Process for production of needle coke

Abstract

High-quality graphite/needle grade coke is produced with reduced impurity levels and improved coefficient of thermal expansion using an integrated hydrotreatment, catalytic cracking and coking reaction sections, employing a combination of highly paraffinic hydrotreated VGO stream and aromatic CLO stream, which is thereafter processed in a delayed coking section.

Claims

1. A process for production of graphite/needle grade coke with reduced impurity levels and improved coefficient of thermal expansion, wherein the process comprises: (a) routing a vacuum gas oil (VGO) feed to a riser reactor of a fluid catalytic cracking unit, wherein the VGO feed reacts with a hot catalyst supplied from a regenerator, and wherein the fluid catalytic cracking unit is operated at a reactor outlet temperature of 550 to 650° C., at a pressure in a range of 0.7 to 2.5 Kg/cm.sup.2 (g) and having a catalyst to oil ratio in a range of 10 to 25; (b) sending products of reaction from step (a) along with a catalyst to a stripper for separation of a hydrocarbon vapor product from the catalyst; (c) sending the hydrocarbon vapor product to a first fractionator column for separation into different products comprising off gases with naphtha, light cycle oil (LCO), and heavy cycle oil (HCO); (d) mixing a VGO stream with H.sub.2 and sending to a furnace for heating to obtain a hot feed; (e) sending the hot feed from step (d) to a fixed bed reactor, wherein hydrotreatment of the VGO stream occurs to obtain a hydrotreated VGO stream at a reactor pressure in a range of 30-55 Kg/cm.sup.2 (g) and a temperature in a range of 300-380° C., and wherein reaction products are sent to a high-pressure separator where lighter gases are removed and sent to a low-pressure separator; (f) sending a liquid after removing the lighter gases from the reaction products to a second fractionator column for further separation of lighter products; (g) routing a stream consisting of the hydrotreated VGO stream from the second fractionator column and a clarified oil (CLO) product fraction to a bottom section of the first fractionator column, wherein the clarified oil (CLO) product fraction is generated in the fluid catalytic cracking unit, wherein the hydrotreated VGO stream comprises aromatics about 19 wt % and a mixture of paraffins and naphthenes about 80 wt %, wherein the CLO product fraction comprises aromatics about 98 wt % and a mixture of paraffins and naphthenes about 2 wt %; (h) exchanging heat between the hydrotreated VGO stream and the CLO product fraction occurring in the bottom section of the first fractionator column and forming a homogenous mixture, wherein a lighter fraction in the hydrotreated VGO stream boiling at a temperature of not more than 350° C. is separated in the first fractionator column, wherein weight percentage of the hydrotreated VGO stream in the homogenous mixture is in a range of 20-50 wt %; (i) sending the homogenous mixture through a parallel filtration assembly for separation of entrained catalyst fines present; and (j) routing the homogenous mixture after catalyst removal to a third fractionator column of a delayed coking section.

2. The process as claimed in claim 1, wherein the homogenous mixture is mixed with an internal recycle fraction in the third fractionator column of the delayed coking section and is withdrawn from the third fractionator column as a secondary feed.

3. The process as claimed in claim 2, wherein the secondary feed is heated in a furnace and a hot feed is produced.

4. The process as claimed in claim 3, wherein the hot feed is sent to coke drums operated at a temperature in a range of 460-515° C., drum pressure in a range of 2-10 Kg/cm.sup.2 (g) and cycle time of 18-42 hrs for delayed coking reaction.

5. The process as claimed in claim 1, wherein a vapor product generated in the coke drums is sent to the third fractionator column for further separation into various streams comprising off gas with naphtha, light coker gas oil (LCGO), heavy coker gas (HCGO) and coker fuel oil (CFO).

6. The process as claimed in claim 1, wherein a needle coke produced in the coke drums is removed after a filling cycle by high pressure water jet cutting.

7. The process as claimed in claim 1, wherein after step (f) an aromatic CLO stream is injected at a bottom section of the second fractionator column to mix with the hydrotreated VGO stream.

8. The process as claimed in claim 1, wherein sulfur content of the CLO product fraction is not more than 1 wt % and sulfur content of the hydrotreated VGO stream is not more than 0.4 wt %.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 illustrates a schematic process flow diagram of the invented process; and

(2) FIG. 2 illustrates an embodiment of the invented process.

DETAILED DESCRIPTION OF THE INVENTION

(3) Those skilled in the art will be aware that the present disclosure is subject to variations and modifications other than those specifically described. It is to be understood that the present disclosure includes all such variations and modifications. The disclosure also includes all such steps of the process, features of the system, referred to or indicated in this specification, individually or collectively, and any and all combinations of any or more of such steps or features.

Definitions

(4) For convenience, before further description of the present disclosure, certain terms employed in the specification, and examples are collected here. These definitions should be read in the light of the remainder of the disclosure and understood as by a person of skill in the art. The terms used herein have their meanings recognized and known to those of skill in the art, however, for convenience and completeness, particular terms and their meanings are set forth below.

(5) The articles “a”, “an” and “the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.

(6) The terms “comprise” and “comprising” are used in the inclusive, open sense, meaning that additional elements may be included. It is not intended to be construed as “consists of only”.

(7) Throughout this specification, unless the context requires otherwise the word “comprise”, and variations such as “comprises” and “comprising”, will be understood to imply the inclusion of a stated element or step or group of element or steps but not the exclusion of any other element or step or group of element or steps.

(8) The term “including” is used to mean “including but not limited to”. “Including” and “including but not limited to” are used interchangeably.

(9) Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosure, the preferred methods, and materials are now described. All publications mentioned herein are incorporated herein by reference.

(10) The present disclosure is not to be limited in scope by the specific embodiments described herein, which are intended for the purposes of exemplification only. Functionally equivalent products and methods are clearly within the scope of the disclosure, as described herein.

(11) The present invention provides a process for production of graphite/needle grade coke using a highly paraffinic hydrotreated VGO stream mixed with CLO stream without employing any heat soaking step. The invention also provides an integration of VGO hydrotreater unit and Fluid catalytic cracking unit which increases the efficiency of catalyst removal from CLO stream as well as process heat integration. The invention also relates to the delayed coking process for production of needle coke.

(12) In an embodiment of the invention, the present invention provides a process for production of graphite/needle grade coke with reduced impurity levels and improved coefficient of thermal expansion, wherein the process comprises (a) routing a VGO feed (1) to a riser reactor (2) of a fluid catalytic cracking unit, wherein the VGO feed reacts with a hot catalyst supplied from a regenerator (4); (b) products of reaction from step (a) along with a catalyst are sent to a stripper (3) for separation of a hydrocarbon vapor product (5) from the catalyst; (c) the hydrocarbon vapor product (5) is sent to a first fractionator column (6) for separation into different products like off gases with naphtha (32), LCO (33), and HCO (34); (d) a VGO stream (7) is mixed with H2 (8) and is sent to a furnace (9) for heating; (e) hot feeds (10) from step (d) are sent to a fixed bed reactor (11), wherein the hydrotreatment of a vacuum gas oil occurs and reaction products (12) are sent to a high-pressure separator (13) where lighter gases (14) are removed and sent to a low-pressure separator; (f) remaining liquid (15) is sent to a second fractionator column (16) for further separation of lighter products (17); (g) a hydrotreated VGO stream (18) from the second fractionator column (16) is routed to a bottom section of the first fractionator column (6), wherein it is mixed with a CLO product fraction generated in the fluid catalytic cracking unit; (h) heat exchange between the hydrotreated VGO stream (18) and the CLO product fraction occurs in the bottom section of the first fractionator column (6) and a homogenous mixture is formed; (i) the homogenous mixture is sent through a parallel filtration assembly (20) for separation of entrained catalyst fines present coming through the CLO product fraction; and (j) the homogenous mixture after catalyst removal is routed to a third fractionator column (22) of a delayed coking section.

(13) In another embodiment of the invention, any lighter fraction in the hydrotreated VGO stream (18) boiling at a temperature of not more than 350° C. is separated in the first fractionator column (6).

(14) In yet another embodiment of the invention, the homogenous mixture is mixed with an internal recycle fraction in the third fractionator column (22) of the delayed coking section and is withdrawn from the third fractionator column (22) as a secondary feed (27).

(15) Further, in an embodiment of the invention, the secondary feed (27) is heated in a furnace (28) and a hot feed (29) is produced. This hot feed (29) is sent to a coke drums (30) for delayed coking reaction.

(16) In an embodiment of the invention, a vapor product (31) generated in the coke drums (30) is sent to the third fractionator column (22) for further separation into various streams like off gas with naphtha (26), LCGO (23), HCGO (24) and CFO (25). The needle coke produced in the coke drums (30) is removed after a filling cycle by high pressure water jet cutting.

(17) Additionally, an embodiment of the above process is that rather than sending the hydrotreated VGO stream (18) from the second fractionator column to the bottom section of the first fractionator column (6) where it is mixed with the CLO product fraction generated in the fluid catalytic cracking reactions, the aromatic CLO stream (60) is injected at the bottom section of the second fractionator column (59), which mixes with the hydrotreated VGO product.

(18) In yet another embodiment of the invention, the sulfur content of the CLO product fraction is not more than 1 wt % and sulfur content of the hydrotreated VGO stream is not more than 0.4 wt %. Also, the weight percentage of the hydrotreated VGO stream in the homogenous mixture is present in a range of 1-50 wt %.

(19) In an embodiment of the invention, the present invention provides an integrated system for production of graphite/needle grade coke, comprising of (a) a fluid catalytic cracking unit comprising (i) a riser reactor (2); (ii) a regenerator (4); and (iii) a stripper (3) for separation of vapor product (5); (b) a VGO hydrotreater comprising (i) a furnace (9); (ii) a fixed bed reactor (11) for hydrotreatment of vacuum gas oil; (iii) a high-pressure separator (13); and (iv) a second fractionator column (16) for separation of lighter products (17); (c) a first fractionator column (6), wherein a hydrotreated VGO stream (18) from the second fractionator column (16) is mixed with a CLO product fraction generated in the fluid catalytic cracking unit; (d) a parallel filtration assembly (20) for separation of entrained catalyst fines present coming through the CLO product fraction; and (e) a delayed coking section comprising (i) a third fractionator column (22); (ii) a furnace (28); and (iii) coke drums (30).

(20) In yet another embodiment of the invention, the VGO hydrotreater unit is operated at a reactor pressure in a range of 30-55 Kg/cm2 (g) and a temperature in a range of 300-380° C. The fluid catalytic cracking unit is operated at a high reactor outlet temperature of 550 to 650° C., preferably between 580 to 620° C. Reactor pressure shall vary in the range of 0.7 to 2.5 Kg/cm.sup.2 (g), preferably in the range of 0.8 to 1.5 Kg/cm.sup.2 (g). The catalyst to oil ratio is selected from a range of 10 to 25, preferably in the range of 15 to 20. Further, the delayed coking process is operated at a temperature in a range of 460-515° C., drum pressure in a range of 2-10 Kg/cm2 (g) and cycle time of 18-42 hrs.

(21) Feedstock:

(22) The hydrocarbon feedstock to be used in the process is selected from hydrocarbon feed streams like CLO, Coal tar pitch and hydrotreated VGO, wherein the hydrotreated VGO stream has lesser impurities like sulfur, nitrogen, etc., compared to the other feedstocks in the mixture. The feedstock to the fluid catalytic cracking unit for production of CLO is selected from hydrocarbon streams like VGO, hydrotreated VGO, atmospheric residue, etc. The sulfur content of the CLO is 1 wt % (max.) and that of hydrotreated VGO is 0.4 wt % (max.).

(23) Process Conditions:

(24) The VGO hydrotreater unit is operated at a reactor pressure in the range of 30-55 Kg/cm2 (g) and temperature of 300-380° C. The fluid catalytic cracking unit is operated at a high reactor outlet temperature of 550 to 650° C. Reactor pressure shall vary in the range of 0.7 to 2.5 Kg/cm.sup.2 (g). The catalyst to oil ratio is kept in the range of 10 to 25. The Delayed coking process section is carried out at a temperature range of 460-515° C., Drum pressure of 2-10 Kg/cm2 (g) and cycle time of 18-42 hrs. The weight percentage of Hydrotreated VGO in the mixture with CLO is kept in the range of 1-50 wt %, while feeding into the fractionator bottom section of the fluid catalytic cracking unit.

(25) Process Description:

(26) The process of the present invention is exemplified by, but not limited to the following figures.

(27) A schematic process flow diagram of the invented process is provided as FIG. 1. According to the main embodiment, VGO feed (1) is routed to the Riser reactor (2) of the fluid catalytic cracking unit where it reacts in contact with the hot catalyst supplied from the Regenerator (4) and the product of reactions along with catalyst are sent to the Stripper (3) for separation of the vapor product (5) from the catalyst. The hydrocarbon vapor product is sent to the first fractionator column (6) for separation into different products like off gases with naphtha (32), LCO (33), HCO (34), etc. Meanwhile, a VGO stream (7) is mixed with H.sub.2 (8) and is sent to a furnace (9) for heating. The hot feeds (10) are sent to a fixed bed reactor (11) where the hydro-treatment of the vacuum gas oil occur, and the reaction products (12) are sent to a high-pressure separator (13) where the lighter gases (14) are removed and sent to a low-pressure separator. The remaining liquid (15) is sent to a second fractionator column (16) for separation of further lighter products (17). The hydrotreated VGO stream (18) from the second fractionator column is routed to the bottom section of the first fractionator column (6) where it is mixed with the CLO product fraction generated in the fluid catalytic cracking reactions. In the bottom section of the said fractionator, the heat exchange between hydrotreated VGO and the CLO streams occur and form a homogeneous mixture. Any lighter fraction in the hydrotreated VGO boiling below 350° C. is separated in the said fractionator column. The combined mixed feed is then sent through the parallel filtration assembly (20) for separation of entrained catalyst fines present coming through the CLO stream. The mixed feed stream (21) after catalyst removal is routed to a third fractionator column (22) of the Delayed Coking section. In the bottom section of the third fractionator column, the mixed feedstock is mixed with the internal recycle fraction and is withdrawn from the column as the secondary feed (27). The secondary feed is heated in a furnace (28) and the hot feed (29) is sent to the coke drums (30) for delayed coking reactions. The vapor product (31) generated in the coke drums is sent to the fractionator column (22) for further separation into various streams like off gas with naphtha (26), LCGO (23), HCGO (24) and CFO (25). Needle coke which is produced in the coke drums are removed after a filling cycle by high pressure water jet cutting.

(28) An embodiment of the present invention is provided in FIG. 2. VGO stream (50) is mixed with H.sub.2 (51) and is sent to a furnace (52) for heating. The hot feeds (53) are sent to a fixed bed reactor (54) where the hydro-treatment of the vacuum gas oil occur, and the reaction products (55) are sent to a high-pressure separator (56) where the lighter gases (57) are removed and sent to a low-pressure separator. The remaining liquid (58) is sent to a second fractionator column (59) for separation of further lighter products (61). At the bottom section of the fractionator column, aromatic CLO stream (60) is injected, which mixes with the hydrotreated VGO product and the mixed feedstock (62) is then subjected to filtration (63) for separation of entrained catalyst fines present coming through the CLO stream. The mixed feed stream (21) after catalyst removal is routed to a third fractionator column (65) of the Delayed Coking section. In the bottom section of the third fractionator column, the mixed feedstock is further mixed with the internal recycle fraction and is withdrawn from the column as the secondary feed (66). The secondary feed is heated in a furnace (71) and the hot feed (72) is sent to the coke drums (73) for delayed coking reactions. The vapor product (74) generated in the coke drums is sent to the fractionator column (65) for further separation into various streams like off gas with naphtha (70), LCGO (67), HCGO (68) and CFO (69). Needle coke which is produced in the coke drums are removed after a filling cycle by high pressure water jet cutting.

EXAMPLES

(29) Having described the basic aspects of the present invention, the following non-limiting examples illustrate specific embodiment thereof. Those skilled in the art will appreciate that many modifications may be made in the invention without changing the essence of invention. The process of present invention is exemplified by the following non-limiting examples.

(30) In order to validate the process of present invention, aromatic CLO and hydrotreated VGO stream were collected, and the properties were analyzed, and the results are provided in the Table 1.

(31) TABLE-US-00001 TABLE 1 Properties of feedstock Property CLO HDT VGO Density, g/cc 1.1095 0.8991 CCR, wt % 6.1 0.05 Asphaltene 0.48 0.01 Sulfur, wt % 0.32 0.04 Nitrogen, wt % 0.077 0.016 Aromatics, wt % 98.2 19.3 Paraffins + Naphthenes, wt % 1.8 80.7

(32) In order to find out the Needle Coke quality which can be generated from the CLO stream alone, thermal cracking experiment (Run-1) using the same was carried out in a 1 bbl/day capacity Delayed Coker Pilot Plant. A furnace outlet temperature of 495° C. along with a pressure of 3 Kg/cm2 (g) was carried out.

(33) In order to simulate the integration of the VGO hydrotreater and FCCU, both the CLO and HDT VGO streams were blended offline at the desired ratios of 10 wt % and 20 wt % and thermal cracking experiments (Run-2 & Run-3) were carried out at the same experimental conditions as Run-1.

(34) The green coke samples generated from all runs were collected and subjected to calcination in a laboratory coke calciner unit and the properties like Coefficient of Thermal Expansion (CTE), Sulfur content and Nitrogen content were measured. The experimental results are provided in the Table-2. Therefore, experiments were carried out in DCU pilot plant using the neat CLO as well as mixtures of CLO+HDT VGO streams at identified operating conditions which are maintained same for all the runs. The yields from the experiments along with the characteristics of the calcined coke samples are provided in the Table-2.

(35) TABLE-US-00002 TABLE 2 Results of Delayed Coking experiments Parameter Run-1 Run-2 Run-3 Feed CLO CLO + 10% CLO + 20% HDT VGO HDT VGO Gas, wt % 7.5 6.6 7.7 Distillates, wt % 51.4 60.5 60.3 Coke, wt % 41.1 32.9 32 CTE, 10.sup.−6/° C. 1.35 1.31 1.26 Coke sulfur, wt % 0.41 0.38 0.33 Coke nitrogen, wt % 0.15 0.14 0.12

(36) From the Table-2, it can be seen that the CTE value of the Needle Coke improved from 1.35×10.sup.−6/° C. in case of neat CLO to 1.26×10.sup.−6/° C. in case of mixture of CLO+20% HDT VGO stream. In case of impurity content like sulfur, there is decrease of ˜0.08 wt % from the initial value of 0.41 wt %. Similar decrease in nitrogen content was also observed from 0.15 wt % to 0.12 wt % in the feed case with 20 wt % blending of HDT VGO in CLO stream. This indicates that it is feasible to produce needle coke of better quality in terms of lower sulfur/nitrogen impurity levels as well as CTE by the invented process.