Pre-treatment Process for Conversion of Residual Oils in a Delayed Coker Unit

Abstract

The present invention relates to a sequential thermo-chemical treatment along with adsorption-based pre-treatment process for residual oils having a very high naphthenic acid content. First stage of the process is a thermal pre-treatment step which results into generation of hydrocarbon stream with a reduced naphthenic acid content due to high temperature. In second stage of pre-treatment, generated hydrocarbon stream from stage-1 is subjected to esterification reaction with alcohol, such as methanol, to further reduce the TAN of hydrocarbon stream. After recovery of alcohol from the reaction mixture, depending on TAN reduction required reaction mixture may be subjected to an adsorption stage, third stage pre-treatment, where an adsorbent mixture comprising of FCC spent catalyst is used to adsorb the TAN of feed hydrocarbon stream. The treated hydrocarbon stream is then co-processed with DCU feed stock for producing lighter hydrocarbons.

Claims

1. A multistage process for pre-treating high naphthenic acid content heavy oils prior to co-processing in a DCU, wherein the process comprises: a) pre-heating of a residual oil feedstock in a heat exchanger-1 of the DCU to obtain a pre-heated stream; b) heating the pre-heated stream in a pre-heating zone of a DCU furnace to obtain a stream; c) heating the stream in a heat exchanger-2 of the DCU to obtain a heated stream; d) mixing the heated stream with a fresh alcohol stream and a recycled alcohol stream to form a stream, and routed to a soaker vessel to obtain a soaker effluent stream; e) removal of any non-condensable gases and residue from the soaker effluent stream in a surge vessel or a separator-1 to obtain a condensed liquid stream; f) recovering alcohol from the condensed liquid stream in a separator-2 to obtain a treated stream; g) passing the treated stream through an adsorbent bed-1 through a line or an adsorbent bed-2 through a line for further TAN reduction; h) entry of an adsorbent occurs through a make-up line; and i) sending a treated stream from either of the adsorbent beds to the DCU through a line.

2. The process as claimed in claim 1, wherein in step (d) the recycled alcohol stream along with the fresh alcohol stream is added to the heated stream before entering the soaker vessel to provide additional contact time for higher TAN reduction.

3. The process as claimed in claim 1, wherein in step (g) the adsorbent used may be selected from a group consisting of FCC-spent catalyst, zeolite-based adsorbents, basic oxides like calcium hydroxide, or mixtures thereof.

4. The process as claimed in claim 1, wherein in step (d) a condensed liquid stream is optionally routed to an esterification reactor; and wherein a reactor effluent is routed to a separator-2 for alcohol recovery to obtain a treated stream which is sent to an adsorbent zone.

5. The process as claimed in claim 1, wherein optionally after step (f), the treated stream is directly sent to the DCU for co-processing.

6. The process as claimed in claim 1, wherein the process uses a sequential combination of a thermal treatment, an esterification-based reactive treatment, and a FCC spent catalyst-based adsorbent pre-treatment.

7. The process as claimed in claim 1, wherein the process treats feed with a TAN value in a range of 20-100 mg KOH/g oil.

8. The process as claimed in claim 1, wherein the process treats feed with a Conradson Carbon Residue (CCR) in a range of 3-25 wt. %.

9. The process as claimed in claim 1, wherein a product obtained from the pre-treatment process is blended with the residual oil feedstock to produce light distillates.

10. The process as claimed in claim 9, wherein the residual oil feedstock is selected from a group consisting of vacuum residues, atmospheric residues, aromatic tars, clarified oil, crude oil, biomass derived oils, and wastewater sludge.

11. The process as claimed in claim 1, wherein the high TAN residual oil feed stock is heated to a temperature in a range of 200-400° C. and at a pressure in a range of 1-10 Kg/cm.sup.2 g and a residence time in a range of 10-100 minutes.

12. A system for pre-treating residual oils prior to co-processing in a DCU in multiple reactors to reduce the naphthenic acid content, wherein the system comprises: a residual oil feedstock, an alcohol and a FCC spent catalyst as active components.

13. The system as claimed in claim 12, wherein the alcohol is selected from a group consisting of 1 to 8 carbon atoms.

14. The system as claimed in claim 12, wherein the alcohol comprises methanol.

15. A multistage pre-treatment apparatus for reducing naphthenic acid content of residual oils prior to co-processing in a DCU, wherein the apparatus comprises: a) a first heat exchanger-1 for pre-treating a residual oil feedstock; b) a pre-heating zone of a DCU furnace; c) a second heat exchanger-2 for heating a stream; d) a soaker vessel to obtain a soaker effluent stream; e) a surge vessel or a separator-1 for removal of any non-condensable gases and residue to obtain a condensed liquid stream; f) a separator-2 for alcohol recovery from a condensed liquid stream; and g) an adsorbent bed-1 and an adsorbent bed-2 for further TAN reduction.

16. A process for co-processing pre-treated oils in a DCU, wherein the process comprises: a) mixing a pre-treated stream at a particular rate with a heavy residue feedstock to obtain a primary mixed feed, wherein the primary mixed feed comprises treated oil in a range varying from 0.5 to 5 wt. %, and preferably in a range of 0.5 to 3 wt. %; b) routing the primary mixed feed to a main fractionator operating in a range of 200-350° C. so as to avoid coking, where it mixes with an internal recycle of heavy components of coke drum vapor and a fresh feed to obtain a secondary feed; c) routing the secondary feed to a DCU furnace for initiating thermal cracking reactions; and d) heating the secondary feed stream to thermal cracking temperature and then routing the furnace effluent stream to a coke drum for conversion into product vapors and coke.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0026] FIG. 1 represents a schematic process flow diagram of embodiment-1 of invented process.

[0027] FIG. 2 represents a schematic process flow diagram of embodiment-2 of invented process.

[0028] FIG. 3 represents a schematic process flow diagram of embodiment-3 of invented process.

[0029] FIG. 4 represents a schematic process flow diagram of embodiment-4 of invented process.

[0030] FIG. 5 represents a schematic process flow diagram of embodiment-5 of invented process.

[0031] FIG. 6 represents a schematic process flow diagram of embodiment-6 of invented process.

DESCRIPTION OF THE INVENTION

[0032] 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.

[0033] Definitions

[0034] 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.

[0035] 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.

[0036] 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”.

[0037] 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.

[0038] The term “including” is used to mean “including but not limited to”. “Including” and “including but not limited to” are used interchangeably.

[0039] 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.

[0040] 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.

[0041] The present invention provides a multistage process for pre-treating high naphthenic acid containing (high TAN) residual oils prior to co-processing in a delayed coker unit (DCU). It uses a sequential combination of thermal treatment, esterification-based reactive treatment along with fluid catalytic cracking (FCC) spent catalyst-based adsorbent pre-treatment, for reducing feed TAN to sufficiently low values. Product from the pre-treatment stages can be blended/co-processed with the DCU feed stock for producing light distillates.

[0042] In an embodiment of the invention, the process can treat feed with a very high TAN (20-100 mg KOH/gm oil) and high Conradson Carbon Residue (CCR) in the range of 3-25 wt. %.

[0043] In another embodiment of the invention, Stage I of the process is a thermal pre-treatment step, which results into generation of hydrocarbon stream with a reduced naphthenic acid content due to high temperature. In stage II of pre-treatment, generated hydrocarbon stream from stage I is subjected to esterification reaction with alcohol, such as methanol, to further reduce the TAN of hydrocarbon stream. After recovery of alcohol from the reaction mixture, depending on the TAN reduction required, reaction mixture may be subjected to an adsorption stage, stage III pre-treatment, where an adsorbent mixture comprising of FCC spent catalyst is used to adsorb the TAN of feed hydrocarbon stream.

[0044] In yet another embodiment of the invention, the process provides flexibility in terms of feed handling and easy integration with the existing DCUs. It enables the DCU of a refinery to produce fuel from alternative feed stock and reduce dependence on petroleum-based feeds. The treated stream may also be co-processed without replacing the vacuum residue feed stock by utilizing the over design capacity of units, resulting into yield benefits in terms of lighter hydrocarbons. It does not make use of any hydrotreatment based technique thus resulting in additional cost savings. The present invention provides an attractive option for converting high TAN residual oils to valuable distillates using DCU.

[0045] In an embodiment of the present invention, as shown in FIG. 1, high TAN residual oil feedstock (1) is routed to a heat exchanger-1 (2) of the DCU for pre-heating to obtain a pre-heated stream (3). Pre-heated stream (3) is thereafter heated in the preheating zone of DCU furnace (4) to obtain a stream (5). Subsequently, after heating stream (5) in heat exchanger-2 (6) of the DCU, heated stream (7) mixes with fresh alcohol, such as methanol, stream (17) and recycled alcohol stream (16) and forms stream (8) which is routed to a soaker vessel (9). Alcohol stream is added before the soaker vessel for providing additional contact time for higher TAN reduction. Soaker effluent stream (10) is routed to a surge vessel or separator-1 (11) for removal of any non-condensable gases (12) and residue (13). The condensed liquid stream (14) is thereafter sent for alcohol recovery in separator-2 (15). The treated stream (18) from second stage pre-treatment is routed to an adsorbent zone for further TAN reduction. The stream may enter the adsorbent bed-1 (20) through line (19) or adsorbent bed-2 (22) through line (21). The adsorbent used may be FCC spent catalyst or mixture thereof introduced through make-up line (23). The treated stream from either of the beds as per mode of operation (24) or (25) is sent to DCU through line (26).

[0046] In another embodiment of the invention, as shown in FIG. 2, high TAN residual oil feedstock (27) is routed to a heat exchanger-1 (28) for pre-heating. Pre-heated stream (29) is thereafter heated in the preheating zone of DCU furnace (30). Subsequently, after heating in heat exchanger-2 (32), heated stream (33) mixes with fresh alcohol such as methanol stream (45) and recycled alcohol stream (44) and forms stream (34) which is routed to a soaker vessel (35). Alcohol stream is added before the soaker vessel for providing additional contact time for higher TAN reduction. Soaker effluent stream (36) is routed to a surge vessel or separator-1 (37) for removal of any non-condensable gases (38) and residue (39). The condensed liquid stream (40) is thereafter routed to an esterification reactor (41). The reactor effluent (42) is sent for alcohol recovery in separator-2 (43). The treated stream from second stage pre-treatment (46) is routed to an adsorbent zone for further TAN reduction. The stream may enter the adsorbent bed-1 (48) through line (47) or adsorbent bed-2 (50) through line (49). The adsorbent used may be FCC spent catalyst or mixture thereof introduced through make-up line (51). The treated stream (52) or (53) from either of the beds as per mode of operation is sent to DCU through line (54).

[0047] In yet another embodiment of the present invention, as shown in FIG. 3, high TAN residual oil feedstock (55) is routed to heat exchanger-1 (56) for pre-heating. Pre-heated stream (57) is thereafter heated in the preheating zone of DCU furnace (58). Subsequently, after heating in Heat exchanger-2 (60), heated stream (61) mixes with fresh alcohol such as methanol stream (71) and recycled alcohol stream (70) and forms stream (62) which is routed to a soaker vessel (63). Alcohol stream is added before the soaker vessel for providing additional contact time for higher TAN reduction. Soaker effluent stream (64) is routed to a surge vessel or separator-1 (65) for removal of any non-condensable gases (66) and residue (67). The condensed liquid stream (68) is thereafter sent for alcohol recovery in separator-2 (69). The treated stream (72) with sufficiently low TAN value is routed to DCU for co-processing.

[0048] In yet another embodiment of the invention, as shown in FIG. 4, high TAN residual oil is treated using process described in FIG. 1 (embodiment 1) to obtain treated stream (98). This treated stream (98) is mixed with fresh residual feedstock (99) to generate mixed primary feed stream (100) which is routed to Main Fractionator (101). Secondary Feed (102) from the main fractionator comprising internal recycle of heavy components of coke drum vapor and fresh feed is thereafter routed to DCU furnace (76) for initiating cracking reactions. Furnace effluent stream (107) is routed to either of the Coke drums (109) or (111) depending upon whichever is in the filling cycle. Cracked vapor stream (114) from either of the coke drums is routed to the main fractionator (101) for separating into gases (115), Light Coker gasoil (116) and Heavy Coker gasoil (117).

[0049] In yet another embodiment of the invention, as shown in FIG. 5, high TAN residual oil is treated using process described in FIG. 2 (embodiment 2) to obtain treated stream (145). This treated stream (145) is mixed with fresh residual feedstock (146) to generate mixed primary feed stream (147) which is routed to Main Fractionator (148). Secondary Feed (149) from the main fractionator comprising internal recycle and fresh feed is thereafter routed to furnace (121) for initiating cracking reactions. Heated stream from furnace outlet (154) is routed to either of the Coke drums (156) or (158) depending upon whichever is in the filling cycle. Cracked vapor stream (161) from either of the coke drums is routed to the main fractionator (148) for separating into gases (162), Light Coker gasoil (163) and Heavy Coker gasoil (164).

[0050] In yet another embodiment of the invention, as shown in FIG. 6, high TAN residual oil is treated using process described in FIG. 3 (embodiment 3) to obtain treated stream (182). This treated stream (182) is mixed with fresh residual feedstock (183) to generate mixed primary feed stream (184) which is routed to Main Fractionator (185). Secondary Feed (186) from the main fractionator comprising internal recycle and fresh feed is thereafter routed to furnace (168) for initiating cracking reactions. Heated stream from furnace outlet (191) is routed to either of the Coke drums (193) or (195) depending upon whichever is in the filling cycle. Cracked vapor stream (198) from either of the coke drums is routed to the main fractionator (185) for separating into gases (199), Light Coker gasoil (200) and Heavy Coker gasoil (201).

[0051] In another preferred embodiment, the present invention discloses a system for pre-treating residual oils prior to co-processing in a DCU in multiple reactors to reduce the naphthenic acid content, wherein the system comprises a residual oil feedstock, an alcohol and a FCC spent catalyst as active components. The alcohol is selected from a group consisting of 1 to 8 carbon atoms, and the alcohol preferably comprises methanol.

[0052] In yet another embodiment, the present invention discloses a multistage pre-treatment apparatus for reducing naphthenic acid content of residual oils prior to co-processing in a DCU comprising a first heat exchanger-1 (2) for pre-heating a high TAN residual oil feedstock (1); a pre-heating zone of a DCU furnace (4); a second heat exchanger-2 (6) for heating stream (5); a soaker vessel (9) to obtain a soaker effluent stream (10); a surge vessel or a separator-1 (11) for removal of any non-condensable gases (12) and residue (13) to obtain a condensed liquid stream (14); a separator-2 (15) for alcohol recovery from condensed liquid stream (14); and an adsorbent bed-1 (20) and an adsorbent bed-2 (21) for further TAN reduction.

[0053] In another embodiment, the present invention provides a process for co-processing pre-treated oils in a DCU, wherein the process comprises mixing a pre-treated stream (98) at a particular rate with a heavy residue feedstock (99) to obtain a primary mixed feed (100), wherein the primary mixed feed comprises treated oil in a range varying from 0.5 to 5 wt. %, and preferably in a range of 0.5 to 3 wt. %. Routing the primary mixed feed to a main fractionator (101) operating in a range of 200-350° C. so as to avoid coking, where it mixes with an internal recycle of heavy components of coke drum vapor and a fresh feed to obtain a secondary feed (102). Routing the secondary feed (102) to a DCU furnace (76) for initiating thermal cracking reactions by heating to thermal cracking temperature and then routing the furnace effluent stream (107) to a coke drum (109) or (111) for conversion into product vapors and coke.

[0054] The present invention is further illustrated based on the disclosed embodiments through several non-limiting working examples.

[0055] Feedstock:

[0056] The liquid hydrocarbon feedstock to be used in the process is selected from hydrocarbon feed streams having high TAN contents in the range of 20-100 mg KOH/gm oil, CCR in the range of 5 to 30, density in the range of 1.01 to 1.07 g/cc and carbon content in the range of 75 to 90 wt. %. Alcohol may be chosen from C1 to C8 carbon numbers. Adsorbent may be selected from commercially available zeolite-based adsorbents, basic oxides like calcium hydroxide or more specifically FCC spent catalyst from petroleum refineries.

[0057] Residue feedstock to DCU may be selected from Vacuum Residues, Atmospheric residues, aromatic tars, Clarified Oil etc.

[0058] Process Conditions:

[0059] The thermal treatment of high TAN residual oils may be carried out in the temperature range of 200-400° C. at a pressure in the range of 1-10 Kg/cm.sup.2 (g) and residence time in the range of 10 to 100 minutes. Alcohol may be added in the ratio of 1-40 wt %, more preferably in the range of 1-30 wt %. In the adsorption stage of process, thermo-chemically treated high TAN oil feed is contacted with an adsorbent in an adsorption column at adsorbent to feed ratio of 1:9 to 1:4, in the temperature range of 150-250° C. and residence time varying between 10-240 mins. The adsorption can be of pressure swing type where regenerated adsorbent column is receiving the feed while the saturated adsorbent column is under regeneration cycle.

[0060] Coke drum of DCU operates in the range of 475-505° C. with a filling or cycle time varying in the range of 12-30 hrs.

[0061] Experimental Data:

EXAMPLE 1

[0062] In order to simulate very high TAN residual oil, a heavy oil residue sample was doped with model naphthenic acid compound having average molecular weight of approximately 257 and a residual oil having property as described in Table-1 was prepared.

TABLE-US-00001 TABLE 1 Property of high TAN residual oil Property High TAN residual oil Density @ 15° C. g/cc 1.04 API gravity 4 CCR, wt. % 20.6 Carbon, wt. % 76 KVat 100° C. 124 TAN, mg KOH/gm oil 95.8

[0063] Such high TAN oil was treated thermally, and product stream was analyzed for TAN. Product TAN & experimental condition no. 1 are provided in Table-2.

TABLE-US-00002 TABLE 2 Experimental conditions & Product property S/N Operating Parameter Experiment no. 1 1. Temperature, ° C. 350 2. Pressure, Kg/cm.sup.2 (g) 1 3. Residence time, mins 60 4. Product TAN, 39.1 mg KOH/gm oil

[0064] Further, 0.4 gm of high TAN residual oil as prepared above was mixed with 99.6 gm of Vacuum residue feed stock. The resulting blend TAN was 0.5 mg KOH/gm oil.

EXAMPLE 2

[0065] Experiments were conducted using high TAN residual oil with properties described in Table-1 and alcohol (C1) at different compositions as mentioned in Table-3. The product stream was collected and analyzed for TAN. Product TAN & experimental conditions no. 2 and 3, are provided in Table-3.

TABLE-US-00003 TABLE 3 Experimental conditions & Product property Operating Experiment Experiment S/N Parameter no. 2 no. 3 1. Feed TAN 95.8 95.8 2. Temperature, ° C. 350 350 3. Oil/alcohol ratio 19:1 4:1 4. Pressure, Kg/cm.sup.2 (g) 1 1 5. Residence time, mins 60 60 6. Product TAN, 26.1 15.5 mg KOH/gm oil

EXAMPLE 3

[0066] To simulate the adsorption stage of the pre-treatment process, product collected in Experiment no. 2 was mixed with an adsorbent at different adsorbent to feed ratios. The resultant collected product was analyzed for TAN. Experimental conditions no. 4 and 5, are provided in Table-4.

TABLE-US-00004 TABLE 4 Experimental conditions & Product property Operating Experiment Experiment S/N Parameter no. 4 no. 5 1. Feed TAN 26.1 26.1 2. Adsorbent FCC spent catalyst FCC spent catalyst 3. Temperature, °C 250 250 4. Adsorbent/feed ratio 1:9 1:4 5. Pressure, Kg/cm.sup.2 (g) 1 1 6. Residence time, mins 240 240 7. Product TAN, 21.3 17.3 mg KOH/gm oil

[0067] Further, 2.4 gm of product derived from Experimental condition no. 5 was mixed with 97.6 gm of Vacuum Residue feed stock. Resulting blend had a TAN of 0.5 mg KOH/gm of oil.

EXAMPLE 4

[0068] The product from Experimental condition no. 3 was mixed with typical Vacuum Residue (VR) feed stock as per conditions provided in Table-5 and thermally cracked in a laboratory scale batch thermal cracker unit. Operating conditions & product yield in experimental condition no. 5 is provided in Table-5.

TABLE-US-00005 TABLE 5 Experimental conditions & Product property S/N Operating parameter Experiment no. 5 1. Vacuum residue: Product 98:2 2. Temperature, ° C. 487 3. Pressure, Kg/cm.sup.2 (g) 1 Product Yield, wt. % 1. Gas + Liquid 69 2. Coke 31