CATALYST FOR HYDROGEN CHLORIDE OXIDATION AND PRODUCTION THEREOF

Abstract

The present invention relates to a catalyst for the oxidation of hydrogen chloride to chlorine, wherein the catalyst comprises an inorganic carrier matrix and a zeolite, wherein the inorganic carrier matrix comprises Y, O, and optionally comprises X, wherein the zeolite comprises Y and O in its framework structure, and optionally comprises X in its framework structure, wherein Y is a tetravalent element and X is a trivalent element, wherein the inorganic carrier matrix and the zeolite are loaded with copper and with one or more rare earth metals, and wherein the zeolite is supported within the inorganic carrier matrix. Furthermore, the present invention relates to a molding comprising the catalyst, as well as to a process for the production of the catalyst and the molding, respectively, as well as to their respective use in a process for the oxidation of hydrogen chloride to chlorine.

Claims

1-15. (canceled)

16. A catalyst for the oxidation of hydrogen chloride to chlorine, wherein the catalyst comprises an inorganic carrier matrix and a zeolite, wherein the inorganic carrier matrix comprises Y, O, and optionally comprises X, wherein the zeolite comprises Y and O in its framework structure, and optionally comprises X in its framework structure, wherein Y is a tetravalent element and X is a trivalent element, wherein the inorganic carrier matrix and the zeolite are loaded with copper and with samarium, and wherein the zeolite is supported within the inorganic carrier matrix.

17. The catalyst of claim 16, wherein the inorganic carrier matrix is in the form of microsphere particles having a weight average particle diameter D50 comprised in the range of from 20 to 250 .Math.m, wherein the weight average particle diameter D50 is determined according to ISO 13317-3:2001 and calculated according to ISO 9276-2:2014.

18. The catalyst of claim 16, wherein the inorganic carrier matrix displays an Hg-porosity in the range of from 0.1 to 2.5 mL/g, wherein the Hg-porosity is determined according to ISO 15901-1:2016.

19. The catalyst of claim 16, wherein the ammonia temperature programmed desorption of the inorganic carrier matrix displays: a first peak in the range of from 150 to 270° C.; and a second peak in the range of from 270 to 375° C.; wherein the integration of the first peak offers a concentration of acid sites in the range of from 0.3 to 1.5 mmol/g; and wherein the integration of the second peak offers a concentration of acid sites in the range of from 0.3 to 1.5 mmol/g.

20. The catalyst of claim 16, wherein the catalyst displays a molar ratio Y comprised in the inorganic carrier matrix and the zeolite to X comprised in the inorganic carrier matrix and the zeolite, calculated as YO.sub.2: X.sub.2O.sub.3, in the range of from 0.5:1 to 10:1.

21. The catalyst of claim 16, wherein the zeolite has a framework structure type selected from the group consisting of FAU, GIS, MOR, LTA, FER, TON, MTT, BEA, MEL, MWW, MFS, MFI, and a mixed type of two or more thereof.

22. A molding comprising the catalyst according to claim 16.

23. The molding of claim 22, wherein the molding displays a BET surface area which is comprised in the range of from 50 to 600 m.sup.2/g, wherein the BET surface area is determined according to ISO 9277:2010.

24. The molding of claim 22, wherein the molding displays a total pore volume comprised in the range of from 0.2 to 0.4 cm.sup.3/g, wherein the total pore volume is determined according to ISO 15901-2:2006.

25. The molding of claim 22, wherein the copper loading of the molding is in the range of from 2 to 10 wt.-%, calculated as the element and based on 100 wt.-% of the total amount of Y and X, calculated as the respective oxides YO.sub.2 and X.sub.2O.sub.3, contained in the molding.

26. The molding of claim 22, wherein the rare earth metal loading of the molding is in the range of from 5 to 15 wt.-% wt.-%, calculated as the element(s) and based on 100 wt.-% of the total amount of Y and X, calculated as the respective oxides YO.sub.2 and X.sub.2O.sub.3, contained in the molding.

27. The molding of claim 22, wherein the hydrogen temperature programmed reduction of the molding displays: a first peak in the range of from 175 to 225° C.; and a second peak in the range of from 175 to 275° C.; and wherein the integration of the first peak offers a concentration of reducible sites in the range of from 50 to 250 .Math.mol/g; and wherein the integration of the second peak offers a concentration of reducible sites in the range of from 225 to 600 .Math.mol/g.

28. A process for the production of a catalyst for the oxidation of hydrogen chloride to chlorine according to claim 16, the process comprising (i) providing a carrier comprising an inorganic carrier matrix and a zeolite, wherein the inorganic carrier matrix comprises Y, O, and optionally comprises X, wherein the zeolite comprises Y and O in its framework structure, and optionally comprises X in its framework structure, wherein Y is a tetravalent element and X is a trivalent element, wherein the zeolite is supported within the inorganic carrier matrix; (ii) subjecting the carrier to one or more ion-exchange procedures with copper, further with samarium, obtaining a precursor of the catalyst; (iii) calcining the precursor of the catalyst in a gas atmosphere, obtaining the catalyst.

29. A process for production of a molding comprising a catalyst, the process comprising (a) preparing a mixture comprising water, a binder or a precursor thereof and a catalyst according to claim 16; (b) shaping the mixture obtained from (a), obtaining a precursor of the molding; (c) calcining the precursor of the molding in a gas atmosphere, obtaining the molding.

30. A process for the oxidation of hydrogen chloride to chlorine comprising (A) providing a reactor comprising a reaction zone which comprises the catalyst according to claim 16; (B) passing a reactant gas stream into the reaction zone obtained from (A), wherein the reactant gas stream passed into the reaction zone comprises hydrogen chloride, and oxygen; subjecting said reactant gas stream to reaction conditions in said reaction zone; and removing a product stream from said reaction zone, said product stream comprising chlorine.

Description

DESCRIPTION OF THE FIGURES

[0310] FIG. 1 Results of long-stability test of the catalyst of Example 2 in the fixed-bed reactor according to Example 3 at 380° C. (1000 h, 1.4 NL/h HCl, 0.52 NL/h N.sub.2, 0.7 NL/h O.sub.2), including the results of the initial test conducted at 370° under different conditions (2.8 NL/h HCl, 1.04 NL/h N.sub.2, 1.4 NL/h O.sub.2).

[0311] FIG. 2 H.sub.2-TPR data of the molding of Example 2.

CITED LITERATURE

[0312] US 4,493,902 A [0313] US 5,023,220 A [0314] US 5,395,809 A [0315] US 5,559,067 A [0316] WO 2004/103558 A1 [0317] WO 2017/218879 A1 [0318] WO 95/12454 A1 [0319] EP 2418016 A1 [0320] JP 2010248062 A [0321] WO 2011/118386 [0322] EP 3549907 A1 [0323] EP 2481478 A1 [0324] CN 108097232 A [0325] EP 3450014 A1 [0326] EP 3097976 A1 [0327] CN 106517095