AQUEOUS SUSPENSION COMPRISING A ZEOLITIC MATERIAL AND A ZIRCONIUM CHELATE COMPLEX

Abstract

An aqueous suspension comprising water, a zeolitic material and one or more of copper and iron, and a chelate complex comprising a zirconium ion and a bidentate organic ligand bonded to said zirconium ion via zirconium oxygen bonds from two oxygen atoms comprised in said ligand, said chelate complex being dissolved in the water.

Claims

1. An aqueous suspension comprising: (i) water; (ii) a zeolitic material and one or more ions of copper and iron, wherein the copper and iron is either comprised in the zeolitic material, in a source of copper and iron, or in the zeolitic material and in a source of copper and iron; and (iii) an aqueous chelate complex solution comprising a zirconium ion and a bidentate organic ligand bonded to the zirconium ion via zirconium oxygen bonds from two oxygen atoms comprised in the ligand.

2. The suspension of claim 1, wherein the zeolitic material according to (ii) has framework type chosen from ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFV, AFX, AFY, AHT, ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AVL, AWO, AWW, BCT, BEA, BEC, BIK, BOF, BOG, BOZ, BPH, BRE, BSV, CAN, CAS, CDO, CFI, CGF, CGS, CHA, -CHI, -CLO, CON, CSV, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EEI, EMT, EON, EPI, ERI, ESV, ETR, EUO, *-EWT, EZT, FAR, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU, IFO, IFR, -IFU, IFW, IFY, IHW, IMF, IRN, IRR, -IRY, ISV, ITE, ITG, ITH, *ITN, ITR, ITT, -ITV, ITW, IWR, IWS, IWV, IWW, JBW, JNT, JOZ, JRY, JSN, JSR, JST, JSW, KFI, LAU, LEV, LIO, -LIT, LOS, LOV, LTA, LTF, LTJ, LTL, LTN, MAR, MAZ, MEI, MEL, MEP, MER, MFI, MFS, MON, MOR, MOZ, *MRE, MSE, MSO, MTF, MTN, MTT, MTW, MVY, MWF, MWW, NAB, NAT, NES, NON, NPO, NPT, NSI, OBW, OFF, OKO, OSI, OSO, OWE, -PAR, PAU, PCR, PHI, PON, POS, PSI, PUN, RHO, -RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAF, SAO, SAS, SAT, SAV, SBE, SBN, SBS, SBT, SEW, SFE, SFF, SFG, SFH, SFN, SFO, SFS, *SFV, SFW, SGT, SIV, SOD, SOF, SOS, SSF, *-SSO, SSY, STF, STI, *STO, STT, STW, -SVR, SW, SZR, TER, THO, TOL, TON, TSC, TUN, UEI, UFI, UOS, UOV, UOZ, USI, UTL, UWY, VET, VFI, VNI, VSV, WEI, -WEN, YUG, ZON, a mixture of two or more thereof, and a mixed type of two or more thereof.

3. The suspension of claim 1, wherein from 95 wt. % to 100 wt. %, of the framework structure of the zeolitic material according to (ii) consist of Si, Al, O, and optionally one or more of H and P, and wherein the framework structure of the zeolitic material according to (ii), comprises the molar ratio of Si to Al, calculated as SiO.sub.2:Al.sub.2O.sub.3 ranging from 2:1 to 50:1.

4. The suspension of claim 1, wherein according to (ii), the suspension comprises a zeolitic material and copper, wherein the copper is comprised in the zeolitic material, in a source of copper, or in the zeolitic material and in a source of copper.

5. The suspension of claim 4, wherein the suspension according to (iii) does not comprise a source of copper, in addition to the zeolitic material comprising copper.

6. The suspension of claim 1, wherein the bidentate organic ligand according to (iii) comprises one or more of an alpha hydroxy acid, a beta hydroxy acid, a 2,4-diketone, and a 1,3-dicarbonyl compound.

7. The suspension of claim 1, wherein the bidentate organic ligand according to (iii) consists of the elements carbon, hydrogen and oxygen.

8. The suspension of claim 1, wherein the weight ratio of the water employed according to (i) relative to the total weight of Si, Al and O of the zeolitic material framework structure employed according to (ii), weight (water):weight (total sum of Si, Al and O of the zeolitic material), ranges from 80:20 to 40:60.

9. The suspension of claim 1, wherein the weight ratio of the zirconium ion comprised in the complex according to (iii), calculated as zirconium (IV) oxide, relative to the total weight of Si, Al and O of the zeolitic material framework structure according to (ii), weight (zirconium oxide):weight (total sum of framework Si, Al and O of the zeolitic material), ranges from 0.02:1 to 0.1:1.

10. The suspension of claim 1, wherein the weight ratio of the bidentate organic ligand relative to the zirconium ion, calculated as zirconium (IV) oxide ranges from 0.01 to 2.0.

11. The suspension of claim 1, wherein the liquid phase of the suspension has a pH ranging from 0 to 12, determined at 100 s-1.

12. The suspension of claim 1, further comprising: (iv) one or more of a refractory metal oxide and a precursor of a refractory metal oxide, wherein the one or more of a refractory metal oxide and a precursor of a refractory metal oxide comprises one or more of an alumina, a silica, a titania, an aluminum hydroxide, an aluminum oxyhydroxide, an aluminum salt, a colloidal alumina, a silicon alcoholate, a colloidal silica, a fumed silica, a water glass, a titanium alcoholate, and a colloidal titania wherein the weight ratio of the one or more of a refractory metal oxide and a precursor of a refractory metal oxide relative to the total weight of the framework Si, Al and O of the zeolitic material, weight (iv):weight (total sum of framework Si, Al and O of the zeolitic material), ranges from 0.01:1 to 0.13:1.

13. The suspension of claim 1, wherein the zeolitic material according to (ii) has a particle size distribution with a Dv90 value ranging from 0.5 micrometer to 100 micrometer.

14. The suspension of claim 12, wherein the liquid phase of the suspension has a pH ranging from 0 to 12, and having a viscosity ranging from 2 mPas to 1000 mPas, determined at 100 s-1.

15. The suspension of claim 1, wherein the suspension has a storage stability ranging from 1 d to 120 d.

16. A process for preparing an aqueous suspension, wherein the process comprises: (a) mixing water and a zirconium salt; (b) adding a bidentate organic ligand to the mixture obtained from (a), and obtaining an aqueous chelate complex solution comprising a zirconium ion and the bidentate organic ligand bonded to the zirconium ion via zirconium oxygen bonds from two oxygen atoms comprised in the ligand; and (c) adding a zeolitic material and one or more ions of copper and iron to the aqueous solution obtained from (b), and obtaining an aqueous suspension, wherein the copper and iron is either comprised in the zeolitic material, or in a source of copper and iron, or in the zeolitic material and in a source of copper and iron.

17. (canceled)

18. The aqueous suspension according to claim 1, wherein the aqueous suspension is prepared as a selective catalytic reduction catalyst, or as a selective catalytic reduction catalyst for the treatment of the exhaust gas stream of a diesel engine.

Description

REFERENCE EXAMPLE 1: X-RAY DIFFRACTION

[0253] The mean crystallite size of the zeolitic material was determined via x-ray diffraction using D8 Advance Series 2 (Bruker) and Diffrac. Topas XRD software.

REFERENCE EXAMPLE 2: PARTICLE SIZE DISTRIBUTION

[0254] The particle size distribution and the Dv10, Dv50 and Dv90 values of the zeolitic material were determined using a Mastersizer 3000 (Malvern) equipped with a Hydro MV dispersion unit. Ultrasonication duration: 10 min at 100% power. Temperature during size measurement: 25° C. Laser obscuration: 7-12%. Stirrer speed demand 1000 r.p.m. Analysis model: general purpose. Fine powder modus: on. Analysis sensitivity: normal. Scattering model: Mie with particle refractive index 1.48 particle absorption index 0.10. Size: weighted by volume (v).

Reference Example 3: Determination of pH

[0255] The pH was determined via Portamess type 911 pH (Knick) using a pH electrode type BlueLine 18 pH (Co. SI Analytics). The samples were thoroughly mixed before measurement. The steady pH was recorded.

Reference Example 4: Determination of Viscosity

[0256] All viscosity measurements were conducted with an AntonPaar MCR 302 Rheometer using a plate-plate geometry (diameter 50 mm), 18° C., rotational mode, shear rate from 0.1 s.sup.−1 to 1000 s.sup.−1 (41 measurements points with 2 seconds duration each). Specific values were measured at a shear rate of 10 s.sup.−1, 50 s.sup.−1, 100 s.sup.−1 and 316 s.sup.−1 as indicated in Table 3. The samples were carefully homogenized before measurement to avoid air entrainment.

Reference Example 5: Determination of Storage Stability

[0257] Bidentate ligands in the presence of a zirconium ion source having passed both qualitative visual tests for precipitation described below in Reference Example 8 were evaluated quantitatively by viscosity measurement for storage stability in inventive suspensions with a metal zeolite and optionally alumina.

[0258] Several duplicates of suspensions prepared according to Comparative Examples 1 to 6 and Examples 1 to 12 were transferred into sealable vessels. The suspensions were stored at 23° C. overnight under continuous movement, a portion of the suspension was analyzed according to Reference Example 4 and the results are shown in table 3 under the shear rates labeled initial storage viscosity for shear rates of 10 s.sup.−1, 50 s.sup.−1, 100 s.sup.−1 and 316 s.sup.−1. A portion of the overnight stored suspensions were further heated to 32° C. in closed vessels in a conventional drying oven for 2 hours, respectively, without any movement. The heated samples were then taken out of the oven, cooled to 23° C. under continuous movement, the suspension was analyzed according to Reference Example 4 and the results are shown in table 3 under the shear rates labeled heated storage viscosity for shear rates of 10 s.sup.−1, 50 s.sup.−1, 100 s.sup.−1 and 316 s.sup.−1. Both the ambient temperature and heated samples were analyzed, the results of which are given in Table 3. The samples were considered stable if the percent difference between the heated and initial viscosities did not show a substantial increase in comparison to the same viscosity percent difference observed in the corresponding comparative example free of the bidentate organic ligand.

Reference Example 6: Determination Conductivity, e.g. of Deionized Water

[0259] The conductivity was determined via Portamess type 911 Cond (Knick) using an electrode type Knick, SE 204 (Knick). The steady conductivity was recorded.

Reference Example 7: Zeolitic Materials Having Framework Type CHA

[0260] Reference Example 7.1: A zeolitic material powder was provided having framework type CHA and having a framework structure characterized by a molar ratio silica:alumina (SiO.sub.2:Al.sub.2O.sub.3, SAR) between 20:1 and 30:1, having a copper content, calculated as CuO and based on the total weight of the framework Si, Al and O of the zeolitic material, of up to 5 weight-%, having a Dv90 between 1 and 10 micrometer, determined as described in Reference Example 2, and exhibiting a crystallite size between 50 and 200 nm determined as described in Reference Example 1. Specifically, a zeolitic material was provided characterized by a molar ratio silica:alumina (SiO.sub.2:Al.sub.2O.sub.3, SAR) of 25:1, having a copper content, calculated as CuO and based on the total weight of the framework Si, Al and O of the zeolitic material, of 3.5 weight-%, having a Dv90 of 3.7 micrometer, a Dv50 of 1.3 micrometer, a Dv10 of 0.7 micrometer, determined as described in Reference Example 2, and exhibiting a crystallite size of 149 nm determined as described in Reference Example 1.

[0261] Reference Example 7.2: A zeolitic material powder was provided having framework type CHA and having a framework structure characterized by a molar ratio silica:alumina (SiO.sub.2:Al.sub.2O.sub.3, SAR) between 25:1 and 35:1, having a copper content, calculated as CuO and based on the total weight of the framework Si, Al and O of the zeolitic material, of up to 5 weight-%, having a Dv90 of between 1 and 10 micrometer determined as described in Reference Example 2, and exhibiting a crystallite size between 50 and 200 nm determined as described in Reference Example 1. Specifically, a zeolitic material was provided characterized by a molar ratio silica:alumina (SiO.sub.2:Al.sub.2O.sub.3, SAR) of 28.5:1, having a copper content, calculated as CuO and based on the total weight of the framework Si, Al and O of the zeolitic material, of 3.5 weight-%, having a Dv90 of 3.6 micrometer, a Dv50 of 1.3 micrometer, a Dv10 of 0.7 micrometer, determined as described in Reference Example 2, and exhibiting a crystallite size of 139 nm determined as described in Reference Example 1.

[0262] Reference Example 7.3: A zeolitic material powder was provided having framework type CHA and having a framework structure characterized by a molar ratio silica:alumina (SiO.sub.2:Al.sub.2O.sub.3, SAR) between 10:1 and 25:1, having a copper content, calculated as CuO and based on the total weight of the framework Si, Al and O of the zeolitic material, of up to 5 weight-%, having a Dv90 between 1 and 10 micrometer determined as described in Reference Example 2, and exhibiting a crystallite size between 50 and 200 nm determined as described in Reference Example 1. Specifically, a zeolitic material was provided characterized by a molar ratio silica:alumina (SiO.sub.2:Al.sub.2O.sub.3, SAR) of 18.7:1, having a copper content, calculated as CuO and based on the total weight of the framework Si, Al and O of the zeolitic material, of 4.8 weight-%, having a Dv90 of 6.9 micrometer, a Dv50 of 2.9 micrometer, a Dv10 of 0.7 micrometer, determined as described in Reference Example 2, and exhibiting a crystallite size of 78 nm determined as described in Reference Example 1.

[0263] Reference Example 7.4: A zeolitic material powder was provided having framework type CHA and having a framework structure characterized by a molar ratio silica:alumina (SiO.sub.2:Al.sub.2O.sub.3, SAR) of between 10:1 and 25:1, having a copper content, calculated as CuO and based on the total weight of the framework Si, Al and O of the zeolitic material of up to 5 weight-%, having a Dv90 between 1 and 10 micrometer determined as described in Reference Example 2, and exhibiting a crystallite size between 50 and 200 nm determined as described in Reference Example 1. Specifically, a zeolitic material was provided characterized by a molar ratio silica:alumina (SiO.sub.2:Al.sub.2O.sub.3, SAR) of 18:4, having a copper content, calculated as CuO and based on the total weight of the framework Si, Al and O of the zeolitic material, of 0 weight-%, having a Dv90 of 2.1 micrometer, a Dv50 of 0.6 micrometer, a Dv10 of 0.4 micrometer, determined as described in Reference Example 2, and exhibiting a crystallite size of 102 nm determined as described in Reference Example 1.

Reference Example 8: Zirconium Sol Gel/Precipitation Inhibition Test

[0264] A stability test to evaluate chelating organic bidentate ligands effect on zirconium sol gel formation under acidic and basic pH was conducted. Any precipitation observed during the following test by visual inspection was considered unstable and failed the qualitative analysis stability test. Deionized water and zirconium (IV) acetate Zr(OAc).sub.x solution, having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, were mixed at 23° C. Subsequently, an organic ligand was added (see Table 1 below) with stirring. The results are described below in Table 1, including a control experiment with deionized water and Zr(OAc).sub.x only, without ligand. For samples which showed stable clear solutions the pH was then adjusted to a value of 8-9 with monoethanolamine (MEA). The final formulations had a composition H.sub.2O:zirconium acetate:organic ligand of 90:5:5. The results are described below in Table 2, including a control experiment with deionized water, Zr(OAc).sub.x and MEA only, without ligand.

TABLE-US-00001 TABLE 1 Zirconium sol gel/precipitation test under acidic conditions sample organic ligand pH Appearance a — 3.1 clear b glycolic acid 1.9 clear c lactic acid 2.1 clear d glucuronolactone 3.1 clear e D-glucoronic acid 2.2 clear f ascorbic acid 2.1 clear g acetylacetone 3.5 clear h glycine 4.6 clear i alanine 4.5 clear j acetic acid 2.5 clear k 2,5-dihydroxybenzoic acid — turbid, precipitate l mandelic acid — turbid, precipitate m tartaric acid — turbid, precipitate n citric acid — turbid, precipitate 0 malic acid — turbid, precipitate

TABLE-US-00002 TABLE 2 Zirconium sol gel/precipitation test under basic conditions sample organic ligand pH Appearance a — 9.1 turbid, precipitate b glycolic acid 8.5 clear c lactic acid 8.1 clear d glucuronolactone 8.3 clear e D-glucoronic acid 8.2 clear f ascorbic acid 8.3 clear g acetylacetone 8.1 clear h glycine 8.2 turbid, precipitate i alanine 8.3 turbid, precipitate j acetic acid 8.1 turbid, precipitate

Reference Example 9: pH of Suspensions Consisting of Water and Zeolitic Materials Having Framework Type CHA

[0265] A suspension consisting of deionized water and 31 to 35 wt.-% zeolitic material calculated on the basis of the total weight of the suspension was formed by mixing the two components. The pH of the suspension was measured according to Reference example 3 at 20° C. Results for zeolitic materials according to Reference Examples 7.1 to 7.3 are given below.

[0266] Reference example 9.1: 29.95 grams of zeolitic material according to Reference Example 7.1 was thoroughly mixed with 60.10 grams deionized water and the pH was measured according to Reference Example 3 under stirring at 20° C. The suspension was found to have a pH value of 4.0. The suspension was allowed to stir under the same conditions for 24 hours and measured found to have a pH value of 4.1.

[0267] Reference example 9.2: 30.04 grams of zeolitic material according to Reference Example 7.2 was thoroughly mixed with 59.97 grams deionized water and the pH was measured according to Reference Example 3 under stirring at 20° C. The suspension was found to have a pH value of 6.7. The suspension was allowed to stir under the same conditions for 24 hours and measured found to have a pH value of 6.8.

[0268] Reference example 9.3: 29.99 grams of zeolitic material according to Reference Example 7.3 was thoroughly mixed with 60.00 grams deionized water and the pH was measured according to Reference Example 3 under stirring at 20° C. The suspension was found to have a pH value of 5.8. The suspension was allowed to stir under the same conditions for 24 hours and measured found to have a pH value of 6.3.

Comparative Example 1: Mixture According to Example 1, without Bidentate Organic Ligand

[0269] 68.15 g deionized water having a conductivity of 5 to 20 microSiemens, determined as described in Reference Example 6, 11.26 g of an aqueous zirconium acetate (Zr(OAc)x) solution, having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, and 70.63 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.1 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C.

[0270] The suspension was then stored for 18 hours at a temperature of the suspension of 20° C. and 30° C. for 2 hours followed by cooling to room temperature as described in Reference Example 5. After storage and heating of a portion of the suspension as described in Reference Example 5, the viscosity before and after heating were determined according to reference example 4 and the pH of the suspension as determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

COMPARATIVE EXAMPLE 2: MIXTURE ACCORDING TO EXAMPLE 2, WITHOUT BIDENTATE ORGANIC LIGAND

[0271] 67.44 g deionized water having a conductivity of 5 to 20 micro Siemens/cm, determined as described in Reference Example 6, 11.27 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, and 71.35 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.2 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C.

[0272] The suspension was then stored in the same way as the suspension of Comparative Example 1. After storage and heating of a portion of the suspension as described in Reference Example 5, the viscosity before and after heating were determined according to reference example 4 and the pH of the suspension as determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

COMPARATIVE EXAMPLE 3: MIXTURE ACCORDING TO EXAMPLE 3, WITHOUT BIDENTATE ORGANIC LIGAND

[0273] 69.30 g deionized water having a conductivity of 5 to 20 micro Siemens/cm, determined as described in Reference Example 6, 11.27 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, and 69.49 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.3 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C.

[0274] The suspension was then stored in the same way as the suspension of Comparative Example 1. After storage and heating of a portion of the suspension as described in Reference Example 5, the viscosity before and after heating were determined according to reference example 4 and the pH of the suspension as determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

EXAMPLE 1: SUSPENSION ACCORDING TO THE INVENTION

[0275] The suspension of Example 1 was prepared essentially as the suspension of Comparative Example 1, however with organic bidentate ligand added.

[0276] 66.90 g deionized water having a conductivity of 5 to 20 micro Siemens/cm, determined as described in Reference Example 6, 1.26 g lactic acid (90 weight-%, obtained from Sigma-Aldrich), 11.26 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, and 70.66 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.1 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.049. Further in the finally obtained suspension, the weight ratio of the bidentate organic ligand relative to the zirconium ion, calculated as zirconium (IV) oxide, ligand:Zr(IV), was 0.34.

[0277] The suspension was then stored in the same way as the suspension of Comparative Example 1. After storage and heating of a portion of the suspension as described in Reference Example 5, the viscosity before and after heating were determined according to reference example 4 and the pH of the suspension as determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

EXAMPLE 2: SUSPENSION ACCORDING TO THE INVENTION

[0278] The suspension of Example 2 was prepared essentially as the suspension of Comparative Example 2, however with organic bidentate ligand added.

[0279] 66.19 g deionized water having a conductivity of 5 to 20 micro Siemens/cm, determined as described in Reference Example 6, 1.26 g lactic acid (90 weight-%, obtained from Sigma-Aldrich), 11.26 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, and 71.36 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.2 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.047. Further in the finally obtained suspension, the weight ratio of the bidentate organic ligand relative to the zirconium ion, calculated as zirconium (IV) oxide, ligand:Zr(IV), was 0.34.

[0280] The suspension was then stored in the same way as the suspension of Comparative Example 1. After storage and heating of a portion of the suspension as described in Reference Example 5, the viscosity before and after heating were determined according to reference example 4 and the pH of the suspension as determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

EXAMPLE 3: SUSPENSION ACCORDING TO THE INVENTION

[0281] The suspension of Example 3 was prepared essentially as the suspension of Comparative Example 3, however with organic bidentate ligand added.

[0282] 68.05 g deionized water having a conductivity of 150 to 200 micro Siemens/cm, determined as described in Reference Example 6, 1.27 g lactic acid (90 weight-%, obtained from Sigma-Aldrich), 11.28 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, and 69.48 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.3 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.049. Further in the finally obtained suspension, the weight ratio of the bidentate organic ligand relative to the zirconium ion, calculated as zirconium (IV) oxide, ligand:Zr(IV), was 0.34.

[0283] The suspension was then stored in the same way as the suspension of Comparative Example 1. After storage and heating of a portion of the suspension as described in Reference Example 5, the viscosity before and after heating were determined according to reference example 4 and the pH of the suspension as determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

EXAMPLE 4: SUSPENSION ACCORDING TO THE INVENTION, AS EXAMPLE 1, WITH ADDED ALUMINA

[0284] The suspension of Example 4 was prepared essentially as the suspension of Example 1, however with alumina added to maintain a constant total solid loading of 45 wt.-% calculated on the basis total weight of the suspension.

[0285] 67.24 g deionized water having a conductivity of 150 to 200 micro Siemens/cm, determined as described in Reference Example 6, 1.26 g lactic acid (90 weight-%, obtained from Sigma-Aldrich), 11.27 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, 3.41 g of alumina (Brønsted acid, 1 micrometer<Dv90<10 micrometer), and 66.95 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.1 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.051. Further in the finally obtained suspension, the weight ratio of the bidentate organic ligand relative to the zirconium ion, calculated as zirconium (IV) oxide, ligand:Zr(IV), was 0.34.

[0286] The suspension was then stored in the same way as the suspension of Comparative Example 4. After storage and heating of a portion of the suspension as described in Reference Example 5, the viscosity before and after heating were determined according to reference example 4 and the pH of the suspension as determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

EXAMPLE 5: SUSPENSION ACCORDING TO THE INVENTION, AS EXAMPLE 2, WITH ADDED ALUMINA

[0287] The suspension of Example 5 was prepared essentially as the suspension of Example 2, however with alumina added to maintain a constant total solid loading of 45 wt.-% calculated on the basis total weight of the suspension

[0288] 66.57 g deionized water having a conductivity of 150 to 200 micro Siemens/cm, determined as described in Reference Example 6, 1.26 g lactic acid (90 weight-%, obtained from Sigma-Aldrich), 11.26 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, 3.39 g of alumina (Brønsted acid, 1 micrometer <Dv90<10 micrometer), and 67.59 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.2 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.050. Further in the finally obtained suspension, the weight ratio of the bidentate organic ligand relative to the zirconium ion, calculated as zirconium (IV) oxide, ligand:Zr(IV), was 0.34.

[0289] The suspension was then stored in the same way as the suspension of Comparative Example 5. After storage and heating of a portion of the suspension as described in Reference Example 5, the viscosity before and after heating were determined according to reference example 4 and the pH of the suspension as determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

EXAMPLE 6: SUSPENSION ACCORDING TO THE INVENTION, AS EXAMPLE 3, WITH ADDED ALUMINA

[0290] The suspension of Example 6 was prepared essentially as the suspension of Example 3, however with alumina added to maintain a constant total solid loading of 45 wt.-% calculated on the basis total weight of the suspension.

[0291] 68.34 g deionized water having a conductivity of 150 to 200 micro Siemens/cm, determined as described in Reference Example 6, 1.27 g lactic acid (90 weight-%, obtained from Sigma-Aldrich), 11.26 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, 3.39 g of alumina (Brønsted acid, 1 micrometer <Dv90<10 micrometer), and 65.86 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.3 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.051. Further in the finally obtained suspension, the weight ratio of the bidentate organic ligand relative to the zirconium ion, calculated as zirconium (IV) oxide, ligand:Zr(IV), was 0.34.

[0292] The suspension was then stored in the same way as the suspension of Comparative Example 6. After storage and heating of a portion of the suspension as described in Reference Example 5, the viscosity before and after heating were determined according to reference example 4 and the pH of the suspension as determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

EXAMPLE 7: SUSPENSION ACCORDING TO THE INVENTION, AS EXAMPLE 4, WITH A HIGHER QUANTITY OF ORGANIC BIDENTATE LIGAND ADDED

[0293] The suspension of Example 7 was prepared essentially as the suspension of Example 4, however with a higher quantity of organic bidentate ligand added.

[0294] 65.98 g deionized water having a conductivity of 150 to 200 micro Siemens/cm, determined as described in Reference Example 6, 2.51 g lactic acid (90 weight-%, obtained from Sigma-Aldrich), 11.26 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, 3.39 g of alumina (Brønsted acid, 1 micrometer <Dv90<10 micrometer), and 66.92 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.1 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.050. Further in the finally obtained suspension, the weight ratio of the bidentate organic ligand relative to the zirconium ion, calculated as zirconium (IV) oxide, ligand:Zr(IV), was 0.67.

[0295] The suspension was then stored in the same way as the suspension of Example 4. After storage and heating of a portion of the suspension as described in Reference Example 5, the viscosity before and after heating were determined according to reference example 4 and the pH of the suspension as determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

EXAMPLE 8: SUSPENSION ACCORDING TO THE INVENTION, AS EXAMPLE 5, WITH A HIGHER QUANTITY OF ORGANIC BIDENTATE LIGAND ADDED

[0296] The suspension of Example 8 was prepared essentially as the suspension of Example 5, however with a higher quantity of organic bidentate ligand added.

[0297] 65.33 g deionized water having a conductivity of 150 to 200 micro Siemens/cm, determined as described in Reference Example 6, 2.53 g lactic acid (90 weight-%, obtained from Sigma-Aldrich), 11.29 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, 3.41 g of alumina (Brønsted acid, 1 micrometer <Dv90<10 micrometer; same as in Example), and 67.61 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.2 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.050. Further in the finally obtained suspension, the weight ratio of the bidentate organic ligand relative to the zirconium ion, calculated as zirconium (IV) oxide, ligand:Zr(IV), was 0.67.

[0298] The suspension was then stored in the same way as the suspension of Example 5. After storage and heating of a portion of the suspension as described in Reference Example 5, the viscosity before and after heating were determined according to reference example 4 and the pH of the suspension as determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

EXAMPLE 9: SUSPENSION ACCORDING TO THE INVENTION, AS EXAMPLE 6, WITH A HIGHER QUANTITY OF ORGANIC BIDENTATE LIGAND ADDED

[0299] The suspension of Example 9 was prepared essentially as the suspension of Example 6, however with a higher quantity of organic bidentate ligand added.

[0300] 67.08 g deionized water having a conductivity of 150 to 200 micro Siemens/cm, determined as described in Reference Example 6, 2.51 g lactic acid (90 weight-%, obtained from Sigma-Aldrich), 11.28 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, 3.41 g of alumina (Brønsted acid, 1 micrometer <Dv90<10 micrometer; same as in Example), and 65.84 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.3 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.051. Further in the finally obtained suspension, the weight ratio of the bidentate organic ligand relative to the zirconium ion, calculated as zirconium (IV) oxide, ligand:Zr(IV), was 0.67.

[0301] The suspension was then stored in the same way as the suspension of Example 6. After storage and heating of a portion of the suspension as described in Reference Example 5, the viscosity before and after heating were determined according to reference example 4 and the pH of the suspension as determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

COMPARATIVE EXAMPLE 4: SUSPENSION ACCORDING TO EXAMPLE 4, WITHOUT ORGANIC BIDENTATE LIGAND

[0302] The suspension of Comparative Example 4 was prepared essentially as the suspension of Example 4, however without the addition of organic bidentate ligand.

[0303] 68.51 g deionized water having a conductivity of 150 to 200 micro Siemens/cm, determined as described in Reference Example 6, 11.27 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, 3.41 g of alumina (Brønsted acid, 1 micrometer <Dv90<10 micrometer), and 66.97 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.1 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.050.

[0304] The suspension was then stored in the same way as the suspension of Example 4. After storage, the viscosity was determined as described in Reference Example 4 and the pH of the suspension was determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

COMPARATIVE EXAMPLE 5: SUSPENSION ACCORDING TO EXAMPLE 5, WITHOUT ORGANIC BIDENTATE LIGAND

[0305] The suspension of Comparative Example 5 was prepared essentially as the suspension of Example 5, however without the addition of the organic bidentate ligand.

[0306] 67.58 g deionized water having a conductivity of 150 to 200 micro Siemens/cm, determined as described in Reference Example 6, 11.28 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, 3.41 g of alumina (Brønsted acid, 1 micrometer <Dv90<10 micrometer), and 67.61 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.2 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.050.

[0307] The suspension was then stored in the same way as the suspension of Example 4. After storage, the viscosity was determined as described in Reference Example 4 and the pH of the suspension was determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

COMPARATIVE EXAMPLE 6: SUSPENSION ACCORDING TO EXAMPLE 6, WITHOUT ORGANIC BIDENTATE LIGAND

[0308] The suspension of Comparative Example 6 was prepared essentially as the suspension of Example 6, however without the addition of organic bidentate ligand.

[0309] 69.59 g deionized water having a conductivity of 150 to 200 micro Siemens/cm, determined as described in Reference Example 6, 11.27 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, 3.41 g of alumina (Bronsted acid, 1 micrometer <Dv90<10 micrometer), and 65.87 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.3 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.051.

[0310] The suspension was then stored in the same way as the suspension of Example 4. After storage, the viscosity was determined as described in Reference Example 4 and the pH of the suspension was determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

EXAMPLE 10: SUSPENSION ACCORDING TO THE INVENTION, AS EXAMPLE 1, WITH A HIGHER QUANTITY OF ORGANIC BIDENTATE LIGAND ADDED

[0311] The suspension of Example 10 was prepared essentially as the suspension of Example 1, however with a higher quantity of organic bidentate ligand added.

[0312] 65.66 g deionized water having a conductivity of 150 to 200 micro Siemens/cm, determined as described in Reference Example 6, 2.51 g lactic acid (90 weight-%, obtained from Sigma-Aldrich), 11.27 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, and 70.64 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.1 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.048. Further in the finally obtained suspension, the weight ratio of the bidentate organic ligand relative to the zirconium ion, calculated as zirconium (IV) oxide, ligand:Zr(IV), was 0.67.

[0313] The suspension was then stored in the same way as the suspension of Example 1. After storage, the viscosity was determined as described in Reference Example 4 and the pH of the suspension was determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

EXAMPLE 11: SUSPENSION ACCORDING TO THE INVENTION, AS EXAMPLE 2, WITH A HIGHER QUANTITY OF ORGANIC BIDENTATE LIGAND ADDED

[0314] The suspension of Example 11 was prepared essentially as the suspension of Example 2, however with a higher quantity of organic bidentate ligand added.

[0315] 64.94 g deionized water having a conductivity of 150 to 200 micro Siemens/cm, determined as described in Reference Example 6, 2.52 g lactic acid (90 weight-%, obtained from Sigma-Aldrich), 11.26 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, and 71.35 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.2 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.047. Further in the finally obtained suspension, the weight ratio of the bidentate organic ligand relative to the zirconium ion, calculated as zirconium (IV) oxide, ligand:Zr(IV), was 0.67.

[0316] The suspension was then stored in the same way as the suspension of Example 1. After storage, the viscosity was determined as described in Reference Example 4 and the pH of the suspension was determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

EXAMPLE 12: SUSPENSION ACCORDING TO THE INVENTION, AS EXAMPLE 3, WITH A HIGHER QUANTITY OF ORGANIC BIDENTATE LIGAND ADDED

[0317] The suspension of Example 12 was prepared essentially as the suspension of Example 3, however with more organic bidentate ligand added.

[0318] 66.80 g deionized water having a conductivity of 150 to 200 micro Siemens/cm, determined as described in Reference Example 6, 2.52 g lactic acid (90 weight-%, obtained from Sigma-Aldrich), 11.26 g of an aqueous zirconium acetate (Zr(OAc)x) solution (same as in Comparative Example 1), having a zirconium content, calculated as ZrO.sub.2, of 30 weight-%, and 69.49 g of a copper containing zeolitic material having framework structure CHA according to Reference Example 7.3 were admixed in this order and mixed to a homogenized suspension at a temperature of the suspension of 12 to 25° C. In the finally obtained suspension, the weight ratio of the zirconium ion comprised in the obtained complex, calculated as zirconium (IV) oxide, relative to the total weight of the framework Si, Al and O of the zeolitic material, Zr(IV):zeolitic material, was 0.049. Further in the finally obtained suspension, the weight ratio of the bidentate organic ligand relative to the zirconium ion, calculated as zirconium (IV) oxide, ligand:Zr(IV), was 0.67.

[0319] The suspension was then stored in the same way as the suspension of Example 1. After storage, the viscosity was determined as described in Reference Example 4 and the pH of the suspension was determined as described in Reference Example 3. The pH and the viscosity results are shown in Table 3 below.

TABLE-US-00003 TABLE 3 Stability evaluation for examples for the initial storage followed by heating according to Reference Ex 5 Total solid ratio* Viscosity (mPa .Math. s) initial storage Viscosity (mPa .Math. s) heated storage [ZrO.sub.2:Al.sub.2O.sub.3:CuCHA] Ligand shear rate shear rate Example Zeolite pH ZrO.sub.2:Al.sub.2O.sub.3:CuCHA Wt.-% 10 s.sup.−1 50 s.sup.−1 100 s.sup.−1 316 s.sup.−1 10 s.sup.−1 50 s.sup.−1 100 s.sup.−1 316 s.sup.−1 Co Ex 1 Ref Ex 7.1 4.5 5 0 95 0 223 279 499 1480 547 507 797 1740 Co Ex 2 Ref Ex 7.2 5.5 5 0 95 0 973 405 330 271 944 428 363 315 Co Ex 3 Ref Ex 7.3 4.7 5 0 95 0 406 587 832 1510 1130 926 1100 1700 Ex 1 Ref Ex 7.1 4.3 5 0 95 0.75 400 1070 1210 1270 438 1210 1340 1380 Ex 2 Ref Ex 7.2 5.2 5 0 95 0.75 64 59 67 86 202 130 127 135 Ex 3 Ref Ex 7.3 4.5 5 0 95 0.75 554 1030 1270 1540 475 937 1180 1440 Ex 4 Ref Ex 7.1 4.3 5 5 90 0.75 2060 1790 1680 1510 3100 2470 2270 2070 Ex 5 Ref Ex 7.2 5.2 5 5 90 0.75 35 42 51 71 82 64 67 81 Ex 6 Ref Ex 7.3 4.4 5 5 90 0.75 3850 2450 2200 1910 4430 3010 2610 2150 Ex 7 Ref Ex 7.1 4.2 5 5 90 1.50 2480 1450 1200 994 3970 2820 2460 1960 Ex 8 Ref Ex 7.2 4.9 5 5 90 1.50 31 33 40 60 30 32 39 60 Ex 9 Ref Ex 7.3 4.3 5 5 90 1.50 3480 2010 1640 1150 4800 2870 2360 1810 Co Ex 4 Ref Ex 7.1 4.4 5 5 90 0 316 266 408 1590 n/a n/a n/a n/a Co Ex 5 Ref Ex 7.2 5.5 5 5 90 0 1260 537 450 396 n/a n/a n/a n/a Co Ex 6 Ref Ex 7.3 4.5 5 5 90 0 1480 924 987 1390 n/a n/a n/a n/a Ex 10 Ref Ex 7.1 4.1 5 0 95 1.50 1100 824 779 620 n/a n/a n/a n/a Ex 11 Ref Ex 7.2 4.8 5 0 95 1.50 21 29 38 62 n/a n/a n/a n/a Ex 12 Ref Ex 7.3 4.2 5 0 95 1.50 747 762 903 1100 n/a n/a n/a n/a Table 3 *The total solid ratio is given on a weight to weight basis for a 45 wt. % total solid loading of each example.