MXPA01002615A - Synthesis of and compositions of ecr-40, large pore aluminophosphate - Google Patents

Abstract

The present invention is a large-pore aluminophosphate or substituted aluminophosphate comprising a composition aR:(MxA1yPz) O2, wherein R represents an organic templating agent, and a=0 to 0.4, X=0 to 0.4, y=0.35 to 0.5, and Z=0.25 to 0.5 and characterized by the diffraction pattern of Table 1 and M may be Si, Ga, Ge, Co, Ni, Zn, Fe, V, Ti and mixtures thereof.

Description

SYNTHESIS OF AND COMPOSITION OF ECR-40, ALUMINOFOSFATO DE PORO GRANDE FIELD OF THE INVENTION This invention relates to a new species of molecular sieves of crystalline microporous metal aluminophosphate, and its method of preparation and its use as an adsorbent and catalyst. The species is identified as ECR-40 and is hydrothermally prepared from of gels containing reactive sources of phosphorus, aluminum, organic tempering agents and a metal (preferably silicon) and water.

BACKGROUND OF THE INVENTION Zeolites are crystalline aluminosilicate molecular sieves having a three-dimensional microporous reticular structure. In general, crystalline zeolites are formed from tetrahedra of A102 and Si02 which share a corner and are characterized by having pore openings of uniform dimensions, which have a significant ion exchange capacity and which are capable of reversibly desorbing an adsorbed phase. that is dispersed through the internal holes of the crystal without significantly displacing any atoms that form the ^ g ^ * 8fe ^ - S? ££ s £ & ** n '~ *. ? * - "H ^. Fr,? * ^ - ^ w ^ - ^ permanent crystal structure Zeolites can be represented on an anhydrous basis, by the empirical formula M2 / pO A1203 XS? 02 where M is a cation that has the valence n X is generally equal to or greater than 2 In naturally occurring zeolites M can be Ll Na Ca K, Mg and Ba The M cations can be bound loosely to the structure and are frequently can replace completely or partially with other cations by conventional ion exchange techniques Currently more than 100 species of zeolites are known to occur both naturally occurring and synthetic It is noted that although most commercial patents refer to these phosphate compositions as "molecular sieves" instead of zeolites, the scientific groups include them in the "zeolites" (Barrer Pure and Applied Chem v 51 1091 (1979) Coombs and col Cañad Mineral v 35 0 1571 (1997)) Other microporous compositions are known crystallines which have been called zeolites or molecular sieves and which exhibit the characteristics of ion exchange and / or adsorption of zeolites These include alummophosphates and substituted aluminophosphates as described in U.S. Patent Nos. 4 310,440 and 4,440,871. U.S. Patent No. 4,440,871 discloses a class of aluminum phosphate silica which is identified by the SAPO acronym and which has different structures than those identified by its name. X-ray diffraction pattern The structures are identified by a number after ALPO SAPO, MEAPO, etc. (Flanigen et al Proc 7th Int Zeolite Conf p 103 (1986) and may include substitutions of Al and P by Si, Be, Mg Ge , Zn, Fe, Co, Ni, etc. The present invention is the first synthesis of a phosphate (ALPO / SAPO, etc.) having the characteristic X-ray diffraction pattern shown in Table 1 COMPENDIUM OF THE INVENTION The present invention is a large pore alummophosphate or substituted alummophosphate comprising a composition aR (MxAlyPz) 02 where R represents an organic tempering agent, and a = 0 to 0 4, X = 0 to 0 4 y = 0 35 to 0 5, and Z = 0 25 to 0 5 and characterized by the diffraction pattern of the Table 1 and M can be Yes. Ga, Ge, Co. Ni, Zn, Fe, V Ti and mixtures thereof DESCRIPTION OF THE PREFERRED MODALITY The ECR-40 is made in the presence of relatively simple tempers of methyltriethanol ammonium or (dihydroxyethyl) d? Met? Lamon? O Unlike these substituted phosphates, such as the form of fau? As? Ta (ALPO / SAPO-37), ECR-40 has high thermal stability (and stability in some steam) and adsorption capacity for large molecules, including misythylene, offering uses in FCC and hydrocracking in addition to hydroisomerization and aromatization, where in the Last case the ALPO form provides a non-acidic exponent for metal catalysis The SAPO form allows the preparation of low acid catalysts that will be synthesized directly without the need for subsequent synthesis processing, usually necessary to produce low acid catalysts from alummosilicates The X-ray diffraction pattern shown for ECR-40 is very similar to that previously reported for the aluminosilicate zeolite ZSM-48 (US Patent 3,950,496, Science, Vol. 247, p 1319 (1990)) and may be a new composition for the MEI type structure (Atlas of Zeolite Structure Types Elsevier Press (1996), 4th edition) However, ECR-40 is better marked on an ortho-propellant instead of a hexagonal unit cell characteristic of ZSM-18 Low acidity zeolites are in demand 5 for processes such as hydrocracking and hydroisomepzació. The majority of aluminosil i-cato zeolites, such as FAU and beta, require subsequent synthesis modification to reduce their acidities to acceptable values. In the case of SAPO, the acidity can be tightly controlled by the amount of silica adulterant included in the ALPO structure. Unfortunately, most large pore ALOP and SAPO have mediocre thermal and hydrothermal stability. The ECR-40 does not have any of these problems in that it survives the quenching of the temper at 630QC without loss in crystallinity and has survived for several hours in air flow saturated with water at 600SC without loss of crystallinity or sorption capacity, as measured by hexane, DBM (dimethylbutane), O-xylene and misitylene. Accordingly, the present invention includes a large pore aluminophosphate or substituted aluminophosphate comprising aR: (M2AlyP2) 02 wherein R represents an organic tempering agent and M = 0 to 0 4, X = 0 to 0 4 y = 0 35 to 0 5 and Z = 0 35 to 0 5 and characterized by the diffraction pattern of Figure 1 which It has the essential X-ray diffraction lines (Cu Ka) (or alpha) shown in Table 1 In addition, the present invention includes a process for preparing a substituted alumino phosphate or alummophosphate comprising forming a reaction mixture of S? 02 A1203 and P205 and an organic tempering agent. reaction mixture having a composition expressed in terms of molar oxide ratios of 1 5 to 3 0 of ROH A1203 0 7 to 1 25 of P20s 0 to 0 4 of MOx 40-80 of H20 wherein P is the quenching agent, and M = Si Ga, Ge, Co Ni, Zn, Fe, Ti, V and mixtures thereof The annealing is preferably rnetiltne-ethanolammonium or bis (2-hydroxystem) and dimethylammonium. The aforementioned ECR-40 has a characteristic X-ray diffraction pattern the essential lines of which are given in Table 1 for Cu Ka radiation (alpha) Line intensities are referenced to the strongest line, in this case the first line of approximately 11 35A 20 Minor variations occur as a function of specific composition (P / AI / M ratios) and the specific tempering and its loading (intercalation) in the structure In this case, the intensities are shown in square brackets as follows, using the strongest line = 100 very, very strong (ws) = 100 - 70 very strong (vs) = 70 - 50 strong (s) = 50 - 30 medium (mj = 30 - 10 weak () = < 10 TABLE 1 Interplanar spacing Line Intensity 11 35 + 0 10 ws 6 57 + 0 12 m 5 08 + 0 10 4 64 + 0 10 mw 4 30 ± 0 08 m 4 15 ± 0 08 vs 4 02 + 0 08 w 3 79 ± 0 06 s 3 35 ± 0 06 w 3 28 ± 0 06 m 3 09 + 0 06 m 2 935 + 0 03 mw 2 480 + 0 03 mw 1 895 + 0 03 w DESCRIPTION OF THE PREFERRED MODALITY As stated above, the present invention is a substituted aluminophosphate composition and a process for making it EXAMPLES Example 1 To make a reagent composition of the formula. 2ROH: 0 2 Si02: 0.95 Al303: 0.95 P205: 50 H20 where R is tempered, 12 9 g of Catapal A alumina were mixed with 120.8 gm 25% by weight aqueous solution of bis- (2-h? drox? ethyl) dimethylammonium (RSA Inc) in a mixer for 10 minutes, followed by 3 gm of colloidal silica Ludox AS-40 from DuPont, followed by 24 8 gm of phosphoric acid (85%) The mixing was continued for 10 minutes then aliquots of 52 gm were measured to autoclaves coated with 125 ml of Parr Teflon and reacted at 162eC. A sample was reacted for 57 days. The product was diluted, homogenized and centrifuged, decanted, washed and centrifuged again. The solid product was a single phase that has the characteristic X-ray diffraction pattern that has the essential lines shown in Table 1 and was marked as having an orthohhombic unit cell » £ fe > »8BíK« cfc fe- í-, _ of dimensions a = 16 06 A, b = 11 34 A and c = 6 57A closely similar to that for the composition of alummosilicate ZSM-18 In this preparation, the product is in the form of prismatic crystals having dimensions between 1 ux 1 u cross section and 5 ux 4 u long This phosphate composition is designated as ECR-40 The chemical analysis by means of ICPAES provided a composition 14 95% Al, 12 97% P , 4 36% Si representing a stoichiometry of ECR-40 of (Al ", Si H, P 37) 02 Example 2 The reagent formulation in Example 1 was reformulated using a 50% by weight solution of the hardened and reacted bis- (2-hydroxyl et? L) d? Methalamonium hydroxide (RSA Inc.) at 160aC for 24 days The product had the characteristic X-ray diffraction pattern shown in Table 1 and Figure 1 Thermogravimetric analysis in an airflow showed a 3-step weight loss, including a 10% loss related to the burned from tempering at approximately 300a and 450BC After calcining a sample of this material in air at 6302C for 16 hours, followed by equilibration with water at 88% RH the sample gained 23% by weight An isothermal test of n-hexane at 21aC on The same calcined sample provided a maximum capacity of 16% by weight. A single-point static sorption on ortho-xylene saturated with air gave a sorption capacity of 17.5% by weight and a similar experiment with 2-2-d? m? t lbutane (DMB) capacity of 17 4% by weight confirming the large pore nature of the channel system and its high pore volume. The morphology of this product is similar to that observed in Example 1 with a greater aspect ratio of approximately 5 The chemical analysis by means of ICPAES provided 15 99% of Al 13 54% of P and 4 63% of Si representing a stoichiometry of (Al 49 Si 2T P s 02 EXAMPLE 3 This example demonstrates that ECR-40 can be synthesized from a SAPO gel previously made dry. The SAPO gel was made by reacting a composition of 0 2 of S? 02 0 95 of Al203 0 95 of P205 by mixing vigorously together 675 gm of Al (NO ^) 3 9H20 dissolved in 1200 gm of water and 207 gm of 85% phosphoric acid followed by 57 mg of Na2S? &, 9H2ü dissolved in 250 gm of water Ammonium hydroxide was added slowly until gelation occurred at pH = 7 4 The gel was filtered and washed dried 60 hours at 110aC, then ground to a fine powder Chemical analysis of this product gave a composition ratio of 0.13 of S? 02 Al203- P205 10 gm of this dry gel were reacted with 60 gm of 22.5% by weight of aqueous methyl triethanol hydroxide in a 125 ml autoclave lined with Parr Teflon at 170aC for 43 days, at which time the pump was rapidly cooled. microcpstalino, after separation and drying provides the pattern of specific characteristic X-ray diffraction shown in Table 2 and Figure 1 The data in Table 2 have been tentatively indexed in an orthohomic unit cell having e is approximate a = 16 5 A b = 11 4A. C = 6 58A 15 TABLE 2 Spacing Initization Intensity Observed Pr-Opposite Relative 2-Theta d (A) h k 1 I / I 7 782 11 3506 1 0 0 100 0 9 438 9 3630 1 0 1 0 3 11 018 8 0237 0 0 2 4 1 13 474 6 5663 0 1 0 13 0 15 578 5 6838 2 0 0 2 2 17 440 5 0809 0 1 2 6 9 18 315 4 8401 1 0 3 1 4 TABLE 2 (continued) Spacing Indexing Intensity Observed Relative Proposal 2-Theta d (A) hk 1 I / I 19,115 4.6392 2 0 2 9.7 20,656 4.2965 2 1 0 13 1 21,389 4.1508 0 1 3 55.6 22.102 4.0185 0 0 4 7.5 22.794 3.8980 2 0 3 1.4 23.464 3.7882 3 0 0 44.4 24.113 3.6878 3 0 1 1.7 25.974 3.4276 3 0 2 2.2 26.565 3.3526 2 1 3 7.5 27,163 3.2802 2 0 4 12 8 27,717 3.2159 3 1 1 3 0 28,831 3 0941 3 0 3 13.4 29,376 3.0379 3 1 2 3.3 30.438 2.9343 2 1 4 10.4 30,965 2.8855 0 1 5 2.4 31.425 2.8444 2 2 0 0.6 31.961 2.7979 1 1 5 5.0 32.459 2.7561 3 0 4 1.2 32.929 2.7178 1 2 3 2.7 33.425 2.6786 0 0 6 2.8 34.366 2.6074 1 0 6 1.3 34.830 2.5737 2 1 5 1.6 36.180 2.4807 4 1 2 9.7 37.919 2.3708 - 2 2 2.6 38,345 2.3455 4 1 3 2.3 TABLE 2 (continued) Spacing Indication Intensity Observed P: Relative approach 2-Theta d (A) hk 1 I / lo 39 611 2 2734 5 0 0 1 6 40 005 2 2519 3 2 3 3 2 41 225 2 1880 5 0 2 1 1 41 636 2 1674 0 1 7 1 0 42 024 2 1483 1 -> 0 1 4 42 438 2 1282 4 0 5 0 6 42 798 2 1112 3 2 4 0 6 43 596 2 0744 5 1 2 0 9 44 328 2 0418 1 2 6 3 6 44 693 2 0260 4 1 5 2 0 45 787 1 9801 5 0 4 1 7 46 176 1 9643 3 2 5 0 9 47 980 1 8946 5 1 4 5 1 48 734 1 8670 4 1 6 2 1 49 008 1 8572 5 2 1 2 4

Claims (5)

1 - . 1 - A large pore alummophosphate or substituted alummophosphate comprising a composition aR (MxAlyP2) 02 where R represents an organic tempering agent and a = 0 to 0 4 X = 0 to 0 4, y = 0 35 to 0 5 and Z = 0 25 to 0 5 and characterized by the diffraction pattern of Table 1 and M is If Ga Ge Co Ni, Zn, Fe V Ti or mixtures thereof

2 - The composition according to claim 1, wherein R is methyltriethanolarnonium

3 - The composition according to claim 1 wherein R is an ammonium cation tris-quaternary

4 - The composition according to claim 1 wherein R is cation of bis- (2-h? drox? -ethyl) d? met? lamon?

5 - A process for preparing the composition in accordance with claim 1 comprising crystallizing a reaction mixture including sources of M Al203 and P205 oxides and an organic quenching agent the reaction mixture having an expressed composition in terms of molar oxide ratios of 1.5 to 3 0 ROH: Al2O3: 0 7 to 1.25 P205: 0 to 0.4 MOx: 40-80 H20 where R is the tempering agent. 6. A process according to claim 5, wherein M is silicon 7. The process according to claim 5, wherein R is tris-quaternary ammonium 8. The process according to claim 5, wherein where R is bis- (2-hydroxyethyl) dimethylammonium hydroxide, 9. The process according to claim 5, wherein R is ethyl t-tolnolammonium. 10. The process according to claim 5, wherein the sources of oxides are 15 derive from an amorphous gel, previously dried, previously made twenty 25