# US 12,179,176 B2 · Catalyst for paraffin dehydrogenation

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- Number: US 12,179,176 B2
- Document ID: US12179176B2
- Status: Granted
- Kind: B2
- Application number: 17/282,929
- Filed: 2019-10-04
- Published: 2021-12-16
- Granted: 2024-12-31
- Earliest claimed: 2018-10-05
- Assignees: Sabic Global Technologies B.V.
- Applicants: Sabic Global Technologies B.V.
- Inventors: Biju Maippan Devassy; Rekha Mahadevaiah; Prashant Kumar Raichur Krishtacharya; Vinod Sankaran Nair
- Web page: https://patentgrep.com/patent/US12179176B2

## CPC

- B01J 23/26: Chromium
- B01J 21/04: Alumina
- B01J 35/37: Crush or impact strength
- B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77)
- B01J 35/613: {10-100 m2/g}
- B01J 35/615: {100-500 m2/g}
- B01J 35/633: {less than 0.5 ml/g}
- B01J 37/0009: {Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst}
- B01J 37/0201: {Impregnation}
- B01J 37/0207: {Pretreatment of the support}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/082: {Decomposition and pyrolysis}
- C07C 5/3335: {with metals}
- B01J 23/10: of rare earths
- B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts
- C07C 2521/04: Alumina
- C07C 2523/10: of rare earths
- C07C 2523/26: Chromium
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

Rare earth element containing catalysts for dehydrogenating paraffins and the methods of making the catalysts are disclosed. A rare earth modified alumina support in eta-alumina form, theta-alumina form, or combinations thereof is impregnated with chromium-containing solution. The chromium-impregnated support is then subjected to calcination processes. The produced catalyst contains the rare earth element, chromium, and alumina. The crush strength of the produced catalyst is greater than 0.4 daN/mm.

## Claims

### Claim 1

A paraffin dehydrogenation catalyst having improved crush strength produced by a process comprising:
(a) providing a rare earth element modified alumina support in eta-alumina form comprising a rare earth element-containing compound comprising a rare earth element by:
(i) providing an eta-alumina support;
(ii) impregnating the eta-alumina support with a rare earth element compound containing solution to produce a first support; and
(iii) drying the first support and calcining the dried first support to obtain the rare earth element modified alumina support in eta-alumina form;
(b) impregnating the rare earth element modified alumina support with a chromium-containing solution to produce a second support;
(c) drying the second support to obtain the third support;
(d) calcining the third support to obtain the paraffin dehydrogenation catalyst; wherein the paraffin dehydrogenation catalyst has a crush strength greater than about 0.4 daN/mm, and further wherein the paraffin dehydrogenation catalyst contains 0.5 to 5 wt. % of a rare earth metal oxide, 30 to 40 wt. % of chromium (III) oxide, 0.1 to 5 wt. % of at least one alkali metal component, and the balance the eta-alumina; and wherein the at least one alkali metal component comprises a sodium compound, potassium compound, rubidium compound, cesium compound, or a combination thereof.

### Claim 2 (depends on 1)

The catalyst of claim 1, wherein the calcining at step (g) is performed at a calcination temperature of 700 to 1000° C.

### Claim 3 (depends on 1)

The catalyst of claim 1, wherein the providing in step (a) comprises:
(h) providing a precursor of an eta-alumina support;
(i) contacting the precursor with a rare earth element-containing compound containing solution to produce a contacted precursor;
(j) shaping the contacted precursor to produce shaped contacted precursor;
(k) drying the shaped contacted precursor to produce a dried contacted precursor and calcining the dried contacted precursor to produce the rare earth element modified support in eta-alumina form.

### Claim 4 (depends on 3)

The catalyst of claim 3, wherein the precursor of an eta-alumina support includes bayerite, RHO alumina, gel alumina, or combinations thereof.

### Claim 5 (depends on 3)

The catalyst of claim 3, wherein the shaping in step (j) comprises extrusion.

### Claim 6 (depends on 3)

The catalyst of claim 3, wherein the calcining at step (k) is performed at a calcination temperature of 700 to 1000° C.

### Claim 7 (depends on 3)

The catalyst of claim 3, wherein the rare earth element-containing compound includes a lanthanum compound, a cerium compound, a neodymium compound, or combinations thereof.

### Claim 8 (depends on 1)

The catalyst of claim 1, wherein the chromium-containing solution comprises alkali metal hydroxide, alkali metal chromate, alkali metal dichromate, or combinations thereof.

### Claim 9 (depends on 1)

The catalyst of claim 1, wherein the calcining at step (d) is performed at a calcination temperature of 650 to 850° C.

### Claim 10 (depends on 1)

The catalyst of claim 1, wherein the paraffin dehydrogenation catalyst has a surface area in a range of 60 to 120 m2/g.

### Claim 11

A method for producing a paraffin dehydrogenation catalyst, the method comprising the steps of:
(a) providing a rare earth element modified alumina support in eta-alumina form comprising a rare earth element-containing compound comprising a rare earth element by:
(i) providing an eta-alumina support;
(ii) impregnating the eta-alumina support with a rare earth element compound containing solution to produce a first support; and
(iii) drying the first support and calcining the dried first support to obtain the rare earth element modified alumina support in eta-alumina form;
(b) impregnating the rare earth element modified alumina support with a chromium-containing solution to produce a second support;
(c) drying the second support to obtain the third support;
(d) calcining the third support to obtain the paraffin dehydrogenation catalyst;
wherein the paraffin dehydrogenation catalyst has a crush strength greater than about 0.4 daN/mm,
wherein the paraffin dehydrogenation catalyst contains 0.5 to 5 wt. % of a rare earth metal oxide, 17 to 40 wt. % of chromium (III) oxide, 0.1 to 5 wt. % of at least one alkali metal component, and the balance the eta-alumina; and
wherein the at least one alkali metal component comprises a sodium compound, potassium compound, rubidium compound, cesium compound, or a combination thereof.

### Claim 12 (depends on 11)

The method of claim 11, wherein the method to produce the catalyst further comprises a shaping step.