CN109663613A - A kind of metal-modified ZSM-5 molecular sieve catalyst and its preparation and application - Google Patents
A kind of metal-modified ZSM-5 molecular sieve catalyst and its preparation and application Download PDFInfo
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- CN109663613A CN109663613A CN201710965900.3A CN201710965900A CN109663613A CN 109663613 A CN109663613 A CN 109663613A CN 201710965900 A CN201710965900 A CN 201710965900A CN 109663613 A CN109663613 A CN 109663613A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 60
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 95
- 239000002245 particle Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- -1 hydrocarbons Hydrocarbon Chemical class 0.000 claims description 7
- 238000007233 catalytic pyrolysis Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 241000209094 Oryza Species 0.000 claims 2
- 235000007164 Oryza sativa Nutrition 0.000 claims 2
- 235000009566 rice Nutrition 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 22
- 239000000377 silicon dioxide Substances 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 13
- 229910044991 metal oxide Inorganic materials 0.000 description 11
- 238000004230 steam cracking Methods 0.000 description 10
- 150000004706 metal oxides Chemical class 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000004523 catalytic cracking Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004231 fluid catalytic cracking Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 150000002910 rare earth metals Chemical group 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 229910021144 KVO3 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/46—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of metal-modified ZSM-5 molecular sieve catalyst and its preparations and application.The catalyst be by modified metal element in the form of its nano-oxide, ZSM-5 molecular sieve is modified by hydro-thermal method and is prepared, the modified metal element is selected from one of Mn, Cu, Fe, Zr, Ti and Mo or a variety of any mixing, it is in terms of 100% by the ZSM-5 molecular sieve total weight in the catalyst being prepared, the weight ratio of the modified metal element is 0.005-15%.Molecular sieve catalyst and preparation method of the invention has the advantages that easy to operate, and no high-temperature operation reduces energy consumption, improves the utilization rate of modifying element.
Description
Technical field
The present invention relates to chemical fields, particularly relate to catalyst field, more particularly to hydrocarbon pyrolysis system
The catalyst field of standby alkene, then particularly relate to a kind of metal-modified ZSM-5 molecular sieve catalyst and its preparation and answer
With.
Background technique
Ethylene, propylene are important industrial chemicals.Since nearly half a century, ethylene is mainly derived from steam cracking, and
Propylene is mainly derived from the by-product of naphtha steam cracking and fluid catalytic cracking (FCC) process.For steam cracking be
850 DEG C or more of high temperature carries out the process of vapor thermal cracking to naphtha, and on the one hand its process energy input is produced in petrochemical industry
It is the largest in industry, although continuing to optimize for steam cracking process, does not solve the problems, such as from source, causes the technique
Process energy consumption and carbon emission still remain high.In addition, the influence of the impacted type in raw material of steam cracking process itself is very
Greatly, and Pyrolysis Mechanism causes it that cannot effectively control the ratio of the product of naphtha pyrolysis propylene and ethylene.Catalytic pyrolysis
Producing light olefins technique then in the presence of a catalyst, using compared with the lower reaction temperature of steam cracking (600-650 DEG C) to lighter hydrocarbons
Catalytic cracking reaction is carried out, process energy consumption, which is not only greatly reduced, reduces carbon emission, and since the effect technique of catalyst can
Develop into the highly selective technology for preparing low-carbon alkene.In recent years, the industrial requirement of ethylene, propylene constantly increases, and especially third
Alkene growth rate is greater than ethylene.In recent years, in order to meet growing propylene demand, exploitation Deep Catalytic Cracking process substitution tradition is steamed
Vapour cracking olefin process processed obtains government and industrial department and researcher more and more pays close attention to, and the implementation of the technique is not only realized
Energy saving technology consumption reduction, and propylene and ethylene ratio (P/E ratio) can be controlled, improve the flexibility of device.
Both at home and abroad is in the research of Deep Catalytic Cracking process the primary stage at present, the core emphasis of technique is still catalysis
Agent designs and prepares.In order to improve yield of light olefins, people once used multiple catalysts metal oxide catalyst and solid
Acid catalyst etc..Since nineteen sixty, people begin to use metal oxide catalyst such as CaO, Al2O3, SrO, MgO, TiO2,
MnO2, Mn2O3, ZrO2, K2O and In2O3Deng.Using metal oxide catalyst under different reaction raw materials and reaction temperature second
Alkene yield is in 24-40%, and propene yield is in 15-22%.Using load K2CO3Calcium aluminate and load KVO3Aluminium oxide urge
Agent result is preferable, and 5-10% is improved compared with the steam cracking under 780-820 DEG C of part.Metal oxide catalyst has been used,
Deactivation prob of the catalyst under high reaction temperature and a large amount of steaming not can solve for the improvement of metal oxide catalyst
Vapour consumption, carbon distribution is too fast to be greatly reduced capacity usage ratio.
What it is for catalytic cracking catalyst most study is exactly solid acid catalyst, wherein most widely used and most importantly
Molecular sieve catalyst.Molecular sieve is widely used in industrialized petroleum refining and chemical field.Such as ZSM-5 molecular sieve is being urged
Change cracking reaction, be alkylated, is widely applied in aromatisation and isomerization reaction as active component or carrier, mainly due to it
Acidity, shape selectivity, ion exchange property and unique pore structure and biggish specific surface area.Although molecular sieve catalyst
It has many good qualities, but it has a short service life for high temperature hydro-thermal reaction, the very fast disadvantage of carbon distribution makes it in industrialized production
On need to be further improved.Returning its reason, mainly molecular sieve plug-hole or acidic site caused by carbon deposit cover during the reaction
Lid, there are also framework dealuminations caused by high temperature hydro-thermal during the reaction, these are the reason of causing molecular sieve to inactivate.It is general next
It says, coking deactivation can be such that molecular sieve activity replys by regenerating molecular sieve, and the latter is non-renewable irreversible inactivation, because
While how this, which passes through modification, is regulated the acidic site of molecular sieve, keep stablizing for its acidic site most important.
In recent years, people have carried out various modifications to molecular sieve, this just includes modification of the rare earth element to it.It is rare earth modified
Good application has been obtained on FCC catalyst, can be improved the stability of catalyst, the production of activity and gasoline component
Rate.By the way that using a variety of hydro carbons as raw material, low-carbon alkene receipts can be improved using modified ZSM-5 as the deep catalytic cracking technology of catalyst
Rate.Catalytic cracking reaction temperature is at 550-600 DEG C, this about 200 DEG C lower than steam cracking temperature, diene yield and steam cracking are bright
It is aobvious to improve.Influence of the selection of raw material for catalytic pyrolysis, can be by adjusting catalyst unlike so big to steam cracking
Sour type, acid distribution and change reaction condition control P/E.Research is established relevant theory practice basis and is split with serving in catalysis
The industrialized production of solution.
Patent CN1093952A discloses a kind of hydrothermal modification method for improving rare earth exchanged rate, has obtained highest friendship
Change the La of rate 70%3+Exchange ZSM-5 catalyst.The rare-earth salts of 0.5-2mol/L is added in this method selection in closed pressure resistant container
Solution, is added liquor capacity and molecular sieve volume ratio is 5-50, and exchange temperature is 100-300 DEG C, and exchange pressure is 101.3Kpa-
8590Kpa.The patent proposes preferable modified thinkings, but reaction temperature is higher, and pressure is larger and rare-earth salt solution is added
It is denseer, there may be excessive rare earth element ion, cause molecular sieve pore passage obstruction and the decline of modified acidic zeolite excessive,
It is unfavorable for its application in the reaction.
In view of the foregoing, The present invention gives a kind of method of modifying of new introducing transition metal element.
Summary of the invention
It is an object of the present invention to provide a kind of metal-modified ZSM-5 molecular sieve catalyst.Molecular sieve of the invention
Acidity obtain reasonable modulation, carried out in light hydrocarbon cracking reaction process using the catalyst, higher reaction work can be obtained
Property and ethylene, propylene selectivity.
Another object of the present invention is to provide the preparation methods of the metal-modified ZSM-5 molecular sieve catalyst.It should
Method is compared with traditional infusion process, it is possible to reduce modifying element additional amount improves the utilization rate of modifying element, preparation process letter
It is single controllable, and modified performance is obviously improved.
A further object of the present invention is to provide a kind of methods that lighter hydrocarbons catalytic pyrolysis prepares low-carbon alkene.
In order to achieve the above object, on the one hand, the present invention provides a kind of metal-modified ZSM-5 molecular sieve catalyst, wherein institute
Stating catalyst is modified by hydro-thermal method to ZSM-5 molecular sieve by modified metal element in the form of its nano-oxide
It is prepared, the modified metal element is selected from one of Mn, Cu, Fe, Zr, Ti and Mo or a variety of mixing, to be prepared into
To catalyst in ZSM-5 molecular sieve total weight be 100% meter, the weight ratio of the modified metal element is 0.005-
15%.
The ZSM-5 molecular sieve that wherein present invention uses can be prepared by literature methods, or be bought by commercial sources,
And some specific embodiments according to the present invention, wherein the silica alumina ratio of the ZSM-5 molecular sieve is 10-500.
Some specific embodiments according to the present invention, wherein the silica alumina ratio of the ZSM-5 molecular sieve is 20-300.
Some specific embodiments according to the present invention, wherein the reaction condition of the hydro-thermal method includes: that temperature is 100-
300℃。
Some specific embodiments according to the present invention, wherein the reaction condition of the hydro-thermal method includes: that temperature is 180-
270℃。
Some specific embodiments according to the present invention, wherein the reaction condition of the hydro-thermal method further include: reaction pressure is
101-8000Kpa。
Some specific embodiments according to the present invention, wherein the reaction condition of the hydro-thermal method further include: reaction pressure is
1000-5500Kpa。
Some specific embodiments according to the present invention, wherein the reaction condition of the hydro-thermal method include: the reaction time be 6-
48h。
Some specific embodiments according to the present invention, wherein the reaction condition of the hydro-thermal method includes: the reaction time to be
10-24h。
Some specific embodiments according to the present invention, wherein the reaction condition of the hydro-thermal method includes: temperature 100-300
DEG C, reaction pressure 101Kpa-8000Kpa, reaction time 6-48h.
Some specific embodiments according to the present invention, wherein the reaction condition of the hydro-thermal method includes: that temperature is 180-
270 DEG C, reaction pressure 1000-5500Kpa, reaction time 10-24h.
The nano-metal-oxide that wherein present invention uses is bought by commercial sources, and some specific realities according to the present invention
Apply scheme, wherein the particle diameter of the nano-oxide of the modified metal element is 10-500nm.
In order to obtain the more uniform oxide of size distribution, other specific embodiments according to the present invention, wherein institute
Nano-metal-oxide is stated according to document Catalytic effect of two-phase intergrowth and
coexistence CuO–CeO2[J] (Jiahui Ma, Guangzhou Jin, Junbin Gao, waits ..Journal of
Materials Chemistry A, 2015,3 (48): 24358-24370.) provided by method prepare (present invention implement
The metal nano oxide particle of example is according to document Catalytic effect of two-phase intergrowth and
coexistence CuO–CeO2It is made).
Some specific embodiments according to the present invention, wherein the particle of the nano-oxide of the modified metal element is straight
Diameter is 15-150nm.
Some specific embodiments according to the present invention, wherein the particle of the nano-oxide of the modified metal element is straight
Diameter is distributed in the range of ± 30nm.
Some specific embodiments according to the present invention, wherein the particle of the nano-oxide of the modified metal element is straight
Diameter is distributed in the range of ± 15nm.
Some specific embodiments according to the present invention, wherein the particle of the nano-oxide of the modified metal element is straight
Diameter is distributed in the range of ± 10nm.
Some specific embodiments according to the present invention, wherein the nano-oxide of the modified metal element be selected from MnO,
MnO2、Mn2O3、CuO、CuO2、FeO、Fe2O3、Fe3O4、TiO2、ZrO2、MoO2、MoO3One of or a variety of combinations.
Some specific embodiments according to the present invention, wherein the hydro-thermal method is by the nano oxidized of modified metal element
Object and ZSM-5 molecular sieve are reacted in the medium after mixing.
Some specific embodiments according to the present invention, wherein the present invention is under stiring by the nanometer of modified metal element
Oxide and ZSM-5 molecular sieve are mixed, and continuing stirring after charging keeps molecular sieve and modifying element oxide sufficiently mixed
It closes.
Some specific embodiments according to the present invention, wherein continue after charging stir 15min-5h make molecular sieve with
Modifying element oxide is sufficiently mixed.
Some specific embodiments according to the present invention, wherein mass of medium is 1-10 times of molecular sieve quality.
Some specific embodiments according to the present invention, wherein the medium is water.
Some specific embodiments according to the present invention, wherein after hydro-thermal reaction, further include by reaction solution filter or
Dry step, to obtain the metal-modified ZSM-5 molecular sieve catalyst.
Some specific embodiments according to the present invention, wherein after hydro-thermal reaction, directly done without filtering
It is dry, to obtain the metal-modified ZSM-5 molecular sieve catalyst.
The present invention can guarantee that whole metal oxides, which are added, to be remained in modified sample, does not have pumping without suction filtration
It is lost caused by filter.
Some specific embodiments according to the present invention, wherein 50-150 DEG C of dry temperature range.
Some specific embodiments according to the present invention, wherein the dry time is 2h-20h.
On the other hand, described the present invention also provides the preparation method of the metal-modified ZSM-5 molecular sieve catalyst
Method includes being modified by hydro-thermal method to ZSM-5 molecular sieve by modified metal element in the form of its nano-oxide, from
And obtain the metal-modified ZSM-5 molecular sieve catalyst.
In another aspect, the present invention also provides a kind of methods that lighter hydrocarbons catalytic pyrolysis prepares low-carbon alkene, wherein the side
Method include using lighter hydrocarbons as raw material, using metal-modified ZSM-5 molecular sieve catalyst described in any one of the present invention as catalyst into
Row reaction prepares low-carbon alkene.
Some specific embodiments according to the present invention, wherein the lighter hydrocarbons are the alkane and/or alkene that carbon atom number is 4-8
Hydrocarbon.
Some specific embodiments according to the present invention, wherein the lighter hydrocarbons are ethylene, propylene, 1- butylene, 2- butylene, different
One of butylene and 1,3- butadiene or a variety of mixing.
Some specific embodiments according to the present invention, wherein the condition of the reaction includes: that reaction temperature is 500-700
℃。
Some specific embodiments according to the present invention, wherein reaction condition further includes that air speed is 0.5-15h-1。
Some specific embodiments according to the present invention, wherein reaction condition further includes that pressure is normal pressure.
Some specific embodiments according to the present invention, wherein reaction condition further includes that carrier gas is nitrogen or vapor, carrier gas
It is 5-15 with raw gas flow ratio.
Some specific embodiments according to the present invention, wherein reactor is fixed bed or fluidized-bed reactor.
In conclusion the present invention provides a kind of metal-modified ZSM-5 molecular sieve catalyst and its preparations and application.This hair
Bright catalyst has the advantages that
Molecular sieve catalyst and preparation method of the invention has the advantages that easy to operate, and no high-temperature operation reduces
Energy consumption, modified effect is more preferable than traditional approach, improves catalyst to the selectivity of low-carbon alkene, in long period reaction substantially
Degree strengthens the reaction service life, has preferable application value.
Detailed description of the invention
Fig. 1 is experimental example reaction process equipment schematic diagram of the present invention.
Fig. 2 is the XRD spectrum of various embodiments of the present invention and comparative example product.
The a of Fig. 3 is the electron microscope of 1 catalyst of embodiment, and b is the electron microscope of 2 catalyst of comparative example.
Fig. 4 is the MnO of embodiment 12Particle electron microscope, as can be seen from Figure metal oxide particle size distribution are concentrated；
Also there is the metal oxide particle electron microscope of other embodiments the metal oxide particle size distribution similar with Fig. 4 to concentrate
Characteristic.
Specific embodiment
Below by way of the beneficial effect of the specific embodiment implementation process that the present invention will be described in detail and generation, it is intended to which help is read
Reader more fully understands essence and feature of the invention, does not limit the scope of the present invention.
Embodiment 1
The partial size that 0.03g is prepared is the MnO of 80nm ± 10nm2Particle (electron microscope is as shown in Figure 4) and 10g silica alumina ratio
It is sufficiently mixed for 20 HZSM-5, is sufficiently stirred after being slowly added to 20g deionized water, it is anti-that which is transferred to high temperature
It answers in kettle, takes out reaction kettle after reacting 12h at 240 DEG C, reaction pressure is normal pressure, is cooled to room temperature in air, is opened anti-
Kettle cover is answered, 10h is dried at 100 DEG C, obtains catalyst fines.The catalyst is pushed into sheetmolding in 20Mpa, sieves 40-80
Purpose particle obtains the catalyst for evaluation.The XRD spectrum of product is as shown in Fig. 2, product electromicroscopic photograph is as shown in Figure 3.
Embodiment 2
The CuO particle that the partial size that 0.01g is prepared is 100nm ± 10nm and the HZSM-5 that 10g silica alumina ratio is 100 are abundant
Mixing, is sufficiently stirred after being slowly added to 20g deionized water, which is transferred in pyroreaction kettle, at 240 DEG C
Reaction kettle is taken out after reaction 12h, reaction pressure is normal pressure, is cooled to room temperature in air, reaction kettle cover is opened, at 100 DEG C
10h is dried, catalyst fines are obtained.The catalyst is pushed into sheetmolding in 20Mpa, the particle of 40-80 mesh is sieved, is used for
The catalyst of evaluation.
Embodiment 3
The partial size that 0.02g is prepared is the Fe of 120nm ± 10nm2O3The HZSM-5 that particle is 200 with 10g silica alumina ratio fills
Divide mixing, is sufficiently stirred after being slowly added to 20g deionized water, which is transferred in pyroreaction kettle, at 240 DEG C
Reaction kettle is taken out after lower reaction 12h, reaction pressure is normal pressure, is cooled to room temperature in air, reaction kettle cover is opened, at 100 DEG C
Lower drying 10h, obtains catalyst fines.The catalyst is pushed into sheetmolding in 20Mpa, the particle of 40-80 mesh is sieved, is used
In the catalyst of evaluation.
Embodiment 4
The partial size that 2g is prepared is the MnO of 120nm ± 10nm2The HZSM-5 that particle and 10g silica alumina ratio are 300 is sufficiently mixed
It closes, is sufficiently stirred after being slowly added to 20g deionized water, which is transferred in pyroreaction kettle, it is anti-at 150 DEG C
Reaction kettle is taken out after answering 12h, reaction pressure is normal pressure, is cooled to room temperature in air, opens reaction kettle cover, dries at 80 DEG C
10h obtains catalyst fines.The catalyst is pushed into sheetmolding in 20Mpa, the particle of 40-80 mesh is sieved, obtains for evaluating
Catalyst.
Embodiment 5
The partial size that 2.5g is prepared is the MnO of 150nm ± 10nm2The partial size of particle and 0.15g are 130nm ± 10nm's
The HZSM-5 that CuO and 10g silica alumina ratio is 50 is sufficiently mixed, and is sufficiently stirred after being slowly added to 20g deionized water, which is mixed
Object is transferred in pyroreaction kettle, takes out reaction kettle after reacting 12h at 260 DEG C, reaction pressure is normal pressure, is cooled down in air
To room temperature, reaction kettle cover is opened, 10h is dried at 110 DEG C, obtains catalyst fines.By the catalyst 20Mpa lower sheeting at
Type sieves the particle of 40-80 mesh, obtains the catalyst for evaluation.
Embodiment 6
The partial size that 0.03g is prepared is the MnO of 150nm ± 10nm ± 10nm2The partial size of particle and 0.02g are 300nm
The Fe of ± 10nm3O4The HZSM-5 for being 30 with 10g silica alumina ratio is sufficiently mixed, and is sufficiently stirred after being slowly added to 20g deionized water, will
The solidliquid mixture is transferred in pyroreaction kettle, takes out reaction kettle after reacting 12h at 210 DEG C, and reaction pressure is normal pressure,
It is cooled to room temperature in air, opens reaction kettle cover, dry 10h at 100 DEG C, obtain catalyst fines.The catalyst is existed
20Mpa pushes sheetmolding, sieves the particle of 40-80 mesh, obtains the catalyst for evaluation.
Embodiment 7
The partial size of CuO particle and 0.02g that the partial size that 0.01g is prepared is 70nm ± 10nm is 500nm ± 10nm's
Fe3O4The Fe for being 100nm ± 10nm with 0.01g partial size2O3The HZSM-5 for being 30 with 10g silica alumina ratio is sufficiently mixed, and is slowly added to
It is sufficiently stirred after 20g deionized water, which is transferred in pyroreaction kettle, taken out after reacting 12h at 240 DEG C
Reaction kettle, reaction pressure are normal pressure, are cooled to room temperature in air, open reaction kettle cover, dry 10h at 140 DEG C, urged
Agent powder.The catalyst is pushed into sheetmolding in 20Mpa, the particle of 40-80 mesh is sieved, obtains the catalyst for evaluation.
Embodiment 8
The partial size that 0.01g is prepared is the ZrO of 200nm ± 10nm2The partial size of particle and 0.02g are 200nm ± 10nm
Fe3O4The Fe for being 100nm ± 10nm with 0.01g partial size2O3The HZSM-5 for being 30 with 10g silica alumina ratio is sufficiently mixed, and is slowly added to
It is sufficiently stirred after 20g deionized water, which is transferred in pyroreaction kettle, taken out after reacting 6h at 240 DEG C
Reaction kettle, reaction pressure are normal pressure, are cooled to room temperature in air, open reaction kettle cover, dry 10h at 140 DEG C, urged
Agent powder.The catalyst is pushed into sheetmolding in 20Mpa, the particle of 40-80 mesh is sieved, obtains the catalyst for evaluation.
Embodiment 9
The partial size that 0.01g is prepared is the MnO of 150nm ± 10nm2The partial size of particle and 0.02g are 130nm ± 10nm
ZrO2The Fe for being 100nm ± 10nm with 0.01g partial size2O3The HZSM-5 for being 30 with 10g silica alumina ratio is sufficiently mixed, and is slowly added to
It is sufficiently stirred after 20g deionized water, which is transferred in pyroreaction kettle, reacted at 240 DEG C and take out afterwards for 24 hours
Reaction kettle, reaction pressure are normal pressure, are cooled to room temperature in air, open reaction kettle cover, dry 10h at 140 DEG C, urged
Agent powder.The catalyst is pushed into sheetmolding in 20Mpa, the particle of 40-80 mesh is sieved, obtains the catalyst for evaluation.
Embodiment 10
The partial size of CuO particle and 0.02g that the partial size that 0.02g is prepared is 150nm ± 10nm is 100nm ± 10nm's
ZrO2The HZSM-5 for being 30 with 10g silica alumina ratio is sufficiently mixed, and is sufficiently stirred after being slowly added to 20g deionized water, which is mixed
It closes object to be transferred in pyroreaction kettle, takes out reaction kettle after reacting 12h at 240 DEG C, reaction pressure is normal pressure, cold in air
But to room temperature, reaction kettle cover is opened, 10h is dried at 140 DEG C, obtains catalyst fines.By the catalyst in 20Mpa lower sheeting
Molding sieves the particle of 40-80 mesh, obtains the catalyst for evaluation.
Embodiment 11
The partial size of CuO particle and 0.01g that the partial size that 0.02g is prepared is 150nm ± 10nm is 100nm ± 10nm's
TiO2The HZSM-5 for being 30 with 10g silica alumina ratio is sufficiently mixed, and is sufficiently stirred after being slowly added to 20g deionized water, which is mixed
It closes object to be transferred in pyroreaction kettle, takes out reaction kettle after reacting 12h at 240 DEG C, reaction pressure is normal pressure, cold in air
But to room temperature, reaction kettle cover is opened, 10h is dried at 140 DEG C, obtains catalyst fines.By the catalyst in 20Mpa lower sheeting
Molding sieves the particle of 40-80 mesh, obtains the catalyst for evaluation.
Embodiment 12
The partial size that 0.02g is prepared is the Fe of 150nm ± 10nm2O3The partial size of particle and 0.01g are 100nm ± 10nm
MoO2The HZSM-5 for being 30 with 10g silica alumina ratio is sufficiently mixed, and is sufficiently stirred after being slowly added to 20g deionized water, by the solid-liquid
Mixture is transferred in pyroreaction kettle, takes out reaction kettle after reacting 12h at 240 DEG C, reaction pressure is normal pressure, in air
It is cooled to room temperature, opens reaction kettle cover, dry 10h at 140 DEG C, obtain catalyst fines.The catalyst is pushed in 20Mpa
Sheetmolding sieves the particle of 40-80 mesh, obtains the catalyst for evaluation.
Embodiment 13
The partial size that 0.02g is prepared is the MnO of 150nm ± 30nm2The partial size of particle and 0.01g are 100nm ± 10nm
MoO3The HZSM-5 for being 30 with 10g silica alumina ratio is sufficiently mixed, and is sufficiently stirred after being slowly added to 20g deionized water, by the solid-liquid
Mixture is transferred in pyroreaction kettle, takes out reaction kettle after reacting 12h at 240 DEG C, reaction pressure is normal pressure, in air
It is cooled to room temperature, opens reaction kettle cover, dry 10h at 140 DEG C, obtain catalyst fines.The catalyst is pushed in 20Mpa
Sheetmolding sieves the particle of 40-80 mesh, obtains the catalyst for evaluation.
Comparative example 1
20g deionized water is slowly added in the HZSM-5 molecular sieve that 10g silica alumina ratio is 20 and is sufficiently stirred after being sufficiently mixed
It mixes, which is transferred in pyroreaction kettle, take out reaction kettle after reacting 12h at 240 DEG C, cool down in air
To room temperature, material dries 10h at 140 DEG C, obtains catalyst fines.The catalyst is pushed into sheetmolding, screening in 20Mpa
The particle of 40-80 mesh obtains the catalyst for evaluation.
Comparative example 2
The partial size that 0.06g is prepared is the MnO of 100nm2The HZSM-5 for being 20 with 10g silica alumina ratio is sufficiently mixed, slowly
It is sufficiently stirred after 20g deionized water is added, which is transferred in pyroreaction kettle, after reacting 12h at 50 DEG C
Reaction kettle is taken out, is cooled to room temperature in air, reaction kettle cover is opened, dries 10h at 100 DEG C, obtain catalyst fines.It will
The catalyst pushes sheetmolding in 20Mpa, sieves the particle of 40-80 mesh, obtains the catalyst for evaluation.
Comparative example 3
0.6g manganese acetate is added in 100ml volumetric flask and prepares solution, the HZSM-5 for being 20 with 10g silica alumina ratio is sufficiently mixed
It closes, is sufficiently stirred after being slowly added to 20g deionized water, which is transferred in pyroreaction kettle, it is anti-at 240 DEG C
Reaction kettle is taken out after answering 12h, is cooled to room temperature in air, reaction kettle cover is opened, dries 10h at 100 DEG C, obtain catalyst
Powder.The catalyst is pushed into sheetmolding in 20Mpa, the particle of 40-80 mesh is sieved, obtains the catalyst for evaluation.
Experimental example
The reactivity worth evaluation of catalyst carries out in continuous fixed bed reactor, and process is as shown in Figure 1, reaction tube
Internal diameter is 10mm, a length of 400mm, loaded catalyst 0.5g, and silica wool is loaded at both ends.N is used before reaction2Purge 1h, reactant
Reactor is squeezed into using micro pump, before entering the reactor with carrier N2Enter reactor, reactor outlet end product after mixing
Divide two-way, a part is directly entered gas-chromatography on-line quantitative analysis by heat preservation, and another part directly empties.Catalyst is commented
Valence condition are as follows: 630 DEG C, normal pressure, reaction raw materials are model compound n-hexane, and feedstock quality air speed is 8h-1.Product is by SP-
3420 type gas-chromatography on-line analyses, reaction product pass through gas-chromatography on-line analysis.
Product distribution and calculation method
When using n-hexane as raw material, the conversion ratio and selectivity of n-hexane calculate as follows respectively:
In formulaWithN-hexane mass fraction respectively in raw material and product, wCiHjtFor something in product
The mass fraction of matter.
Catalyst life data, which are used, drops to for 90% time for reference from starting to be fed to conversion ratio.As a result such as table 1
It is shown.
The reaction result of 1 embodiment and comparative example of table
Claims (10)
1. a kind of metal-modified ZSM-5 molecular sieve catalyst, wherein the catalyst is by modified metal element with its nano oxygen
The form of compound, is modified ZSM-5 molecular sieve by hydro-thermal method and is prepared, the modified metal element be selected from Mn, Cu,
One of Fe, Zr, Ti and Mo or a variety of any mixing, with the ZSM-5 molecular sieve total weight in the catalyst that is prepared
For 100% meter, the weight ratio of the modified metal element is 0.005-15%.
2. metal-modified ZSM-5 molecular sieve catalyst according to claim 1, wherein the sial of the ZSM-5 molecular sieve
Than for 10-500, preferably 20-300.
3. metal-modified ZSM-5 molecular sieve catalyst according to claim 1, wherein the reaction condition of the hydro-thermal method
Include: temperature be 100-300 DEG C, the preferably 180-270 DEG C (reaction condition of the preferably described hydro-thermal method further include: reaction pressure
For 101-8000Kpa, preferably 1000-5500Kpa).
4. metal-modified ZSM-5 molecular sieve catalyst according to claim 1 or 3, wherein the reaction item of the hydro-thermal method
Part include: the reaction time be 6-48h, preferably 10-24h.
5. metal-modified ZSM-5 molecular sieve catalyst according to claim 1, wherein the modified metal element is received
The particle diameter of rice oxide is 10-500nm, preferably 15-150nm.
6. metal-modified ZSM-5 molecular sieve catalyst according to claim 5, wherein the modified metal element is received
The particle diameter of rice oxide is distributed in the range of ± 30nm；Preferably ± 15nm；More preferably ± 10nm.
7. metal-modified ZSM-5 molecular sieve catalyst according to claim 1, wherein the hydro-thermal method is will to be modified gold
Belong to element nano-oxide and ZSM-5 molecular sieve after mixing medium (preferably mass of medium be molecular sieve quality 1-
10 times) it is reacted in (the preferably described medium be water).
8. metal-modified ZSM-5 molecular sieve catalyst according to claim 1 or claim 7, wherein after hydro-thermal reaction,
(preferably 50-150 DEG C of drying temperature range, more preferably dry time are 2h-20h) is directly dried without filtering, from
And obtain the metal-modified ZSM-5 molecular sieve catalyst.
9. the preparation method of metal-modified ZSM-5 molecular sieve catalyst, the method described in claim 1~8 any one
Including modified metal element in the form of its nano-oxide, is modified ZSM-5 molecular sieve by hydro-thermal method, thus
To the metal-modified ZSM-5 molecular sieve catalyst.
10. a kind of method that lighter hydrocarbons catalytic pyrolysis prepares low-carbon alkene, wherein the method includes (preferably described light with lighter hydrocarbons
Hydrocarbon is the alkane and/or alkene that carbon atom number is 4-8) it is raw material, with metal-modified described in claim 1~7 any one
ZSM-5 molecular sieve catalyst is that catalyst carries out reaction and prepares low-carbon alkene (condition of the preferably described reaction includes: reaction temperature
For 500-700 DEG C, (preferred reaction conditions further include that air speed is 0.5-15h-1；(preferably pressure is normal pressure)；(preferably carrier gas is nitrogen
Or vapor, carrier gas and raw gas flow ratio are 5-15))).
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| CN112322322A (en) * | 2020-10-21 | 2021-02-05 | 中国石油大学(北京) | Alkane-alkene co-cracking catalyst and alkane-alkene mixed catalytic cracking method |
| CN114146724A (en) * | 2021-12-01 | 2022-03-08 | 南宁师范大学 | Preparation method of modified ZSM-5 molecular sieve |
| CN115261057A (en) * | 2022-07-17 | 2022-11-01 | 中国石油化工股份有限公司 | Method for directly producing olefin and aromatic hydrocarbon by catalytically cracking gasoline |
| DE112022005508T5 (en) | 2022-09-30 | 2024-09-19 | Petrochina Company Limited | METAL-MODIFIED ZSM-5 MOLECULAR SIEVE CATALYST, PRODUCTION PROCESS AND APPLICATION THEREOF |
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