CN105772065A - Modified ZSM-5 molecular sieve based catalyst and preparing method thereof - Google Patents
Modified ZSM-5 molecular sieve based catalyst and preparing method thereof Download PDFInfo
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- CN105772065A CN105772065A CN201610227693.7A CN201610227693A CN105772065A CN 105772065 A CN105772065 A CN 105772065A CN 201610227693 A CN201610227693 A CN 201610227693A CN 105772065 A CN105772065 A CN 105772065A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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Abstract
The invention discloses a preparing method of a modified ZSM-5 molecular sieve based catalyst.The preparing method comprises the following steps that firstly, modification preparation of a Cu/ZSM-5 molecular sieve is carried out, wherein an equivalent-volume impregnation method is adopted, a copper nitrate solution and a ZSM-5 molecular sieve are mixed evenly according to the copper loading amount of 1-10wt%, room-temperature impregnation is carried for 2-12 h, and the mixture is dried to the constant weight at 50-120 DEG C, roasted for 2 h at 550 DEG C, then subjected to reduction roasting for 2-6 h at 200-400 DEG C in a hydrogen atmosphere, and then cooled to the room temperature; secondly, modification preparation of an I-Cu/ZSM-5 molecular sieve is carried out, wherein the equivalent-volume impregnation method is adopted, an iodine-containing speciation solution and the Cu/ZSM-5 molecular sieve obtained in the first step are mixed evenly according to the loading amount of 1-10wt%, room-temperature ultrasonic impregnation is carried for 10-30 min first, then conventional impregnation is carried out for 2-12 h, and the mixture is dried to the constant weight at 50-105 DEG C.By means of the preparing method of the modified ZSM-5 molecular sieve based catalyst, the low-temperature conversion rate of methyl alcohol can be increased, the low-carbon olefin selectivity can be improved, and the service life is long.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to the preparation method of a kind of ZSM-5 Type Zeolites agent.
Background technology
ZSM-5 molecular sieve is that the one that develops of Mobile company of the U.S. is by SiO4And AlO4Tetrahedron forms and has the zeolite micropore molecular sieve of three dimensional intersection network straight passage structures.The feature such as have that hydrothermal stability is good, specific surface area big because of it and shape selective catalysis function is strong, has been widely used in coal-based methanol preparing low-carbon olefins (MTO) technical matters.
Owing to ZSM-5 molecular sieve duct is relatively big and surface acidity is relatively strong, this molecular sieve generally need to be modified by industrial applications.At present, mainly take the methods such as various metallic element dipping or doping, soda acid or high temperature hydro-thermal desiliconization dealuminzation that ZSM-5 molecular sieve is modified.It is now recognized that compare at preparing light olefins from methanol (MTO) technological reaction temperature (430-550 DEG C) conveniently, the work of these study on the modification has a significant effect to improving catalytic efficiency, and modified ZSM-5 molecular sieve has relatively high methanol conversion ratio and target product selectivity.But in industrialization, higher reaction temperatures not only increases product specific energy consumption, also can accelerate formation of carbon, causes rapid catalyst deactivation to need frequent regeneration, and production cost increases further.Visible, existing MTO technique exist reaction temperature higher cause that product specific energy consumption is high, catalyst easy carbon distribution inactivation and need the deficiencies such as frequent regeneration.
Owing to reaction temperature is notable on methanol conversion impact, reduce product specific energy consumption by the approach reducing reaction temperature, it is necessary to solve how to improve the key issue of low-temperature methanol conversion ratio.
Summary of the invention
It is an object of the invention to overcome disadvantages mentioned above and provide one can improve low-temperature methanol conversion ratio and selectivity of light olefin, service life length the preparation method of ZSM-5 Type Zeolites agent.
It is an object of the invention to be achieved through the following technical solutions.
The preparation method of a kind of ZSM-5 Type Zeolites agent of the present invention, comprises the following steps:
(1) the modified preparation of Cu/ZSM-5 molecular sieve: use equi-volume impregnating, by copper load capacity 1-10 wt.%, copper nitrate solution is mixed homogeneously with ZSM-5 molecular sieve, normal temperature dipping 2-12h, dry to constant weight in 50-120 DEG C, after 550 DEG C of roasting 2h in hydrogen atmosphere 200-400 DEG C of reduction roasting 2-6h, after be cooled to room temperature；
(2) the modified preparation of I-Cu/ZSM-5 molecular sieve: use equi-volume impregnating, iodine species solution Cu/ZSM-5 molecular sieve prepared with step (1) will be contained by load capacity 1-10 wt.% to mix homogeneously, first room temperature ultrasonic immersing 10-30min, rear conventional dipping 2-12h, dry to constant weight in 50-105 DEG C.
The preparation method of above-mentioned a kind of ZSM-5 Type Zeolites agent, wherein: described ZSM-5 molecular sieve refers to the Hydrogen ZSM-5 molecular sieve that silica alumina ratio is 100-400；
The preparation method of above-mentioned a kind of ZSM-5 Type Zeolites agent, wherein: described is iodo-methanol solution, hydroiodic acid solution, iodic acid solution, iodomethane solution, IodineSodium Solution or liquor kalii iodide containing iodine species solution.
The present invention is compared with prior art, there is obvious beneficial effect, as can be known from the above technical solutions: on the one hand ZSM-5 molecular sieve surface acid property and pore passage structure can be regulated and controled by Cu atom, ZSM-5 molecular sieve can be carried out electric charge modification after what is more important Cu atomic surface chemisorbed iodine species, coordinated regulation surface chemical reaction active acid center kind and quantity, strengthen the catalyst absorption dissociation capability at a lower temperature to methanol.When the I-Cu/ZSM-5 molecular sieve i.e. prepared with modification of the present invention is for catalyst, while keeping greater catalytic efficiency, it is substantially reduced MTO technique desired reaction temperature.Reaction temperature reduces, and makes the decline of catalyst carbon deposit generating rate, single pass life improve and regeneration times reduces, and final goal production cost is greatly reduced, it is achieved methanol-to-olefins reaction under relatively temperate condition.
Below by way of detailed description of the invention, the invention will be further described.
Detailed description of the invention
Embodiment
1
The preparation method of a kind of ZSM-5 Type Zeolites agent, comprises the following steps:
(1) the modified preparation of Cu/ZSM-5 molecular sieve: use equi-volume impregnating, by copper load capacity 10 wt.%, copper nitrate solution is mixed homogeneously with ZSM-5 molecular sieve (silica alumina ratio 100), normal temperature dipping 12h, dry to constant weight in 120 DEG C, after 550 DEG C of roasting 2h in hydrogen atmosphere 400 DEG C of reduction roasting 2h, after be cooled to room temperature；
(2) the modified preparation of I-Cu/ZSM-5 molecular sieve: use equi-volume impregnating, by load capacity 10 wt.%, with step (1), hydroiodic acid solution is prepared Cu/ZSM-5 molecular sieve to mix homogeneously, first room temperature ultrasonic immersing 30min, rear conventional dipping 12h, dry to constant weight in 105 DEG C.
Modified prepare I-Cu/ZSM-5 catalyst apply in MTO technique (under normal pressure, reaction temperature: 330 DEG C, weight (hourly) space velocity (WHSV): 2.4h-1, nitrogen flow rate: 10ml/min), record methanol conversion 100%, selectivity of light olefin 89%.
Embodiment
2
The preparation method of a kind of ZSM-5 Type Zeolites agent, comprises the following steps:
(1) the modified preparation of Cu/ZSM-5 molecular sieve: use equi-volume impregnating, by copper load capacity 1 wt.%, copper nitrate solution is mixed homogeneously with ZSM-5 molecular sieve (silica alumina ratio 100), normal temperature dipping 2h, dry to constant weight in 50 DEG C, after 550 DEG C of roasting 2h in hydrogen atmosphere 200 DEG C of reduction roasting 6h, after be cooled to room temperature；
(2) the modified preparation of I-Cu/ZSM-5 molecular sieve: use equi-volume impregnating, by load capacity 1 wt.%, with step (1), liquor kalii iodide is prepared Cu/ZSM-5 molecular sieve to mix homogeneously, first room temperature ultrasonic immersing 10min, rear conventional dipping 2h, dry to constant weight in 50 DEG C.
Modified prepare I-Cu/ZSM-5 catalyst apply in MTO technique (under normal pressure, reaction temperature: 330 DEG C, weight (hourly) space velocity (WHSV): 2.4h-1, nitrogen flow rate: 10ml/min), record methanol conversion 97%, selectivity of light olefin 84%.
Embodiment
3
The preparation method of a kind of ZSM-5 Type Zeolites agent, comprises the following steps:
(1) the modified preparation of Cu/ZSM-5 molecular sieve: use equi-volume impregnating, by copper load capacity 1 wt.%, copper nitrate solution is mixed homogeneously with ZSM-5 molecular sieve (silica alumina ratio 400), normal temperature dipping 2h, dry to constant weight in 50 DEG C, after 550 DEG C of roasting 2h in hydrogen atmosphere 200 DEG C of reduction roasting 6h, after be cooled to room temperature；
(2) the modified preparation of I-Cu/ZSM-5 molecular sieve: use equi-volume impregnating, by load capacity 1 wt.%, with step (1), iodo-methanol solution is prepared Cu/ZSM-5 molecular sieve to mix homogeneously, first room temperature ultrasonic immersing 10min, rear conventional dipping 2h, dry to constant weight in 50 DEG C.
Modified prepare I-Cu/ZSM-5 catalyst apply in MTO technique (under normal pressure, reaction temperature: 330 DEG C, weight (hourly) space velocity (WHSV): 2.4h-1, nitrogen flow rate: 10ml/min), record methanol conversion 98%, selectivity of light olefin 85%.
Embodiment
4
The preparation method of a kind of ZSM-5 Type Zeolites agent, comprises the following steps:
(1) the modified preparation of Cu/ZSM-5 molecular sieve: use equi-volume impregnating, by copper load capacity 1 wt.%, copper nitrate solution is mixed homogeneously with ZSM-5 molecular sieve (silica alumina ratio 200), normal temperature dipping 2h, dry to constant weight in 50 DEG C, after 550 DEG C of roasting 2h in hydrogen atmosphere 200 DEG C of reduction roasting 6h, after be cooled to room temperature；
(2) the modified preparation of I-Cu/ZSM-5 molecular sieve: use equi-volume impregnating, by load capacity 1 wt.%, with step (1), iodic acid solution is prepared Cu/ZSM-5 molecular sieve to mix homogeneously, first room temperature ultrasonic immersing 10min, rear conventional dipping 2h, dry to constant weight in 50 DEG C.
Modified prepare I-Cu/ZSM-5 catalyst apply in MTO technique (under normal pressure, reaction temperature: 330 DEG C, weight (hourly) space velocity (WHSV): 2.4h-1, nitrogen flow rate: 10ml/min), record methanol conversion 99%, selectivity of light olefin 86%.
Embodiment
5
The preparation method of a kind of ZSM-5 Type Zeolites agent, comprises the following steps:
(1) the modified preparation of Cu/ZSM-5 molecular sieve: use equi-volume impregnating, by copper load capacity 10 wt.%, copper nitrate solution is mixed homogeneously with ZSM-5 molecular sieve (silica alumina ratio 300), normal temperature dipping 12h, dry to constant weight in 120 DEG C, after 550 DEG C of roasting 2h in hydrogen atmosphere 400 DEG C of reduction roasting 2h, after be cooled to room temperature；
(2) the modified preparation of I-Cu/ZSM-5 molecular sieve: use equi-volume impregnating, by load capacity 10 wt.%, with step (1), iodomethane solution is prepared Cu/ZSM-5 molecular sieve to mix homogeneously, first room temperature ultrasonic immersing 30min, rear conventional dipping 12h, dry to constant weight in 105 DEG C.
Modified prepare I-Cu/ZSM-5 catalyst apply in MTO technique (under normal pressure, reaction temperature: 330 DEG C, weight (hourly) space velocity (WHSV): 2.4h-1, nitrogen flow rate: 10ml/min), record methanol conversion 98%, selectivity of light olefin 87%.
Embodiment
6
The preparation method of a kind of ZSM-5 Type Zeolites agent, comprises the following steps:
(1) the modified preparation of Cu/ZSM-5 molecular sieve: use equi-volume impregnating, by copper load capacity 10 wt.%, copper nitrate solution is mixed homogeneously with ZSM-5 molecular sieve (silica alumina ratio 100), normal temperature dipping 12h, dry to constant weight in 120 DEG C, after 550 DEG C of roasting 2h in hydrogen atmosphere 400 DEG C of reduction roasting 2h, after be cooled to room temperature；
(2) the modified preparation of I-Cu/ZSM-5 molecular sieve: use equi-volume impregnating, by load capacity 10 wt.%, with step (1), IodineSodium Solution is prepared Cu/ZSM-5 molecular sieve to mix homogeneously, first room temperature ultrasonic immersing 30min, rear conventional dipping 12h, dry to constant weight in 105 DEG C.
Modified prepare I-Cu/ZSM-5 catalyst apply in MTO technique (under normal pressure, reaction temperature: 330 DEG C, weight (hourly) space velocity (WHSV): 2.4h-1, nitrogen flow rate: 10ml/min), record methanol conversion 96%, selectivity of light olefin 86%.
The above, it it is only presently preferred embodiments of the present invention, not the present invention is made any pro forma restriction, any without departing from technical solution of the present invention content, any simple modification, equivalent variations and the modification made above example according to the technical spirit of the present invention, all still falls within the range of technical solution of the present invention.
Claims (3)
1. a preparation method for ZSM-5 Type Zeolites agent, comprises the following steps:
(1) the modified preparation of Cu/ZSM-5 molecular sieve: use equi-volume impregnating, by copper load capacity 1-10 wt.%, copper nitrate solution is mixed homogeneously with ZSM-5 molecular sieve, normal temperature dipping 2-12h, dry to constant weight in 50-120 DEG C, after 550 DEG C of roasting 2h in hydrogen atmosphere 200-400 DEG C of reduction roasting 2-6h, after be cooled to room temperature；
(2) the modified preparation of I-Cu/ZSM-5 molecular sieve: use equi-volume impregnating, iodine species solution Cu/ZSM-5 molecular sieve prepared with step (1) will be contained by load capacity 1-10 wt.% to mix homogeneously, first room temperature ultrasonic immersing 10-30min, rear conventional dipping 2-12h, dry to constant weight in 50-105 DEG C.
The preparation method of a kind of ZSM-5 Type Zeolites agent the most as claimed in claim 1, wherein: described ZSM-5 molecular sieve refers to the Hydrogen ZSM-5 molecular sieve that silica alumina ratio is 100-400.
The preparation method of a kind of ZSM-5 Type Zeolites agent the most as claimed in claim 1 or 2, wherein: described is iodo-methanol solution, hydroiodic acid solution, iodic acid solution, iodomethane solution, IodineSodium Solution or liquor kalii iodide containing iodine species solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114345400A (en) * | 2021-11-24 | 2022-04-15 | 中国科学院大连化学物理研究所 | Transition metal-molecular sieve catalyst, modification method and application |
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| CN104399522A (en) * | 2014-10-21 | 2015-03-11 | 贵州大学 | Catalyst for production of low carbon olefin from methanol through iodination method, and preparation method thereof |
| US20150086456A1 (en) * | 2012-10-19 | 2015-03-26 | Basf Corporation | Mixed Metal 8-Ring Small Pore Molecular Sieve Catalyst Compositions, Catalytic Articles, Systems, and Methods |
| CN105016954A (en) * | 2014-04-28 | 2015-11-04 | 中国科学院大连化学物理研究所 | Method for preparing propylene and aromatic hydrocarbon from methyl alcohol or/and dimethyl ether |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101555022A (en) * | 2009-04-22 | 2009-10-14 | 神华集团有限责任公司 | Preparation method of metal-modified SAPO-34 molecular sieve and catalyst containing the molecular sieve |
| US20150086456A1 (en) * | 2012-10-19 | 2015-03-26 | Basf Corporation | Mixed Metal 8-Ring Small Pore Molecular Sieve Catalyst Compositions, Catalytic Articles, Systems, and Methods |
| CN104250183A (en) * | 2013-06-26 | 2014-12-31 | 中石化洛阳工程有限公司 | Method for preparing aromatic hydrocarbons from methanol with low carbon olefin as byproduct, and apparatus thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114345400A (en) * | 2021-11-24 | 2022-04-15 | 中国科学院大连化学物理研究所 | Transition metal-molecular sieve catalyst, modification method and application |
| CN114345400B (en) * | 2021-11-24 | 2023-03-14 | 中国科学院大连化学物理研究所 | Transition metal-molecular sieve catalyst, modification method and application |
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