US20070154389A1 - Boron-containing molecular sieve cha - Google Patents

Boron-containing molecular sieve cha Download PDF

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US20070154389A1
US20070154389A1 US11/688,719 US68871907A US2007154389A1 US 20070154389 A1 US20070154389 A1 US 20070154389A1 US 68871907 A US68871907 A US 68871907A US 2007154389 A1 US2007154389 A1 US 2007154389A1
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boron
oxide
cha
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Lun-Teh Yuen
Stacey Zones
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Chevron USA Inc
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Priority claimed from US12/015,364 external-priority patent/US7507393B2/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline 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
    • C01B39/06Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/12Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7015CHA-type, e.g. Chabazite, LZ-218
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/86Borosilicates; Aluminoborosilicates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30After treatment, characterised by the means used
    • B01J2229/37Acid treatment

Abstract

A boron-containing molecular sieve having the CHA crystal structure and comprising (1) silicon oxide and (2) boron oxide or a combination of boron oxide and aluminum oxide, iron oxide, titanium oxide, gallium oxide and mixtures thereof is prepared using a quaternary ammonium cation derived from 1-adamantamine, 3-quinuclidinol or 2-exo-aminonorbornane as structure directing agent. The molecular sieve can be used for gas separation or in catalysts to prepare methylamine or dimethylamine, to convert oxygenates (e.g., methanol) to light olefins, or for the reduction of oxides of nitrogen n a gas stream (e.g., automotive exhaust).

Description

  • This application claims the benefit under 35 USC 119 of copending Provisional Application No. 60/632022, filed Nov. 30, 2004.
  • BACKGROUND
  • Chabazite, which has the crystal structure designated “CHA”, is a natural zeolite with the approximate formula Ca6Al12Si24O72. Synthetic forms of chabazite are described in “Zeolite Molecular Sieves” by D. W. Breck, published in 1973 by John Wiley & Sons. The synthetic forms reported by Breck are: zeolite “K-G”, described in J. Chem. Soc., p. 2822 (1956), Barrer et al.; zeolite D, described in British Patent No. 868,846 (1961), and zeolite R, described in U.S. Pat. No. 3,030,181, issued Apr. 17, 1962 to Milton et al. Chabazite is also discussed in “Atlas of Zeolite Structure Types” (1978) by W. H. Meier and D. H. Olson.
  • The K-G zeolite material reported in the J. Chem. Soc. Article by Barrer et al. is a potassium form having a silica:alumina mole ratio (referred to herein as “DAR”) of 2.3:1 to 4.15:1. Zeolite D reported in British Patent No. 868,846 is a sodium-potassium form having a SAR of 4.5:1 to 4.9:1. Zeolite R reported in U.S. Pat. No. 3,030,181 is a sodium form which has a SAR of 3.45:1 to 3.65:1.
  • Citation No. 93:66052y in Volume 93 (1980) of Chemical Abstracts concerns a Russian language article by Tsitsishrili et al. in Soobsch. Akad. Nauk. Gruz. SSR 1980, 97(3) 621-4. This article teaches that the presence of tetramethylammonium ions in a reaction mixture containing K2O-Na2O-SiO2-Al2O3-H2O promotes the crystallization of chabazite. The zeolite obtained by the crystallization procedure has a SAR of 4.2:3.
  • The molecular sieve designated SSZ-13, which has the CHA crystal structure, is disclosed in U.S. Pat. No. 4,544,538, issued Oct. 1, 1985 to Zones. SSZ-13 is prepared from nitrogen-containing cations derived from 1-adamantamine, 3-quinuclidinol and 2-exo-aminonorbornane. Zones discloses that the SSZ-13 of U.S. Pat. No. 4,544,538 has a composition as-synthesized and in the anhydrous state, in terms of mole ratios of oxides as follows:
  • (0.5 to 1.4)R2O:(0 to 0.5)M2O:W2O3:(greater than 5)YO2 wherein M is an alkali metal cation, W is selected from aluminum, gallium and mixtures thereof, Y is selected from silicon, germanium and mixtures thereof, and R is an organic cation. U.S. Pat. No. 4,544,538 does not, however, disclose boron-containing SSZ-13.
  • U.S. Pat. No. 6,709,644 issued Mar. 23, 2004 to Zones et al., discloses zeolites having the CHA crystal structure and having small crystallite sizes. It does not, however, disclose a CHA zeolite containing boron. It is disclosed that the zeolite can be used for separation of gasses (e.g., separating carbon dioxide from natural gas), and in catalysts used for the reduction of oxides of nitrogen in a gas stream (e.g., automotive exhaust), converting lower alcohols and other oxygenated hydrocarbons to liquid products, and for producing dimethylamine.
  • SUMMARY OF THE INVENTION
  • In accordance with the present invention there is provided a boron-containing molecular sieve having the CHA crystal structure and comprising (1) silicon oxide and (2) boron oxide or a combination of boron oxide and aluminum oxide, iron oxide, titanium oxide, gallium oxide and mixtures thereof. Preferably, oxide (2) is more than 50% boron oxide on a molar basis.
  • In accordance with this invention there is provided a method for preparing a boron-containing molecular sieve having the CHA crystal structure and comprising (1) silicon oxide and (2) boron oxide or a combination of boron oxide and aluminum oxide, iron oxide, titanium oxide, gallium oxide and mixtures thereof, said method comprising:
  • A. forming an aqueous reaction mixture comprising a composition in terms of mole ratios falling within the following ranges: YO2/WaOb  >2-2,000 OH—/YO2 0.2-0.45 Q/YO2 0.2-0.45 M2/n/YO2   0-0.25 H2O/YO2  22-80
  • wherein Y is silicon, W is boron or a combination of boron and aluminum, iron, titanium, gallium and mixtures thereof; a is 1 or 2 and b is 2 when a is 1 (i.e., W is tetravalent) or b is 3 when a is 2 (i.e., W is trivalent); M is an alkali metal or alkaline earth metal, n is the valence of M (i.e., 1 or 2), and Q is a quaternary ammonium cation derived from 1-adamantamine, 3-quinuclidinol or 2-exo-aminonorbornane, and
  • B. maintaining said aqueous mixture under sufficient crystallization conditions until crystals are formed.
  • In accordance with this invention, there is also provided a boron-containing molecular sieve having the CHA crystal structure and having a composition, as-synthesized and in the anhydrous state, in terms of mole ratios of oxides as follows: YO2/WcOd   20-2,000 M2/nO/YO2   0-0.03 Q/YO2 0.02-0.05

    wherein Y is silicon, W is boron or a combination of boron and aluminum, iron, titanium, gallium and mixtures thereof; c is 1 or 2, d is 2 when c is 1 (i.e., W is tetravalent) or d is 3 or 5 when c is 2 (i.e., d is 3 when W is trivalent or 5 when W is pentavalent); M is an alkali metal cation, alkaline earth metal cation or mixtures thereof, n is the valence of M (i.e., 1 or 2); and Q is a quaternary ammonium cation derived from 1-adamantamine, 3-quinuclidinol or 2-exo-aminonorbornane.
  • DETAILED DESCRIPTION
  • The present invention relates to molecular sieves having the CHA crystal structure and containing boron in their crystal framework.
  • Boron-containing CHA molecular sieves can be suitably prepared from an aqueous reaction mixture containing sources of sources of an oxide of silicon; sources of boron oxide or a combination of boron oxide and aluminum oxide, iron oxide, titanium oxide, gallium oxide and mixtures thereof; optionally sources of an alkali metal or alkaline earth metal oxide; and a cation derived from 1-adamantamine, 3-quinuclidinol or 2-exo-aminonorbornane. The mixture should have a composition in terms of mole ratios falling within the ranges shown in Table A below: TABLE A YO2/WaOb  >2-2,000 OH—/YO2 0.2-0.45 Q/YO2 0.2-0.45 M2/nO/YO2   0-0.25 H2O/YO2  22-80

    wherein Y is silicon; W is boron or a combination of boron and aluminum, iron, titanium, gallium and mixtures thereof; M is an alkali metal or alkaline earth metal; n is the valence of M (i.e., 1 or 2) and Q is a quaternary ammonium cation derived from 1-adamantamine, 3-quinuclidinol or 2-exo-aminonorbornane (commonly known as a structure directing agent or “SDA”).
  • The quaternary ammonium cation derived from 1-adamantamine can be a N,N,N-trialkyl-1-adamantammonium cation which has the formula:
    Figure US20070154389A1-20070705-C00001

    where R1, R2, and R3 are each independently a lower alkyl, for example methyl. The cation is associated with an anion, A, which is not detrimental to the formation of the molecular sieve. Representative of such anions include halogens, such as fluoride, chloride, bromide and iodide; hydroxide; acetate; sulfate and carboxylate. Hydroxide is the preferred anion. It may be beneficial to ion exchange, for example, a halide for hydroxide ion, thereby reducing or eliminating the alkali metal or alkaline earth metal hydroxide required.
  • The quaternary ammonium cation derived from 3-quinuclidinol can have the formula:
    Figure US20070154389A1-20070705-C00002

    where R1, R2, R3 and A are as defined above.
  • The quaternary ammonium cation derived from 2-exo-aminonorbornane can have the formula:
    Figure US20070154389A1-20070705-C00003

    where R1, R2, R3 and A are as defined above.
  • The reaction mixture is prepared using standard molecular sieve preparation techniques. Typical sources of silicon oxide include fumed silica, silicates, silica hydrogel, silicic acid, colloidal silica, tetra-alkyl orthosilicates, and silica hydroxides. Sources of boron oxide include borosilicate glasses and other reactive boron compounds. These include borates, boric acid and borate esters. Typical sources of aluminum oxide include aluminates, alumina, hydrated aluminum hydroxides, and aluminum compounds such as AlCl3 and Al2(SO4)3. Sources of other oxides are analogous to those for silicon oxide, boron oxide and aluminum oxide.
  • It has been found that seeding the reaction mixture with CHA crystals both directs and accelerates the crystallization, as well as minimizing the formation of undesired contaminants. In order to produce pure phase boron-containing CHA crystals, seeding may be required. When seeds are used, they can be used in an amount that is about 2-3 weight percent based on the weight of YO2.
  • The reaction mixture is maintained at an elevated temperature until CHA crystals are formed. The temperatures during the hydrothermal crystallization step are typically maintained from about 120° C. to about 160° C. It has been found that a temperature below 160° C., e.g., about 120° C. to about 140° C., is useful for producing boron-containing CHA crystals without the formation of secondary crystal phases.
  • The crystallization period is typically greater than 1 day and preferably from about 3 days to about 7 days. The hydrothermal crystallization is conducted under pressure and usually in an autoclave so that the reaction mixture is subject to autogenous pressure. The reaction mixture can be stirred, such as by rotating the reaction vessel, during crystallization.
  • Once the boron-containing CHA crystals have formed, the solid product is separated from the reaction mixture by standard mechanical separation techniques such as filtration. The crystals are waterwashed and then dried, e.g., at 90° C. to 150° C. for from 8 to 24 hours, to obtain the as-synthesized crystals. The drying step can be performed at atmospheric or subatmospheric pressures.
  • The boron-containing CHA molecular sieve has a composition, as-synthesized and in the anhydrous state, in terms of mote ratios of oxides as indicated in Table B below: TABLE B As-Synthesized Boron-Containing CHA Composition YO2/WcOd   20-2,000 M2/nO/YO2   0-0.03 Q/YO2 0.02-0.05

    where Y, W, M, n and Q are as defined above.
  • The boron-containing CHA molecular sieves, as-synthesized, have a crystalline structure whose X-ray powder diffraction (“XRD”) pattern shows the following characteristic lines: TABLE I As-Synthesized Boron-Containing CHA XRD 2 Theta(a) d-spacing (Angstroms) Relative Intensity(b) 9.68 9.13 S 14.17 6.25 M 16.41 5.40 VS 17.94 4.94 M 21.13 4.20 VS 25.21 3.53 VS 26.61 3.35 W-M 31.11 2.87 M 31.42 2.84 M 31.59 2.83 M
    (a)±0.10

    (b)The X-ray patterns provided are based on a relative intensity scale in which the strongest line in the X-ray pattern is assigned a value of 100: W(weak) is less than 20; M(medium) is between 20 and 40; S(strong) is between 40 and 60; VS(very strong) is greater than 60.
  • Table IA below shows the X-ray powder diffraction lines for as-synthesized boron-containing CHA including actual relative intensities. TABLE IA As-Synthesized Boron-Containing CHA XRD 2 Theta(a) d-spacing (Angstroms) Relative Intensity (%) 9.68 9.13 55.2 13.21 6.70 5.4 14.17 6.25 33.5 16.41 5.40 81.3 17.94 4.94 32.6 19.43 4.56 6.8 21.13 4.20 100 22.35 3.97 15.8 23.00 3.86 10.1 23.57 3.77 5.1 25.21 3.53 78.4 26.61 3.35 20.2 28.37 3.14 6.0 28.57 3.12 4.4 30.27 2.95 3.9 31.11 2.87 29.8 31.42 2.84 38.3 31.59 2.83 26.5 32.27 2.77 1.4 33.15 2.70 3.0 33.93 2.64 4.7 35.44 2.53 3.9 35.84 2.50 1.2 36.55 2.46 10.9 39.40 2.29 1.8 40.02 2.25 1.3 40.44 2.23 1.0 40.73 2.21 6.0
    (a)±0.10
  • After calcination, the boron-containing CHA molecular sieves have a crystalline structure whose X-ray powder diffraction pattern include the characteristic lines shown in Table II: TABLE II Calcined Boron-Containing CHA XRD 2 Theta(a) d-spacing (Angstroms) Relative Intensity 9.74 9.07 VS 13.12 6.74 M 14.47 6.12 W 16.38 5.41 W 18.85 4.78 M 21.07 4.21 M 25.98 3.43 W 26.46 3.37 W 31.30 2.86 W 32.15 2.78 W
    (a)±0.10
  • Table IIA below shows the X-ray powder diffraction lines for calcined boron-containing CHA including actual relative intensities. TABLE IIA Calcined Boron-Containing CHA XRD 2 Theta(a) d-spacing (Angstroms) Relative Intensity (%) 9.74 9.07 100 13.12 6.74 29.5 14.47 6.12 4.6 16.38 5.41 14.2 18.85 4.78 22.1 19.60 4.53 2.2 21.07 4.21 32.9 22.84 3.89 2.2 23.68 3.75 0.8 25.98 3.43 13.1 26.46 3.37 8.7 28.27 3.15 1.3 29.24 3.05 1.6 30.32 2.95 1.7 31.30 2.86 14.4 32.15 2.78 9.0 32.56 2.75 0.2 35.26 2.54 2.4
    (a)±0.10
  • The X-ray powder diffraction patterns were determined by standard techniques. The radiation was the K-alpha/doublet of copper and a scintillation counter spectrometer with a strip-chart pen recorder was used. The peak heights I and the positions, as a function of 2 Theta where Theta is the Bragg angle, were read from the spectrometer chart. From these measured values, the relative intensities, 100× I/Io, where Io is the intensity of the strongest line or peak, and d, the interplanar spacing in Angstroms corresponding to the recorded lines, can be calculated.
  • Variations in the diffraction pattern can result from variations in the mole ratio of oxides from sample to sample. The molecular sieve produced by exchanging the metal or other cations present in the molecular sieve with various other cations yields a similar diffraction pattern, although there can be shifts in interplanar spacing as well as variations in relative intensity. Calcination can also cause shifts in the X-ray diffraction pattern. Also, the symmetry can change based on the relative amounts of boron and aluminum in the crystal structure. Notwithstanding these perturbations, the basic crystal lattice structure remains unchanged.
  • Boron-containing CHA molecular sieves are useful in adsorption, in catalysts useful in converting methanol to olefins, synthesis of amines (such as dimethylamine), in the reduction of oxides of nitrogen in gasses (such as automobile exhaust), and in gas separation.
  • EXAMPLES Examples 1-14
  • Boron-containing CHA is synthesized by preparing the gel compositions, i.e., reaction mixtures, having the compositions, in terms of mole ratios shown in the table below. The resulting gel is placed in a Parr bomb reactor and heated in an oven at the temperature indicated below while rotating at the speed indicated below. Products are analyzed by X-ray diffraction (XRD) and found to be boron-containing molecular sieves having the CHA structure. The source of silicon oxide is Cabosil M-5 fumed silica or HiSil 233 amorphous silica (0.208 wt. % alumina). The source of boron oxide is boric acid and the source of aluminum oxide is Reheis F 2000 alumina. Ex. # SiO2/B2O3 SiO2/Al2O3 H2O/SiO2 OH—/SiO2 Na+/SiO2 SDA/SiO2 Rx Cond.1 Seeds %1-ada2  1 2.51 1,010 23.51 0.25 0.20 0.25 140/43/5 d yes 100  2 12.01 1,010 22.74 0.25 0.08 0.25 140/43/5 d yes 100  3 12.33 1,010 22.51 0.25 0.08 0.25 140/43/5 d yes 100  4 12.07 288,900 23.00 0.26 0.09 0.26 140/43/5 d no 100  5 12.33 37,129 22.51 0.25 0.09 0.25 140/43/5 d yes 100  6 12.33 248,388 22.51 0.25 0.09 0.25 140/43/5 d yes 100  7 12.33 248,388 22.53 0.25 0.09 0.25 140/43/5 d yes 100  8 12.33 248,388 22.53 0.25 0.00 0.25 140/43/5 d yes 100  9 12.33 248,388 22.51 0.25 0.09 0.25 160/43/4 d yes 100 10 11.99 288,900 23.18 0.26 0.09 0.26 160/43/4 d no 100 11 12.13 288,900 32.22 0.43 0.21 0.21 160/43/4 d no 100 12 11.99 288,900 23.16 0.26 0.00 0.26 160/43/4 d no 100 13 11.99 288,900 23.18 0.26 0.09 0.26 160/43/4 d no 100 14 3.08 248,388 22.51 0.25 0.00 0.25 140/43/6 d yes 100
    1° C./RPM/Days

    21-ada Quaternary ammonium cation derived from 1-adamantamine
  • Examples 15-20 Deboronation
  • Boron is removed from samples of the molecular sieves prepared as described in Example 13 above and then calcined. The sample is heated in an acid solution under the conditions indicated in the table below. The results are shown in the table. Starting Deboronation Rx Ex. No. (B) SSZ-13 15 16 17 18 19 20 Acid used Acetic acid acetic acid acetic acid HCl HCl HCl Acid Molarity 1.0 M 0.01 M 0.0001 M 0.01 M 0.001 M 0.0001 M Rx Cond 45 C./0 rpm/19 hr 45 C./0 rpm/19 hr 45 C./0 rpm/19 hr 45 C./0 rpm/19 hr 45 C./0 rpm/19 hr 45 C./0 rpm/19 hr Untreated Treated Treated Treated Treated Treated Treated Analysis Results Boron 0.66% 614 ppm 513 ppm 420 ppm 421 ppm 506 ppm 552 ppm XRD CHA CHA CHA CHA CHA CHA CHA

Claims (5)

1. A boron-containing molecular sieve having the CHA crystal structure and comprising (1) silicon oxide and (2) boron oxide or a combination of boron oxide and aluminum oxide, iron oxide, titanium oxide, gallium oxide and mixtures thereof.
2. The molecular sieve of claim 1 wherein oxide (2) is more than 50% boron oxide on a molar basis.
3-6. (canceled)
7. A boron-containing molecular sieve having the CHA crystal structure and containing oxides only of (1) silicon and (2) boron.
8-9. (canceled)
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US7749471B2 (en) * 2004-11-30 2010-07-06 Chevron U.S.A. Inc. Reduction of oxides of nitrogen in a gas stream using boron-containing molecular sieve CHA
US7507393B2 (en) * 2007-03-20 2009-03-24 Chevron U. S. A. Inc. Boron-containing molecular sieve CHA
US20060115400A1 (en) * 2004-11-30 2006-06-01 Chevron U.S.A. Inc. Treatment of engine exhaust using boron-containing molecular sieve CHA
JP5295953B2 (en) * 2006-06-08 2013-09-18 シェブロン ユー.エス.エー. インコーポレイテッド Molecular sieve SSZ-75 composition and its synthesis
AU2007329464A1 (en) * 2006-12-01 2008-06-12 Stategics, Inc. Thrombopoietin mimetics
US9296620B2 (en) 2013-08-09 2016-03-29 Chevron U.S.A. Inc. Preparation of high-silica cha-type molecular sieves using a mixed template

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