# US 2004/0069682 A1 · Modified thermal processing of heavy hydrocarbon feedstocks

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- Number: US 2004/0069682 A1
- Document ID: US20040069682A1
- Status: Published application
- Kind: A1
- Application number: 10/419,053
- Filed: 2003-04-17
- Published: 2004-04-15
- Earliest claimed: 2002-10-11
- Assignees: Ivanhoe Energy, Inc.
- Inventors: Barry Freel; Jerry F. Kriz; Doug Clarke
- Web page: https://patentgrep.com/patent/US20040069682A1

## CPC

- C10G 70/00: Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
- C10G 9/28: with preheated moving solid material
- C10G 51/023: {only thermal cracking steps}
- C10G 2300/1033: Oil well production fluids
- C10G 2300/107: Atmospheric residues having a boiling point of at least about 538 °C
- C10G 2300/1077: Vacuum residues
- C10G 2300/203: Naphthenic acids, TAN
- C10G 2300/207: Acid gases, e.g. H2S, COS, SO2, HCN
- C10G 2300/405: Limiting CO, NOx or SOx emissions
- C10G 2300/807: Steam
- 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

## Abstract

The present invention is directed to the upgrading of heavy petroleum oils of high viscosity and low API gravity that are typically not suitable for pipelining without the use of diluents. It utilizes a short residence-time pyrolytic reactor operating under conditions that result in a rapid pyrolytic distillation with coke formation. Both physical and chemical changes taking place lead to an overall molecular weight reduction in the liquid product and rejection of certain components with the byproduct coke. The liquid product is upgraded primarily because of its substantially reduced viscosity, increased API gravity, and the content of middle and light distillate fractions. While maximizing the overall liquid yield, the improvements in viscosity and API gravity can render the liquid product suitable for pipelining without the use of diluents. This invention particularly relates to reducing sulfur emissions during the combustion of byproduct coke (or coke and gas), to reducing the total acid number (TAN) of the liquid product, and to reducing the hydrogen sulfide content of one, or more than one component of the product stream. The method comprises introducing a particulate heat carrier into an up-flow reactor, introducing the feedstock at a location above the entry of the particulate heat carrier, allowing the heavy hydrocarbon feedstock to interact with the heat carrier for a short time, separating the vapors of the product stream from the particulate heat carrier and liquid and byproduct solid matter, regenerating the particulate heat carrier in the presence of the calcium compound, and collecting a gaseous and liquid product from the product stream.

## Claims

### Claim 1

A method of reducing the hydrogen sulfide content of one, or more than one component of a product stream derived from rapid thermal processing of a heavy hydrocarbon feedstock, comprising:
(i) rapid thermal processing of the heavy hydrocarbon feedstock in the presence of a calcium compound;
(ii) rapid thermal processing of the heavy hydrocarbon feedstock in the presence of a calcium compound, and regeneration of a particulate heat carrier in a reheater in the presence of a calcium compound, or
(iii) rapid thermal processing of the heavy hydrocarbon feedstock, and regeneration of a particulate heat carrier in a reheater in the presence of a calcium compound.

### Claim 2 (depends on 1)

The method of claim 1, wherein the rapid thermal processing comprises allowing the heavy hydrocarbon feedstock to interact with the particulate heat carrier in a reactor for less than about 5 seconds, to produce the product stream, wherein the ratio of the particulate heat carrier to the heavy hydrocarbon feedstock is from about 10:1 to about 200:1.

### Claim 3 (depends on 2)

The method of claim 2, further comprising a step of removing a mixture comprising the product stream and the particulate heat carrier from the reactor.

### Claim 4 (depends on 3)

The method of claim 3, further comprising a step of separating the product stream and the particulate heat carrier from said mixture.

### Claim 5 (depends on 4)

The method of claim 4, further comprising a step of regenerating the particulate heat carrier in the reheater.

### Claim 6 (depends on 4)

The method of claim 4, further comprising a step of collecting a distillate product and a bottoms product from the product stream.

### Claim 7 (depends on 6)

The method of claim 6, wherein the bottoms product is subjected to a further step of rapid thermal processing.

### Claim 8 (depends on 7)

The method of claim 7, wherein the further step of rapid thermal processing comprises allowing the bottoms product to interact with a particulate heat carrier in the reactor for less than about 5 seconds, wherein the ratio of the particulate heat carrier to the heavy hydrocarbon feedstock is from about 10:1 to about 200:1 to produce a product stream.

### Claim 9 (depends on 2)

The method of claim 2, wherein the feedstock is combined with the calcium compound before being introduced into the reactor.

### Claim 10 (depends on 5)

The method of claim 5, wherein the reheater is run at a temperature in the range from about 600 to about 900° C.

### Claim 11 (depends on 5)

The method of claim 5, wherein the reheater is run at a temperature in the range of from about 600 to about 815° C.

### Claim 12 (depends on 5)

The method of claim 5, wherein the reheater is run at a temperature in the range of from about 700 to about 800° C.

### Claim 13 (depends on 2)

The method of claim 2, wherein the reactor is run at a temperature in the range from about 450° C. to about 600° C.

### Claim 14 (depends on 2)

The method of claim 2, wherein the reactor is run at a temperature in the range from about 480° C. to about 550° C.

### Claim 15 (depends on 5)

The method of claim 5, wherein the calcium compound is added to the reheater.

### Claim 16 (depends on 15)

The method of claim 15, wherein the calcium compound is added to both the reactor and to the reheater.

### Claim 17 (depends on 1)

The method of claim 1, wherein the amount of the calcium compound that is added is from about 0.2 to about 5 fold the stoichiometric amount of sulfur in the feedstock.

### Claim 18 (depends on 1)

The method of claim 1, wherein the amount of the calcium compound that is added is from about 1.7 to about 2 fold the stoichiometric amount of sulfur in the feedstock.

### Claim 19 (depends on 1)

The method of claim 1, wherein the calcium compound is selected from the group consisting of calcium acetate, calcium formate, calcium proprionate, a calcium salt-containing bio-oil composition, a calcium salt isolated from a calcium salt-containing bio-oil composition, Ca(OH)2, CaO, CaCO3, and a mixture thereof.

### Claim 20 (depends on 1)

The method of claim 1, wherein the calcium compound is combined with the feedstock and 0-5 (wt/wt) % water.

### Claim 21 (depends on 18)

The method of claim 18, wherein the water is in the form of steam.

### Claim 22 (depends on 1)

The method of claim 1, wherein sulfur-based gas emissions in flue gas are reduced.

### Claim 23 (depends on 1)

The method of claim 1, wherein TAN in a liquid product is reduced.

### Claim 24 (depends on 1)

The method of claim 1, wherein prior to the step of rapid thermal processing, the feedstock is introduced into a fractionation column that separates a volatile component of the feedstock from a liquid component of the feedstock, and the liquid component is subjected to rapid thermal processing.

### Claim 25 (depends on 24)

The method of claim 24, wherein the feedstock is combined with the calcium compound before being introduced into the fractionation column.