# US 11,701,645 B2 · Calcination of microporous molecular sieve catalysts

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- Number: US 11,701,645 B2
- Document ID: US11701645B2
- Status: Granted
- Kind: B2
- Application number: 17/284,636
- Filed: 2019-10-10
- Published: 2021-12-23
- Granted: 2023-07-18
- Earliest claimed: 2018-10-30
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Larry L. Iaccino; Jeremy W. Bedard; Xiaoying Bao; Andrew P. Palermo; Nitish Mittal; Maria Milina; Doron Levin; William R. Gunther; Wenyih F. Lai; Tilman W. Beutel
- Web page: https://patentgrep.com/patent/US11701645B2

## CPC

- B01J 23/42: Platinum
- B01J 29/44: Noble metals
- B01J 6/002: {using rotating drums}
- B01J 6/004: {using hot gas streams in which the material is moved}
- B01J 8/0285: {Heating or cooling the reactor (for tubular reactors in furnaces B01J8/062)}
- B01J 8/1836: {Heating and cooling the reactor (B01J8/42 takes precedence)}
- B01J 23/50: Silver
- B01J 23/72: Copper
- B01J 23/8926: {Copper and noble metals}
- B01J 29/46: Iron group metals or copper
- B01J 37/0009: {Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst}
- B01J 37/0207: {Pretreatment of the support}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/082: {Decomposition and pyrolysis}
- C07C 5/373: with simultaneous isomerisation
- B01J 2208/00123: Fingers
- B01J 2208/065: Heating or cooling the reactor
- C07C 2529/44: Noble metals
- C07C 2529/46: Iron group metals or copper
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

A catalyst comprising a microporous crystalline metallosilicate having a Constraint Index of 12, or 10, or 8, or 6 or less, a binder, a Group 1 alkali metal or a compound thereof and/or a Group 2 alkaline earth metal or a compound thereof, a Group 10 metal or a compound thereof, and, optionally, a Group 11 metal or a compound thereof; wherein the catalyst is calcined in a first calcining step before the addition of the Group 10 metal or compound thereof and optionally the Group 11 metal or compound thereof; and wherein the first calcining step includes heating the catalyst to first temperatures of greater than 500° C.; and wherein the catalyst is calcined in a second calcining step after the addition of the Group 10 metal or compound thereof and optionally the Group 11 metal or compound thereof wherein the second calcining step includes heating the catalyst to temperatures of greater than 400° C.

## Claims

### Claim 1

A catalyst comprising: (i) a microporous crystalline metallosilicate having a Constraint Index of 12 or less, (ii) a binder, (iii) a Group 1 alkali metal or a compound thereof and/or a Group 2 alkaline earth metal or a compound thereof, (iv) a Group 10 metal or a compound thereof, and, (v) optionally a Group 11 metal or a compound thereof; wherein the catalyst is calcined in a first calcining step of calcining the catalyst before the addition of the Group 10 metal or compound thereof and optionally the Group 11 metal or compound thereof; and wherein the first calcining step includes heating the catalyst to temperatures of greater than 500° C.; and calcinating the catalyst in a second calcining step after the addition of the Group 10 metal or compound thereof and optionally the Group 11 metal or compound thereof wherein the second calcining step includes heating the catalyst to temperatures of greater than 400° C.

### Claim 2 (depends on 1)

The catalyst of claim 1, wherein the catalyst is calcined in either first or second calcining steps in a rotary calciner or a fixed bed calciner in an air atmosphere.

### Claim 3 (depends on 1)

The catalyst of claim 1, wherein the first temperature is greater than 525° C.; and wherein the second temperature is greater than 450° C.

### Claim 4 (depends on 1)

The catalyst of claim 1, wherein the catalyst is calcined in either the first or second calcining steps by heating at 500° C. to 800° C. and then holding in continuous air (oxygen/nitrogen) flow at this temperature for 0.5 to 1 hour.

### Claim 5 (depends on 1)

The catalyst of claim 1, wherein the second calcination step is performed at least partially in conjunction with the process unit where the converting of acyclic C5s to cyclic C5 compounds is performed.

### Claim 6 (depends on 1)

The catalyst of claim 1, wherein the calcined catalyst presents an IR band intensity ratio greater than about 0.06 of the integrated IR band area at 1445 cm−1 measured after adsorption and evacuation of pyridine at 150° C. divided by the integrated IR band area of silica bands between 2100 cm−1 and 1740 cm−1 measured after evacuation at 400° C.

### Claim 7 (depends on 1)

The catalyst of claim 1, wherein the catalyst is formed into one or more of the shapes of extrudates (cylindrical, lobed, asymmetric lobed, spiral lobed), spray dried particles, oil drop particles, mulled particles, spherical particles, and/or wash coated substrates; wherein the substrates may be extrudates, spherical particles, foams, microliths and/or monoliths.

### Claim 8 (depends on 1)

The catalyst of claim 1, wherein the microporous crystalline metallosilicate comprises a metallosilicate framework type selected from the group consisting of MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO, and FAU.

### Claim 9 (depends on 1)

The catalyst of claim 1, wherein the microporous crystalline metallosilicate is an aluminosilicate selected from the group consisting of Zeolite beta, mordenite, faujasite, Zeolite L, ZSM-5, ZSM-11, ZSM-30, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, MCM-22 family material, and mixtures thereof.

### Claim 10 (depends on 1)

The catalyst of claim 1, wherein the binder is selected from silica, titania, zirconia, alkali metal silicates, Group 13 metal silicates, carbides, nitrides, aluminum phosphate, aluminum molybdate, aluminate, surface passivated alumina, or mixtures thereof.

### Claim 11 (depends on 1)

The catalyst of claim 1, wherein the molar ratio of the Group 1 alkali metal to aluminum is at least 1, and/or the molar ratio of the Group 2 alkaline earth metal to aluminum is at least 1 and the Group 1 alkali metal is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and mixtures of two or more thereof, and/or the Group 2 alkaline earth metal is selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, and mixtures thereof.

### Claim 12 (depends on 1)

The catalyst of claim 1, wherein the catalyst has an Alpha Value of less than 14.

### Claim 13 (depends on 1)

The catalyst of claim 1, wherein the Group 10 metal is platinum, and wherein the platinum is derived from compounds selected from the group consisting of platinum nitrate, chloroplatinic acid, platinous chloride, platinum amine compounds, tetraamine platinum hydroxide, and mixtures thereof.

### Claim 14 (depends on 1)

The catalyst of claim 1, wherein the optional Group 11 metal is included, and the Group 11 metal includes copper and/or silver, wherein the copper is derived from copper nitrate, copper nitrite, copper acetate, copper hydroxide, copper acetylacetonate, copper carbonate, copper lactate, copper sulfate, copper phosphate, copper chloride, or mixtures thereof, and wherein the silver is derived from silver nitrate, silver nitrite, silver acetate, silver hydroxide, silver acetylacetonate, silver carbonate, silver lactate, silver sulfate, silver phosphate, or mixtures thereof.

### Claim 15 (depends on 1)

The catalyst of claim 1, wherein the catalyst is combined with acyclic C5 s to form cyclic C5 compounds including cyclopentadiene.

### Claim 16 (depends on 15)

An article formed from cyclic C5 compounds of claim 15, wherein the article is derived from a Diels-Alder reaction of the cyclic C5 compounds with a double bond containing compound.

### Claim 17 (depends on 16)

The article of claim 16, wherein the cyclic C5 compounds are selected from the group consisting of cyclopentadiene, dicyclopentadiene, cyclopentene, cyclopentane, substituted norbomenes, Diels Alder (conjugated diene+substituted diene) reaction derivatives of cyclopentadiene, cyclic olefin copolymers, cyclic olefin polymers, polycyclopentene, unsaturated polyester resins, hydrocarbon resin tackifiers, formulated epoxy resins, polydicyclopentadiene, metathesis polymers of norbomene or substituted norbomenes or dicyclopentadiene, and combinations thereof.

### Claim 18

A process to make a catalyst comprising: (i) providing a microporous crystalline metallosilicate having a Constraint Index of 12, or 10, or 8, or 6 or less, (ii) a binder, (iii) a Group 1 alkali metal or a compound thereof and/or a Group 2 alkaline earth metal or a compound thereof, (iv) a Group 10 metal or a compound thereof, and, (v) optionally a Group 11 metal or a compound thereof; calcining in a first calcination step the combination of materials before the addition of the Group 10 metal or compound and optional Group 11 metal or compound thereof; adding the Group 10 metal or compound thereof and then calcining in a second calcination step prior to addition of the optional Group 11 metal; adding the optional Group 11 metal or compound thereof and then calcining in a third calcination step wherein calcining includes heating the catalyst to temperatures of greater than 500° C. in the first calcination step and includes heating the catalyst to temperatures of greater than 400° C. in the second calcination step and includes heating the catalyst to temperatures of greater than 500° C. in the third calcination step.

### Claim 19 (depends on 18)

The process of claim 18, wherein the first calcination step takes place at a temperature greater than 525° C.; wherein the second calcination step takes place at a temperature greater than 425° C.; and wherein the third calcination step takes place at a temperature greater than 550° C.

### Claim 20 (depends on 18)

The process of claim 18, wherein the catalyst is calcined in any of the calcination steps by heating at 500° C. to 800° C. and then holding in continuous air (oxygen/nitrogen) flow at this temperature for 0.5 to 1 hour.