WO2006048188A1

WO2006048188A1 - Improved process for the preparation of zms-5 zeolites

Info

Publication number: WO2006048188A1
Application number: PCT/EP2005/011550
Authority: WO
Inventors: Agostino Zatta; Maria Roberta Rabaioli; Pierino Radici; Rosario Aiello; Fortunato Crea; Patrizia Frontera; Giuseppe Giuffrida
Original assignee: Sasol Italy S.P.A.
Priority date: 2004-11-08
Filing date: 2005-10-25
Publication date: 2006-05-11
Also published as: WO2006048188A8; JP2008518874A; US20090053135A1; DK1817258T3; EP1817258B1; DE602005026434D1; SI1817258T1; ITMI20042136A1; ATE498584T1; EP1817258A1

Abstract

Process for the synthesis of ZMS-5 zeolites essentially consisting of: a. preparing two aqueous solutions of sodium aluminate and silicate; b. putting the two solutions in contact with each other under stirring at room temperature; c. adding a solution of a mineral acid to solution (a) or to solution (b) or to solution (a) + (b), in such a quantity that the molar ratio OH-/H20 ranges from 0.02 to 0.03; d. adding a quantity of water sufficient for maintaining fluid the reacting mixture and the molar ratio OH-/H20 from 0.017 to 0.022; e. pre-heating the final mixture obtained at the end of steps (a) - (d) at a temperature ranging from 20 to 60°C; and f. heating the mixture, under stirring, at a temperature ranging from 100 to 200°C.

Description

IMPROVED PROCESS FOR THE PREPARATION OF ZMS-5 ZEOLITES

The present invention relates to an improved process for the preparation of ZSM-5 zeolites. More specifically, the present invention relates to an improved process for the preparation of ZSM-5 zeolites characterized by an Si/Al atomic ratio higher than 5, pref¬ erably ranging from 12 to 50.

Zeolites are crystalline alumino-silicates of a micro- porous nature having a regular, well-defined three- dimensional structure characterized by a large number of micro-cavities interconnected by means of a channel system. The three-dimensional structure of zeolites consists of TO₄ tetrahedral forms, wherein T can be a silicon or aluminum atom. The valence of the aluminum atoms is balanced by the presence in the crystal of alkaline, alkaline-earth metal ions, ammonium cations. The space available inside the three-dimensional structure can be occupied by absorbed wa¬ ter molecules, which can be reversibly removed by heating the zeolite. Zeolites are officially classified into small-, medium- and large-pore zeolites. This classification is based on the number of oxygen atoms on the larger ring which delim¬ its the access to the pore system. The ZSM-5 zeolite has a structure consisting of a channel system delimited by rings with 10 atoms. The chemical formula of the elementary cell in its anhydrous form can be represented by the following symbolic formula:

M_x Al_x Si_{96 -X} Oi₉₂ wherein M represents an ion of an alkaline metal or the am¬ monium ion and x is lower than 27.

ZSM-5 zeolites crystallize in the "orthorhombic" system with an elementary cell having the following dimensions:

a_o = 20.096 A α = 90.00° b_o = 19.948 A β = 90.00° c_o = 13.428 A γ = 90.00°

The three-dimensional structure of ZSM-5 zeolites can be described by two interconnected channel systems, the first consisting of straight-line channels parallel to the "b" axis and the other comprising a "zigzag" channel system parallel to the "a" axis. The two channel systems intersect in a repetitive and regular manner so that each unitary cell contains four intersections.

In general, zeolites are normally prepared by reacting, in an aqueous medium, and possibly heating, suitable mix- tures of oxides and salts of silicon and aluminum atoms in the presence of alkaline metal ions such as sodium and po¬ tassium. The product, which crystallizes after a certain period of time according to the reaction parameters, such as temperature and concentration, is then filtered, washed with water and possibly dried or calcined at a maximum tem¬ perature of 550⁰C until a completely anhydrous zeolite is obtained.

The synthesis of zeolites having a high silicon con- tent, such as ZSM-5 zeolites, is normally effected by put¬ ting a solution of an organo-silicate product, prepared by dissolving an organic substance in a solution of silicon oxide (for example of colloidal silica, LUDOX, fume silica, silicic acid) , in contact with a solution prepared by dis- solving an organic base and an aluminum salt in water. The mixture or "gel" thus obtained is reacted in an autoclave, at a high temperature and pressure. The efficiency of the synthesis is defined by the weight of crystallized aluminum silicate which is recovered, after filtration and washing with water, with respect to the silicon and aluminum oxides initially present in the "gel" . The chemical composition and the purity of the reagents used in the synthesis can be a critical factor for obtaining a completely crystalline product, not containing other zeolite phases. The synthesis of ZSM-5 zeolites was described for the first time in the English patent GB 1,161,974, wherein a preparation is described based on hydrothermal synthesis starting from a gel containing silica, alumina, alkaline metal ions, and a quaternary ammonium compound (tetrapropyl ammonium hydroxide (n-C₃H₇)₄NOH) .

The zeolites obtained through this preparation process are microcrystalline solids consisting of silicon, alumi¬ num, sodium and oxygen, containing the tetrapropyl ammonium ion (which, as a result of its structure, occupies in the unitary cell the positions corresponding to the four inter¬ sections of the two channel systems) and are materials whose chemical composition can be suitably expressed by the formula:

M_x-4 Q₄ Al_x Si_96-X O₁₉₂ n H₂O wherein Q represents the tetrapropyl ammonium ion, M an al¬ kaline metal ion, and n is the number of water molecules. The tetrapropyl ammonium ion cannot be exchanged by means of conventional ion exchange processes and is removed through calcination treatment at high temperatures, up to about 600⁰C.

A considerable number of papers have been developed from this first patent. Synthesis processes have been found in the presence of a wide variety of organic compounds, as described, for example, in USA patents US 4,175,114 and US 4,431,621. In US patent 4,175,114, the ZSM-5 zeolite is crystallized starting from reagents cited in literature, comprising silica, alumina, and alkaline metal ions, in the presence of zeolite seeds or mixtures of zeolite seeds with alcohols and/or ammonia. In US patent 4,431,621, the ZSM-5 zeolite is synthe¬ sized in reacting mixtures containing organic compounds with hydroxyl groups, preferably alcohols and phenols, gly¬ cols and polyglycols. It is known that the organic compound acts as a "template" in the sense that it acts as a "mold" during the formation of the zeolite structure.

It is also known that, when the ZSM-5 zeolite is pre¬ pared starting from the systems cited in literature, it is not possible to obtain the pure zeolite if the amount of alkaline metal ions, for example sodium ions, is too high. These alkaline metal ions are introduced into the system through the raw materials and, as known, the sodium sili¬ cate and aluminate solutions produced industrially by the alkaline etching of silica and alumina sand, require a high NaOH concentration. As a result of this restriction, the synthesis systems prepared starting from solutions of sodium silicates and aluminates, necessarily contain such high concentrations of sodium that they oppose or do not allow the crystallization of the ZSM-5 zeolite, but favour the formation of other phases, both zeolitic and non-zeolitic . The present invention, described in more detail in the enclosed claims, relates to a process for the preparation of ZSM-5 zeolites from sodium silicate and sodium aluminate solutions, without the drawbacks present in the production processes of the known art. Said solutions are prepared from sands and aluminas of an extractive origin. An example is represented by the solutions of sodium silicate obtained from crystalline silica, such as quartz. A large quantity of sodium ions are introduced due to the use of these solu- tions of silicate and aluminate, in addition to silicon and aluminum. As these sodium ions are present in a high con¬ centration in the reagents, the ratio between the sodium oxide and the aluminum oxide is higher with respect to that obtained with the other reagents . The Applicant has found a process capable of solving the problem which arises when alkaline ions are introduced in a high quantity into the synthesis system.

According to a preferred embodiment of the process ob¬ ject of the present invention, once the solutions of sodium silicate and sodium aluminate have been put in contact with each other, with certain molar ratios between silica and alumina (SiO₂/Al₂O₃) and at a controlled temperature, rang¬ ing from 10 to 30⁰C (room temperature) , possibly in the presence of a templating agent selected from the salts or compounds of quaternary ammonium from linear aliphatic amines, a specific amount of a solution of a mineral acid is introduced, for example sulphuric acid or hydrochloric acid.

It is necessary to add mineral acid in order to keep the OH^"/H₂O molar ratio lower than 0.03, preferably ranging from 0.02 to 0.03, wherein OH^" represents the number of moles of NaOH which have not been neutralized by the min¬ eral acid. When the ratio between silica and alumina in¬ creases, it is preferable to balance the amount of water and the amount of mineral acid, so as to maintain the OH^" /H₂O ratio constant within the mentioned terms. According to the present invention, the mineral acid solution can be added to the silicate alone, to the aluminate alone or to the silicate-aluminate mixture already formed. Both a temperature increase and a considerable increase in the viscosity of the mixture is observed by the addition of the mineral acid. As far as the operating time for the acid treatment is concerned, it is preferable to operate with addition times of the acid of over 5 minutes, gener- ally between 20 and 30 minutes.

It has been observed that the systems are more reactive only under stirring conditions, leading to the formation of ZSM-5 zeolites in short times. In order to effect an effi¬ cient mixing-stirring during the subsequent phase, once the addition of the mineral acid solution is completed, a fur- ther amount of distilled water is added to make the system more fluid. In order to optimise both the reaction times and yields, the dilution is carried out with a quantity of water which is such that the OH^"/H₂O ratio does not change significantly, and can be maintained at 0.017-0.022.

The synthesis mixture thus prepared is then subjected to pre-heating, still under stirring, at a low temperature ranging from 20 to 60⁰C, for times ranging from thirty min¬ utes to five hours, to favour the nucleation of the ZSM-5 zeolite with respect to non-zeolite phases, such as, for example, quartz. The reactivity of the systems varies in relation to the pre-heating time carried out at a low tem¬ perature. The formation of the ZSM-5 zeolite is unfavoured when the system is brought to temperatures which are too low, for example lower than 15⁰C. Pre-heating to tempera¬ tures higher than 60⁰C favours the formation of mordenite and quartz. The duration also varies in relation to the pre-heating temperature of the "gel" , as the lower the tem¬ perature, the more preferable it is to extend said nuclea- tion period. At room temperature, for example, the best re¬ sults have been obtained by extending this period up to two-three hours.

At the end of this phase, the crystallization continues under hydrothermal conditions, under stirring, at a tem- perature ranging from 100 to 200⁰C and for a sufficient time ranging from 6 to 72 hours. The crystallization kinet¬ ics change in relation to the temperature. The crystalliza¬ tion times for the formation of ZSM-5 zeolites decrease with an increase in the temperature. At a temperature of 160⁰C, for example, the crystallization times have been higher than 24 hours and high crystallizations are reached after 72 hours of reaction; in any case, the formation of other zeolite phase different from ZSM-5 zeolite, is not observed. At 180⁰C, 24 hours are sufficient. As previously specified, the gels are particularly vis¬ cous and clotted and, very likely, the dimensions of these clots regulate the nucleation times and the crystallization rate. It is therefore important to reduce the dimensions of these clots as much as possible, both during the pre- heating and crystallization phase. In preparing the synthe¬ sis, it would be preferable that the additions of the rea¬ gents be carried out in a reactor equipped with an external thermostat-regulated system and mechanically stirred with an anchor or propeller suitable for a high rev rate. The process, in relation to the ratio between the sil¬ ica and alumina of the reagent blend, can be applied for the preparation of ZSM-5 zeolites in the presence of or without the quaternary ammonium salt .

By controlling the critical factors and obviously in- eluding the SiO₂/Al₂O₃ ratio of the reacting mix, the molar ratios between the reagents in which the ZSM-5 zeolite can be crystallized as a pure and completely crystalline phase, starting from solutions of sodium silicate and sodium alu- minate, are the following: - SiO₂Ml₂O₃ from 20 to 200, extremes included;

- Na₂O/Al₂O₃ from 14 to 100, extremes included;

- X/A1₂O₃ from 5 to 50, extremes included;

- Q/AI₂O₃ from 0 to 2, extremes included;

- OH^"/H₂O from 0.017 to 0.022, extremes included; wherein X represents the anion of a mineral acid and Q is an organic compound of quaternary ammonium from a linear amine (tertiary) . OH^" represents the number of moles of NaOH after the addition of the mineral acid.

The range of SiO₂ZAl₂O₃ ratios in which the ZSM-5 zeo- lite can be obtained without the necessity of introducing the quaternary ammonium organic compound from a linear amine, varies from 20 to 60, extremes included.

If present, the concentration of the organic compound of quaternary ammonium is controlled so as to not have an organic residue in the reaction water, which would then re¬ quire a specific treatment for eliminating the residue from the reaction. Examples of organic compounds of quaternary ammonium are those having the general formula:

(RiR₂R₃R₄) ₄N⁺ - X^" wherein Ri R₂ R₃ and R₄, the same or different, represent a Ci-C₃ linear alkyl radical and X is an anion, for example a halide, sulphate, acetate or the OH^" group. Particular examples of these compounds are tetrapropyl ammonium hy¬ droxide or bromide. Furthermore, the content of the organic compound of quaternary ammonium in the structural cavities of the ZSM-5 zeolite with a high Si/Al ratio, is lower than 2 moles per unitary cell. Considering that in the synthesis system, the Q/SiO₂ ratio is at the most equal to 0.01, this fact con- firms that, during the crystallization process, the ZSM-5 zeolite, uses practically the whole amount of organic com¬ pound available in the system.

As a result of all these factors, the industrial em¬ bodiment of the process, object of the present invention, is particularly advantageous; the raw materials are avail¬ able at a low cost, as they are solutions of sodium sili¬ cate or aluminate, the organic compound is absent or, at the most, is used at a low concentration, the whole process is run at such a concentration as to allow a high produc- tion capacity and the preparation times are suitable for an industrial production. The overall production times of the ZSM-5 zeolite range from a minimum of 6 to a maximum of 72 hours.

The residual sodium ions in the ZSM-5 zeolite crystals can be exchanged with an acid to obtain the zeolite in acid form.

By following a preferred embodiment of the process, ob¬ ject of the present invention, the ZSM-5 zeolite is ob¬ tained according to a method which essentially consists of : a) preparing two aqueous solutions of sodium aluminate and sodium silicate, containing, respectively:

- Al₂O₃ and Na₂O wherein the Na₂O/Al₂O₃ weight ratio is higher than 0.8, generally ranging from 1.1 to 1.5, and, optionally, an organic compound of quaternary am- monium from a linear amine; and

SiO₂ and Na₂O wherein the SiO₂/Na₂O weight ratio is higher than 1, generally ranging from 2 to 3.5; b) putting the two solutions prepared during the previous step in contact with each other, under stirring, regulating the quantity of reagents so as to respect the above molar ratios, operating at room temperature, preferably from 10 to 30⁰C over a period of time ranging from 15 to 30 min¬ utes; c) adding a solution of mineral acid, such as sulphuric acid or hydrochloric acid, over a period of more than 5 minutes, preferably between 20 and 30 minutes, to solution

(a) or solution (b) , or to solution (a) + (b) , in such a quantity as to maintain the OH^"/H₂O molar ratio between

0.02 and 0.03; d) adding a quantity of water sufficient for maintaining the reagent mix fluid during the subsequent phases and wherein the water addition is such as to have a final H₂O/A1₂O₃ ratio in the reacting mixture, ranging from 400 to 2,000 and an OH^"/H₂O molar ratio from 0.017 to 0.022; e) pre-heating the final mixture obtained at the end of steps (a) - (d) for a time ranging from 30 minutes to 5 hours, under stirring, at a temperature ranging from 20 to 60⁰C, preferably from 20 to 40⁰C; f) heating the mixture, under stirring, for a sufficient time, ranging from 6 to 72 hours, at a temperature ranging from 100 to 200⁰C, preferably from 150 to 180⁰C.

Some illustrative and non-limiting examples are pro¬ vided hereunder for a better understanding of the present invention and for its embodiment. The zeolites obtained with the following examples were identified on the basis of the X-ray diffraction pattern. The chemical composition was determined on the anhydrous product, obtained by subjecting the sample to a calcination treatment at 550⁰C for over 16 hours, by means of ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) analysis. In the example, the parts and percentages are in¬ tended, unless otherwise specified, as parts and percent¬ ages by weight. EXAMPLE 1 The following solutions are poured, under stirring and at room temperature (about 2O⁰C) , into a 1-liter steel re¬ actor, equipped with an anchor stirrer, thermometer and ex¬ ternal electric heating system: sodium silicate (442 parts) with 28.2% of SiO₂ and 14.0% of Na₂O; sodium aluminate (35.25 parts) with 13.4% of Al₂O₃ and 14.2% of Na₂O;

A gel mass is obtained to which a solution of sulphuric acid is added, consisting of 85 parts at 96% and 89 parts of water, over a period of 30 minutes, maintaining the sys¬ tem under stirring. At the end, a quantity of water is added, equal to 138 parts, obtaining a low viscosity mass. The gel thus obtained is pre-heated to 40⁰C under stirring for two hours and 30 minutes and, at the end, is reacted at 180⁰C for 24 hours, still under stirring. The suspension is filtered under vacuum, the solid washed with demineralized water, dried in an oven at 100⁰C for about 3 hours and left to stabilize in air. An aliquot of this product was ana¬ lyzed with X-rays and identified as pure ZSM-5 zeolite. The X-ray diffraction pattern, which is characteristic of the product, is shown in figure 1. An aliquot was sub¬ jected to calcination at 55O⁰C for 16 hours in air, until an anhydrous zeolite was obtained, which was subjected to ICP-AES analysis in order to determine the SiO₂/Al₂O₃ molar ratio, which proved to be equal to 29.3, corresponding to a composition of : 91.4% SiO₂; 5.3% Al₂O₃; 3.3% Na₂O. EXAMPLE 2

The following solutions are poured, under stirring and at room temperature (about 20⁰C) , into a 1-liter steel re- actor, equipped with an anchor stirrer, thermometer and ex¬ ternal electric heating system: sodium silicate (442 parts) with 28.7% of SiO₂ and 13.5% of Na₂O; sulphuric acid, 81 parts at 96% and 103 parts of wa- ter.

Maintaining the system under stirring, the solution of sodium aluminate (26.95 parts) with 13.4% of Al₂O₃ and 14.2% of Na₂O, is added.

A gel mass is obtained to which a quantity of water equal to 105 parts is added, at the end, obtaining a low viscosity mass. The gel thus obtained is pre-heated to 4O⁰C under stirring for two hours and 30 minutes and, is subse¬ quently reacted at 160⁰C for 72 hours, still under stir¬ ring. The suspension is filtered under vacuum, the solid product washed with demineralized water, dried in an oven at 100⁰C for about 3 hours and left to stabilize in air.

A pure ZSM-5 zeolite is obtained having an X-ray dif¬ fraction pattern, whose characteristic peaks are shown in figure 2. The SiO₂/Al₂O₃ molar ratio of the calcined product at 55O⁰C for 16 hours, proved to be equal to 52.9, corre- sponding to a composition of : 95.1% of SiO₂; 3.05% of Al₂O₃; 1.85% of Na₂O on the anhydrous product. EXAMPLE 3

The following solutions are poured, under stirring and at room temperature (about 2O⁰C) , into a 1-liter steel re¬ actor, equipped with an anchor stirrer, thermometer and ex¬ ternal electric heating system: sodium silicate (472 parts) with 30.5% of SiO₂ and 9.2% of Na₂O; - sulphuric acid, (46 parts) at 96%.

A mass is obtained, which is kept under stirring for 10 minutes. A solution is then added, containing: sodium aluminate (18.2 parts) with 13.5% of Al₂O₃ and 14.2% of Na₂O; - demineralized water (133 parts) ; n-tetrapropyl ammonium bromide (3.2 parts) . Demineralized water (73 parts) is then introduced under stirring. A gel mass is obtained which is pre-heated for 2 hours to 4O⁰C. The mass is then heated to about 180⁰C and is maintained at this temperature for 72 hours. The solid formed is filtered under vacuum, washed with demineralized water, dried at 100⁰C for 4 hours, and left to stabilize in air. A pure ZSM-5 zeolite is obtained, as shown in the pat¬ tern in Figure 3. The SiO₂/Al₂O₃ molar ratio of the calcined product at 550⁰C for 16 hours, proved to be equal to 100.6, corresponding to : 97.6% SiO₂; 1.65% Al₂O₃; 0.75% Na₂O,

Claims

1. A process for the preparation of ZSM-5 zeolites essen¬ tially consisting of: a) preparing two aqueous solutions of sodium aluminate and sodium silicate, containing, respectively:

Al₂O₃ and Na₂O wherein the Na₂θ/Al₂O₃ weight ratio is higher than 0.8, and, optionally, an organic compound of quaternary ammonium from a linear amine; and

SiO₂ and Na₂O wherein the SiO₂/Na₂O weight ratio is higher than 1; b) putting the two solutions prepared during the previous step, in contact with each other, under stirring, regulat¬ ing the quantity of reagents so as to respect the above mo¬ lar ratios, operating at room temperature, for a period of time ranging from 15 to 30 minutes; c) adding a solution of mineral acid, over a period of over 5 minutes, to solution (a) or solution (b) , or to so¬ lution (a) + (b) , in such a quantity as to maintain the OH^" /H₂O molar ratio within the range of 0.02 to 0.03; d) adding a quantity of water sufficient for keeping the reacting mixture fluid during the subsequent phases and wherein the water addition is such as to have a final H₂O/A1₂O₃ ratio in the reacting mixture, ranging from 400 to 2,000 and an OH^"/H₂O molar ratio from 0.017 to 0.022; e) pre-heating the final mixture obtained at the end of steps (a) - (d) for a time ranging from 30 minutes to 5 hours, under stirring, at a temperature ranging from 20 to 6O⁰C; f) heating the mixture, under stirring, for a sufficient time, ranging from 6 to 72 hours, to a temperature ranging from 100 to 200⁰C.

2. The process according to claim 1, wherein the molar ratios between the reagents are:

- SiO₂/Al₂O₃ from 20 to 200, extremes included; - Na₂CVAl₂O₃ from 14 to 100, extremes included;

- X/A1₂O₃ from 5 to 50, extremes included;

- 0_./Al₂O₃ from 0 to 2, extremes included;

- 0H^"/H₂0 from 0.017 to 0.022, extremes included; wherein X represents the anion of a mineral acid and Q is an organic compound of quaternary ammonium from a linear amine.

3. The process according to claim 1 or 2, wherein the ZSM-5 zeolite has an Si/Al atomic ratio higher than 5.

4. The process according to claim 1, 2 or 3 , wherein the range of SiO₂/Al₂O₃ ratios within which the ZSM-5 zeolite can be obtained without the necessity of introducing the organic compound of quaternary ammonium, varies from 20 to 60, extremes included.

5. The process according to any of the previous claims, wherein the mineral acid is selected from sulphuric acid and hydrochloric acid.

6. The process according to any of the previous claims, wherein the organic compound of quaternary ammonium is se¬ lected from those having the general formula:

(RiR₂R₃R₄) ₄N⁺ - X^" wherein R₁ R₂ R₃ and R₄, the same or different, represent a Ci-C₃ linear alkyl radical and X is an anion, selected from a hydroxide, a halide, a sulphate and an acetate.