Single step process for the simultaneous production of aromatics, naphthenics and isoparaffins using transition metal functionalized zeolite based catalyst

Patent metadata

Field	Value
Publication number	US-11318452-B2
Application number	US-202016937151-A
Country	US
Kind code	B2
Filing date	Jul 23, 2020
Priority date	Jul 24, 2019
Publication date	May 3, 2022
Grant date	May 3, 2022

Abstract

Hydrocarbon composition plays vital role in fuel quality. For gasoline/motor spirit applications the hydrocarbon should have more octane-possessing molecules from the groups of aromatics, naphthenics and isoparaffins, while n-paraffins are not preferred due to their poor octane. Among the high-octane groups, again aromatics occupy the top but not more than 35 vol % aromatics can be mixed in gasoline for engine applications to avoid harmful emission, But there is no single process that addresses so far the issue of co-producing all the desired hydrocarbon components in a single process. Thus, it is interesting to have a single once-through process working on single catalyst system to produce mixture of all three high-octane molecules namely, aromatics, naphthenics and isoparaffins directly from low-value, low-octane n-paraffin feed. Herein, we report a novel single-step catalytic process for the simultaneous production of aromatics, naphthenics and isoparaffins for gasoline and petrochemical applications.

First claim

We claim:

1. A catalyst consisting of:
a binder and a HZSM-5 zeolite in a weight ratio of HZSM-5 zeolite:binder as 3:2;

wherein the HZSM-5 zeolite has a framework of silicon and aluminium in a ratio of 100-300; wherein the HZSM-5 zeolite is a cobalt and platinum functionalized HZSM-5 zeolite, wherein the catalyst is a bi-metallic catalyst, wherein cobalt is from cobalt nitrate hexa hydrate salt, and platinum is from tetra amine platinum (II) nitrate salt, wherein the catalyst has acid sites originating from the presence of the HZSM-5 zeolite and a hydrogenation-dehydrogenation functionality by presence of the cobalt and platinum, wherein the catalyst is effective to promote a simultaneous production of aromatics, naphthenics and isoparaffins from n-heptane, and wherein a conversion of the n-heptane is 94.1 wt %.

2. The catalyst as claimed in claim 1 , wherein the binder is an inert alumina binder, and wherein the binder is pseudo boehmite.

3. The catalyst as claimed in claim 1 , wherein the catalyst has a surface area in a range of 350-430 m 2 /g, a total pore volume in a range of 0.32-0.37 cm 2 /g, and an average particle size in a range of 139-170 Å.

4. A process for preparing a catalyst, the process consisting of:
a. preparing a support by mixing a H-ZSM-5 zeolite with an inert alumina binder in a weight ratio of 3:2 (zeolite:binder) with continuous grinding to obtain a zeolite-binder support, wherein the H-ZSM-5 zeolite has a framework of silicon and aluminium in a ratio of 100-300, and wherein the alumina binder is pseudo boehmite;
b. adding 3 vol % glacial acetic acid to the zeolite-binder support and allowing peptization to obtain a resultant paste;
c. wet extruding the resultant paste for formation of wet extrudates, followed by drying and calcination;
d. impregnating cobalt on the extrudate obtained in step (c) by drop-wise addition of a solution of cobalt nitrate hexa hydrate salt for a uniform wet impregnation to obtain a cobalt functionalized zeolite extrudate followed by impregnating platinum on the cobalt functionalized zeolite extrudate by drop-wise addition of a solution of tetra amine platinum (II) nitrate salt for a uniform wet impregnation followed by drying and calcination to obtain the catalyst, wherein the catalyst is a bi-metallic catalyst, wherein the catalyst has acid sites originating from the presence of the HZSM-5 zeolite and a hydrogenation-dehydrogenation functionality by presence of the cobalt and platinum, wherein the catalyst is effective to promote a simultaneous production of aromatics, naphthenics and isoparaffins from n-heptane, and wherein a conversion of the n-heptane is 94.1 wt %.

5. The process as claimed in claim 4 , wherein the solution of cobalt nitrate hexa hydrate salt is prepared by dissolving the cobalt nitrate hexa hydrate salt in distilled water, and the solution of tetra amine platinum (II) nitrate salt is prepared by dissolving the tetra amine platinum (II) nitrate salt in distilled water.

6. A single-step catalytic process for simultaneous production of aromatics, naphthenics and isoparaffins the process consisting of:
a. preparing a support by mixing a HZSM-5 zeolite with an inert alumina binder in a weight ratio of 3:2 (zeolite:binder) with continuous grinding to obtain a zeolite-binder support, wherein the HZSM-5 zeolite has a framework of silicon and aluminium in a ratio of 100-300, and wherein the alumina binder is pseudo boehmite;
b. adding 3 vol % glacial acetic acid to the zeolite-binder support and allowing peptization to obtain a resultant paste;
c. wet extruding the resultant paste for formation of wet extrudates, followed by drying and calcination;
d. impregnating cobalt on the extrudate obtained in step (c) by drop-wise addition of a solution of cobalt nitrate hexa hydrate salt for a uniform wet impregnation to obtain a cobalt functionalized zeolite extrudate followed by impregnating platinum on the cobalt functionalized zeolite extrudate by drop-wise addition of a solution of tetra amine platinum (II) nitrate salt for a uniform wet impregnation followed by drying and calcination to obtain a catalyst, wherein the catalyst is a bi-metallic catalyst, wherein the catalyst has acid sites originating from the presence of the HZSM-5 zeolite and a hydrogenation-dehydrogenation functionality by presence of the cobalt and platinum, wherein the catalyst is effective to promote a simultaneous production of aromatics, naphthenics and isoparaffins from n-heptane, and wherein a conversion of the n-heptane is 94.1 wt %;
e. loading the catalyst into a micro-reactor and reducing the catalyst in presence of a continuous hydrogen flow; and
f. passing a feed over the catalyst obtained in step (a) at a feedstock flow rate ranging from 2-6 WHSV (weight hourly space velocity) and at a reaction temperature ranging from 350-550° C.; wherein the feed consists of n-heptane.

7. The process as claimed in claim 6 , wherein yields of isoparaffins are 72.7 wt % with aromatics and naphthenics in an amount of 7.5 wt % and 11 wt. %, respectively, and with a calculated research octane number (RON) of 56.

Assignees

• Council Scient Ind Res

Inventors

• Viswanadham Nagabhatla
• Ray Anjan
• Saxena Sandeep Kumar
• Panwar Rajiv

Classifications

• B01J35/45

  Nanoparticles · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J29/40

  of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively · CPC title

• B01J37/0036

  Grinding · CPC title

• C07C5/2708

  with crystalline alumino-silicates, e.g. molecular sieves · CPC title