AU2020101871A4 - A Method for Preparing ZSM-5 Zeolite by Using Solid wastes - Google Patents
A Method for Preparing ZSM-5 Zeolite by Using Solid wastes Download PDFInfo
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- AU2020101871A4 AU2020101871A4 AU2020101871A AU2020101871A AU2020101871A4 AU 2020101871 A4 AU2020101871 A4 AU 2020101871A4 AU 2020101871 A AU2020101871 A AU 2020101871A AU 2020101871 A AU2020101871 A AU 2020101871A AU 2020101871 A4 AU2020101871 A4 AU 2020101871A4
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
of Descriptions
The invention relates to a method for preparing ZSM-5 zeolite by using solid wastes, in
particular to a preparation process for synthesizing ZSM-5 zeolite by taking solid wastes,
such as rice husk ash, iron tailings, gold tailings as raw materials to provide Si/Al sources,
which required for synthesizing ZSM-5. Meanwhile, the ZSM-5 is successfully synthesized
without using solvent or NaOH. Si source, The ZSM-5 were prepared by adding Si source, Al
source, Na2CO3 -10H 2 0, template agent or seeds to a rotating mortar. The powder mixture was
mixed and transferred to an autoclave, and sealed. The synthesis process without secondary
pollution generated due to using Na 2CO3 -10H20 as alkali source. In this invention, the ZSM-5
was provided by a solvent-free method that uses solid wastes, such as rice husk ash, iron
tailings, gold tailings iron ore tailings as raw materials, the process is simple, and the
application range is wide, so that not only can environmental problems caused by the solid
wastes be relieved, but also high added value utilization of the solid wastes can be realized.
Drawings of Descriptions
35000
30000
25000
= 20000
S15000
10000
5000
0
0 5 10 15 20 25 30 35 40 45
20 (degree)
Figure1I
11/1
Description
Drawings of Descriptions
35000
30000
25000
= 20000
S15000
10000
5000
0
0 5 10 15 20 25 30 35 40 45 20 (degree)
Figure1I
11/1
Descriptions
A Method for Preparing ZSM-5 Zeolite by Using Solid wastes
Technical Field The invention belongs to the field of zeolite preparation and environmental protection. In particular to a method for preparing a ZSM-5 zeolite using solid wastes, wherein rice husk
ash, iron tailings and gold tailings are used to provide silicon sources and aluminum sources required for synthesizing ZSM-5, and meanwhile, hierarchically porous ZSM-5 is synthesized without the participation of solvent and NaOH.
Technical Background ZSM-5 zeolite have been widely applied in many oil refining and chemical processes
owing to their unique pore structure and shape-selective catalysis, which was first reported in 1972 by Mobil Company(USP3702886). The preparation method has been continuously improved. The initial synthesis with organic amine template agent and the subsequent
synthesis without amine method have significantly reduced the manufacturing cost of ZSM-5. Furthermore, the application field of ZSM-5 has been continuously expanded through technological advances such as post-modification treatment of synthesized ZSM-5 products.
For example, ZSM- 5 are not used in the early fluid catalytic cracking (FCC) catalysts applied in the oil refining industry, while ZSM-5 are mostly added to the FCC catalysts today to improve the performance of the catalysts and further improve the product distribution. As
FCC catalyst is a kind of catalyst with a large demand, the consumption in the Chinese market alone reached tens of thousands of tons last year, which led to an increase in the demand for ZSM-5 and also required a further reduction in the production cost of ZSM-5.
On the other hand, zeolites, including ZSM-5, are used as active components in FCC catalysts and other catalysts. Good dispersion of active components is very important to the
catalyst, thus improving the utilization efficiency of the active components. An important measure to improve the dispersity of zeolite active components in the catalyst is to use zeolite products with the smallest crystal size. It is well known that the reduction of the size of
zeolite particles to nanoscale is considered to be an effective approach to optimize the performance of zeolites in catalytic and sorption applications, owning to the shorter diffusion path lengths, which provides more exposed acidic sites and increases the external surface area.
However, the size of zeolite crystals synthesized by the existing solvent-free method is usually in the range of several microns, so it is a great challenge to synthesize nanocrystalline
Descriptions
zeolite by the solvent-free method.
Generally, ZSM-5 is prepared by alkaline silica-alumina gel system. The system consists of sodium oxide, aluminum oxide, silicon oxide and water. The silicon source used for synthesizing raw materials is generally water glass, silica gel, and the aluminum source is generally aluminum sulfate, sodium aluminate and the like. Prior to the 1980s, quaternary ammonium salt or other organic amines were generally used as template agents to synthesize ZSM-5 zeolite (hereinafter referred to as "amine method"). Due to the high price of organic template agents such as quaternary ammonium salt, the technology of synthesizing ZSM-5 by using ZSM-5 seed crystals (i.e., "seed method" or "amine-free method") emerged after the 1980s, which significantly reduced the preparation cost of ZSM-5.
The synthesis process of ZSM-5 zeolite basically adopts hydrothermal method, dry gel conversion method, solvent-free method, etc. Hydrothermal synthesis system needs to contain a large amount of alkaline solution, and the raw materials need to be stirred, aged, etc. to reduce the synthesis efficiency of zeolites before the synthesis process in a reaction kettle. The dry gel conversion method is a method for solid phase synthesis of zeolite, including gas phase conversion method and steam assisted method. It is necessary to mix silicon source, aluminum source and water to prepare gel, and the dry gel after water removal is used to prepare zeolite. In the process of preparing ZSM-5 by the above methods, the use of solvent cannot be completely avoided, a large amount of alkali-containing wastewater is generated, and the space utilization rate of zeolite synthesis equipment is reduced. Solvent-free method means that no solvent is used in the zeolite preparation process. At present, solvent-free method mainly uses pure chemical reagents as raw materials, and is directly put into a autoclave for sealing and standing synthesis at a certain temperature after simple mixing and grinding. This process is simple and has high utilization rate of equipment. However, the synthetic raw materials contain NH4F, NH 4C1 and other substances harmful to the environment, which are not suitable for industrial large-scale application. At present, there is no report of using solid wastes as raw materials to synthesize zeolite by solvent-free method.
Summary of the Invention In order to solve the above-mentioned problems, the main purpose of the present invention is to provide a method for synthesizing hierarchical ZSM-5 made of zeolite nanosheets via a green and low-cost method, by mixing solid raw materials followed by
Descriptions
thermal treatment in an autoclave. Therefore, this method can eliminate NH4F, NH 4 Cl and other substances harmful to the environment in the raw materials.
The raw materials contain solid wastes such as rice husk ash, gold tailings, iron tailings, etc. The Si02 content in the rice husk ash reaches about 90% and is amorphous, which can be directly used as a silicon source to prepare ZSM-5. The components of iron tailings and gold
tailings in raw materials mainly include quartz, albite, potash feldspar, anorthite, magnetite, pyrite, cordierite, talc and illite. The components of gold tailings and iron tailings are complex and contain a variety of silicate minerals as well as magnetite and pyrite impurities. The Si0 2
content accounts for more than 60%, and the silicate minerals in gold tailings and iron tailings need to be activated.
The technical scheme of the invention is as follows: a method for preparing ZSM-5 zeolite by using solid wastes, which specifically comprises the following steps:
Step 1: taking solid wastes as Si source, adding Si source, Al source, sodium carbonate decahydrate, and template into a rotating mortar and mixing for I to 10 minutes;;
Step 2: putting the mixture obtained in step 1 into a autoclave, heating at 100-200°C for 3-96 hours, At the end of the reaction time, the autoclave was quenched with water to room temperature, the hierarchically Porous ZSM-5 zeolite was collected by filtration followed
repeated washing with deionized water, washing and drying.
Further, the ratio of the silicon source, sodium carbonate decahydrate, aluminum source
substance and template agent is: n (TPAB)/n (Si0 2) = 0.1-2.0; n(Na 2 CO 3 -10H2 0)/n(SiO 2 )= 0.1~10; n(Si02)/n(Al203)=20-+oo.
Further, the solid wastes is rice husk ash, iron tailings or gold tailings, and when iron tailings and gold tailings are used, the iron tailings and gold tailings need to be activated.
Furthermore, the activation treatment process comprises the following steps of: gold tailings and iron tailings are activated by alkali sintering, n (NaOH)/n (Si0 2 ) = 1-4, the activation treatment temperature is 200-1000°C, and the activation treatment time is 1-10
hours. The activated alkali sintering product is mixed with water and stirred for 50-70 minutes,
Descriptions
the product is divided into water-soluble substances and water-insoluble solids, the pH=9 value of the solution is directly adjusted to 9 without solid-liquid separation, the solution is ) left standing for 6-24 hours, and the solid powder is obtained by constant temperature drying at 80°C.
Further, the composition of the iron tailings or gold tailings: the composition of the iron tailings or gold tailings mainly comprises quartz , albite, potash feldspar, anorthite, magnetite, pyrite, cordierite, talc and illite.
Furthermore, the iron tailings and the gold tailings are not subjected to acid leaching purification treatment before activation, thus avoiding the generation of acid-containing waste liquid.
The synthetic ZSM-5 zeolite and the preparation method provided by the invention have the following characteristics:
(1) The raw material range for synthesizing ZSM-5 zeolite by solvent-free method is expanded, new uses are found for solid wastes such as rice husk ash, iron tailings, gold tailings and the like, and the raw material cost for preparing ZSM-5 zeolite is reduced.
(2) The ZSM-5 zeolte is prepared according to the method of the invention, and the raw materials of the reaction mixture do not contain solvent and sodium hydroxide. The method can improve the utilization rate of zeolite synthesis equipment, reduce the zeolite production cost and reduce the pollution in the zeolite production process.
(3) The ZSM-5 provided by the invention has high crystallinity and nanocrystals, and can shorten the diffusion path of reactant and product molecules in the zeolite crystal and improve the catalytic production efficiency.
(4) Compared with the ZSM-5 synthesized by the traditional method, the ZSM-5 product prepared by solvent-free method has a hierarchically pore structure.
Brief Description of Drawings Fig. 1 is an x-ray diffraction (XRD) spectrum of ZSM-5 synthesized by rice husk ash as
Descriptions
a raw material of the Embodiment 1 of the present invention.
Fig. 2 is a flow chart of a method for preparing ZSM-5 using solid wastes according to
the present invention.
Detailed Description of the Preferred Embodiments
The technical scheme of the present invention will be further explained below with reference to specific Embodiment.
The invention relates to a method for preparing ZSM-5 by using solid wastes, which specifically comprises the following steps:
Step 1: taking solid wastes as Si source, adding Si source, Al source, sodium carbonate decahydrate, and template into a rotating mortar and mixing for I to 10 minutes;
Step 2: putting the mixture obtained in step 1 into a autoclave, heating at 100-200°C for 3-96 hours, At the end of the reaction time, the autoclave was quenched with water to room temperature, the hierarchically Porous ZSM-5 zeolite was collected by filtration followed
repeated washing with deionized water, washing and drying.
Further, the ratio of the silicon source, sodium carbonate decahydrate, aluminum source
substance and template agent is: n (TPABr)/n (Si0 2 ) = 0.1-2.0; n(Na 2 CO 3 -10H2 0)/n(SiO 2 )= 0.1~10; n(Si02)/n(Al203)=20-+oo.
Further, the solid wastes is rice husk ash, iron tailings or gold tailings, and when iron tailings and gold tailings are used, the iron tailings and gold tailings need to be activated.
Furthermore, the activation treatment process comprises the following steps of: gold tailings and iron tailings are activated by alkali sintering, n (NaOH)/n (Si0 2 ) = 1-4, the activation treatment temperature is 200-1000°C, and the activation treatment time is 1-10
hours. The activated alkali sintering product is mixed with water and stirred for 50-70 minutes, the product is divided into water-soluble substances and water-insoluble solids, the pH=9 value of the solution is directly adjusted to 9 without solid-liquid separation, the solution is
left standing for 6-24 hours, and the solid powder is obtained by constant temperature drying
Descriptions
at 80°C.
Further, the composition of the iron tailings or gold tailings: the composition of the iron
tailings or gold tailings mainly comprises quartz, albite, potash feldspar, anorthite, magnetite, pyrite, cordierite, talc and illite, and the content of silicate in the iron tailings or gold tailings is not less than 50%.
Furthermore, the iron tailings and the gold tailings are not subjected to acid leaching purification treatment before activation, thus avoiding the generation of acid-containing waste
liquid.
Furthermore, the ZSM-5 with the hierarchically pore structure can also be used as a
seed crystal of the ZSM-5 zeolite.
Embodiment 1:
200 mesh rice husk ash is taken as a raw material, 2g of rice husk ash is taken, 0.2g of sodium aluminate, 2.5g of Na 2 CO 3 -10H 2 0 and 0.2g of TPABr are sequentially added, the
mixture is placed in a mortar for grinding and mixing for 5 minutes, the mixture is placed in a autoclave, the temperature is raised to 100°C, the temperature is kept constant, the crystallization is carried out for 72 hours. After crystallization, the filter cake is rapidly cooled,
washed and dried to obtain a crystallized product. According to X-ray diffraction (XRD) test, the product belongs to ZSM-5, the crystal size of ZSM-5 is 40-200 nm, Fe and Mn impurities in the raw materials enter the zeolite framework, and the obtained ZSM-5 product contains
micropores and mesopores simultaneously. The XRD phase diagram is shown in fig. 1.
Embodiment 2:
Using iron tailings as raw materials with SiO 2 content of 67%, 1Og iron tailings were activated in muffle furnace at 500°C for 3 hours, the activated product was soaked in water
for 1 hour, the pH value of the filtrate was adjusted to 9, the filtrate was allowed to stand for 12 hours, and the powder obtained by drying was used as the synthetic raw material of ZSM-5. 2g of filter residue, 0.2g of sodium aluminate, 2.5 g of Na 2 CO 3 -10H2 0 and 0.2 g of TPABr
are placed in a mortar for grinding and mixing for 5 minutes, and the mixture is placed in
Descriptions
autoclave to be heated to 100°C, kept at a constant temperature and crystallized for 72 hours. After crystallization is finished, the filter cake is rapidly cooled, washed and dried to obtain a crystallized product, the crystal size of the ZSM-5 is 40-200nm, Fe and Mn impurities in the
raw materials enter the zeolite framework, and the obtained ZSM-5 product simultaneously contains micropores and mesopores. The XRD phase result is the same as that of Embodiment 1.
Embodiment 3:
Using iron tailings as raw materials with SiO 2 content of 67%, 1Og iron tailings were activated in muffle furnace at 500°C for 3 hours, the activated product was soaked in water for 1 hour, the pH value of the filtrate was adjusted to 9, the filtrate was allowed to stand for
12 hours, and the powder obtained by drying was used as the synthetic raw material of ZSM-5 zeolite. 2g of filter residue, 0.2g of sodium aluminate, 2.5g of Na2 CO 3 -10H2 0 and 0.2g of ZSM-5 obtained in embodiment 1 are placed in a mortar to be ground and mixed for 5
minutes, and the mixture is placed in autoclave to be heated to 100°C, kept at a constant temperature and crystallized for 72 hours. After crystallization is finished, the filter cake is rapidly cooled, washed and dried to obtain a crystallized product, the crystal size of the
ZSM-5 is 40~ 200nm, Fe and Mn impurities in the raw materials enter the zeolite framework, and the obtained ZSM-5 product simultaneously contains micropores and mesopores. The XRD phase result is the same as that of Embodiment 1.
Embodiment 4:
Gold tailings are used as raw materials with SiO 2 content of 71%. 10g of iron tailings are activated at 500°C for 3 hours in a muffle furnace, the activated product is soaked in water for 1 hour, the pH value of the filtrate is adjusted to 9, the filtrate is allowed to stand for 12
hours, and the powder obtained by drying is used as a synthetic raw material of ZSM-5. 3g of filter residue, 0.2g of sodium aluminate, 3 g of Na 2 CO 3 -10H 2 0 and 0.2g of TPABr are placed in a mortar to be ground and mixed for 5 minutes, and the mixture is placed in autoclave to be
heated to 100°C, kept at a constant temperature and allowed to stand for crystallization for 72 hours. After crystallization is finished, the filter cake is rapidly cooled, washed and dried to obtain a crystallized product, the crystal size of the ZSM-5 is 40-200 nm, Fe and Mn
impurities in the raw materials enter the zeolite framework, and the obtained ZSM-5 product
Descriptions
simultaneously contains micropores and mesopores. The XRD phase results are the same as those of the first embodiment.
Embodiment 5:
Gold tailings are used as raw materials with SiO 2 content of 71%. 10g of iron tailings are
activated at 500°C for 3 hours in a muffle furnace, the activated product is soaked in water for 1 hour, the pH value of the filtrate is adjusted to 9, the filtrate is allowed to stand for 12 hours, and the powder obtained by drying is used as a synthetic raw material of ZSM-5. 3g of
filter residue, 0.2g of sodium aluminate, 3 g of Na 2 CO 3 -10H2 0 and 0.2g of ZSM-5 obtained in embodiment 1 are placed in a grinding bowl to be ground and mixed for 5 minutes, and the mixture is placed in autoclave to be heated to 100°C, kept at a constant temperature and
crystallized for 72 hours. After crystallization is finished, the filter cake is rapidly cooled, washed and dried to obtain a crystallized product, the crystal size of the ZSM-5 is 40-200nm, Fe and Mn impurities in the raw materials enter the zeolite framework, and the obtained
ZSM-5 product simultaneously contains micropores and mesopores. The XRD phase result is the same as that of Embodiment 1.
Claims (6)
1. The invention relates to a method for preparing a hierarchically porous ZSM-5 zeolite, which specifically comprises the following steps:
Step 1: taking solid wastes as Si source, adding Si source, Al source, sodium carbonate decahydrate, and template into a rotating mortar and mixing for I to 10 minutes;
Step 2: putting the mixture obtained in step 1 into a autoclave, heating at 100-200°C for 3-96 hours, At the end of the reaction time, the autoclave was quenched with water to room temperature, the hierarchically Porous ZSM-5 zeolite was collected by filtration followed
repeated washing with deionized water, washing and drying.
2. The method according to claim 1, characterized in that the ratio of the silicon source,
sodium carbonate decahydrate, aluminum source substance and template agent is: n (TPABr)/n(Si0 2)= 0.1-2.0;n(Na 2CO 3 -10H 20)/n(SiO 2)=0.1~10; n(Si02)/n(AI 2 03)=20~ +oo.
3. The method according to claim 1, characterized in that the solid wastes is rice husk ash, iron tailings or gold tailings, and when iron tailings or gold tailings are used, the iron
tailings and gold tailings need to be activated.
4. The method according to claim 3, characterized in that the activation treatment
process is: gold tailings and iron tailings are activated by alkali sintering, n (NaOH)/n (Si0 2 )
= 1-4, the activation treatment temperature is 200-1000 °C, and the activation treatment time is 1-10 hours. The activated alkali sintering product is mixed with water and stirred for 50-70
minutes, the product is divided into water-soluble substances and water-insoluble solids, the pH=9 value of the solution is directly adjusted to 9 without solid-liquid separation, the solution is left standing for 6-24 hours, and the solid powder is obtained by constant
temperature drying at 80°C.
5. The method according to claim 3, characterized in that the composition of the iron
tailings or gold tailings: the composition of the iron tailings or gold tailings mainly comprises quartz, albite, potash feldspar, anorthite, magnetite, pyrite, cordierite, talc and illite.
Claims
6. The method according to claim 3, characterized in that the iron tailings and the gold tailings are not subjected to acid leaching and purification treatment before activation to avoid ) the generation of acid-containing waste liquid.
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| CN112500000A (en) * | 2020-12-07 | 2021-03-16 | 安徽东巨新型建材有限公司 | Method for preparing silicate cement siliceous correction raw material by using iron tailings |
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| CN112500000A (en) * | 2020-12-07 | 2021-03-16 | 安徽东巨新型建材有限公司 | Method for preparing silicate cement siliceous correction raw material by using iron tailings |
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| CN114506856A (en) * | 2022-01-21 | 2022-05-17 | 贵州理工学院 | Method for preparing ZSM-5 molecular sieve from industrial silicon waste |
| CN116177562A (en) * | 2022-12-05 | 2023-05-30 | 华侨大学 | Method for preparing porous molecular sieve by taking unfired rice hulls as templates |
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