Synthesis of sapo-18 and its catalytic applications (Machine-translation by Google Translate, not le

专利摘要:
Synthesis of sapo-18 and its catalytic applications. Synthesis of the silicoaluminophosphate and metalosilicoaluminophosphate polymorphs of the molecular sieve sapo-18 using cyclic quaternary ammoniums as organic structure directing agents (adeo), and their use as a catalyst. (Machine-translation by Google Translate, not legally binding)
公开号:ES2555804A1
申请号:ES201430852
申请日:2014-06-03
公开日:2016-01-08
发明作者:Avelino Corma Canós；Manuel MOLINER MARÍN；Raquel MARTÍNEZ FRANCO
申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
IPC主号:

专利说明:

DESCRIPTION

Synthesis of toad-18 and its catalytic applications.

Field of technique 5

The present invention relates to a new method of synthesis of the SAPO-18 molecular sieve in its silicoaluminophosphate and metalosilicoaluminophosphate form (Me-SAPO-18), using cyclic quaternary ammoniums as structure directing agents. This procedure involves the combination of the various sources that are required for the preparation of a silicoaluminophosphate (SAPO), such as silicon, aluminum, and phosphorus; next to a cyclic quaternary ammonium, and a source of a metal, in the case of the preparation of Me-SAPO-18. The present invention, in addition to referring to the method of synthesis, also refers to the application of said materials as catalysts.
 fifteen
Background of the Invention

In 1982, UOP first described the preparation of a family of molecular sieves, called aluminophosphates (AlPOs) (Wilson, S. T., et al. J. Am Chem. Soc. 1982, 104, 1146). The composition of the microporous crystalline structure of these materials is formed by Al and P tetrahedra that share the vertices through O atoms. Silicoaluminophosphates (SAPOs) are a particular case of AlPOs, where some of the structure's atoms they are partially substituted by silicon atoms (Chen, JS et al. J. Phys.Chem., 1994, 98, 10216). This substitution can take place through two different mechanisms: a) substitution of an atom of P by an atom of Si, generating a negative charge on the structure (isolated silicon), or b) substitution of an atom of Al and an atom of P for two atoms of Si, giving rise to the formation of domains rich in silicon (silicon islands). Only when silicon is isolated, do SAPOs exhibit excellent cation exchange capacity that allows the presence of different active species, suitable for various catalytic applications. Possibly, the 30 most common SAPOs are in protonated form. The protons associated with the Si substitution of the structure, give these materials a high acidity, which allows their application as catalysts in acid catalytic processes, such as in the synthesis of methanol to olefins (SW Kaiser, US Patent 4,499,327; 1985 ).
 35
Thus, the distribution of silicon on the walls of the SAPOs is possibly the most important factor in controlling the acidity of these materials. The organic structure directing agent (ADEO) used in the preparation of SAPOs not only influences the crystallization of a certain structure, but also the positioning and coordination of silicon atoms in the crystalline structure of the molecular sieve. 5

The SAPO-18 silicoaluminophosphate is a three-dimensional molecular sieve with a small pore (openings of 8 atom channels with pore diameters of about 3.8 Å) with large cavities inside. As observed in the literature, the conventional preparation of SAPO-18 is carried out using as an ADEO the organic molecule N, N-10 diisopropylethylamine (Chen et al. Catal. Lett., 1994, 28, 241; Chen et al. J. Phys. Chem., 1994, 98, 10216; Hunger et al., Catal. Lett., 2001, 74, 61; Wragg et al. J. Catal., 2011, 397). This SAPO-18 synthesis procedure allows to obtain silicoaluminophosphates with mixtures of isolated silicon and silicon islands. The presence of silicon islands confers a lower Brönsted acidity to said SAPO-18 (Chen et al. J. Phys. Chem., 1994, 98, 10216; Hunger et al., 15 Catal. Lett., 2001, 74, 61 ; Wragg et al. J. Catal., 2011, 397). Recently, the synthesis of SAPO-18 using tetraethylammonium as ADEO has been described, but this synthesis procedure also shows large silicon environments forming islands (Fan et al., J. Mater. Chem., 2012, 22, 6568), and therefore, lower Brönsted acidity.
 twenty
Other cations, other than protons, can also be introduced into SAPOs. Conventionally, the introduction of cationic metal species in SAPOs (Me-SAPO) is carried out through post-synthetic cation exchange procedures. However, said post-synthetic procedure requires numerous intermediate stages to obtain the Me-SAPO: SAPO hydrothermal synthesis, calcination, transformation in the ammonium form (if required), cationic exchange of the metal, and finally, calcination for get the final Me-SAPO. All this number of intermediate steps translates into an increase in the cost of synthesis of the corresponding Me-SAPO.

In addition, when you want to introduce a cationic metal in extra-net positions in a SAPO, it is very important that the silicon species are isolated in the crystalline network, because they are the ones that will generate the negative charges that will allow compensating and stabilizing the charges positive of cationic metals.

In recent years, the preparation of molecular sieves substituted with metals, and particularly, molecular sieves of small pore size with large cavities
In their structure substituted with cationic copper, they have received great attention due to their high activity and stability for the selective catalytic reduction (RCS) of nitrogen oxides (NOx) with ammonia or hydrocarbons in the presence of oxygen (I. Bull, et al ., US Patent 0,226,545, 2008). In this sense, the formation of NOx during the combustion of fossil fuels, especially in transport, is one of the great current environmental challenges.

Recently, the introduction of cationic Cu species into the structure of the SAPO-18 material by post-synthetic cation exchange (Li et al. WO2008 / 118434; Ye et al. Appl. Catal. A, 2012, 427, 34; Ye et al., CN102626653). However, the synthesis of the molecular sieve 10 Cu-SAPO-18 requires a considerable number of steps for the final obtaining of the catalyst: hydrothermal synthesis of SAPO-18, elimination by thermal treatment of the organic matter contained inside the pores / cavities during synthesis, previous cation exchange with ammonium cations, cation exchange with copper, and finally, calcination to obtain the Cu-SAPO-18. This material shows a good catalytic activity for NOx CSR, but less hydrothermal stability than other catalysts, such as Cu-SSZ-13 or Cu-SAPO-34 (Ye et al. Appl. Catal. A, 2012, 427, 3. 4). The fact that the synthesis of the original SAPO-18 is carried out according to the procedure described in the reference (Chen et al. J. Phys. Chem., 1994, 98, 10216), where part of the silicon is aggregated in island forms , prevents a good stabilization of the 20 extra-network cations, and therefore, the corresponding Cu-SAPO-18 shows less stability.

Description of the invention
 25
The present invention relates to a synthesis procedure of SAPO-18, which may comprise at least the following steps:
i) Preparation of a mixture containing at least water, at least one source of silicon, at least one source of aluminum, at least one source of phosphorus, one or more ADEOs where at least one of them is a cyclic quaternary ammonium and 30 where the final synthesis mixture has the following molar composition:
a Yes: 0.5 Al: b P: c ADEO: d H2O
where a is in the range of 0.01 to 0.3, preferably between 0.03 to 0.3, and more preferably between 0.05 to 0.3;
where b is in the range of 0.2 to 0.49, preferably between 0.2 to 35 0.47, and more preferably between 0.2 to 0.45;
where c is in the range of 0.001 to 2, preferably between 0.1 to 1, and more preferably between 0.2 to 0.7;
where d is in the range of 1 to 200, preferably 2 to 100, and more preferably 3 to 50.
ii) Crystallization stage in which the mixture is hydrothermally treated at a temperature between 80-200 ° C until the formation of the material is crystalline.
iii) Recovery of the crystalline material.

The main objectives of the present invention will be to carry out an efficient method of synthesis that allows on the one hand the synthesis of the silicoaluminophosphate form of SAPO-18 with a good distribution of silicon in isolated positions to improve its Brönsted acidity, and on the other On the one hand, the synthesis in a single stage (direct synthesis) of the metalosilicoaluminophosphate form of SAPO-18 (Me-SAPO-18) with metallic cationic species in extra-net positions and isolated silicon in the crystalline network. In this way, it will be possible not only to reduce the high number of stages required for the synthesis of Me-SAPO-18, but also to improve the hydrothermal stability of the cationic metal species, and therefore, the hydrothermal stability of the material.

This synthesis procedure is carried out using the different required sources 20 in the preparation of a conventional SAPO such as any source of silicon, aluminum and phosphorus, together with at least one ADEO, at least one of them being preferably a cyclic quaternary ammonium selected from N, N-dimethyl-3,5-dimethylpiperidinium (DMDMP), N, N-diethyl-2,6-dimethylpiperidinium (DEDMP), N, N-dimethyl-2,6-dimethylpiperidinium, N-ethyl-N- methyl-2,6-dimethylpiperidinium and combinations thereof, as well as any variation thereof. The other ADEO, if any, may be another cyclic quaternary ammonium or any other organic molecule, such as, for example, any amine, quaternary ammonium, phosphine, phosphonium, phosphazene and combinations thereof.

According to a particular embodiment, the crystallization step described in (ii) can be carried out in autoclaves under both static and dynamic conditions. In addition, the temperature of the crystallization process may be preferably in the temperature range between 100 and 200 ° C, more preferably between 130 and 190 ° C, and more preferably between 150 and 190 ° C and the crystallization time may be between 1 hour and 50 days, preferably between 1 and 10 days, and more preferably between 2 and 8 days. It is important to keep in mind that the components of the
Synthesis mixture can come from various sources, and depending on this, the time and crystallization conditions may vary.

According to the process of the present invention, SAPO-18 crystals can be added to the final synthesis mixture of "i" as sowing, being able to reach up to 25% by weight 5 of the total oxides introduced in the synthesis.

After the crystallization process, the crystals of the SAPO-18 material are separated from the mother liquors, and recovered. The solid can be washed and separated from the mother liquors by different techniques, preferably the technique of decantation, filtration, ultrafiltration, centrifugation, or other solid-liquid separation techniques and combinations thereof can be used.

According to a particular embodiment, the objective may be to produce the calcined crystalline material. In this case, the process described according to the present invention further comprises a step of removing the occluded organic matter inside the material, which can be performed by a technique selected from extraction, heat treatment and combinations thereof to temperatures above 25 ° C, for periods between 2 minutes and 25 hours.
 twenty
The material produced through the present invention can be pelletized according to known techniques.

According to a preferred embodiment, the synthesis procedure described above may further comprise at least one metal source, where the final synthesis gel would have the following molar composition:
a Si: 0.5 Al: b P: e X: c ADEO: d H2O
where a is in the range of 0.01 to 0.3; preferably between 0.03 to 0.3, and more preferably between 0.05 to 0.3;
where b is in the range of 0.2 to 0.49; preferably between 0.2 to 30 0.47, and more preferably between 0.2 to 0.45;
where c is in the range of 0.001 to 2; preferably between 0.1 to 1, and more preferably between 0.2 to 0.7;
where d is in the range of 1 to 200, preferably 2 to 100, and more preferably 3 to 50 35
where e is in the range of 0.00 to 0.6; preferably between 0.01 to 0.4, and more preferably from 0.015 to 0.2.

In this embodiment, he describes a direct synthesis procedure in which the Me-SAPO-18 product is obtained where Me is a metal. Preferably said metal is selected from Cu, Ni, Fe, Pt, Pd, Mn, Ca, Mg, Zn, Cd, Co, Ti, Sn, and combinations thereof. Preferably said metal is Cu.

In addition, the present invention also relates to the product obtained according to the procedure described above which can have the following molar composition:

X0.0-0.6 Si0.01-0.3Al0.40-0.55P0.20-0.49O2

According to a particular embodiment, the product obtained according to the process of the present invention can have the following molar composition:

X0.005-0.6 Si0.01-0.3Al0.40-0.55P0.20-0.49O2

According to the present invention, X is a metal selected from Cu, Ni, Fe, Pt, Pd, Mn, Ca, Mg, Zn, Cd, Co, Ti, Sn and combinations thereof, and according to a particular embodiment X 20 is Cu.

The metal source can be any precursor thereof, such as, for example, nitrates, oxalates, sulfates, organometallic complexes as well as combinations thereof among others. 25

In particular, the direct synthesis procedure of the Me-SAPO-18 described above uses Cu as a metal for the direct synthesis of the Me-SAPO-18. According to said procedure, any source of copper can be used for the preparation of Cu-SAPO-18, including the use of Cu organometallic complexes. In this sense, any amine or mixtures of amines, capable of forming organometallic complexes with copper, can be used independently of the number of N atoms they have in their structure, regardless of their form (cyclic, linear, branched ...), and regardless of the nature of the amine (primary, secondary, tertiary). Some examples of amines may be tetraethylene pentamine (TEPA), triethylenetetramine (TETA), 35
1,4,8,11-tetraazacyclotetradecane or 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane and combinations thereof among others.

According to a particular embodiment, the product obtained presents the metal in extra-net positions directly and in a single stage, avoiding the use of successive post-synthetic stages. The combination of the ADEOs described, at least one cyclic quaternary ammonium, allows an excellent distribution of the silicon centers in isolation in the structure of the SAPO-18, allowing to compensate and stabilize the positive charges of the cationic or extra-net metals.
 10
The present invention also relates to the use of the materials described above and obtained according to the process of the present invention as catalysts for the conversion of feeds formed by organic compounds into products of higher added value, or for their removal / separation of the reactive current contacting said feed with the material described in its active form. fifteen

According to a particular embodiment, Me-SAPO-18 can be used as catalysts in selective catalytic reduction (RCS) reactions of NOx (nitrogen oxide) in a gas stream. It has been proven that Cu-SAPO-18 gives very good results in this type of reactions. In particular, Cu-SAPO-18 molecular sieves, in accordance with the present invention, are used as catalysts in the NOx RCS in the presence of a reducer such as ammonium, urea and / or hydrocarbons.

According to a preferred embodiment, according to the process of the present invention, it is possible to synthesize Cu-SAPO-18 in a single stage by preferably positioning the cationic Cu 25 in extra-net positions, which gives the material specific qualities, both of activity as of hydrothermal stability, for the reaction of selective catalytic reduction of nitrogen oxides.

Throughout the description and claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention.

35
Brief description of the figures

Figure 1: X-ray diffraction patterns of the solids synthesized in examples 3 and 6 described in the present invention.
 5
Figure 2: Nuclear magnetic resonance (NMR) spectra of 29Si solids of the samples synthesized according to examples 3 and 6.

Figure 3: UV-Vis spectra of the sample synthesized in Example 6 of the present invention in its uncalcined form, and of the Cu-TETA complex in aqueous solution. 10

Examples

The following examples are provided by way of illustration and are not intended to be limiting of the present invention. fifteen

Example 1: Synthesis of ADEO N, N-dimethyl-3,5-dimethylpiperidinium iodide (DMDMP)

10 g of 3,5-dimethylpiperidine (Sigma-Aldrich, ≥ 96% by weight) are mixed with 19.51 g of potassium bicarbonate (KHCO3, Sigma-Aldrich; 99.7% by weight) and dissolved in 140 ml of 20 methanol. Then 54 ml of methyl iodide (CH3I, Sigma-Aldrich, ≥ 99% by weight) are added, and the resulting mixture is kept under stirring for 5 days at room temperature. After this time, the reaction mixture is filtered to remove potassium bicarbonate. The filtered solution is partially concentrated by rotary evaporator. Once the methanol is partially evaporated, the solution is washed with chloroform several times and magnesium sulfate (MgSO4, Sigma-Aldrich, ≥ 99.5% by weight) is added. The mixture is then filtered to remove magnesium sulfate. The ammonium salt is obtained by precipitation with diethyl ether and subsequent filtration. The final yield of N, N-dimethyl-3,5-dimethylpiperidinium iodide is 85%.
To prepare the hydroxide form of the above organic salt: 10.13 g of the organic salt are dissolved in 75.3 g of water. They are then added with 37.6 g of an anion exchange resin (Dower SBR), and the resulting mixture is kept under stirring for 24 hours. Finally, the solution is filtered and N, N-dimethyl-3,5-dimethylpiperidinium hydroxide is obtained (with an exchange rate of 94%).
 35
Example 2: Synthesis of ADEO N, N-diethyl-2,6-dimethylpiperidinium iodide (DEDMP)

36 g of cis-2,6-dimethylpiperidine (Sigma-Aldrich, 98% by weight) are mixed with 320 ml of methanol and 64 g of potassium bicarbonate (KHCO3, Sigma-Aldrich; 99.7% by weight). Subsequently, 200 g of ethyl iodide (Sigma-Aldrich, 99% by weight) are added, and the resulting mixture is refluxed for 5 days. After this time, the reaction mixture is filtered to remove potassium bicarbonate. The filtered solution is partially concentrated by rotary evaporator. Once the methanol has partially evaporated, the solution is washed with chloroform several times and magnesium sulfate (MgSO4, Sigma-Aldrich, ≥ 99.5% by weight) is added. The mixture is then filtered to remove magnesium sulfate. The ammonium salt is obtained by precipitation with diethyl ether and subsequent filtration. The final yield of N, N-diethyl-2,6-dimethylpiperidinium iodide is 75%.
To prepare the hydroxide form of the above organic salt: 10 g of the organic salt are dissolved in 75 g of water. They are then added with 40 g of an anion exchange resin (Dower SBR), and the resulting mixture is kept under stirring for 24 hours. Finally, the solution is filtered and N, N-diethyl-2,6-dimethylpiperidinium hydroxide is obtained (with an exchange rate of 90%).

Example 3: Synthesis of SAPO-18 material using DMDMP as ADEO
 twenty
First, 1324.3 mg of orthophosphoric acid (85% wt, Aldrich) is mixed with 6287.0 mg of a 19% by weight aqueous solution of DMDMP hydroxide and kept under stirring for 10 minutes. Next, 1043.8 mg of alumina (75% wt, Condea) and 304.2 mg of a colloidal silica suspension (Ludox AS40 40% wt, Aldrich) are introduced. The resulting mixture is kept under stirring for the time necessary to evaporate the excess water 25 until the desired gel concentration is reached. The final gel composition is:

0.066 SiO2: 0.19 P2O5: 0.25 Al2O3: 0.24 DMDMP: 4.6 H2O

The gel is transferred to a Teflon coated autoclave, and heated at 190 ° C for 30 days in dynamic conditions. After the hydrothermal crystallization process, the sample is filtered and washed with plenty of distilled water and finally dried at 100 ° C.

The sample is characterized by X-ray diffraction (DRX), observing the formation of the characteristic DRX pattern of SAPO-18 (see Figure 1). 35
As demonstrated by the nuclear magnetic resonance (NMR) spectrum of Si solids, the synthesized SAPO-18 exclusively shows the presence of Si isolated in its structure (see the band centered at -90 ppm in the sample Example 3 of Figure 2).

The sample is calcined at 550 ° C in air to remove the fractions of organic matter occluded inside the microporous material during the crystallization process.

Example 4: Synthesis of SAPO-18 material using DMDMP as ADEO

First, 1365.3 mg of orthophosphoric acid (85% wt, Aldrich) is mixed with 6282.0 mg of 10, a 19% by weight aqueous solution of DMDMP hydroxide and kept under stirring for 10 minutes. Next, 1016.3 mg of alumina (75% wt, Condea) and 195.3 mg of a colloidal silica suspension (Ludox AS40 40% wt, Aldrich) are introduced. The resulting mixture is kept under stirring for the time necessary to evaporate the excess water until the desired gel concentration is reached. The final composition of the gel is: 15

0.043 SiO2: 0.20 P2O5: 0.25 Al2O3: 0.25 DMDMP: 4.8 H2O

The gel is transferred to a Teflon coated autoclave, and heated at 190 ° C for two days in dynamic conditions. After the hydrothermal crystallization process, sample 20 is filtered and washed with plenty of distilled water and finally dried at 100 ° C.

The sample is characterized by X-ray diffraction, to determine the structure obtained after the crystallization process, observing the characteristic diffraction pattern of SAPO-18. 25

The sample is calcined at 550 ° C in air to remove fractions of organic matter occluded inside the microporous material during the crystallization process.

Example 5: Synthesis of SAPO-18 material using DEDMP as ADEO 30

First, 107.5 mg of orthophosphoric acid (85% wt, Aldrich) is mixed with 712.2 mg of a 15% by weight aqueous solution of DEDMP hydroxide and kept under stirring for 10 minutes. Next, 83.5 mg of alumina (75% wt, Condea) and 17.9 mg of a colloidal silica suspension (Ludox AS40 40% wt, Aldrich) are introduced. The mix 35
The resulting time is kept under stirring the time necessary to evaporate the excess water until the desired gel concentration is reached. The final gel composition is:

0.048 SiO2: 0.19 P2O5: 0.25 Al2O3: 0.23 DEDMP: 5.0 H2O
 5
The gel is transferred to a Teflon coated autoclave, and heated at 190 ° C for two days in dynamic conditions. After the hydrothermal crystallization process, the sample is filtered and washed with plenty of distilled water and finally dried at 100 ° C.

The sample is characterized by X-ray diffraction, to determine the structure obtained after the crystallization process, observing the characteristic diffraction pattern of SAPO-18.

The sample is calcined at 550 ° C in air to remove fractions of organic matter occluded inside the microporous material during the crystallization process. fifteen

Example 6: Direct synthesis of Cu-SAPO-18 material using Cu-triethylenetetramine (Cu-TETA) as a precursor to Cu and DMDMP as ADEO.

The first step is the preparation of the Cu-TETA copper complex. For this, 20 405.9 mg of a 20% by weight aqueous solution of copper (II) sulfate (98% wt, Alpha) are mixed with 74.5 mg of triethylenetetramine (TETA, 99% wt, Aldrich), keeping it under stirring for 2 hours. Next, 2700 mg of distilled water and 1035.8 mg of orthophosphoric acid (85% wt, Aldrich) are added, keeping the resulting solution under stirring for 5 minutes. Subsequently, 8840 mg of a 17.1% by weight aqueous solution of DMDMP hydroxide is added, and it is kept under stirring for another 5 minutes. Finally, 734.7 mg of alumina (75% wt, Condea), and 241.5 mg of a colloidal silica suspension (Ludox AS40 40% wt, Aldrich) are introduced. The resulting mixture is kept under stirring for 30 minutes, or the time necessary to evaporate the excess water until the desired gel concentration is reached. The final composition of the gel is: 30

0.074 SiO2: 0.21 P2O5: 0.25 Al2O3: 0.023 Cu-TETA: 0.44 DMDMP: 27.8 H2O

The gel is transferred to a Teflon coated autoclave, and heated at 175 ° C for 6 days in dynamic conditions. After the hydrothermal crystallization process, the sample is filtered and washed with plenty of distilled water and finally dried at 100 ° C.
The sample is characterized by X-ray diffraction, to determine the structure obtained after the crystallization process (see DRX pattern in Figure 1).

The uncalcined sample is characterized by ultraviolet-visible spectroscopy (UV-Vis) to verify that the copper atoms are in extra-net positions. The UV-Vis spectrum of the sample in its uncalcined form has a single band centered at ~ 260 nm, which demonstrates the presence of the intact organometallic complex in the solid in extra-net positions (see Figure 3).

As demonstrated by the nuclear magnetic resonance (NMR) spectrum of Si solids, 10 the synthesized SAPO-18 exclusively shows the presence of Si isolated in its structure (see the band centered at -90 ppm in the sample Example 6 of the Figure 2).

The sample is calcined at 550 ° C in air to remove fractions of organic matter occluded inside the microporous material during the crystallization process. fifteen

Example 7: Direct synthesis of Cu-SAPO-18 material using Cu-triethylenetetramine (Cu-TETA) as a precursor to Cu and DMDMP as ADEO.

The first step is the preparation of the Cu-TETA copper complex. To do this, 20,799.2 mg of a 20% by weight aqueous solution of copper (II) sulfate (98% wt, Alpha) are mixed with 145.5 mg of triethylenetetramine (TETA, 99% wt, Aldrich), keeping it under stirring for 2 hours. Next, 2800 mg of distilled water and 1043.2 mg of orthophosphoric acid (85% wt, Aldrich) are added, keeping the resulting solution under stirring for 5 minutes. Subsequently, 8405 mg of a 17.1% by weight aqueous solution of DMDMP hydroxide is added, and it is kept under stirring for another 5 minutes. Finally, 734.5 mg of alumina (75% wt, Condea), and 254.2 mg of a colloidal silica suspension (Ludox AS40 40% wt, Aldrich) are introduced. The resulting mixture is kept under stirring for 30 minutes, or the time necessary to evaporate the excess water until the desired gel concentration is reached. The final composition of the gel is: 30

0.078 SiO2: 0.21 P2O5: 0.25 Al2O3: 0.046 Cu-TETA: 0.42 DMDMP: 28.8 H2O

The gel is transferred to a Teflon coated autoclave, and heated at 175 ° C for 6 days in dynamic conditions. After the hydrothermal crystallization process, the sample is filtered and washed with plenty of distilled water and finally dried at 100 ° C.
The sample is characterized by X-ray diffraction, to determine the structure obtained after the crystallization process, observing the characteristic diffraction pattern of SAPO-18.

The sample is calcined at 550 ° C in air to remove the fractions of organic matter occluded inside the microporous material during the crystallization process.

Example 8: Direct synthesis of Cu-SAPO-18 material using Cu-triethylenetetramine (Cu-TETA) as a precursor to Cu and DMDMP as ADEO.
 10
The first step is the preparation of the Cu-TETA copper complex. For this, 1591.4 mg of a 20% by weight aqueous solution of copper (II) sulfate (98% wt, Alpha) are mixed with 296.4 mg of triethylenetetramine (TETA, 99% wt, Aldrich), keeping it under stirring for 2 hours. Next, 1056.0 mg of orthophosphoric acid (85% wt, Aldrich) is added, keeping the resulting solution under stirring for 5 minutes. Subsequently, 10031 mg of a 12.2% by weight aqueous solution of DMDMP hydroxide is added, and it is kept under stirring for another 5 minutes. Finally, 735.0 mg of alumina (75% wt, Condea), and 242.1 mg of a colloidal silica suspension (Ludox AS40 40% wt, Aldrich) are introduced. The resulting mixture is kept under stirring for 30 minutes, or the time necessary to evaporate the excess water until the desired gel concentration is reached. The final gel composition is:

0.074 SiO2: 0.21 P2O5: 0.25 Al2O3: 0.093 Cu-TETA: 0.36 DMDMP: 29.3 H2O

The gel is transferred to a Teflon coated autoclave, and heated at 175 ° C for 25 days in dynamic conditions. After the hydrothermal crystallization process, the sample is filtered and washed with plenty of distilled water and finally dried at 100 ° C.

The sample is characterized by X-ray diffraction, to determine the structure obtained after the crystallization process, observing the characteristic diffraction pattern of SAPO-18.

The sample is calcined at 550 ° C in air to remove fractions of organic matter occluded inside the microporous material during the crystallization process.
 35
Example 9: Direct synthesis of Cu-SAPO-18 material using Cu-triethylenetetramine (Cu-TETA) as a precursor to Cu and DMDMP as ADEO.

The first step is the preparation of the Cu-TETA copper complex. To do this, 400.8 mg of a 20% by weight aqueous solution of copper (II) sulfate (98% wt, Alpha) 5 are mixed with 72.9 mg of triethylenetetramine (TETA, 99% wt, Aldrich), keeping it under stirring for 2 hours. Next, 1076.8 mg of orthophosphoric acid (85% wt, Aldrich) is added, keeping the resulting solution under stirring for 5 minutes. Subsequently, 8692 mg of a 17.4% by weight aqueous solution of DMDMP hydroxide is added, and it is kept under stirring for another 5 minutes. Finally, 10,734.5 mg of alumina (75% wt, Condea), and 251.6 mg of a colloidal silica suspension (Ludox AS40 40% wt, Aldrich) are introduced. The resulting mixture is kept under stirring for 30 minutes, or the time necessary to evaporate the excess water until the desired gel concentration is reached. The final gel composition is:
 fifteen
0.077 SiO2: 0.21 P2O5: 0.25 Al2O3: 0.023 Cu-TETA: 0.44 DMDMP: 31.2 H2O

The gel is transferred to a Teflon coated autoclave, and heated at 190 ° C for 3 days in dynamic conditions. After the hydrothermal crystallization process, the sample is filtered and washed with plenty of distilled water and finally dried at 100 ° C. twenty

The sample is characterized by X-ray diffraction, to determine the structure obtained after the process of observing the characteristic diffraction pattern of SAPO-18.

The sample is calcined at 550 ° C in air to remove the fractions of organic matter occluded inside the microporous material during the crystallization process.

Example 10: Direct synthesis of Cu-SAPO-18 material using Cu-triethylenetetramine (Cu-TETA) as a precursor to Cu and DMDMP as ADEO.
 30
The first step is the preparation of the Cu-TETA copper complex. To do this, 799.2 mg of a 20% by weight aqueous solution of copper (II) sulfate (98% wt, Alpha) are mixed with 145.4 mg of triethylenetetramine (TETA, 99% wt, Aldrich), keeping it under stirring for 2 hours. Next, 1061.6 mg of orthophosphoric acid (85% wt, Aldrich) is added, keeping the resulting solution under stirring for 5 minutes. Subsequently, 8244 mg of a 17.4% aqueous solution by weight of
DMDMP hydroxide, and kept stirring for another 5 minutes. Finally, 735.4 mg of alumina (75% wt, Condea), and 248.1 mg of a colloidal silica suspension (Ludox AS40 40% wt, Aldrich) are introduced. The resulting mixture is kept under stirring for 30 minutes, or the time necessary to evaporate the excess water until the desired gel concentration is reached. The final composition of the gel is: 5

0.076 SiO2: 0.21 P2O5: 0.25 Al2O3: 0.046 Cu-TETA: 0.42 DMDMP: 32.5 H2O

The gel is transferred to a Teflon coated autoclave, and heated at 190 ° C for 3 days in dynamic conditions. After the hydrothermal crystallization process, the sample is filtered and washed with plenty of distilled water and finally dried at 100 ° C.

The sample is characterized by X-ray diffraction, to determine the structure obtained after the crystallization process, observing the characteristic diffraction pattern of SAPO-18. fifteen

The sample is calcined at 550 ° C in air to remove fractions of organic matter occluded inside the microporous material during the crystallization process.

Example 11: Chemical analysis of different Cu-SAPO-18 materials obtained in the present invention

Molar ratios of Si and Cu obtained by ICP of the materials synthesized in examples 6, 7, 8, 9 and 10 (see Table 1).
 25
Table 1: Molar ratios of the synthesized solids according to examples 7, 8 and 9 of the present invention.

 Example  Yes / (Al + P) Cu / (Al + P)
 5  0.097 0.028
 7  0.101 0.058
 8  0.104 0.063
 9  0.089 0.029
 10  0.090 0.064

30
Example 12: Heat treatments in the presence of steam

The hydrothermal stability of some of the samples synthesized in the examples of the present invention is studied by treating them with steam (2.2 ml / min) at 750 ° C for 13 hours.
 5
Example 13: Catalytic test for the RCS reaction of NOx using different Cu-SAPO-18 materials synthesized according to the present invention.

The activity of these samples for the selective catalytic reduction of NOx is studied using a fixed bed quartz tubular reactor 1.2 cm in diameter and 20 cm long. In a typical experiment, the catalyst is compacted into particles of size between 0.25-0.42 mm, introduced into the reactor, and the temperature is increased to 550 ° C (see reaction conditions in Table 2); subsequently, that temperature is maintained for one hour under a flow of nitrogen. Once the desired temperature has been reached, the reaction mixture is fed. The NOx RCS is studied using NH3 as a reducer. The NOx present at the outlet of the gases from the reactor is analyzed continuously by means of a chemiluminescent detector (Thermo 62C).

Table 2: Reaction conditions of the NOx RCS.
 twenty
 Total gas flow (ml / min)  300
 Catalyst Load (mg)  40
 NO concentration (ppm)  500
 NH3 concentration (ppm)  530
 O2 concentration (%)  7
 H2O concentration  5
 Temperature range tested (ºC)  170-550

The catalytic results of some of the catalysts synthesized in any of the examples of the present invention are summarized in Table 3. In Table 3, the catalytic results of the materials synthesized in Examples 7, 9 and 10 are also described, then having been treated with steam at 750 ° C for 13 hours (Example 7-25 750 ° C, Example 9-750 ° C and Example 10-750 ° C, respectively).

Table 3: Conversion (%) of NOx at different temperatures (200, 250, 300, 350, 400, 450, 500 ° C) using different Cu-SAPO-18 materials synthesized by the synthesis methodology described in the present invention.

 Conversion (%) of NOx at different temperatures
 210ºC 250ºC 300ºC 350ºC 400ºC 450ºC 500ºC 550ºC
 Example 6  63.1 82.0 81.2 82.6 87.4 90.6 83.5 52.9
 Example 7  79.0 93.5 94.1 94.3 94.3 91.9 78.2 54.9
 Example 8  75.9 85.5 85.8 87.2 89.4 89.3 75.2 47.2
 Example 7-750 ° C  84.6 92.9 91.5 91.7 90 88.3 74.6 61.1
 Example 9-750 ° C  84.6 93.3 90.9 92.4 92.2 93.9 89.1 82.2
 Example 10-750 ° C  93.2 99 98.6 99.4 98.4 97.1 88.7 82.6
 5

权利要求:
Claims (25)
[1]
REDEMPTIONS
1.- SAPO-18 synthesis procedure, characterized in that it comprises at least the following steps:
i) Preparation of a mixture containing, at least water, at least one source of 5 silicon, at least one source of aluminum, at least one source of phosphorus, one or more ADEOs where at least one of them is a cyclic quaternary ammonium and where the final synthesis mixture has the following molar composition:
a Yes: 0.5 Al: b P: c ADEO: d H2O
where a is in the range of 0.01 to 0.3; 10
where b is in the range of 0.2 to 0.49;
where c is in the range of 0.001 to 2;
where d is in the range of 1 to 200.
ii) Crystallization stage in which the mixture is hydrothermally treated at a temperature between 80-200 ° C until the formation of the material is crystalline.
iii) Recovery of the crystalline material.

[2]
2. Method of synthesis of SAPO-18 according to claim 1, characterized in that the final synthesis mixture has the following molar composition:
a Yes: 0.5 Al: b P: c ADEO: d H2O
where a is in the range of 0.03 to 0.3;
where b is in the range of 0.2 to 0.47;
where c is between the range of 0.1 to 1;
where d is in the range of 2 to 100. 25

[3]
3. Method of synthesis of SAPO-18 according to claim 1, characterized in that the cyclic quaternary ammonium is selected from N, N-dimethyl-3,5-dimethylpiperidinium (DMDMP), N, N-diethyl-2,6-dimethylpiperidinium (DEDMP), N, N-dimethyl-2,6-dimethylpiperidinium, N-ethyl-N-methyl-2,6-dimethylpiperidinium and combinations thereof. 30

[4]
4. Synthesis procedure of SAPO-18 according to claim 1, characterized in that any source of silicon, aluminum, phosphorus can be used in the synthesis process.

[5]
5. Synthesis procedure of SAPO-18 according to claim 1, characterized in that the crystallization stage described in (ii) is carried out in autoclaves under both static and dynamic conditions.

[6]
6. Synthesis procedure of SAPO-18 according to claim 1, characterized in that the temperature of the crystallization process described in (ii) is in the temperature range between 100 and 200 ° C.

[7]
7. Method of synthesis of SAPO-18 according to claim 1, characterized in that the crystallization time described in (ii) is between 1 hour and 50 days. 10

[8]
8. Method of synthesis of SAPO-18 according to any of the preceding claims, characterized in that crystals of SAPO-18 material are added in the synthesis mixture as sowing.
 fifteen
[9]
9. Synthesis procedure of SAPO-18 according to claim 9, characterized in that the amount of SAPO-18 crystals can be up to 25% by weight of the total oxides introduced in the synthesis.

[10]
10. Method of synthesis of SAPO-18 according to any of the preceding claims 20, characterized in that the crystals of SAPO-18 are separated from the mother liquors by a technique selected from decantation, filtration, ultrafiltration, centrifugation, other solid separation techniques -liquid and combinations thereof.

[11]
11. Method of synthesis of SAPO-18 according to any of the preceding claims, characterized in that it also comprises a step of eliminating the organic matter occluded inside the material.

[12]
12. Method of synthesis of SAPO-18 according to claim 11, characterized in that this removal is done by a technique selected from extraction, heat treatment or combinations thereof and at temperatures above 25 ° C, for periods between 2 minutes and 25 hours.

[13]
13. Method of synthesis of SAPO-18 according to any of the preceding claims, characterized in that the material obtained is pelletized according to known techniques.
[14]
14. Method of synthesis of SAPO-18 according to any of the preceding claims, characterized in that the mixture also comprises at least one metal source, where the final synthesis gel has the following molar composition:
a Si: 0.5 Al: b P: e X: c ADEO: d H2O
where a is in the range of 0.01 to 0.3; 5
where b is in the range of 0.2 to 0.49;
where c is in the range of 0.001 to 2;
where d is in the range of 1 to 200;
where e is in the range of 0.00 to 0.6.
 10
[15]
15.- SAPO-18 synthesis method according to claim 14, characterized in that it is a direct synthesis procedure and the product Me-SAPO-18 is obtained where Me is a metal.

[16]
16. Synthesis procedure of SAPO-18 according to claim 15, characterized in that said metal is selected from Cu, Ni, Fe, Pt, Pd, Mn, Ca, Mg, Zn, Cd, Co, Ti, Sn, and combinations thereof.

[17]
17.- SAPO-18 synthesis method according to claim 16, characterized in that said metal is Cu. twenty

[18]
18. Product obtained according to the procedure described in claims 1 to 17 characterized in that it has the following molar composition:
X0.0-0.6 Si0.01-0.3Al0.40-0.55P0.20-0.49O2
 25
[19]
19. Product according to claim 18, characterized in that it has the following molar composition:
X0.005-0.6 Si0.01-0.3Al0.40-0.55P0.20-0.49O2
 30
[20]
20. Product according to claim 19 characterized in that X is a metal selected from Cu, Ni, Fe, Pt, Pd, Mn, Ca, Mg, Zn, Cd, Co, Ti, Sn and combinations thereof.

[21]
21. Product according to claim 20, characterized in that the metal is Cu.
 35
[22]
22. Product according to any of claims 20 and 21, characterized in that the metal is in extra-net positions.

[23]
23. Use of the product obtained according to the procedure described in claims 1 to 17 and described in claims 18 to 22, as catalysts for the conversion of a feed formed by organic compounds, into products of high added value.

[24]
24. Use of the product obtained according to the procedure described in claims 1 to 17 and described in claims 18 to 22, as a catalyst for the removal / separation of organic compounds from the reactive stream. 10

[25]
25. Use of the product obtained according to the process described in claims 1 to 17 and described in claims 18 to 22, as a catalyst for the selective reduction of nitrogen oxides in a gas stream.
  fifteen

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同族专利:

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公开号 | 公开日

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WO2015185781A1|2015-12-10|

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CN107074570A|2017-08-18|

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EP3153471B1|2019-08-07|

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ES2555804B1|2016-10-13|

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JP2017521349A|2017-08-03|

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US20170259253A1|2017-09-14|

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EP3153471A1|2017-04-12|

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US10005076B2|2018-06-26|

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BR112016028250A2|2017-08-22|

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EP3153471A4|2018-01-03|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

DE4131268A1|1991-09-20|1993-03-25|Basf Ag|METHOD FOR PRODUCING ALUMO AND SILICOALUMOPHOSPHATES WITH AEL STRUCTURE USING 1,2-BIS ETHANE|

---

US5958370A|1997-12-11|1999-09-28|Chevron U.S.A. Inc.|Zeolite SSZ-39|

---

US6537941B2|2001-01-04|2003-03-25|Exxonmobil Chemical Patents, Inc.|Rejuvenating SAPO molecular sieve by freeze drying|

---

US6685905B2|2001-12-21|2004-02-03|Exxonmobil Chemical Patents Inc.|Silicoaluminophosphate molecular sieves|

---

WO2007130231A1|2006-04-25|2007-11-15|Exxonmobil Chemical Patents Inc.|Method of synthesizing molecular sieves|

---

US7622417B2|2008-03-21|2009-11-24|Exxonmobil Chemical Patents Inc.|Synthesis and use of AEI structure-type molecular sieves|

---

JP5831367B2|2011-06-27|2015-12-09|三菱樹脂株式会社|Process for producing transition metal-containing zeolite|

---

RU2602085C2|2012-04-27|2016-11-10|Хальдор Топсеэ А/С|Method for direct synthesis of cu-sapo-34|

---

CN103706394B|2014-01-06|2015-08-05|神华集团有限责任公司|A kind of sub-micron SAPO-5/SAPO-18 composite molecular screen and preparation method thereof|CN106315617A|2016-08-24|2017-01-11|合肥神舟催化净化器有限公司|Preparing method for Cu-SAPO-18 molecular sieve catalyst of high hydrothermal stability|

---

GB2569754A|2016-09-30|2019-06-26|Johnson Matthey Plc|Synthesis of AEI and Cu-AEI zeolites|

---

CN106914273A|2017-02-23|2017-07-04|华中科技大学|The preparation method and its usage of the molecular sieve catalysts of one-step method fabricated in situ Cu SAPO 18|

---

US10280089B1|2018-06-22|2019-05-07|Uop Llc|Crystalline metallophosphates, their method of preparation, and use|

---

CN113318782A|2021-05-28|2021-08-31|江西农业大学|Preparation method and application of Mn-SAPO-18 molecular sieve catalyst rich in manganese|

---

CN113522232A|2021-06-28|2021-10-22|东风商用车有限公司|Passive NOxAdsorbent and preparation method and application thereof|

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ES201430852A|ES2555804B1|2014-06-03|2014-06-03|SUMMARY OF SAPO-18 AND ITS CATALYTIC APPLICATIONS|ES201430852A| ES2555804B1|2014-06-03|2014-06-03|SUMMARY OF SAPO-18 AND ITS CATALYTIC APPLICATIONS|

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US15/315,200| US10005076B2|2014-06-03|2015-06-03|Synthesis of SAPO-18 and the catalytic applications thereof|

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JP2017516212A| JP2017521349A|2014-06-03|2015-06-03|Synthesis of SAPO-18 and its catalytic use|

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EP15802461.2A| EP3153471B1|2014-06-03|2015-06-03|Synthesis of sapo-18|

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BR112016028250A| BR112016028250A2|2014-06-03|2015-06-03|frog-18 synthesis procedure, product obtained according to said procedure and use of said product|

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PCT/ES2015/070438| WO2015185781A1|2014-06-03|2015-06-03|Synthesis of sapo-18 and the catalytic applications thereof|

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CN201580039140.2A| CN107074570A|2014-06-03|2015-06-03|SAPO 18 synthesis and its catalysis use|