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CN111886202B - Process for the synthesis of zeolite SSZ-13 - Google Patents

Process for the synthesis of zeolite SSZ-13 Download PDF

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CN111886202B
CN111886202B CN201980020854.7A CN201980020854A CN111886202B CN 111886202 B CN111886202 B CN 111886202B CN 201980020854 A CN201980020854 A CN 201980020854A CN 111886202 B CN111886202 B CN 111886202B
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ssz
zeolite
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ammonium
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CN111886202A (en
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达南杰·普拉巴卡尔·萨布德
阿尔希亚·阿尔塔夫·拉勒吉
拉杰什库马尔·马努拜·帕特尔
维贾伊·索潘·纳赫德
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Sade Chemicals India Private Ltd
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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
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent

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  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
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Abstract

The main process by means of which aluminosilicate zeolite SSZ-13 having chabazite structure is synthesized. The synthesis employs quaternary ammonium salts, i.e., chloride or hydroxide salts of 3-chloro-2-hydroxypropyl trimethylammonium [ (CH 3) 3N+CH2-CHOH-CH2Cl ] or 2, 3-dihydroxypropyl trimethylammonium [ (CH 3) 3N+CH2-CHOH-CH2OH ] solution (referred to herein as Q1), silica, alumina and alkali metal cations, and small amounts of NNN-trimethyl-adamantylammonium hydroxide (referred to herein as Q2) to synthesize SSZ-13. The SSZ-13 synthesized by means of it can be further ion-exchanged into the ammonium form and then calcined to the H form.

Description

Process for the synthesis of zeolite SSZ-13
The method is characterized by comprising the following steps:
natural zeolites and synthetic zeolites are important and useful compositions. Many of these zeolites or aluminosilicates are porous and have a well-defined, unique crystal structure and chemical composition. The crystals have a large number of cavities and pores therein, the size and shape of which varies from zeolite to zeolite. Variations in chemical composition, pore size and shape cause variations in the adsorption and catalytic properties of these zeolites. Because of their unique molecular sieve characteristics, as well as their potentially acidic nature, shape selectivity, ion exchange capacity, zeolites are particularly useful as adsorbents in hydrocarbon processing and as catalysts for cracking, reforming, and other hydrocarbon conversion reactions and environmental applications. Although many different crystalline aluminosilicates have been prepared and tested for wide-ranging applications, new zeolites useful in hydrocarbon and chemical processing are still sought.
In recent years, small pore zeolites have attracted attention due to their promising activity in a wide range of applications such as SCR, methanol to olefins. Among many small pore zeolites, SSZ-13, one of the synthetic zeolites having the chabazite structure (CHA topology), has been found to be promising for SCR applications due to high NOx conversion, higher N2 selectivity, thermal stability, and hydrothermal stability.
As a growing concern for protecting the environment and human health from vehicle air pollutants, emissions standards are continually tightened throughout the years to control pollutants (such as CO, NOx, HC and PM) from stationary and mobile engines. Particularly for mobile gasoline applications operating at stoichiometric air/fuel ratios, so-called modern three-way catalytic converters (now standard components on vehicles) have helped dramatically reduce emissions of CO, HC and NOx. Thus, the introduction of catalytic converter technology significantly improves air quality and correspondingly human health.
Catalytic converter technology for gasoline-based engines cannot be directly applied to lean-burn engines operating at high air/fuel ratios. In conventional diesel engines, simultaneous control of both NOx and Particulate Matter (PM) emissions is challenging due to existing NOx-PM trade-offs. Furthermore, reducing NOx in an oxygen-rich environment increases the complexity of emission control. In order to meet stringent NOx and PM emission standards for diesel engines, clean diesel technology and highly efficient exhaust aftertreatment system applications are required. In order to further comply with current and future regulations for light and heavy duty diesel engines, it is necessary to minimize both NOx and PM significantly for the most advanced diesel engines of today.
For the control and regulation of NOx, rarely demonstrated technologies such as vanadium-tungsten-titanium (VWT) catalysts and metals like Fe, cu incorporated into zeolite catalysts for SCR aftertreatment systems are commercially available. The temperature window of the V-based catalyst is 180 ℃ to 450 ℃ and the conversion rate in the low temperature zone is limited. The operating temperature ranges of the base metal (Cu or Fe) zeolite catalysts are different. Fe-based zeolite catalysts exhibit excellent activity at high temperature systems, whereas low temperature activity for NOx conversion on Fe-zeolite is poor. Recently, cu-based zeolites, particularly Cu-SSZ-13, have become more attractive due to their wide operating temperature range and better durability.
The main concerns of the base metal/zeolite catalysts used for SCR reactions are sulfur poisoning and thermal durability due to the high sulfur levels in the fuel prior to BS-IV. The effect of sulfur, particularly on Cu-based catalysts, is more severe than on Fe-based zeolite catalysts for NOx activity. However, due to the availability of fuels with less than 10ppm sulfur for BS-VI applications, the use of Cu-containing catalysts becomes feasible for aftertreatment systems.
In recent literature, several efforts have been reported to design and develop robust Cu-SSZ-13 catalysts using various preparation methods such as chemical vapor deposition, liquid phase ion exchange methods, one-pot synthesis, and the like. In particular, catalysts prepared via the wet chemical route show excellent deNOx activity and high selectivity to N2.
Technical Field
The present invention relates to the synthesis of zeolite SSZ-13 having the chabazite structure. SSZ-13 is a small pore zeolite. The SSZ-13 framework consists of SiO4 and AlO4 tetrahedra (tetrahedra) connected by co-angles of oxygen atoms to form the CHA structure. SSZ-13 is a porous material with pore openings of 0.38X0.38 nanometers and contains a well-defined and unique crystalline structure that can be determined by X-ray diffraction. Because the crystalline structure of SSZ 13 contains a large number of cavities and pores with varying pore sizes and pore diameters, SSZ-13 can be effectively used in catalyst formulations to remove nitrogen oxide emissions from exhaust gases emitted by the automotive and manufacturing industries. SSZ-13 is also promising for other applications, such as the conversion of methanol to olefins and the production of methylamine from methanol and ammonia.
The invention further relates to a cost-effective preparation of SSZ-13 having different physicochemical properties. More particularly, the present invention relates to the synthesis of SSZ-13, which is intended to meet the specific requirements of various applications employing SSZ-13 as a catalyst, catalyst support and starting material.
Background
The unique physicochemical properties or combinations of properties of SSZ-13 zeolite are desirable in a variety of applications. For certain applications, individual characteristics are required, such as silica to alumina molar ratio (SiO 2/Al2O 3), SEM grain size, powder particle size, carbon content, phase purity, alkali content and surface area, or combinations thereof. The molar ratio of silica to alumina (SiO 2/Al2O 3), SEM grain size, powder particle size, carbon content, phase purity, alkali content and surface area, which are directly related to the subject matter of the present invention, are explained below.
Silica to alumina molar ratio (SiO 2/Al2O 3): the SiO2/Al2O3 molar ratio of the zeolite is determined by wet chemical analytical methods or instrumental techniques such as XRF or ICP. The SiO2/Al2O3 molar ratio of a particular zeolite affects the acidity of the zeolite and the exchange capacity of the active metals/elements at the exchange sites. For SCR applications, the zeolite is typically exchanged/loaded with Cu or Fe. The Cu and/or Fe content at the exchange sites determines the NOx conversion activity of a particular zeolite. Thus, the SiO2/Al2O3 molar ratio is an important criterion to consider for zeolites used in SCR or any other application.
SEM grain size: the crystallite size of the zeolite was determined by Scanning Electron Microscopy (SEM). SEM is a type of electron microscope that produces an image of a sample by scanning a surface with a focused electron beam. The crystallite size of a zeolite of a particular zeolite is known to affect aggregate size, stability under a set of conditions, and performance in a particular application.
Particle size: the particle size of the zeolite is determined by a number of techniques. One common technique is by laser diffraction. For SCR applications, particle size is known to affect the coating thickness of the active component. Especially for filter applications (SCRF), smaller and narrower particles are needed as they will affect the eluting coating thickness. If the particle size distribution of the eluting coating is high, the eluting coating may block the pores of the substrate (honeycomb carrier) thereby limiting the access of reactant molecules to the active component. In an effective catalyst, there is no resistance to internal diffusion, i.e., diffusion of reactant molecules through the pores of the catalyst/catalyst support.
Carbon content: the carbon content was determined by CHN/combustion analyzer. A common source of carbon content in zeolites is due to incomplete calcination/removal of the organic amine template from the zeolite pores. In certain applications, the presence of carbon content affects the activity of the zeolite to some extent.
Alkali content: the alkali content of the zeolite was determined by flame photometer. Common alkali contents in zeolites are Na and K. The presence of a base content in the zeolite above a certain level affects the activity of the zeolite.
Surface area: surface area is an important characteristic of zeolites. The surface area of the zeolite was measured using an N2 adsorption technique. The surface area of a zeolite is related to porosity, particle morphology and size. The surface area is known to affect catalytic activity.
Phase purity: the phase purity and crystallinity of the zeolite were determined by XRD. The impurity content in zeolites is known to affect properties and activity for particular applications.
It follows, therefore, that optimal SiO2/Al2O3 molar ratios, alkali content, carbon content, SEM grain size and particle size are required for a particular application.
The conventional method for synthesizing SSZ-13 is expensive because it involves the use of NNN trimethylammonium alkylammonium hydroxide as a template. The present invention employs quaternary ammonium salts, i.e., chloride or hydroxide salts of 3-chloro-2-hydroxypropyl trimethylammonium [ (CH 3) 3N+CH2-CHOH-CH2Cl ] or 2, 3-dihydroxypropyl trimethylammonium [ (CH 3) 3N+CH2-CHOH-CH2OH ] solution (referred to herein as Q1), silica, alumina and alkali metal cations, and small amounts of NNN-trimethyl adamantylammonium hydroxide (referred to herein as Q2) to synthesize SSZ-13. The synthesis optionally includes a chloride or hydroxide salt of Q1. The synthesis also optionally includes the use of SSZ-13 zeolite itself (which may be used as a seed material) which may be added to a mixture of 3-chloro-2-hydroxypropyl trimethylammonium salt solution and NNN-trimethyl adamantylammonium hydroxide and silica, alumina and alkali metal cation solutions of the desired molar gel composition described above. The addition of a seeding material, namely SSZ-13 zeolite, helps to produce the desired morphology and phase and reduces hydrothermal crystallization time. SSZ 13 is produced as a result when the above mixture is subjected to hydrothermal synthesis. The process was found to be more cost effective and the resulting SSZ-13 produced effectively removed nitrogen oxide emissions from the automotive and manufacturing industries.
US 4544438 relates to a process for the preparation of SSZ-13 from organic nitrogen-containing cations derived from 1-amantadine, 3-quinitol and 2-exo-aminonorbornane. The prior art employs mixtures of active material compounds such as sodium silicate, water, aluminum sulfate, sodium hydroxide and trimethyl adamantyl ammonium salts. The mixture was subjected to hydrothermal synthesis for 6 days.
US 4665110 relates to a process for preparing a crystalline molecular sieve composition requiring a reaction mixture comprising an adamantane compound as a templating agent for crystallizing the same. The prior art employs mixtures of active material compounds such as water and trimethyl adamantyl ammonium salts. Another mixture of aluminum sulfate and sodium hydroxide was prepared and then added to the trimethyladamantyl ammonium salt solution. The mixture was subjected to hydrothermal synthesis for 6 days.
US 20110251048 relates to the synthesis of chabazite-type zeolites which are expected to have durability and heat resistance, which are desirable practical characteristics for catalyst supports and adsorbents. The prior art uses mixtures of active material compounds such as sodium hydroxide or potassium hydroxide with NNN trimethyl adamantyl ammonium salts. A solution of NNN trimethyl adamantyl ammonium salt was prepared, KOH/NaOH solution was prepared and added to the salt solution. Sodium aluminosilicate was prepared using sodium silicate and aluminum sulfate, respectively. The aluminosilicate gel was added to the NNN trimethylammonium salt solution. The gel was mixed for some time and then subjected to hydrothermal synthesis in an autoclave. The gel mixture was subjected to hydrothermal synthesis for 6 days. It is important to note that the prior art is directed to the production of chabazite-type zeolites having a crystallite size greater than 1.5 microns.
US 20140147378 relates to a process for preparing CHA-type molecular sieves using a colloidal aluminosilicate composition comprising at least one cyclic nitrogen containing cation suitable as a structure directing agent for synthesizing CHA-type molecular sieves. The prior art uses mixtures of active material compounds such as colloidal aluminosilicates containing NNN trimethyl adamantyl ammonium hydroxide, SSZ-13 seed crystals to produce SSZ-13. Whereas the prior art shows that the present invention should necessarily comprise a colloidal aluminosilicate composition containing at least one cyclic nitrogen cation which will act as a structure directing agent.
Thus, the prior art reveals that not only is the synthesis time longer, but the process is resource intensive and costly. The following mentions the drawbacks for each prior art;
a) US 4544438, US 4665110, US 20110251048 and US 20140147378 use NNN trimethylammonium adamantylammonium salts as templates, which are expensive
b) Furthermore, the synthesis time is longer, i.e. typically 6 days, which makes it resource intensive
c) In addition, the product characteristics obtained are narrow, i.e. SSZ-13 is synthesized which aims at producing a silica to alumina ratio (SiO 2/Al2O 3) and SEM grain size within a narrow range.
d) Synthesis includes a colloidal aluminosilicate composition that includes a cyclic nitrogen cation as part of its active material. In addition, colloidal aluminosilicate compositions are expensive.
Thus, there is an urgent and long felt need for a versatile synthesis formulation and method by varying the synthesis formulation and synthesis conditions to ensure economy in terms of synthesis time, resources and cost effective raw materials, and also to provide a tailored method to obtain the desired characteristics in terms of silica to alumina ratio (SiO 2/Al2O 3) and SEM grain size.
The inventors have conducted extensive studies to design a) a synthesis recipe for preparing SSZ-13 in a shorter synthesis time, b) a synthesis recipe comprising a cost-effective structure directing agent, c) unexpectedly provide versatility to a tailored method of SSZ-13 with desired physicochemical properties, wherein the properties are not limited to a narrow range of silica to alumina ratios (SiO 2/Al2O 3) and SEM grain sizes. The individual characteristics or combinations of characteristics can be tailored to the requirements of the various industrial processes in which SSZ-13 is employed.
To overcome the shortcomings of the prior art methods, the inventors explored alternative formulations comprising low cost templating agents and small amounts of NNN trimethyl adamantylammonium salts. After several trials of various combinations including the usual templating agents used in the art, the alternative templating agent 3-chloro-2 hydroxypropyl trimethylammonium salt was tested. The compound is similar in structure to NNN trimethylammonium salt. It has surprisingly been found that a combination of 3-chloro-2 hydroxypropyl trimethylammonium salt and a minor amount of NNN trimethyl adamantylammonium salt is suitable for use in the manufacture of SSZ-13. This combination also provides advantages in terms of cost.
The present invention employs a compound such as sodium hydroxide or potassium hydroxide, alumina and silica in admixture which is then added to a solution of 3-chloro-2 hydroxypropyl trimethylammonium salt and/or a small amount of NNN trimethylammonium adamantylammonium salt or both. SSZ-13 seeds are also optionally added to the gel to direct the synthesis to the pure phase and reduce crystallization time. This also shows that SSZ-13 produced using the present invention is unique in that the compounds used to produce the crystalline molecular sieve composition are different from the compounds of the prior art.
The present invention is directed to producing a wide range of grain sizes, namely SSZ-13 grain sizes of 0.1 to 5 microns. It can also be noted that the present invention does not comprise such a colloidal aluminosilicate composition comprising a cyclic nitrogen cation as part of its active material (which is used in the prior art for the efficient synthesis of SSZ-13).
Object of the Invention
It is an object of the present invention to prepare SSZ-13 which can be used for the production of catalyst formulations for the efficient removal of nitrogen oxide emissions from exhaust gases emitted by the automotive and manufacturing industries.
It is another object of the present invention to prepare SSZ-13 in a cost-effective manner by employing relatively low cost templating agents. The resulting product should be less resource intensive (economical) than competing processes in the art.
The main object of the present invention is to provide a formulation for the manufacture of SSZ-13 having the desired physicochemical properties. The formulation involves fewer steps, is more energy efficient, and has lower synthesis time and hydrothermal synthesis temperature.
Another principal object of the invention is to provide a formulation for producing SSZ-13 with tailored physicochemical properties by varying the synthesis formulation and process conditions during zeolite synthesis.
Disclosure of Invention
The main process by means of which aluminosilicate zeolite SSZ-13 having chabazite structure is synthesized. The synthesis employs quaternary ammonium salts, i.e., chloride or hydroxide salts of 3-chloro-2-hydroxypropyl trimethylammonium [ (CH 3) 3N+CH2-CHOH-CH2Cl ] or 2, 3-dihydroxypropyl trimethylammonium [ (CH 3) 3N+CH2-CHOH-CH2OH ] solution (referred to herein as Ql), silica, alumina and alkali metal cations, and small amounts of NNN-trimethyl-adamantylammonium hydroxide (referred to herein as Q2) to synthesize SSZ-13. By means of which the synthesized SSZ-13 can be further ion-exchanged into the ammonium form. Subsequently, the ammonium form or the calcined H form is further ion exchanged with copper and/or iron salts. Ion-exchanged zeolites are then used as catalysts to effectively remove nitrogen oxide emissions from exhaust gases emitted by the automotive and manufacturing industries.
Detailed Description
The present invention relates to the synthesis of aluminosilicate zeolite SSZ-13 having a chabazite structure. The H-SSZ-13 or NH4-SSZ-13 obtained after ion exchange with ammonium and/or mineral acid has the following characteristics:
x-ray diffraction value: pure phase with chabazite structure
2. Silica to alumina ratio: 5 to 100
3. Total alkali content (Na 2O and K2O): < 5000 parts per million
4. Surface area: 500 square meters/gram
5. Grain size: 0.1 to 5 micrometers
6. Carbon content: <0.5 wt%
The invention is synthesized using the following mole gel composition relative to one mole of alumina:
1.0 to 4 mol of 3-chloro-2-hydroxypropyl trimethyl ammonium salt solution
2.0.2 to 8 mol of trimethyl adamantyl ammonium hydroxide salt solution
3.0 to 10 moles of potassium hydroxide or sodium hydroxide
4.5 to 150 silicon dioxide
5.200 to 2000 Water
Methods of synthesizing SSZ-13, which is an aluminosilicate zeolite having a chabazite structure, are used in catalyst formulations for the effective removal of nitrogen oxide emissions from exhaust gases emitted by automotive and manufacturing industries.
Preparing a solution of 3-chloro-2-hydroxypropyl trimethylammonium salt or a solution of NNN-trimethyl adamantylammonium hydroxide or a mixture of both.
Sodium hydroxide solution is added to a solution of 3-chloro-2-hydroxypropyl trimethylammonium salt or NNN-trimethyl adamantylammonium hydroxide or a mixture of both to produce a mixture.
In another aspect of the invention, wherein a potassium hydroxide solution may instead of sodium hydroxide be added to a solution of 3-chloro-2-hydroxypropyl trimethylammonium salt or a solution of NNN-trimethyl adamantylammonium hydroxide or a mixture of both to produce a mixture.
In another aspect of the invention, wherein, alternatively, a solution of 2, 3-dihydroxypropyl trimethylammonium salt may be used in place of 3-chloro-2-hydroxypropyl trimethylammonium salt.
Alumina sol or alumina metal or aluminium hydroxide or pseudoboehmite alumina or aluminium alkoxide or alumina in the form of aluminium sulphate or aluminium nitrate is then added to the above mixture.
Then adding precipitated silica or silica sol or fumed silica or silica alkoxide, silica in the form of sodium silicate to the above mixture to which alumina has been added to produce a gel-based mixture.
In another aspect of the invention, the order of addition of the silica source and the alumina source may be reversed. In another aspect of the present invention, the order of addition of other materials may be changed.
The gel-based mixture obtained above is then subjected to stirring for 30 to 120 minutes.
The above gel-based mixture is then optionally mixed with SSZ-13 seeds to accelerate the process of synthesizing the SSZ-13 zeolite mixture and/or to avoid other crystalline impurities. The gel was subjected to uniform mixing for 5 to 30 minutes.
The resulting mixture is then subjected to hydrothermal synthesis in an autoclave at a temperature range of 80 to 200 degrees celsius for 1/2 to 6 days under autogenous pressure to produce SSZ-13.
Calcining the SSZ-13 thus obtained in nitrogen and/or air at 450 to 650 degrees celsius for 4 to 12 hours to remove the organic materials associated with the SSZ-13 zeolite.
The SSZ-13 obtained is then treated with ammonium salts or dilute mineral acids to obtain SSZ-13 in ammonium form or H form, respectively.
Calcining SSZ-13 in the ammonium form obtained by treating the ammonium salt to obtain SSZ-13 in the hydrogen form.
In order to provide a clear understanding of the present invention and not to limit the scope of the invention, some embodiments thereof are described below as examples and the accompanying tables to show the wide variety of attributes of SSZ-13 zeolite products.
1) Example 1: synthesis of H-SSZ-13 with input SAR 26
40g of NNN trimethyl adamantylammonium hydroxide (TMAGAOH) template solution (25 wt% in water) was taken and mixed with 13.6g of the hydroxide salt of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (HPTMAOH solution, 25wt% in water) together with 137g of water. A solution of 8g KOH in 91g water was then added and mixed for 10 minutes. 156.8g of silica sol (30 wt% SiO 2) was slowly added to the above mixture and stirred for a further 30 minutes. An aluminum sulfate solution was prepared separately by adding 19.2g of aluminum sulfate 16H2O (16 wt.% Al2O 3) to 54.74g of water to obtain a clear solution. An aluminum sulfate solution is slowly added to a solution containing a template, a base, and a silica precursor. The gel mixture was stirred for 1 hour.
The molar gel composition (composition) at this stage is as follows
26 SiO2:Al2O3:2 K2O:1.57 TMADAOH:0.65 HPTMAOH:802 H2O
The pH of the gel composition was set to pH 12 by adding a 20wt% strength KOH solution. To the above gel composition was added 1.64g of SSZ-13 seed crystals and thoroughly mixed for 30 minutes.
The molar gel composition was heated from room temperature to 170 ℃ in a closed autoclave with stirring, and subjected to hydrothermal synthesis at 170 ℃ for 4 days. XRD was performed after crystallization. After hydrothermal synthesis, the contents of the autoclave were cooled and subjected to filtration. The wet cake is washed with desalted water to remove the templating agent and other soluble impurities. The washed wet cake was subjected to drying at 120 ℃ for 12 hours. The phase purity was confirmed by XRD. The total yield was 38 g. The grain size by SEM is in the range of 0.2 to 1.0 microns. The as-synthesized zeolite is calcined at 550 ℃ to limit the alkali content in the zeolite to less than 500ppm prior to ion exchange with the mineral acid or ammonium salt solution. The zeolite in H form is then obtained by drying and calcining. The SiO2/Al2O3 molar ratio of the zeolite was confirmed by chemical analysis.
2) Example 2: synthesis of H-SSZ-13 with input SAR 26
26.7g of NNN trimethyl adamantylammonium hydroxide (TMAGAOH) template solution (25 wt% in water) was taken and mixed with 26.7g of the hydroxide salt of 3-chloro 2-hydroxypropyl trimethyl ammonium chloride (HPTMAOH solution, 25wt% in water) together with 137g of water. A solution of 8g KOH in 91g water was then added and mixed for 10 minutes. 156.8g of silica sol (30 wt% SiO 2) was slowly added to the above mixture and stirred for a further 30 minutes. An aluminum sulfate solution was prepared separately by adding 19.2g of aluminum sulfate 16H2O (16 wt.% Al2O 3) to 54.74g of water to obtain a clear solution. An aluminum sulfate solution is slowly added to a solution containing a template, a base, and a silica precursor. The gel mixture was stirred for 1 hour.
The molar gel composition (composition) at this stage is as follows
26 SiO2:Al2O3:2 K2O:1.0 TMADAOH:1.3 HPTMAOH:802 H2O
The pH of the gel composition was set to pH 12 by adding a 20wt% strength KOH solution. To the above gel composition was added 1.64g of SSZ-13 seed crystals and thoroughly mixed for 30 minutes.
The molar gel composition was heated from room temperature to 170 ℃ in a closed autoclave with stirring, and subjected to hydrothermal synthesis at 170 ℃ for 4 days. XRD was performed after crystallization. After hydrothermal synthesis, the contents of the autoclave were cooled and subjected to filtration. The wet cake is washed with desalted water to remove the templating agent and other soluble impurities. The washed wet cake was subjected to drying at 120 ℃ for 12 hours. The phase purity was confirmed by XRD. The total yield was 35 g. The grain size by SEM is in the range of 0.2 to 1.0 microns. The as-synthesized zeolite is calcined at 550 ℃ to limit the alkali content in the zeolite to less than 500ppm prior to ion exchange with the mineral acid or ammonium salt solution. The zeolite in H form is then obtained by drying and calcining. The SiO2/Al2O3 molar ratio of the zeolite was confirmed by chemical analysis.
3) Example 3: synthesis of H-SSZ-13 with input SAR of 17
52.4g of NNN trimethyl adamantylammonium hydroxide (TMDAOH) template solution (25 wt% in water) was taken together with 134g of water. A solution of 7.9g KOH in 90g water was then added and mixed for 10 minutes. To the above mixture 154g of silica sol (30 wt% sio 2) was slowly added and stirred for a further 30 minutes. An aluminum sulfate solution was prepared separately by adding 28.8g of aluminum sulfate 16H2O (16 wt.% Al2O 3) to 54g of water to obtain a clear solution. An aluminum sulfate solution is slowly added to a solution containing a template, a base, and a silica precursor. The gel mixture was stirred for 1 hour.
The molar gel composition (composition) at this stage is as follows
17 SiO2:Al2O3:1.3 K2O:1.37 TMADAOH:524 H2O
The pH of the gel composition was set to pH 12 by adding a 20wt% strength KOH solution. To the above gel composition was added 1.6g of SSZ-13 seed crystals and thoroughly mixed for 30 minutes.
The molar gel composition was heated from room temperature to 170 ℃ in a closed autoclave with stirring, and subjected to hydrothermal synthesis at 170 ℃ for 4 days. XRD was performed after crystallization. After hydrothermal synthesis, the contents of the autoclave were cooled and subjected to filtration. The wet cake is washed with desalted water to remove the templating agent and other soluble impurities. The washed wet cake was subjected to drying at 120 ℃ for 12 hours. The phase purity was confirmed by XRD. The grain size by SEM is in the range of 0.4 to 1.0 microns. The as-synthesized zeolite is calcined at 550 ℃ to limit the alkali content in the zeolite to less than 500ppm prior to ion exchange with the mineral acid or ammonium salt solution. The zeolite in H form is then obtained by drying and calcining. The SiO2/Al2O3 molar ratio of the zeolite was confirmed by chemical analysis.
4) Example 4: synthesis of H-SSZ-13 with input SAR 35
54g of NNN trimethyl adamantylammonium hydroxide (TMDAOH) template solution (25 wt% in water) was taken together with 99g of water. A solution of 8g KOH in 91g water was then added and mixed for 10 minutes. To the above mixture was slowly added 211g of silica sol (30 wt% sio 2) and stirred for a further 30 minutes. An aluminum sulfate solution was prepared separately by adding 19.2g of aluminum sulfate 16H2O (16 wt.% Al2O 3) to 54.74g of water to obtain a clear solution. An aluminum sulfate solution is slowly added to a solution containing a template, a base, and a silica precursor. The gel mixture was stirred for 1 hour.
The molar gel composition (composition) at this stage is as follows
35 SiO2:Al2O3:2 K2O:2 TMADAOH:802 H2O
The pH of the gel composition was set to pH 12 by adding a 20wt% strength KOH solution. To the above gel composition was added 1.64g of SSZ-13 seed crystals and thoroughly mixed for 30 minutes.
The molar gel composition was heated from room temperature to 170 ℃ in a closed autoclave with stirring, and subjected to hydrothermal synthesis at 170 ℃ for 4 days. XRD was performed after crystallization. After hydrothermal synthesis, the contents of the autoclave were cooled and subjected to filtration. The wet cake is washed with desalted water to remove the templating agent and other soluble impurities. The washed wet cake was subjected to drying at 120 ℃ for 12 hours. The phase purity was confirmed by XRD. The grain size by SEM is in the range of 0.6 to 1.2 microns. The as-synthesized zeolite is calcined at 550 ℃ to limit the alkali content in the zeolite to less than 500ppm prior to ion exchange with the mineral acid or ammonium salt solution. The zeolite in H form is then obtained by drying and calcining. The SiO2/Al2O3 molar ratio of the zeolite was confirmed by chemical analysis.
5) Example 5: synthesis of H-SSZ-13 with input SAR 26
54g of NNN trimethyl adamantylammonium hydroxide (TMDAOH) template solution (25 wt% in water) was taken together with 137g of water. A solution of 8g KOH in 91g water was then added and mixed for 10 minutes. 156.8g of silica sol (30 wt% SiO 2) was slowly added to the above mixture and stirred for a further 30 minutes. An aluminum sulfate solution was prepared separately by adding 19.2g of aluminum sulfate 16H2O (16 wt.% Al2O 3) to 54.74g of water to obtain a clear solution. An aluminum sulfate solution is slowly added to a solution containing a template, a base, and a silica precursor. The gel mixture was stirred for 1 hour.
The molar gel composition (composition) at this stage is as follows
26 SiO2:Al2O3:2 K2O:2 TMADAOH:802 H2O
The pH of the gel composition was set to pH 12 by adding a 20wt% strength KOH solution. To the above gel composition was added 1.64g of SSZ-13 seed crystals and thoroughly mixed for 30 minutes.
The molar gel composition was heated from room temperature to 160 ℃ in a closed autoclave with stirring, and subjected to hydrothermal synthesis at 160 ℃ for 4 days. XRD was performed after crystallization. After hydrothermal synthesis, the contents of the autoclave were cooled and subjected to filtration. The wet cake is washed with desalted water to remove the templating agent and other soluble impurities. The washed wet cake was subjected to drying at 120 ℃ for 12 hours. The phase purity was confirmed by XRD. The grain size by SEM is in the range of 1 to 3 microns. The as-synthesized zeolite is calcined at 550 ℃ to limit the alkali content in the zeolite to less than 500ppm prior to ion exchange with the mineral acid or ammonium salt solution. The zeolite in H form is then obtained by drying and calcining. The SiO2/Al2O3 molar ratio of the zeolite was confirmed by chemical analysis.
6) Example 6: synthesis of H-SSZ-13 with input SAR of 17
29.5g of NNN trimethyl adamantylammonium hydroxide (TMDAOH) template solution (25 wt% in water) was taken together with 287g of water. A solution of 5.5g NaOH in 50g water was then added and mixed for 10 minutes. To the above mixture was slowly added 56.4g of silica sol (30 wt% sio 2) and stirred for a further 30 minutes. An aluminum sulfate solution was prepared separately by adding 10.5g of aluminum 16H2O (16 wt.% Al2O 3) to 81g of water to obtain a clear solution. An aluminum sulfate solution is slowly added to a solution containing a template, a base, and a silica precursor. The gel mixture was stirred for 1 hour.
The molar gel composition (composition) at this stage is as follows
17 SiO2:Al2O3:4.1 Na2O:2.1 TMADAOH:1610 H2O
The pH of the gel composition was set to pH 12 by adding a 20wt% NaOH solution. 0.64g of SSZ-13 seed crystals were added to the above gel composition and thoroughly mixed for 30 minutes.
The molar gel composition was heated from room temperature to 170 ℃ in a closed autoclave with stirring, and subjected to hydrothermal synthesis at 170 ℃ for 4 days. XRD was performed after crystallization. After hydrothermal synthesis, the contents of the autoclave were cooled and subjected to filtration. The wet cake is washed with desalted water to remove the templating agent and other soluble impurities. The washed wet cake was subjected to drying at 120 ℃ for 12 hours. The phase purity was confirmed by XRD. The grain size by SEM is in the range of 0.1 to 0.4 microns. The as-synthesized zeolite is calcined at 550 ℃ to limit the alkali content in the zeolite to less than 500ppm prior to ion exchange with the mineral acid or ammonium salt solution. The zeolite in H form is then obtained by drying and calcining. The SiO2/Al2O3 molar ratio of the zeolite was confirmed by chemical analysis.
7) Example 7: synthesis of H-SSZ-13 with input SAR 26
27.8g of NNN trimethyl adamantylammonium hydroxide (TMDAOH) template solution (25 wt% in water) was taken together with 266g of water. A solution of 5.4g NaOH in 50g water was then added and mixed for 10 minutes. To the above mixture was slowly added 85.1g of silica sol (30 wt% sio 2) and stirred for a further 30 minutes. An aluminum sulfate solution was prepared separately by adding 10.42g aluminum sulfate 16H2O (16 wt.% Al2O 3) to 76g water to obtain a clear solution. An aluminum sulfate solution is slowly added to a solution containing a template, a base, and a silica precursor. The gel mixture was stirred for 1 hour.
The molar gel composition (composition) at this stage is as follows
26 SiO2:Al2O3:4.1 Na2O:2.0 TMADAOH:1610 H2O
The pH of the gel composition was set to pH 12 by adding 20wt% NaOH solution and thoroughly mixed for 30 minutes.
The molar gel composition was heated from room temperature to 170 ℃ in a closed autoclave with stirring, and subjected to hydrothermal synthesis at 170 ℃ for 4 days. XRD was performed after crystallization. After hydrothermal synthesis, the contents of the autoclave were cooled and subjected to filtration. The wet cake is washed with desalted water to remove the templating agent and other soluble impurities. The washed wet cake was subjected to drying at 120 ℃ for 12 hours. The phase purity was confirmed by XRD. The grain size by SEM is in the range of 0.1 to 0.4 microns. The as-synthesized zeolite is calcined at 550 ℃ to limit the alkali content in the zeolite to less than 500ppm prior to ion exchange with the mineral acid or ammonium salt solution. The zeolite in H form is then obtained by drying and calcining. The SiO2/Al2O3 molar ratio of the zeolite was confirmed by chemical analysis.
8) Example 8: synthesis of H-SSZ-13 with input SAR as 100
54g of NNN trimethyl adamantylammonium hydroxide (TMDAOH) template solution (25 wt% in water) was taken together with 137g of water. A solution of 8g KOH in 91g water was then added and mixed for 10 minutes. 156.8g of silica sol (30 wt% SiO 2) was slowly added to the above mixture and stirred for a further 30 minutes. An aluminum sulfate solution was prepared separately by adding 5g of aluminum 16H2O (16 wt.% ai 2O 3) to 54.74g of water to obtain a clear solution. An aluminum sulfate solution is slowly added to a solution containing a template, a base, and a silica precursor. The gel mixture was stirred for 1 hour.
The molar gel composition (composition) at this stage is as follows
100 SiO2:Al2O3:7.6 K2O:8 TMADAOH:3080 H2O
The pH of the gel composition was set to pH 12 by adding a 20wt% strength KOH solution. To the above gel composition was added 1.64g of SSZ-13 seed crystals and thoroughly mixed for 30 minutes.
The molar gel composition was heated from room temperature to 170 ℃ in a closed autoclave with stirring, and subjected to hydrothermal synthesis at 170 ℃ for 4 days. XRD was performed after crystallization. After hydrothermal synthesis, the contents of the autoclave were cooled and subjected to filtration. The wet cake is washed with desalted water to remove the templating agent and other soluble impurities. The washed wet cake was subjected to drying at 120 ℃ for 12 hours. The phase purity was confirmed by XRD. The grain size by SEM is in the range of 0.5 to 3.0 microns. The as-synthesized zeolite is calcined at 550 ℃ to limit the alkali content in the zeolite to less than 500ppm prior to ion exchange with the mineral acid or ammonium salt solution. The zeolite in H form is then obtained by drying and calcining. The SiO2/Al2O3 molar ratio of the zeolite was confirmed by chemical analysis.
Table 1:

Claims (13)

1. a process for producing SSZ-13 zeolite, said process comprising,
a) Providing an aqueous reaction mixture comprising at least one silica source, at least one alumina source, at least one alkali metal hydroxide source, and at least two sources of quaternary ammonium ions, wherein at least one such source of quaternary ammonium ions (Q1) has the formula (CH) 3 ) 3 N+CH 2 -CHOH-CH 2 Cl or (CH) 3 ) 3 N+CH 2 -CHOH-CH 2 OH ion, wherein the second quaternary ammonium ion (Q2) is an N, N, N-trimethyl-alkylammonium ion, and
the aqueous reaction mixture has a molar composition of (1 Al 2 O 3 ) (5 to 150 SiO) 2 ) (0.1 to 4Q 1) (0.2 to 8 second quaternary ammonium ion (Q2)), (0.1 to 10 potassium hydroxide and/or sodium hydroxide) (200 to 2000 water),
b) The resulting mixture was stirred for 30 minutes to 120 minutes,
c) The mixture is then subjected to hydrothermal synthesis in an autoclave at a autogenous pressure in a temperature range of 80 to 200 degrees celsius for 12 to 144 hours to produce SSZ-13,
d) Filtering the zeolite slurry, washing the wet cake with desalted water, drying the wet cake at 120 degrees celsius for 6 to 12 hours, and calcining the resulting SSZ-13 in nitrogen and/or air at 450 to 650 degrees celsius for 4 to 12 hours to remove organic materials associated with the SSZ-13 zeolite,
e) Treating the resulting SSZ-13 with an ammonium salt to obtain SSZ-13 in ammonium form,
f) The resulting ammonium form of SSZ-13 is calcined to obtain the hydrogen form of SSZ-13.
2. The method of claim 1, wherein the molar ratio of the first quaternary ammonium ion (Q1) to the second quaternary ammonium ion (Q2) is from 0.0125 to 20.
3. The process of claim 1, wherein the aqueous reaction mixture of step (a) comprises a silica to alumina molar ratio of from 5 to 150.
4. The process of claim 1, wherein SSZ-13 seeds are optionally added to the aqueous reaction mixture of step (a).
5. The method of claim 3, wherein the SSZ-13 seed crystals are present in the reaction mixture in an amount of SiO 2 From 0.1 to 5% by weight.
6. The method of claim 1, wherein the ammonium salt of step (e) comprises ammonium nitrate or ammonium sulfate or ammonium chloride at a concentration of less than 5wt%.
7. The process according to claim 1, wherein the obtained SSZ-13 obtained after step (d) is treated with a dilute mineral acid to obtain the final SSZ-13 zeolite in hydrogen form.
8. The method of claim 7, wherein the mineral acid comprises nitric acid or sulfuric acid or hydrochloric acid at a concentration of less than 3 wt%.
9. The process according to claim 1 or 7, wherein the resulting SSZ-13 zeolite obtained at the end of step (f) has a total alkali content of less than 5000 parts per million.
10. The process according to claim 1 or 7, wherein the resulting SSZ-13 zeolite obtained at the end of step (f) has a surface area of more than 500 square meters per gram.
11. The process according to claim 1 or 7, wherein the resulting SSZ-13 zeolite obtained at the end of step (f) has a carbon content of less than 0.5% by weight.
12. The process according to claim 1 or 7, wherein the obtained SSZ-13 zeolite obtained at the end of step (f) has SiO 2 /Al2O 3 The molar ratio is in the range of 5 to 100.
13. The process according to claim 1 or 7, wherein the resulting SSZ-13 zeolite obtained at the end of step (f) has a crystallite size by SEM in the range of 0.1 to 5 microns.
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