Calcination of Microporous Molecular Sieve Catalysts

Patent metadata

Field	Value
Publication number	US-2021394163-A1
Application number	US-201917284636-A
Country	US
Kind code	A1
Filing date	Oct 10, 2019
Priority date	Oct 30, 2018
Publication date	Dec 23, 2021
Grant date	—

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.

First 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.

2 . 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.

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

4 . 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.

5 . 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.

6 . 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.

7 . 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.

8 . 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.

9 . 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.

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

11 . 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.

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

13 . 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.

14 . 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.

15 . The catalyst of claim 1 , wherein the catalyst is combined with acyclic C5s to form cyclic C5 compounds including cyclopentadiene.

16 . (canceled)

17 . (canceled)

18 . (canceled)

19 . An article formed from cyclic C5 compounds of claim 14 , wherein the article is derived from a Diels-Alder reaction of the cyclic C5 compounds with a double bond containing compound.

20 . The article of claim 19 , wherein the cyclic C5 compounds are selected from the group consisting of cyclopentadiene, dicyclopentadiene, cyclopentene, cyclopentane, substituted norbornenes, 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 norbornene or substituted norbornenes or dicyclopentadiene, and combinations thereof.

21 . (canceled)

22 . 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.

23 . The process of claim 22 , 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.

24 . The process of claim 22 , 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.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Iaccino Larry L
• Bedard Jeremy W
• Bao Xiaoying
• Palermo Andrew P
• Mittal Nitish
• Milina Maria
• Levin Doron
• Gunther William R
• Lai Wenyih F
• Beutel Tilman W

Classifications

• B01J37/0009

  Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst · CPC title

• B01J6/002

  using rotating drums · CPC title

• C07C2529/46

  Iron group metals or copper · CPC title

• B01J29/46

  Iron group metals or copper · CPC title

• B01J37/0207

  Pretreatment of the support · CPC title