# US 10,864,507 B2 · Method for the synthesis of a ZSM-22 zeolite, a metal containing zeolite and its application in hydromerization of long chain n-paraffins

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- Number: US 10,864,507 B2
- Document ID: US10864507B2
- Status: Granted
- Kind: B2
- Application number: 16/300,179
- Filed: 2017-05-10
- Published: 2019-06-13
- Granted: 2020-12-15
- Earliest claimed: 2016-05-11
- Assignees: Bharat Petroleum Corporation Limited
- Applicants: Bharat Petroleum Corporation Limited
- Inventors: Ananth Kishore Kumar Sontyana; Kuppusamy Munusamy; Sayanti Ghosh; Shivanand Mukund Pai; Lalit Kumar; Mahesh Wamanrao Kasture; Bharat Lakshman Newalkar
- Web page: https://patentgrep.com/patent/US10864507B2

## CPC

- B01J 29/7484: {TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22}
- B01J 21/04: Alumina
- B01J 29/7042: {TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22}
- B01J 29/7684: {TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22}
- B01J 35/394: {Metal dispersion value, e.g. percentage or fraction}
- B01J 35/613: {10-100 m2/g}
- B01J 35/615: {100-500 m2/g}
- B01J 37/0009: {Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst}
- B01J 37/0018: {Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/082: {Decomposition and pyrolysis}
- B01J 37/30: Ion-exchange
- C01B 39/48: using at least one organic template directing agent
- C07C 5/2708: {with crystalline alumino-silicates, e.g. molecular sieves}
- C10G 45/64: containing crystalline alumino-silicates, e.g. molecular sieves
- B01J 2229/186: not in framework positions
- C07C 2521/04: Alumina
- C07C 2529/74: Noble metals
- C07C 2529/76: Iron group metals or copper
- C10G 2300/1011: Biomass
- C10G 2300/1022: Fischer-Tropsch products
- Y02P 30/20: using bio-feedstock
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention provides a process for preparing a zeolite by hydrothermal heating of silica precursor and alumina precursor along with a combination of two structure-directing organic templates, N,N-dimethyl formamide and 1,6-diaminohexane in the presence of an alkali. The use of two structure-directing organic templates, not only reduces the crystallization time but also enables the preparation of more catalytically active ZSM-22 of submicron crystallite size. The present invention also provides a process of preparing a noble metal containing zeolite catalyst for hydroisomerization of long chain n-paraffins.

## Claims

### Claim 1

A process for the synthesis of zeolite from a reaction mixture comprising silica and alumina precursors along with a combination of two structure-directing organic templates, N,N-dimethyl formamide and 1,6-diaminohexane in the presence of an alkali and maintaining said reaction mixture at a sufficient temperature to crystallize the zeolite and recovering the zeolite wherein the zeolite is selected from zeolites of the TON framework structure.

### Claim 2 (depends on 1)

The process as claimed in claim 1, wherein the zeolite is ZSM-22.

### Claim 3 (depends on 1)

The process as claimed in claim 1, wherein said silica precursor is selected from the group consisting of silica sols, tetraalkyl orthosilicates, silicon dioxides such as fumed silicas and precipitated silicas.

### Claim 4 (depends on 1)

The process as claimed in claim 1, wherein said alumina precursor is Al2(SO4)3.18H2O.

### Claim 5 (depends on 1)

The process as claimed in claim 1, wherein the mole ratio of organic 1,6-diaminohexane and N,N-dimethyl formamide is in the range of 1:0.1 to 1:10.

### Claim 6 (depends on 1)

The process as claimed in claim 1, wherein the alkali is sodium hydroxide, potassium hydroxide or combination thereof.

### Claim 7 (depends on 1)

The process as claimed in claim 1, wherein the molar ratio of SiO2/Al2O3 in the zeolite is not more than 300.

### Claim 8 (depends on 1)

The process as claimed in claim 1, further comprising preparing a noble metal containing zeolite catalyst comprising the steps:
(a) calcining the zeolite at sufficient temperature to decompose the organic templates;
(b) converting the zeolite to its acidic form by ion-exchanging with ammonium nitrate and followed by calcination at sufficient temperature to decompose ammonium ions;
(c) treating the acidic form with a metal by the process of ion-exchange with a metal precursor salt to obtain noble metal loaded acidic form of the zeolite;
(d) drying the metal loaded acidic form of the zeolite to obtain a dried material;
(e) extruding the dried material with a binder selected from the group consisting of clays, silicas, aluminas, metal oxides, and mixtures thereof to obtain an extruded catalyst; and
(f) calcining the extruded catalyst under constant air flow to obtain a metal-containing zeolite catalyst.

### Claim 9 (depends on 8)

The process as claimed in claim 8, wherein the acidic form in step (a) is H form which is obtained by exchanging Na+ or K+ or combination of both forms of zeolite with ammonium nitrate and followed by calcination.

### Claim 10 (depends on 9)

The process as claimed in claim 9, wherein said acidic H-form has a surface area in the range of 100-320 m2/gm.

### Claim 11 (depends on 9)

The process as claimed in claim 9, wherein said acidic H-form zeolite has a crystal size of <1 micron.

### Claim 12 (depends on 9)

The process as claimed in claim 9, wherein said acidic H-form has external surface area in the range of 10-80 m2/gm.

### Claim 13 (depends on 9)

The process as claimed in claim 9, wherein the acidic H-form has acidity in the range of 50-300 μmol/gm.

### Claim 14 (depends on 8)

The process as claimed in claim 8, wherein the steps (a and b) are carried out at 550° C.

### Claim 15 (depends on 8)

The process as claimed in claim 8, wherein said metal containing catalyst has metal dispersion over 10 to 95%.

### Claim 16 (depends on 8)

The process as claimed in claim 8, wherein the acidic H-form is loaded with Group-VIII metal by ion-exchange using a precursor salt.

### Claim 17 (depends on 16)

The process as claimed in claim 16, wherein said platinum salt used for ion-exchange is tetra-ammonium platinum nitrate complex.

### Claim 18 (depends on 16)

The process as claimed in claim 16, wherein the wt % of platinum in the metal containing catalyst is 0.05-3 wt %.

### Claim 19 (depends on 8)

The process as claimed in claim 8, wherein said binder is in the percentage of 30 to 70%.

### Claim 20 (depends on 8)

The process as claimed in claim 8, wherein in step(e) 30% w/w to 70% w/w of the dried material is extruded with 70% w/w to 30% w/w of binder.

### Claim 21 (depends on 8)

The process as claimed in claim 8, wherein in step(f) calcination of the extruded catalyst is at 250-400° C. under constant air flow.

### Claim 22 (depends on 1)

The process according to claim 1, wherein the crystallization temperature is in the range of 130 to 180° C.

### Claim 23 (depends on 1)

The process according to claim 1, wherein the crystallization time is in range between 10-96 hrs.