Delayed coking process

• US 4,797,197 A
• Filed: 01/06/1986
• Issued: 01/10/1989
• Est. Priority Date: 02/07/1985
• Status: Expired due to Fees

• Current Assignee: Renato M. Mallari
• Original Assignee: Renato M. Mallari
• Inventors: Mallari, Renato M.
• Primary Examiner(s): MCFARLANE, ANTHONY R
• Application Number:
  US06/816,366
• Time in Patent Office: 1,100 Days
• Field of Search: 208/131, 208/50
• US Class Current: 208/131
• CPC Class Codes: C10B 55/00 Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material cracking oils C10G
• CPC Class Codes: C10G 9/005 Coking (in order to produce liquid products mainly)

Abstract

The impediments of the prior art of delayed coking to enhanced hydrocarbons and minimum coke yields by way of pressure, temperature and recycle ratio have been minimized through the use of an interim drum between the heater and the coke drum, called in this invention as the flasher drum, whereby the heater effluent'"'"'s vapor is separated from its liquid portion which serves as the feed to the coke drum. The vapors from the flasher and coke drums are hence combined and fed to the fractionator for separation of products. This process of separating the coke drum and flasher drum vapors effects the control of hydrocarbon partial pressure and therefore the subsequent controlled vaporization of the heavy hydrocarbons in the coke drum which would otherwise react extensively in repetitive fashion to produce more coke than necessary. Additional heat is furnished to the liquid portion of the flasher drum by way of the various combinations of prescribed rates of hydrogen gas, steam and fuel gas, heated within the same coker heater in a separate coil or through a separate heater. The injection of hydrogen gas for the traditional case of delayed coking accomplishes only a very mild form of hydropyrolysis reaction and moreover, to replenish only the portion which has been lost by flashing in the flasher drum. A more moderate case of hydropyrolysis is possible in the flasher drum by operating at higher hydrogen partial pressure, higher hydrogen comsumption, higher temperature and higher residence time.

Claims

1. In a process for delayed coking of heavy petroleum residue feedstock within a coker heater, a coke drum and a fractionator, wherein the feedstock and recycle material are heated in said heater and then passed to said coke drum to produce coke and overhead vapors, wherein said vapors are fed into a bottom primary section of said fractionator, wherein a heavy gas oil product is fractionated and withdrawn from a secondary section of said fractionator, wherein a light gas oil and other lighter distillates products are fractionated and withdrawn from the succeeding sections of said fractionator, wherein a naphtha and gaseous constituents are fractionated and withdrawn from the top section of said fractionator, wherein a selected portion of said coke drum overhead vapors is condensed as heavy recycle in said primary section of said fractionator and combined with the preheated but unvaporized feedstock, wherein a selected quantity ratio of said heavy recycle and said feedstock is charged to said coker heater, wherein a flow rate of said combined heavy recycle and feedstock is adjusted to operate said coker heater at a selected inlet cold oil velocity, wherein said combined heavy recycle and feedstock is heated to thermal cracking temperature in said coker heater, wherein said temperature is increased further to effect more thermal reactions and additional vaporization of hydrocarbons, wherein a final temperature of the heater effluent is selected to minimize excessive coke deposition in the heater tubes, and wherein said heater effluent of vapor and liquid constituents consists solely of the products of thermal reactions and vaporization of said combined feedstock and heavy recycle at its prevailing pressure and temperature, the improvement comprising:

(a) Feeding and flashing said heater effluent at its prevailing temperature into a flasher drum wherein its vapor and liquid constituents are separated at a selected pressure, and wherein the separated liquid constituent is soaked at a selected residence time to allow further thermal reactions and vaporization in said liquid;

(b) Injecting selected flow rates of heated hydrogen-rich gas and one or more gases selected from the group of steam, light hydrocarbons and refinery fuel gas at a selected temperature into said separated liquid constituent to provide a stripping medium and to provide additional heat for thermal reactions, additional vaporization of hydrocarbons, and minimization of polycyclic aromatic polymerization of bimolecular radicals;

all of said heater effluent flashing, said effluent liquid constituent of thermal reactors, and combining of effluent vapor constituent with the vapor products of thermal reactions and vaporization from the liquid therein being performed in said flasher drum to produce a resultant liquid bottoms with more thermally reacted heavy hydrocarbons than said heater effluent liquid; and

to produce a resultant vapor with more gaseous constituents, more thermally converted light hydrocarbons, and more vaporized hydrocarbons than said heater effluent vapor;

(c) Injecting a selected flow rate of said resultant vapor at selected flasher drum pressure into the feed line of said coke drum at prevailing coke drum inlet pressure, in order to;

(i) reduce the partial pressure of hydrocarbons in the coke drum;

(ii) minimize the coke deposition in the coke drum feed line;

(iii) control the hardness and quality of the coke product;

(iv) control the coke drum overhead vapor temperature;

(d) Flashing to vapor and liquid constituents said resultant liquid bottoms at its prevailing temperature and at prevailing flasher drum pressure into the feed line of said coke drum at prevailing coke drum inlet pressure;

(e) Combining said flashed resultant liquid bottom with said injection vapor in said coke drum feed line at prevailing coke drum inlet pressure;

(f) Feeding said combination of flashed resultant liquid bottoms and injection vapor from the coke drum feed line into said coke drum; and

(g) Removing the remainder of said resultant vapor at its prevailing temperature and at selected flasher drum pressure for further processing.

4. The process of claim 1 or claim 2 or claim 3 wherein said heater effluent is flashed at a selected pressure of 50 psig to 350 psig and a selected heater effluent temperature of 900°

F. to 970°

F., and wherein the separated liquid constituent is soaked in said flasher drum at a selected residence time of 1 to 10 minutes to allow controlled thermal reactions and vaporization in said liquid.

5. The process of claim 1 or claim 2 wherein the flow rate of injection of said hydrogen-rich gas is at least 5.6 standard cubic feet per barrel of heater charge;

the flow rate of injection of steam is at least 3.6 pounds per barrel of heater charge; and

the flow rate of injection of said refinery fuel gas or light hydrocarbons is at least 55.3 standard cubic feet per barrel of heater charge;

all of said hydrogen-rich gas, steam, light hydrocarbons or refinery fuel gas being heated to a selected temperature of 970°

F. to 1,150°

F. prior to injection; and

all said flow rates being limited by one or more restrictions from the group of;

(a) premature coking in said flasher drum;

(b) maximum capacity of said coker fractionator; and

(c) maximum operating temperature of said flasher drum and said coke drums.

6. The process of claim 1 or claim 3 wherein the maximum flow rate of said injection vapor is selected to effect a volatile carbonaceous matter content of no less than four percent in the coke product.

7. The process of claim 1 or claim 2 wherein said heater effluent at its prevailing temperature is flashed at a total selected pressure sufficient to maintain a hydrogen partial pressure of up to 1,200 psig in said flasher drum at the separated liquid constituent is soaked in said flasher drum for at least five minutes residence time to effect the moderate hydropyrolysis of said liquid;

the flow rate of said heated hydrogen-rich gas injection being selected, and the residence time of said liquid being limited, to maintain the desired extent of hydropyrolysis reactions.

8. The process of claim 1 or claim 2 or claim 3 wherein a selected flow rate of liquid light gas oil is sprayed into said resultant flasher drum vapor to stop the continuation of coking reaction in said vapor before leaving said flasher drum, and wherein a selected flow rate of liquid light gas oil is further sprayed into the ensued partially quenched vapors in the flasher drum overhead vapor line to fully quench and control its temperature between 780°

F. and 840°

F.

9. The process of claim 1 or claim 2 or claim 3 wherein said removed resultant flasher drum vapor at its prevailing temperature and at selected flasher drum pressure is processed to recover the hydrocarbons by one or more methods selected from the group of:

(a) combining with the coke drum vapor overhead products a prevailing pressure for processing in said coker fractionator;

(b) feeding into an existing atmospheric crude distillation tower system;

(c) feeding into an existing vacuum reduced crude distillation tower system; and

(d) feeding into a separate and new or existing fractionating tower system other than (a), (b), and (c) specifically designed to process said resultant vapor.

10. The process of claim 1 or claim 2 or claim 3 wherein the flow rate of said resultant flasher drum vapor being removed is adapted to allow flexibility in adjustment of coker heater effluent temperature, heater tube inlet cold oil velocity and total feed ratio to effect the greatest conversion to hydrocarbon product and minimize coke production.

11. The process of claim 10 in which the heater is charged at an equivalent total feed ratio (TFR) of 1.20 to 1.40, an inlet cold oil velocity (COV) of 6.0 to 8.0 feet per second, and heated to a selected effluent temperature of between 935°

F. to 950°

F. for the case of heavy paraffinic residues, or between 950°

F. to 970°

F. for the case of light paraffinic stocks as reduced crude and aromatic stocks as cracked petroleum residues.

12. The process of claim 1 or claim 2 or claim 3 in which the heavy petroleum residue is selected from the group of atmospheric distillation residue, vacuum distillation residue, catalytic cracker decant oil, ethylene pyrolysis residue, asphalt, heavy fuel oil, thermal cracker residue, coal tar pitch, tar sand bitumen and mixture thereof, producing coke selected from the group of fuel grade coke, aluminum electrolytic anode grade coke, premium coke, and fluid coke having a high volatile carbonaceous matter.

2. In a process for delayed coking of heavy petroleum residue feedstock within a coker heater, a coke drum and a fractionator, wherein the feedstock and recycle material are heated in said heater and then passed to said coker drum to produce coke and overhead vapors, wherein said vapors are fed into a bottom primary section of said fractionator, wherein a heavy gas oil product is fractionated and withdrawn from a secondary section of said fractionator, wherein a light gas oil and other lighter distillates products are fractionated and withdrawn from the succeeding sections of said fractionator, wherein a naphtha and gaseous constituents are fractionated and withdrawn from the top section of said fractionator, wherein a selected portion of said coke drum overhead vapors is condensed as heavy recycle in said primary section of said fractionator and combined with the preheated but unvaporized feedstock, wherein a selected quantity ratio of said heavy recycle and said feedstock is charged to said coker heater, wherein a flow rate of said combined heavy recycle and feedstock is adjusted to operate said coker heater at a selected inlet cold oil velocity, wherein said combined heavy recycle and feedstock is heated to thermal cracking temperature in said coker heater, wherein said temperature is increased further to effect more thermal reactions and additional vaporization of hydrocarbons, wherein a final temperature of the heater effluent is selected to minimize excessive coke deposition in the heater tubes, and wherein said heater effluent of vapor and liquid constituents consists solely of the products of thermal reactions and vaporization of said combined feedstock and heavy recycle at its prevailing pressure and temperature, the improvement comprising:

(a) Feeding and flashing said heater effluent at its prevailing temperature into a flasher drum wherein its vapor and liquid constituents are separated at a selected pressure, and wherein the separated liquid constituent is soaked at a selected residence time to allow further thermal reactions and vaporization in said liquid;

(b) Injecting selected flow rates of heated hydrogen-rich gas and one or more gases selected from the group of steam, light hydrocarbons and refinery fuel gas at a selected temperature into said separated liquid constituent to provide a stripping medium and to provide additional heat for thermal reactions, additional vaporization of hydrocarbons, and minimization of polycyclic aromatic polymerization of bimolecular radicals;

all said heater effluent flashing, said effluent liquid constituent reacting operations, and combining of effluent vapor constituent with the vapor products of thermal reactions and vaporization from the liquid therein being performed in said flasher drum to produce a resultant liquid bottoms with more thermally reacted heavy hydrocarbons than said heater effluent liquid; and

to produce a resultant vapor with more gaseous constituents, more converted light hydrocarbons, and more vaporized hydrocarbons than said heater effluent vapor;

(c) Flashing to vapor and liquid constituents said resultant liquid bottoms at its prevailing temperature and at prevailing flasher drum pressure into the feed line of said coke drum at prevailing coke drum inlet pressure;

(d) Feeding said flashed resultant liquid bottoms from the coke drum feed line into said coke drum; and

(e) Removing said resultant vapor at its prevailing temperature and at selected flasher drum pressure for further processing.

3. In a process for delayed coking of heavy petroleum residue feedstock within a coker heater, a coke drum and a fractionator, wherein the feedstock and recycle material are heated in said heater and then passed to said coke drum to produce coke and overhead vapors, wherein said vapors are fed into a bottom primary section of said fractionator, wherein a heavy gas oil product is fractionated and withdrawn from a secondary section of said fractionator, wherein a light gas oil and other lighter distillates products are fractionated and withdrawn from the succeeding sections of said fractionator, wherein a naphtha and gaseous constituents are fractionated and withdrawn from the top section of said fractionator, wherein a selected portion of said coke drum overhead vapors is condensed as heavy recycle in said primary section of said fractionator and combined with the preheated but unvaporized feedstock, wherein a selected quantity ratio of said heavy recycle and said feedstock is charged to said coker heater, wherein a flow rate of said combined heavy recycle and feedstock is adjusted to operate said coker heater at a selected inlet cold oil velocity, wherein said combined heavy recycle and feedstock is heated to thermal cracking temperature in said coker heater, wherein a final selected temperature of the heater effluent is increased further to effect more thermal reactions and additional vaporization of hydrocarbons, and wherein said heater effluent of vapor and liquid constituents consists solely of the products of thermal reactions and vaporization of said combined feedstock and heavy recycle at its prevailing pressure and temperature, the improvement comprising;

(a) Feeding and flashing said heater effluent at its prevailing temperature into a flasher drum wherein its vapor and liquid constituents are separated at a selected pressure high enough to effect increasing the heater effluent temperature to at least 15°

F. higher than the maximum temperature achievable under subcritical pressure of about 50 psig without effecting excessive coke deposition in the heater tubes, and wherein the separated liquid constituent is soaked at a selected residence time to produce a resultant liquid bottoms with more thermally reacted heavy hydrocarbons than said heater effluent liquid; and

to produce a resultant vapor with more gaseous constituents, more thermally converted light hydrocarbons, and more vaporized hydrocarbons than said heater effluent vapor;

(b) Combining therein, as the equivalent of said resultant vapor from (a), the flasher drum vapor products of thermal reactions and vaporization with the heater effluent vapor constituent;

(c) Injecting a selected flow rate of said resultant vapor at selected flasher drum pressure into the feed line of said coke drum at prevailing coke drum inlet pressure, in order to;

(i) minimize coke deposition in the coke drum feed line;

(ii) control the hardness and quality of the coke product;

(iii) control the coke drum overhead vapor temperature;

(d) Flashing to vapor and liquid constituents said resultant liquid bottoms at its prevailing temperature and at prevailing flasher drum pressure into the feed line of said coke drum at prevailing coke drum inlet pressure;

(e) Combining said flashed resultant liquid bottoms with said injection vapor in said coke drum feed line at prevailing coke drum inlet pressure;

(f) Feeding said combination of flashed resultant liquid bottoms and injection vapor from the coke drum feed line into said coke drum; and

(g) Removing the remainder of said resultant vapor at its prevailing temperature and at selected flasher drum pressure for further processing.