# US 6,437,208 B1 · Making an olefin product from an oxygenate

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- Number: US 6,437,208 B1
- Document ID: US6437208B1
- Status: Granted
- Kind: B1
- Application number: 09/481,364
- Filed: 2000-01-11
- Granted: 2002-08-20
- Earliest claimed: 1999-09-29
- Assignees: ExxonMobil Chemical Patents Inc.
- Inventors: Keith H. Kuechler; Marcel J. G. Janssen; Stephen N. Vaughn; Shun C. Fung; Nicolas P. Coute; Jeffrey Scott Smith; James R. Lattner; Jeffrey L. White; Teng Xu; William L. Kuechler, Sr.; Machteld M. Mertens; Cornelius W. M. Van Oorschot
- Web page: https://patentgrep.com/patent/US6437208B1

## CPC

- C10G 50/00: Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- B01J 29/85: Silicoaluminophosphates [SAPO compounds]
- B01J 29/90: Regeneration or reactivation
- C10G 3/49: {containing crystalline aluminosilicates, e.g. molecular sieves}
- C10G 3/57: {according to the fluidised bed technique}
- C10G 3/62: {Catalyst regeneration}
- B01J 35/19: {Catalysts containing parts with different compositions}
- B01J 2229/123: in order to deactivate outer surface
- C10G 2300/1022: Fischer-Tropsch products
- C10G 2300/1029: Gas hydrates
- C10G 2300/4018: Spatial velocity, e.g. LHSV, WHSV
- C10G 2300/708: Coking aspect, coke content and composition of deposits
- C10G 2400/02: Gasoline
- C10G 2400/20: C2-C4 olefins
- C10G 2400/22: Higher olefins
- Y02P 30/20: using bio-feedstock
- Y02P 30/40: Ethylene production
- 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
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Disclosed is a method for making olefin product from an oxygenate-containing feedstock. In the method, a silicoaluminophosphate molecular sieve catalyst is contacted with the oxygenate-containing feedstock in a reactor at an average catalyst feedstock exposure index of at least 1.0. The method produces lower coke yield and provides an olefin product which is low in C1-C4 paraffin content. The invention is particularly effective in producing an olefin product having a very low propane content.

## Claims

### Claim 1

A method for continuous production of olefin product, comprising:
contacting a silicoaluminophosphate molecular sieve catalyst with an oxygenate-containing feedstock in a fluidized bed reactor;
regenerating continuously at least a portion of the molecular sieve catalyst after having been exposed to the oxygenate-containing feedstock;
recirculating the regenerated at least a portion of the molecular sieve catalyst into the fluidized bed reactor;
maintaining an average catalyst feedstock exposure index of at least 1.0;
maintaining, in the fluidized bed reactor, conditions effective to convert the oxygenate-containing feedstock to olefin product; and
producing the olefin product.

### Claim 2 (depends on 1)

The method of claim 1, wherein the oxygenate-containing feedstock comprises at least one compound selected from the group consisting of methanol; ethanol; n-propanol; isopropanol; C4-C20 alcohols; methyl ethyl ether; dimethyl ether; diethyl ether; di-isopropyl ether; formaldehyde; dimethyl carbonate; dimethyl ketone; acetic acid; and mixtures thereof.

### Claim 3 (depends on 1)

The method of claim 1, wherein the silicoaluminophosphate catalyst comprises a silicoaluminophosphate molecular sieve and a binder.

### Claim 4 (depends on 3)

The method of claim 3, wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, metal containing SAPOs thereof, and mixtures thereof.

### Claim 5 (depends on 3)

The method of claim 3, wherein the silicoaluminophosphate molecular sieve has a Si/Al2 molar ratio of less than 0.65.

### Claim 6 (depends on 1)

The method of claim 1, wherein the oxygenate-containing feedstock is contacted with the silicoaluminophosphate catalyst at 200-700° C.

### Claim 7 (depends on 1)

The method of claim 1, wherein the oxygenate-containing feedstock is contacted with the silicoaluminophosphate molecular sieve catalyst in the fluidized bed reactor at an average gas superficial velocity of greater than 1 meter per second.

### Claim 8 (depends on 1)

The method of claim 1, wherein the olefin product is contacted with a polyolefin-forming catalyst under conditions effective to form a polyolefin.

### Claim 9

A method for converting an oxygenate-containing feedstock to an olefin product, comprising:
contacting an oxygenate-containing feedstock with a silicoaluminophosphate catalyst in a fluidized bed reactor under conditions effective to convert the oxygenate-containing feedstock to an olefin product;
separating the olefin product from the catalyst;
regenerating a portion of the separated catalyst;
recirculating the regenerated catalyst into the fluidized bed reactor contacting the regenerated catalyst with the oxygenate-containing feedstock in the fluidized bed reactor; and
selecting a recirculation rate for the regenerated catalyst to maintain an average catalyst feedstock exposure index of at least 1.0.

### Claim 10 (depends on 9)

The method of claim 9, wherein the oxygenate-containing feedstock comprises at least one compound selected from the group consisting of methanol; ethanol; n-propanol; isopropanol; C4 C20 alcohols; methyl ethyl ether; dimethyl ether; diethyl ether; di-isopropyl ether; formaldehyde; dimethyl carbonate; dimethyl ketone; acetic acid; and mixtures thereof.

### Claim 11 (depends on 9)

The method of claim 9, wherein the silicoaluminophosphate catalyst comprises a silicoaluminophosphate molecular sieve and a binder.

### Claim 12 (depends on 11)

The method of claim 11, wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, metal containing SAPOs thereof, and mixtures thereof.

### Claim 13 (depends on 11)

The method of claim 11, wherein the silicoaluminophosphate molecular sieve has a Si/Al2 molar ratio of less than 0.65.

### Claim 14 (depends on 11)

The method of claim 11, wherein the oxygenate-containing feedstock is contacted with the silicoaluminophosphate molecular sieve catalyst in the fluidized bed reactor at an average gas superficial velocity of greater than 1 meter per second.

### Claim 15 (depends on 9)

The method of claim 9, wherein the oxygenate-containing feedstock is contacted with the silicoaluminophosphate catalyst at 200-700° C.

### Claim 16 (depends on 9)

The method of claim 9, wherein regeneration is carried out under conditions effective to obtain a regenerated catalyst having a coke content of less than 2 wt. %.

### Claim 17 (depends on 9)

The method of claim 9, wherein the regenerated catalyst is contacted with the separated olefin product prior to contacting with additional oxygenate-containing feedstock.

### Claim 18 (depends on 9)

The method of claim 9, wherein additional silicoaluminophosphate catalyst is added to the regenerated catalyst and the combination of additional and regenerated catalyst is contacted with additional feedstock.

### Claim 19 (depends on 9)

The method of claim 9, wherein the olefin product is contacted with a polyolefin-forming catalyst under. conditions effective to form a polyolefin.

### Claim 20

A method for converting an oxygenate-containing feedstock to an olefin product, comprising:
contacting an oxygenate-containing feedstock with a silicoaluminophosphate catalyst in a fluidized bed reactor under conditions effective to convert the oxygenate-containing feedstock to an olefin product;
separating the olefin product from the catalyst;
separating the separated catalyst into a first catalyst portion and a second catalyst portion;
regenerating the first catalyst portion under conditions effective to obtain a regenerated catalyst having a coke content of less than 2 wt. %;
combining the regenerated catalyst portion with the second catalyst portion to from a combined catalyst portion;
recirculating the combined catalyst portion into the fluidized bed reactor;
contacting the combined catalyst portion with the oxygenate-containing feedstock in the fluided bed reactor; and
maintaining an average catalyst feedstock exposure index of at least 1.0.

### Claim 21 (depends on 20)

The method of claim 20, wherein the oxygenate-containing feedstock comprises at least one compound selected from the group consisting of methanol; ethanol; n-propanol; isopropanol; C4-C20 alcohols; methyl ethyl ether; dimethyl ether; diethyl ether; di-isopropyl ether; formaldehyde; dimethyl carbonate; dimethyl ketone; acetic acid; and mixtures thereof.

### Claim 22 (depends on 20)

The method of claim 20, wherein the silicoaluminophosphate catalyst comprises a silicoaluminophosphate molecular sieve and a binder.

### Claim 23 (depends on 22)

The method of claim 22, wherein the silicoaluminophosphate molecular sieve comprises at least one molecular sieve selected from the group consisting of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, metal containing SAPOs thereof, and mixtures thereof.

### Claim 24 (depends on 22)

The method of claim 22, wherein the silicoaluminophosphate molecular sieve has a Si/Al2 molar ratio of less than 0.65.

### Claim 25 (depends on 20)

The method of claim 20, wherein the oxygenate-containing feedstock is contacted with the silicoaluminophosphate catalyst at 200-700° C.

### Claim 26 (depends on 25)

The method of claim 25, wherein the oxygenate-containing feedstock is contacted with the silicoaluminophosphate molecular sieve catalyst in the fluidized bed reactor at an average gas superficial velocity of greater an 1 meter per second.

### Claim 27 (depends on 20)

The method of claim 20, wherein the regenerated catalyst is contacted with the separated olefin product prior to combining with the second catalyst portion.

### Claim 28 (depends on 20)

The method of claim 20, wherein the olefin product is contacted with a polyolefin-forming catalyst under conditions effective to form a polyolefin.