PROCESS FOR PREPARATION OF A MOLDING COMPOSITION AND PRODUCTION OF SHAPED BODIES

Abstract

The invention is related to a process for preparation of a molding composition, the process comprising a.sub.1) preparing a mixture, the mixture comprising an at least bidentate organic compound or a salt thereof, a metal salt and a solvent, wherein the solvent comprises 25% to 60% by volume of an alcohol, selected from the group consisting of methanol, ethanol, n-propanol and isopropanol, and 40% to 75% by volume of water, and a.sub.2) producing the molding composition, the molding composition comprising at least a metal-organic framework material and the solvent, wherein the at least bidentate organic compound or a salt thereof and the metal salt react to the metal-organic framework material. The invention is further related to a process for production of shaped bodies.

Claims

1.-15. (canceled)

16. A process for production of shaped bodies, the process comprising a) preparing a molding composition, comprising the steps a.sub.1) preparing a mixture, the mixture comprising an at least bidentate organic compound or a salt thereof, a metal salt and a solvent, wherein the solvent comprises 25% to 60% by volume of an alcohol selected from the group consisting of methanol, ethanol, n-propanol and isopropanol, and 40% to 75% by volume of water, and a.sub.2) producing the molding composition, the molding composition comprising at least a metal-organic framework material and the solvent, wherein the at least bidentate organic compound or a salt thereof and the metal salt react to the metal-organic framework material and wherein the molding composition has a solid content in a range from 30% to 80% by weight, referring to the total mass of the molding composition; b) feeding the molding composition into an extruder or an extrusion press and c) converting the molding composition into shaped bodies, comprising at least the metal-organic framework material, by extrusion.

17. The process according to claim 16, wherein the molding composition has a solid content in a range from 40% to 60% by weight, referring to the total mass of the molding composition.

18. The process according to claim 16, wherein the metal salt comprises a metal selected from the group consisting of Mg, Ca, Al, Y, Sc, Zr, Ti, V, Cr, Mo, Fe, Co, Cu, Ni, Zn and Ln.

19. The process according to claim 16, wherein the mixture comprises comprises at least one binder anchor lubricant.

20. The process according to claim 19, wherein the mixture comprises 1% to 10% by weight of a lubricant, referring to the sum of the initial mass of the at least bidentate organic compound and the initial mass of the metal salt.

21. The process according to claim 19, wherein the lubricant is polyethylene oxide and/or a polysaccharide.

22. The process according to claim 16, wherein the metal salt and the at least bidentate organic compound are used in stoichiometric amounts.

23. The process according to claim 16, wherein step a.sub.2) is carried out a temperature in a range from 15 C. to 70 C.

24. The process according to claim 16, wherein the metal salt is (Cu(OH).sub.2 or [Zn(CO.sub.3)].sub.2[Zn(OH).sub.2].sub.3.

25. The process according to claim 16, wherein the at least bidentate organic compound is benzene-1,3,5-tricarboxylic acid or 2-methylimidazole.

26. The process according to claim 16, wherein at least step a.sub.1) is carried out in a mix muller or a kneader.

27. The process according to claim 16, wherein the molding composition is not filtered before being fed into the extruder or the extrusion press.

28. The process according to claim 16, wherein the molding composition is not dried before being fed into the extruder or the extrusion press.

29. The process according to claim 16, the shaped bodies are dried at a drying temperature in a range from 80 C. to 250 C.

30. The process according to claim 16, wherein the molding composition comprises 30% to 60% by weight of the metal-organic framework material, when being fed into the extruder or extrusion press, referring to the total mass of the molding composition.

31. The process according to claim 16, wherein the metal salt comprises a metal selected from the group consisting of Mg, Zr, Ni, Al, Mo, Y, Sc, Mg, Fe, Cu and Zn.

32. The process according to claim 16, wherein the metal salt comprises a metal selected from the group consisting of Mg, Fe, Zr, Sc, Al, Cu and Zn.

33. The process according to claim 16, wherein the metal salt comprises a metal selected from the group consisting of Mg, Zr, Al, Cu and Zn.

34. The process according to claim 16, wherein the metal salt comprises a metal selected from the group consisting of copper, zinc and aluminum.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0127] FIG. 1 shows the XRD diffractogram of comparative example 1.

[0128] FIG. 2 refers to the XRD diffractogram of comparative example 2.

[0129] FIG. 3 shows the XRD diffractogram of comparative example 3.

[0130] FIG. 4 shows the XRD diffractogram of example 1.

[0131] FIG. 5 shows the XRD diffractogram of example 2.

[0132] FIG. 6 relates the XRD diffractogram of example 4.

[0133] FIG. 7 shows the XRD diffractogram of example 5.

[0134] FIG. 8 refers to the XRD diffractogram of example 6.

EXAMPLES AND COMPARATIVE EXAMPLES

Comparative Examples 1 to 4 (CE1 to CE4) and Examples 1 to 4 (E1 to E4)

[0135] 201.2 g benzene-1,3,5-tricarboxylic acid (BTC) and 145.5 g copper hydroxide where mixed for 10 minutes in a mix muller from Simpson Technologies. The BTC was applied with a purity of 98% and the copper hydroxide was applied with a purity of 95%. The initial ratio of the molar amount of copper to the molar amount of BTC was generally 1.51. For comparative example 2, 165.2 g copper hydroxide were applied and the initial ratio of the molar amount of copper to the molar amount of BTC was 1.71

[0136] Then, at least one lubricant was added and the mixture was additionally mixed for 5 minutes. As lubricant, the polysaccharide Zusoplast PS1 or Zusoplast PS1 and the polyethylene oxide PEO E160, respectively, was applied. Subsequently, varying amounts of a solvent with a varying composition, consisting of ethanol and water, were added to the solid mixture, followed by an additional mixing time of at least 30 minutes.

[0137] The resulting molding composition was fed into an extrusion press, 8MP Modul 40 from RexRoth, and extrudates with a diameter of 3.5 mm were produced at a pressure between 35 bar and 150 bar.

[0138] The resulting extrudates were dried for 16 hours at 120 C. and then measured by x-ray diffractometry (XRD, FIG. 1 to FIG. 6). The specific surface area was measured according to BET (DIN ISO 9277:2003-05).

[0139] A measurement of the cutting hardness was carried out as described in the earlier German patent application no. 103261137.0 of Jun. 6, 2003 (BASF AG): The cutting hardnesses were measured according to DIN EN ISO 9001:2008 on an apparatus from Zwick (model: BZ2.5/TS1S; initial loading: 0.5 N, preliminary advance rate: 10 mm/min; test speed: 1.6 mm/min) and are the means of in each case 10 measured catalyst extrudates. In detail, the cutting hardness was determined as follows: Extrudates were loaded with increasing force by means of a cutter having a thickness of 0.3 mm until the extrudate had been cut through. The force required for this is the cutting hardness in N (Newton). The determination was carried out on a testing apparatus from Zwick, Ulm, having a rotating plate in a fixed position and a freely movable, vertical punch with built-in cutter having a thickness of 0.3 mm. The movable punch with the cutter was connected to a load cell to record the force and during the measurement moved towards the rotating plate on which the extrudate to be measured was located. The test apparatus was controlled via a computer which recorded and evaluated the measurement results. 10 straight, preferably crack-free extrudates were taken from a well-mixed sample and their cutting hardnesses were determined and subsequently averaged.

[0140] Tamped densities of extrudate packings were determined using a jolting volumeter type STAV II from J. Engelsmann AG. The machine has been tested according to DIN ISO 787 (Part 11 of 1995) by the manufacturer. A weighed amount of the respective sample was put into a 1000 or 100 mL scaled cylinder. After tapping the cylinder 3000 times, the resulting volume of the packing was determined and the density calculated by dividing sample weight by sample volume.

Example 5.1 (E5.1)

[0141] Example 5.1 was carried out according to the procedure as described for comparative examples 1 to 4 and examples 1 to 4 with the difference that the extrudates were produced in a larger scale. 2260 g benzene-1,3,5-tricarboxylic acid (BTC) and 2720 g copper hydroxide where applied, resulting in an initial ratio of the molar amount of copper to the molar amount of BTC of 1.71.

[0142] The resulting molding composition was fed into an extrusion press from Loomis for the production of extrudates with a diameter of 3.5. The resulting extrudates were measured by x-ray diffractometry (XRD, FIG. 7).

Example 5.2 (E5.2)

[0143] Example 5.2 was carried out according to the procedure as described for example 5.1 with the difference that the resulting molding composition was fed into an extruder from Sela for the production of extrudates with a diameter of 3.5.

Example 6 (E6)

[0144] Example 6 was carried out according to the procedure as described for comparative examples 1 to 4 and examples 1 to 4 with the difference that instead of BTC and copper hydroxide, 368.2 g 2-methylimidazole and 250 g zinc carbonate hydroxide hydrate where mixed, resulting in an initial ratio of the molar amount of zinc to the molar amount of 2-methylimidazole of 1.5.

[0145] The specific compositions of the mixture and the results of comparative examples 1 to 4 and examples 1 to 6 are summarized in table 1. The content of the lubricants is given in % by weight, referring to the sum of the initial mass of BTC and the initial mass of copper hydroxide and the sum of the initial mass of 2-methylimidazole and zinc carbonate hydroxide hydrate, respectively, and the solid content refers to the total mass of the molding composition. Stable extrudates are understood to be cut or broken from continuous strands, providing a constant diameter, which were produced by the extruder or extrusion press. The stable extrudates further possessed a homogeneous distribution of cutting strength.

[0146] The extrudates were measured by X-ray diffractometry (XRD, FIG. 8).

TABLE-US-00001 TABLE 1 Lubricant BET Solvent Solid Zusoplast PEO Tamped Cutting surface Ethanol Water content PS1 E160 density strength area stable No. [vol. %] [vol. %] [wt. %] [wt. %] [wt. %] [g/L] [N] [m.sup.2/g] extrudates CE1 15 85 49 2 2 403.3 27 422 no CE2 15 85 46 2 2 283 9.5 246 no CE3 67.5 32.5 51 2 2 340 28.3 1036 no CE4 80 20 55 2 2 380 23.7 966 no E1 32.5 67.5 44 2 2 300 21.2 1057 yes E2 42.5 57.5 49 5 0 329 15.9 1129 yes E3 50 50 46 2 2 376 36.8 951 yes E4 50 50 49 5 0 360 25.1 1089 yes E5.1 50 50 49 2 2 475 33 1013 yes E5.2 50 50 49 2 2 514 44 1022 yes E6 50 50 69 2 2 416 12 1032 yes

[0147] The XRD diffractograms related to comparative example 3 and to examples 1, 2 and 4 to 6 show that the metal-organic framework copper BTC was formed. For an ethanol content in the solvent of less than 20%, a drastic decrease in the BET surface area was observed.