20g of carrier into the impregnation solution, sealing the triangular bottle mouth with a sealing film, and placing on a shaking table to shake and impregnate for 4h. Taking off the triangular flask, removing the redundant impregnation liquid, placing in an oven, drying at 120 ℃ for 2h, and transferring to a tubular furnace for roasting. The temperature is raised by a program, the heating rate is 2 ℃/min, and the air space velocity for roasting is 16min -1 0.6% concentration prepared by carrying deionized water before air enters the tube furnaceAnd (3) feeding hydrochloric acid with the concentration into a tubular furnace, roasting for 6 hours at 500 ℃, purging with nitrogen, replacing into a hydrogen atmosphere, and reducing for 4 hours to obtain the dehydrogenation catalyst, wherein the composition data of the dehydrogenation catalyst are shown in Table 1.
(3) Dehydrogenation process
Dehydrogenation is carried out in a fixed bed reaction system, 10g of prepared dehydrogenation catalyst is filled in a reactor, the pressure of a reaction device is set to be 0.1MPa, and the mass space velocity is set to be 2h -1 The molar ratio of hydrogen to oil was 0.5, the temperature was raised from 260 ℃ after feeding the raw material, and the temperature was raised to 20 ℃ until 420 ℃ after sampling every 6 hours. And analyzing the product composition of the sample by adopting GC-MS, and calculating the conversion rate of dehydrogenation of the raw material and the selectivity of generating the target aromatic hydrocarbon toluene according to the composition. The dehydrogenation conversion performance of the catalysts for hydrogenated aromatic compounds such as benzene, toluene, xylene, naphthalene, methylnaphthalene, carbazole, and N-ethylcarbazole was evaluated, and the dehydrogenation effect of methylcyclohexane at different temperatures is shown in table 2.
Example 2
(1) Catalyst and process for producing the same
The carrier adopts a striping agent, gamma-Al 2 O 3 The content is 96wt%, and the specific surface area is 220.2m 2 The pore volume is 0.72mL/g, and the pore diameter is 8.8nm. Pt content 1.0wt% and Cl content 0.66wt%.
(2) Catalyst preparation
13.3mL of chloroplatinic acid salt solution with the concentration of 15mg/mL and 5mL of hydrochloric acid solution with the concentration of 80mg/mL are added into a triangular flask in sequence, 27mL of deionized water is added, and the pH value is adjusted to 1. Configured as a dipping solution. Adding 20g of carrier into the impregnation solution, sealing the triangular bottle mouth with a sealing film, and placing on a shaking table to shake and impregnate for 4h. Taking off the triangular flask, removing the redundant impregnation liquid, placing in an oven, drying at 120 ℃ for 2h, and transferring to a tubular furnace for roasting. The air space velocity for roasting is 16min -1 Air carrying deionized water enters a tube furnace, roasting is carried out for 6 hours at 500 ℃, nitrogen purging is carried out, then hydrogen atmosphere is replaced, and reduction is carried out for 4 hours to obtain the dehydrogenation catalyst, wherein the composition data of the dehydrogenation catalyst are shown in Table 1.
(3) Dehydrogenation reaction method
Referring to example 1, the dehydrogenation effect on methylcyclohexane at different temperatures is shown in Table 2.
Example 3
(1) Catalyst and process for preparing same
The support was the same as in example 1, except that the Pt content was 0.4wt% and the Cl content was 1.0wt%.
(2) Catalyst preparation
5.3mL of chloroplatinic acid salt solution with the concentration of 15mg/mL and 8mL of hydrochloric acid solution with the concentration of 80mg/mL are added into a triangular flask in sequence, 27mL of deionized water is added, and the pH value is adjusted to 0.5. Configured as a dipping solution. Adding 20g of carrier into the impregnation solution, sealing the triangular bottle mouth with a sealing film, and placing on a shaking table to shake and impregnate for 4h. Taking off the triangular flask, removing the redundant impregnation liquid, placing in an oven, drying at 120 ℃ for 2h, and transferring to a tubular furnace for roasting. Adopts temperature programming with the heating rate of 2 ℃/min and the air space velocity for roasting of 16min -1 Before air enters the tube furnace, 0.6% hydrochloric acid prepared by deionized water and carried water enter the tube furnace, the mixture is roasted for 4 hours at 500 ℃, and after nitrogen purging, the mixture is replaced by hydrogen atmosphere and reduced for 4 hours to obtain the dehydrogenation catalyst, wherein the composition of the catalyst is shown in Table 1.
(3) Dehydrogenation process
Dehydrogenation is carried out in a fixed bed reaction system, 10g of prepared dehydrogenation catalyst is filled in a reactor, the pressure of a reaction device is set to be 0.5MPa, and the mass space velocity is set to be 2h -1 The molar ratio of hydrogen to oil was 0.5, the temperature was raised from 260 ℃ after feeding the raw material, and the temperature was raised to 20 ℃ until 420 ℃ after sampling every 6 hours. And analyzing the product composition of the sample by adopting GC-MS, and calculating the conversion rate of dehydrogenation of the raw material and the selectivity of generating the target aromatic hydrocarbon toluene according to the composition. The dehydrogenation conversion performance of the catalysts for hydrogenated aromatic compounds such as benzene, toluene, xylene, naphthalene, methylnaphthalene, carbazole, and N-ethylcarbazole was evaluated, and the dehydrogenation effect of methylcyclohexane at different temperatures is shown in table 2.
Example 4
(1) Carrier
The carrier adopts a striping agent, gamma-Al 2 O 3 The content is 96wt%, and the specific surface area is 198.8m 2 The pore volume is 0.53mL/g, the pore diameter is 7.9nm, the Pt content is 0.6wt%, and the Cl content is 0.52wt%.
(2) Catalyst preparation
8mL of chloroplatinic acid salt solution with the concentration of 15mg/mL and 5mL of hydrochloric acid solution with the concentration of 80mg/mL are added into a triangular flask in sequence, 23mL of deionized water is added, and the pH value is adjusted to 1 to prepare an impregnation solution. Adding 20g of carrier into the impregnation solution, sealing the triangular bottle mouth with a sealing film, and placing on a shaking table to shake and impregnate for 4h. Taking off the triangular flask, removing the redundant maceration extract, placing in an oven, drying at 120 deg.C for 2 hr, and transferring to a tubular furnace for roasting. The air space velocity for roasting is 16min -1 Carrying hot steam into a tube furnace, roasting for 4h at 500 ℃, replacing into hydrogen atmosphere after nitrogen purging, and reducing for 4h to obtain a catalyst D, wherein the composition of the catalyst is shown in Table 1..
(3) Dehydrogenation process
Dehydrogenation is carried out in a fixed bed reaction system, 10g of prepared dehydrogenation catalyst is filled in a reactor, the pressure of a reaction device is set to be 0.1MPa, and the mass space velocity is set to be 1h -1 The molar ratio of hydrogen to oil was 1.0, the temperature was raised from 260 ℃ after feeding the raw material, and the temperature was raised to 20 ℃ until 420 ℃ after sampling every 6 hours. And analyzing the product composition of the sample by adopting GC-MS (gas chromatography-Mass spectrometer), and calculating the conversion rate of dehydrogenation of the raw material and the selectivity of generating target aromatic hydrocarbon toluene according to the composition. The catalysts were evaluated for dehydrogenation conversion performance of hydrogenated aromatic compounds such as benzene, toluene, xylene, naphthalene, methylnaphthalene, carbazole, and N-ethylcarbazole, and the dehydrogenation effect of methylcyclohexane at different temperatures is shown in table 2.
Comparative example 1
(1) Catalyst and process for preparing same
Same as in example 1
(2) Catalyst preparation
4mL of chloroplatinic acid salt solution with the concentration of 15mg/mL and 5mL of hydrochloric acid solution with the concentration of 80mg/mL are added into a triangular flask in sequence, 27mL of deionized water is added, and the pH value is adjusted to 1. Configured as a dipping solution. Adding 20g of carrier into the impregnation solution, sealing the triangular bottle mouth with a sealing film, and placing on a shaking table to shake and impregnate for 4h. Taking off the triangular flask, removing the redundant maceration extract, placing in an oven, drying at 120 deg.C for 2 hr, and transferring to a tubular furnace for roasting. Air space velocity for calcination of16min -1 Directly feeding air into a tubular furnace, roasting for 6h at 500 ℃, replacing to be a hydrogen atmosphere after nitrogen purging, and reducing for 4h to obtain the dehydrogenation catalyst, wherein the composition of the catalyst is shown in Table 1.
(3) Dehydrogenation reaction method
The evaluation results are shown in Table 2, similarly to example 1.
Comparative example 2
(1) Catalyst and process for producing the same
Same as in example 1.
(2) Catalyst preparation
4mL of chloroplatinic acid salt solution with the concentration of 15mg/mL and 5mL of hydrochloric acid solution with the concentration of 80mg/mL are sequentially added into a triangular flask, 27mL of deionized water is added, and the pH value is adjusted to 1 to prepare an impregnation solution. Adding 20g of carrier into the impregnation solution, sealing the triangular bottle mouth with a sealing film, and placing on a shaking table to carry out shaking impregnation for 4h. Taking off the triangular flask, removing the redundant maceration extract, placing in an oven, drying at 120 deg.C for 2 hr, and transferring to a tubular furnace for roasting. The air space velocity for roasting is 16min -1 Air carrying deionized water enters a tube furnace, roasting is carried out for 8 hours at 500 ℃, nitrogen purging is carried out, then hydrogen atmosphere is replaced, and reduction is carried out for 4 hours to obtain a catalyst F, wherein the composition of the catalyst is shown in Table 1.
(3) Dehydrogenation process
The evaluation results are shown in Table 2, in the same manner as in example 1.
Example 5
(1) Catalyst and process for preparing same
The catalyst of example 1 was used.
(2) Catalyst preparation
Same as in example 1
(3) Dehydrogenation reaction method
The dehydrogenation is carried out in a fixed bed reaction system, 10g of prepared dehydrogenation catalyst is filled in a reactor, the pressure of a reaction device is set to be 0.1MPa, and the mass space velocity is set to be 0.5h -1 The hydrogen-oil molar ratio is 0, the reaction is carried out by adopting a nitrogen-adjacent reaction, the reaction raw material is methylcyclohexane, the temperature is increased after the raw material is fed, the operation is continuously carried out at 320 ℃, and the sampling is carried out every 12 hours. Analyzing the product composition of the sample by GC-MS, calculating the dehydrogenation of the raw material according to the compositionAnd selectivity to the target aromatic hydrocarbon toluene. The dehydrogenation effect on the continuous operation of methylcyclohexane is shown in Table 3.
Example 6
(1) Catalyst and process for producing the same
The catalyst of example 1 was used.
(2) Catalyst preparation
Same as in example 1
(3) Dehydrogenation process
The dehydrogenation is carried out in a fixed bed reaction system, 10g of prepared dehydrogenation catalyst is filled in a reactor, the pressure of a reaction device is set to be 0.1MPa, and the mass space velocity is set to be 0.5h -1 The hydrogen-oil molar ratio was 0.5, the reaction material was methylcyclohexane, the temperature was raised after the introduction of the raw material, the operation was continued at 320 ℃ and samples were taken every 12 hours. And analyzing the product composition of the sample by adopting GC-MS, and calculating the conversion rate of dehydrogenation of the raw material and the selectivity of generating the target aromatic hydrocarbon toluene according to the composition. The dehydrogenation effect on the continuous operation of methylcyclohexane is shown in Table 3.
It can be seen from comparison of examples 5 and 6 that although the initial activity of the reaction is higher in the non-hydrogen-contacting condition, the activity of the long-term operation decreases faster, and therefore the hydrogen-contacting condition is more advantageous for the long-term operation of the catalyst.
Comparative example 3
(1) Catalyst and process for preparing same
Catalyst a from example 1 was used.
(2) Catalyst preparation
Same as in example 1
(3) Dehydrogenation process
Dehydrogenation is carried out in a fixed bed reaction system, 10g of prepared catalyst A is filled in a reactor, the pressure of a reaction device is set to be 2.5MPa, and the mass space velocity is set to be 2h -1 The hydrogen-oil molar ratio is 1.5, methylcyclohexane is used as a raw material, the temperature is raised after the raw material is added, and the temperature is raised by 20 ℃ from 260 ℃ after sampling every 6 hours until the temperature is raised to 420 ℃. And analyzing the product composition of the sample by adopting GC-MS, and calculating the conversion rate of dehydrogenation of the raw material and the selectivity of generating the target aromatic hydrocarbon toluene according to the composition. The dehydrogenation effect on methylcyclohexane at different temperatures is shown in Table 2.
The comparison shows that the process condition selection has great influence on the dehydrogenation conversion rate besides the catalyst composition, and the low-pressure high-temperature conversion rate is higher. Under the low temperature condition, the catalyst composition and the reaction condition have great influence on the conversion rate, and under the high temperature condition, the temperature becomes the reaction leading factor, and the influence of the catalyst composition and the reaction condition is small.
For several raw materials participating in evaluation, the difficulty of the reaction of methylcyclohexane is the greatest in addition to cyclohexane, and the influence of the reaction performance of the catalyst and the process conditions on the conversion rate can be reflected, so that only the dehydrogenation conversion rate of methylcyclohexane is described in the examples.
TABLE 1 composition and Properties of the catalyst
TABLE 2 dehydrogenation effect of catalyst on methylcyclohexane
TABLE 3 Effect of hydrogen presence or absence on long-term operation of dehydrogenation system
| Running time, h | Example 5 non-Hydrogen | Example 6 Hydrogen |
| 12 | 100.00 | 99.62 |
| 100 | 74.85 | 99.50 |
It should be noted that the above examples are only used to illustrate the technical solution of the present invention and not to limit it. Although the present invention has been described in detail with reference to the examples given, it will be apparent to those skilled in the art that modifications and equivalents can be made thereto without departing from the spirit and scope of the invention as set forth in the appended claims.
Claims (10)
1. A process for the dehydrogenation of a hydrogenated aromatic compound, characterized in that a feed rich in hydrogenated aromatic compound and a dehydrogenation catalyst are fed to a dehydrogenation reactor at a temperature: 240-420 ℃, pressure: 0.01-2 MPa, mass space velocity: 1 to 5 hours -1 Carrying out dehydrogenation reaction under the condition that the molar ratio of hydrogen to oil is 0-1.0; the dehydrogenation catalyst is a non-sulfidation type catalyst and comprises an active component, chloride ions and a carrier; the active component at least contains a noble metal component in the VIII group, and accounts for 0.1-3% of the total weight of the dehydrogenation catalyst; the chloride ion accounts for 0.3 to 1.2 percent of the total weight of the dehydrogenation catalyst; the carrier is mainly gamma-Al 2 O 3 。
2. The dehydrogenation process of claim 1, wherein the active component comprises from 0.1 to 0.6% by weight of the total dehydrogenation catalyst; the chloride ion accounts for 0.3 to 0.9 percent of the total weight of the dehydrogenation catalyst; the specific surface area of the carrier is 180-240 m 2 The pore volume is 0.5-2.0 mL/g, and the pore diameter is 2-20 nm; the carrier is in the shape of at least one of a sphere, a bar, a cylinder and a clover.
3. The dehydrogenation process of claim 1, wherein the active component comprises at least one of Pt, pd, rh.
4. The dehydrogenation process of claim 3, wherein the active component is Pt.
5. The dehydrogenation process of claim 1, wherein the feedstock rich in hydrogenated aromatics is a fully or partially hydrogenated product obtained by hydrogenating aromatics rich feedstock.
6. The dehydrogenation process of claim 5, wherein the aromatic compound comprises 1-3 ring aromatics and 1-3 ring N-containing heteroarenes; the 1-3 cyclic aromatic hydrocarbon contains 0-3 side chains, and the length of the side chain is 1-3 carbon numbers.
7. The dehydrogenation method according to claim 1, wherein the dehydrogenation reaction has a reaction temperature of 260 to 320 ℃, a reaction pressure of 0.01 to 0.5MPa, and a mass space velocity of 1 to 3h -1 The molar ratio of hydrogen to oil is 0-0.6.
8. The dehydrogenation process of claim 1, wherein the dehydrogenation catalyst is prepared by:
s1: preparing a metal salt solution containing active components, and adjusting the pH value to 0-3 to form chlorine-containing impregnation liquid;
s2: mixing the impregnation liquid and the carrier, impregnating for 3-6 h, removing residual solution, drying for 2-6 h at 120-200 ℃, transferring into a tubular furnace, roasting for 4-8 h at 400-600 ℃, and cooling to obtain a dehydrogenation catalyst precursor;
s3: and reducing the dehydrogenation catalyst precursor for 4-8 h in a hydrogen atmosphere at the temperature of 300-600 ℃ to obtain the dehydrogenation catalyst.
9. The dehydrogenation process of claim 8, wherein the metal salt solution of the active component is at least one of a chlorate solution, a nitrate solution, and a sulfate solution; the chlorine contained in the chlorine-containing impregnating solution is derived from a chlorate solution of the active component and/or a chlorine-containing acid and/or a chloride component of the metal auxiliary.
10. The dehydrogenation process according to claim 8, wherein the roasting process of step S2 is performed in a circulating air atmosphere containing deionized water; the roasting process is a temperature programming process, and the temperature rising rate is 2-5 ℃/min.
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