CN105772063B - A kind of molecular sieve catalyst of modified ZSM-5 5 and preparation method thereof - Google Patents
A kind of molecular sieve catalyst of modified ZSM-5 5 and preparation method thereof Download PDFInfo
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- CN105772063B CN105772063B CN201610227496.5A CN201610227496A CN105772063B CN 105772063 B CN105772063 B CN 105772063B CN 201610227496 A CN201610227496 A CN 201610227496A CN 105772063 B CN105772063 B CN 105772063B
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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
- B01J29/44—Noble metals
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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 kind of preparation method of the molecular sieve catalyst of modified ZSM-5 5, comprise the following steps：（1）The modified preparation of the molecular sieves of Ag/ZSM 5：Using equi-volume impregnating, silver nitrate solution is well mixed with the molecular sieves of ZSM 5 by the wt.% of silver load capacity 1 10, normal temperature dipping 10h, is dried to constant weight in 85 DEG C, 550 DEG C of roasting 5h, after be cooled to room temperature；（2）The modified preparation of the molecular sieves of I Ag/ZSM 5：Using equi-volume impregnating, iodine species solution and step will be contained by the wt.% of load capacity 1 10（1）The molecular sieves of Ag/ZSM 5 are made to be well mixed, the first 30min of normal temperature ultrasonic immersing 10,2 12h of rear conventional dipping, constant weight are dried in 50 105 DEG C.The present invention can improve low-temperature methanol conversion ratio and selectivity of light olefin, service life length.
Description
Technical field
The invention belongs to chemical technology field, and in particular to a kind of preparation method of ZSM-5 Type Zeolites agent.
Background technology
ZSM-5 molecular sieve be Mobile companies of the U.S. develop one kind by SiO4And AlO4Tetrahedron is formed and had
There is the zeolite micropore molecular sieve of three dimensional intersection network straight passage structures.Because its have that hydrothermal stability is good, specific surface area is big and
The features such as shape selective catalysis function is strong, coal-based methanol preparing low-carbon olefins have been widely used in it（MTO）Technical matters.
Because ZSM-5 molecular sieve duct is larger and surface acidity is stronger, industrial applications need to generally be carried out to the molecular sieve
It is modified.At present, the methods of mainly taking various metallic elements dippings or doping, soda acid or high temperature hydro-thermal desiliconization dealuminzation is to ZSM-5
Molecular sieve is modified.It is now recognized that than convenient preparing light olefins from methanol (MTO) technological reaction temperature（430-550℃）
Under, the work of these study on the modification has a significant effect to improving catalytic efficiency, and modified ZSM-5 molecular sieve has higher first
Alcohol conversion and target product selectivity.But higher reaction temperatures not only increase unit of the product energy consumption in industrializing, and can also accelerate
Carbon deposit is formed, and is caused rapid catalyst deactivation and is needed frequent regeneration, and production cost further increases.It can be seen that existing MTO works
Reaction temperature higher the deficiencies of causing unit of the product high energy consumption, catalyst easy carbon distribution inactivation and needing frequent regeneration be present in skill.
Because reaction temperature influences significantly, unit of the product energy to be reduced by the approach for reducing reaction temperature on methanol conversion
Consumption, it is necessary to solve the key issue for how improving low-temperature methanol conversion ratio.
The content of the invention
It is an object of the invention to overcome disadvantages mentioned above and low-temperature methanol conversion ratio and low-carbon alkene can be improved by providing one kind
Selectivity, the preparation method of the ZSM-5 Type Zeolites agent of service life length.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of ZSM-5 Type Zeolites agent of the present invention, comprises the following steps：
（1）The modified preparation of Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, by silver load capacity 1-10 wt.% by nitre
The silver-colored solution of acid is well mixed with ZSM-5 molecular sieve, normal temperature dipping 10h, and constant weight, 550 DEG C of roasting 5h, rear cooling are dried in 85 DEG C
To room temperature；
（2）The modified preparation of I-Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, will contain by load capacity 1-10 wt.%
Iodine species solution and step（1）Ag/ZSM-5 molecular sieves are made to be well mixed, first normal temperature ultrasonic immersing 10-30min, rear conventional leaching
Stain 2-12h, constant weight is dried in 50-105 DEG C.
A kind of preparation method of above-mentioned ZSM-5 Type Zeolites agent, wherein：The ZSM-5 molecular sieve refers to sial
Than the Hydrogen ZSM-5 molecular sieve for 100-400；
A kind of preparation method of above-mentioned ZSM-5 Type Zeolites agent, wherein：The species solution containing iodine is iodo-
Methanol solution, hydroiodic acid solution, iodic acid solution, iodomethane solution, IodineSodium Solution or liquor kalii iodide.
The present invention compared with prior art, has obvious beneficial effect, as can be known from the above technical solutions：One side Ag is former
Son can regulate and control to ZSM-5 molecular sieve surface acid property and pore passage structure, what is more important Ag atomic surface chemisorbeds
After iodine species can to ZSM-5 molecular sieve carry out electric charge modification, coordinated regulation surface chemical reaction activity acid site type and quantity,
Strengthen the catalyst absorption dissociation capability to methanol at a lower temperature.I.e. with the modified I-Ag/ZSM-5 molecules prepared of the present invention
Sieve for catalyst when, substantially reduce reaction temperature needed for MTO techniques while greater catalytic efficiency is kept.Reaction temperature drops
It is low, decline catalyst carbon deposit generating rate, single pass life improves and regeneration times reduction, final goal production cost are big
It is big to decline, realize compared with methanol-to-olefins reaction under temperate condition.
Below by way of embodiment, the invention will be further described.
Embodiment
Embodiment 1
A kind of preparation method of ZSM-5 Type Zeolites agent, comprises the following steps：
（1）The modified preparation of Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, by the wt.% of silver load capacity 10 by nitric acid
Silver-colored solution and ZSM-5 molecular sieve（Silica alumina ratio 100）It is well mixed, normal temperature dipping 10h, constant weight, 550 DEG C of roastings are dried in 85 DEG C
5h, after be cooled to room temperature；
（2）The modified preparation of I-Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, by the wt.% of load capacity 10 by hydrogen iodine
Acid solution and step（1）Ag/ZSM-5 molecular sieves are made to be well mixed, first normal temperature ultrasonic immersing 30min, rear conventional dipping 12h,
Constant weight is dried in 105 DEG C.
Modified obtained I-Ag/ZSM-5 catalyst is applied in MTO techniques（Under normal pressure, reaction temperature：330 DEG C, weigh space-time
Speed：2.4h-1, nitrogen flow rate：10ml/min）, measure methanol conversion 100%, selectivity of light olefin 89%.
Embodiment 2
A kind of preparation method of ZSM-5 Type Zeolites agent, comprises the following steps：
（1）The modified preparation of Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, by the wt.% of silver load capacity 1 by silver nitrate
Solution and ZSM-5 molecular sieve（Silica alumina ratio 100）It is well mixed, normal temperature dipping 10h, constant weight, 550 DEG C of roastings are dried in 85 DEG C
5h, after be cooled to room temperature；
（2）The modified preparation of I-Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, by the wt.% of load capacity 1 by KI
Solution and step（1）Ag/ZSM-5 molecular sieves are made to be well mixed, first normal temperature ultrasonic immersing 10min, rear conventional dipping 2h, in 50
DEG C it is dried to constant weight.
Modified obtained I-Ag/ZSM-5 catalyst is applied in MTO techniques（Under normal pressure, reaction temperature：330 DEG C, weigh space-time
Speed：2.4h-1, nitrogen flow rate：10ml/min）, measure methanol conversion 97%, selectivity of light olefin 84%.
Embodiment 3
A kind of preparation method of ZSM-5 Type Zeolites agent, comprises the following steps：
（1）The modified preparation of Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, by the wt.% of silver load capacity 1 by silver nitrate
Solution and ZSM-5 molecular sieve（Silica alumina ratio 400）It is well mixed, normal temperature dipping 10h, constant weight, 550 DEG C of roastings are dried in 85 DEG C
5h, after be cooled to room temperature；
（2）The modified preparation of I-Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, by the wt.% of load capacity 1 by iodo- first
Alcoholic solution and step（1）Ag/ZSM-5 molecular sieves are made to be well mixed, first normal temperature ultrasonic immersing 10min, rear conventional dipping 2h, in
50 DEG C are dried to constant weight.
Modified obtained I-Ag/ZSM-5 catalyst is applied in MTO techniques（Under normal pressure, reaction temperature：330 DEG C, weigh space-time
Speed：2.4h-1, nitrogen flow rate：10ml/min）, measure methanol conversion 98%, selectivity of light olefin 85%.
Embodiment 4
A kind of preparation method of ZSM-5 Type Zeolites agent, comprises the following steps：
（1）The modified preparation of Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, by the wt.% of silver load capacity 1 by silver nitrate
Solution and ZSM-5 molecular sieve（Silica alumina ratio 200）It is well mixed, normal temperature dipping 10h, constant weight, 550 DEG C of roastings are dried in 85 DEG C
5h, after be cooled to room temperature；
（2）The modified preparation of I-Ag/ZSM-5 molecular sieves：It is by the wt.% of load capacity 1 that acid iodide is molten using equi-volume impregnating
Liquid and step（1）Ag/ZSM-5 molecular sieves are made to be well mixed, first normal temperature ultrasonic immersing 10min, rear conventional dipping 2h, in 50 DEG C
It is dried to constant weight.
Modified obtained I-Ag/ZSM-5 catalyst is applied in MTO techniques（Under normal pressure, reaction temperature：330 DEG C, weigh space-time
Speed：2.4h-1, nitrogen flow rate：10ml/min）, measure methanol conversion 99%, selectivity of light olefin 86%.
Embodiment 5
A kind of preparation method of ZSM-5 Type Zeolites agent, comprises the following steps：
（1）The modified preparation of Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, by the wt.% of silver load capacity 10 by nitric acid
Silver-colored solution and ZSM-5 molecular sieve（Silica alumina ratio 300）It is well mixed, normal temperature dipping 10h, constant weight, 550 DEG C of roastings are dried in 85 DEG C
5h, after be cooled to room temperature；
（2）The modified preparation of I-Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, by the wt.% of load capacity 10 by iodine first
Alkane solution and step（1）Ag/ZSM-5 molecular sieves are made to be well mixed, first normal temperature ultrasonic immersing 30min, rear conventional dipping 12h,
Constant weight is dried in 105 DEG C.
Modified obtained I-Ag/ZSM-5 catalyst is applied in MTO techniques（Under normal pressure, reaction temperature：330 DEG C, weigh space-time
Speed：2.4h-1, nitrogen flow rate：10ml/min）, measure methanol conversion 98%, selectivity of light olefin 87%.
Embodiment 6
A kind of preparation method of ZSM-5 Type Zeolites agent, comprises the following steps：
（1）The modified preparation of Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, by the wt.% of silver load capacity 10 by nitric acid
Silver-colored solution and ZSM-5 molecular sieve（Silica alumina ratio 100）It is well mixed, normal temperature dipping 10h, constant weight, 550 DEG C of roastings are dried in 85 DEG C
5h, after be cooled to room temperature；
（2）The modified preparation of I-Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, by the wt.% of load capacity 10 by iodate
Sodium solution and step（1）Ag/ZSM-5 molecular sieves are made to be well mixed, first normal temperature ultrasonic immersing 30min, rear conventional dipping 12h,
Constant weight is dried in 105 DEG C.
Modified obtained I-Ag/ZSM-5 catalyst is applied in MTO techniques（Under normal pressure, reaction temperature：330 DEG C, weigh space-time
Speed：2.4h-1, nitrogen flow rate：10ml/min）, measure methanol conversion 96%, selectivity of light olefin 86%.
The above described is only a preferred embodiment of the present invention, not making any formal limitation to the present invention, appoint
Without departing from technical solution of the present invention content, what the technical spirit according to the present invention was made to above example any simply repaiies for what
Change, equivalent variations and modification, in the range of still falling within technical solution of the present invention.
Claims (2)
1. a kind of preparation method of ZSM-5 Type Zeolites agent, comprises the following steps：
（1）The modified preparation of Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, by silver load capacity 1-10 wt.% by silver nitrate
Solution is well mixed with ZSM-5 molecular sieve, normal temperature dipping 10h, is dried to constant weight in 85 DEG C, 550 DEG C of roasting 5h, after be cooled to room
Temperature；
（2）The modified preparation of I-Ag/ZSM-5 molecular sieves：Using equi-volume impregnating, iodine thing will be contained by load capacity 1-10 wt.%
Kind solution and step（1）Ag/ZSM-5 molecular sieves are made to be well mixed, first normal temperature ultrasonic immersing 10-30min, rear conventional dipping 2-
12h, constant weight is dried in 50-105 DEG C；
Wherein：The species solution containing iodine is iodo- methanol solution, hydroiodic acid solution, iodic acid solution, iodomethane solution, sodium iodide
Solution or liquor kalii iodide.
2. a kind of preparation method of ZSM-5 Type Zeolites agent as claimed in claim 1, wherein：The ZSM-5 molecules
Sieve refers to the Hydrogen ZSM-5 molecular sieve that silica alumina ratio is 100-400.
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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 |
| 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 |
| 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 |
| 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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| EP2908947B1 (en) * | 2012-10-19 | 2021-09-29 | BASF Corporation | Mixed metal 8-ring small pore molecular sieve catalytic articles and methods |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
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