Process for conversion of high acidic crude oils

Abstract

The present invention relates to crude oil processing, particularly related to conversion of crude oil containing high amount of naphthenic acid compounds to lighter hydrocarbon materials with minimum capital expenditure. The invented process utilizes a novel scheme for high TAN crude oils by employing thermal cracking process to maximize the residue conversion to valuable products, which require minimum modifications in unit metallurgies and corrosion inhibitor injection schemes in refineries.

Claims

1. A method for processing a high acidic crude oil by thermal cracking process, the method comprising: a) desalting the high acidic crude oil to obtain a desalted crude; b) separating the desalted crude in a pre-fractionator column into a lighter hydrocarbon material and a heavier boiling material, wherein the lighter hydrocarbon material does not contain acidic compounds; c) routing the heavier boiling material from the pre-fractionator to a bottom section of a fractionator column and mixing with an internal recycle component in the fractionator column and drawing out from the fractionator column as a secondary feed; d) heating the secondary feed obtained in step (c) to a high temperature in a furnace to disintegrate acidic compounds of the high acidic crude oil and to obtain a hot feed; e) thermally reacting the hot feed obtained in step (d) in reactors to obtain product vapors; and f) routing the product vapors obtained in step (e) to the fractionator column for fractionation into product fractions.

2. The method as claimed in claim 1, wherein the desalting step (a) is carried out under application of an electric field.

3. The method as claimed in claim 1, wherein the high acidic crude oil has high contents of acidic compounds with a total acidic number (TAN) greater than 0.5 mg KOH/g Oil.

4. The method as claimed in claim 1, wherein the high acidic crude oil is a blend of low TAN and high TAN crude oils, wherein the TAN of the blend is greater than 0.5 mgKOH/g oil.

5. The method as claimed in claim 1, wherein the lighter hydrocarbon material has a boiling point lower than 200 C.

6. The method as claimed in claim 1, wherein the heavier boiling material has a boiling point greater than 200 C.

7. The method as claimed in claim 1, wherein removal of the lighter hydrocarbon and heavier boiling material from the desalted crude in step (b) is carried out at a pressure in the range of 1-2 Kg/cm.sup.2 (g) and at a top temperature in the range of 150 to 250 C.

8. The method as claimed in claim 1, wherein the secondary feed is heated in step (d) at a temperature in the range of 470 to 520 C.

9. The method as claimed in claim 1, wherein thermally reacting the hot feed in step (e) comprises reacting at a temperature in the range of 470 to 520 C. and at a pressure in the range of 0.5 to 5 Kg/cm.sup.2 (g).

10. The method as claimed in claim 1, wherein thermally reacting the hot feed in step (e) comprises thermally reacting for a residence time of more than 10 hours.

11. The method as claimed in claim 1, wherein thermally reacting the hot feed comprises thermally reacting in the reactors that operate in feeding mode of operation.

12. The method as claimed in claim 1, wherein the product fractions obtained in step (f) comprises offgases with naphtha, light gasoil product, heavy gasoil, and fuel oil.

13. The method as claimed in claim 12, wherein the offgases with naphtha are passed to a gas separation section to separate gaseous products comprising a fuel gas and LPG.

14. The method as claimed in claim 12, wherein the heavy gasoil is sent to a secondary processing unit to obtain products including naphtha, wherein the secondary processing unit is at least one of a hydrocracker unit and a fluid catalytic cracking unit.

15. The method as claimed in claim 14, wherein the lighter hydrocarbon material, the naphtha from the gas separation section and the naphtha from the secondary processing unit are treated to obtain a desired lighter product.

16. The method as claimed in claim 1, wherein the thermal cracking process produces a solid petroleum coke as a byproduct.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 represents schematic of conventional high TAN crude processing scheme by blending.

(2) FIG. 2 represents schematic of high TAN crude processing scheme of present invention.

DESCRIPTION OF THE INVENTION

(3) While the invention is susceptible to various modifications and/or alternative processes and/or compositions, specific embodiment thereof has been shown by way of example in tables and will be described in detail below. It should be understood, however that it is not intended to limit the invention to the particular processes and/or compositions disclosed, but on the contrary, the invention is to cover all modifications, equivalents, and alternative falling within the spirit and the scope of the invention as defined by the appended claims.

(4) The tables and protocols have been represented where appropriate by conventional representations, showing only those specific details that are pertinent to understanding the embodiments of the present invention so as not to obscure the disclosure with details that will be readily apparent to those of ordinary skill in the art having benefit of the description herein.

(5) The following description is of exemplary embodiments only and is NOT intended to limit the scope, applicability or configuration of the invention in any way. Rather, the following description provides a convenient illustration for implementing exemplary embodiments of the invention. Various changes to the described embodiments may be made in the function and arrangement of the elements described without departing from the scope of the invention.

(6) Any particular and all details set forth herein are used in the context of some embodiments and therefore should NOT be necessarily taken as limiting factors to the attached claims. The attached claims and their legal equivalents can be realized in the context of embodiments other than the ones used as illustrative examples in the description below.

(7) The present invention relates to a method of processing high total acid number (TAN) crude oils by thermal cracking process to deacidify the crude oil along with converting it into valuable lighter hydrocarbons.

(8) A conventional way of processing of high TAN crude oils include blending of the same with low TAN crude oils to bring the acidity levels to below 0.5 mgKOH/g oil and then processing through the normal route. This involves passing the mixed crude oil to the crude desalter unit. The desalted crude oil is then sent to the atmospheric column where separation of lighter products from reduced crude oil or long residue takes place. The reduced crude oil is then sent to a vacuum distillation unit where the vacuum gasoils are separated from the vacuum residue or short residue. Naphtha components are normally processed in different units like hydrotreaters, isomerization units, reformer etc. to produce finished products like LPG, motor spirit or naphtha. Vacuum gasoils are sent to secondary processing unit(s) like hydrocracker unit (HCU) or Fluid catalytic cracking unit (FCC) for further catalytic conversion to lighter hydrocarbon products. The vacuum residue is sent to a delayed coker unit for thermal cracking to lighter products and petroleum coke.

(9) According to one embodiment of the present invention, a method for processing of liquid hydrocarbon feedstock by thermal cracking process, wherein the said method comprises the steps of: a) desalting neat high acidic crude oil to obtain desalted crude; b) separating the desalted crude in a pre-fractionator column into lighter hydrocarbon material and heavier boiling material, wherein the lighter hydrocarbon material comprises of hydrocarbons boiling below 200 C.; c) routing the heavier boiling material to the bottom section of a fractionator column and mixing with internal recycle component to obtain a secondary feed; d) heating the secondary feed obtained in step (c) to a high temperature to obtain a hot feed; e) thermally reacting the hot feed obtained in step (d) in reactor to obtain product vapors; f) routing the product vapors obtained in step (e) to the fractionator column for fractionation into product fractions.

(10) In a preferred embodiment of the present invention, the liquid feedstock is crude oil having high contents of acidic compounds with total acidic number (TAN) greater than 0.5 mg KOH/g Oil. In another embodiment of the present invention, the liquid hydrocarbon feedstock is a blend of low TAN and high TAN crude oils, wherein the TAN of the mixture of the crude oils may be greater than 0.5 mgKOH/g oil.

(11) In another feature of the present invention, the liquid feedstock is crude oil having high contents of acidic compounds with TAN lower than 0.5 mg KOH/g Oil. In yet another embodiment of the present invention, the liquid hydrocarbon feedstock is a blend of low TAN and high TAN crude oils, wherein the TAN of the mixture of the crude oils may be lower than 0.5 mgKOH/g oil.

(12) In general, TAN is a measure of the naphthenic acid compounds in a hydrocarbon material. Naphthenic acids are the general compound class, which cause corrosion of equipment and fouling of heat exchangers etc. In an embodiment of the present invention, high TAN crudes comprises of high metal and chloride contents and may have low as well as high sulfur contents. In another embodiment of the present invention, non-limiting examples of high TAN crudes include North Gujarat Crude, Mondo, Liuhua, Duli, Hange, Kuitu, Liaohe, Duoba, and Fula.

(13) In another preferred feature of the present invention, the density of the crude oil may be more than 0.8 g/cc and Conradson Carbon Residue (CCR) content greater than 0.1 wt %.

(14) In another feature of the present invention, the heavier hydrocarbon material and the lighter boiling material has boiling point greater or lower than 200 C. In a preferred embodiment of the present invention, the lighter hydrocarbon material has boiling point lower than 200 C. and the heavier boiling material has boiling point greater than 200 C.

(15) In a preferred feature of the present invention, the product fractions obtained comprises of offgases with naphtha, light gasoil product, heavy gasoil, and fuel oil. The light gasoil product is withdrawn and passed to a treater unit. The treater unit is preferably hydrotreater unit. Further, the offgases with naphtha is passed to a gas separation section to separate gaseous products comprising of fuel gas and LPG from naphtha product and the heavy gasoil stream is sent to a secondary processing unit like hydrocracker or fluid catalytic cracker.

(16) In another preferred feature of the present invention, the process scheme is carried out using a single pre-fractionator column, without requirement of separate crude distillation unit or vacuum distillation unit.

(17) In yet another feature of the present invention, the process conditions are to be fine-tuned to enable separation of lighter boiling naphtha range compounds from the crude. The boiling point of the lighter boiling naphtha may be preferably lower than 200 C.

(18) In an embodiment of the present invention, removal of the lighter hydrocarbon and heavier boiling material from the desalted crude in step (b) is carried out at pressure in the range of 1-2 Kg/cm.sup.2 (g) and top temperature in the range of 150 to 250 C., preferably in the range of 190 to 210 C.

(19) In another feature of the present invention, the secondary feed is heated in step (d) at the temperature in the range of 470 C. to 520 C., preferably in the range of 480 C. to 500 C.

(20) In yet another feature of the present invention, the thermal reactions in step (e) are carried out at the desired operating temperature in the range of 470 to 520 C., preferably between 480 C. to 500 C. and desired operating pressure in the range of 0.5 to 5 Kg/cm (g), preferably between 0.6 to 3 Kg/cm (g). Further, the thermal cracking reactions in step (e) are carried out with residence time of more than 10 hours.

(21) In another feature of the present invention, the thermal cracking reaction in step (e) is carried out in feeding mode of operation in at least two reactor drums.

(22) The process of the present invention provides major advantages including complete destruction of naphthenic acid compounds into harmless compounds which do not cause corrosion of equipment and pipelines. This in turn benefits the refiner in terms of lesser or nil requirement of corrosion inhibitor dosing schemes. Also, in the thermal cracking process, the heavy metals, chlorides, nitrogen and similar impurities which act as poisons for catalysts of downstream units get deposited in the solid petroleum coke. The process of the present invention reduces the impurities and thereby provides relatively cleaner feedstock to the downstream units.

DESCRIPTION OF PROCESS FLOW SCHEME

(23) In accordance with FIG. 1, a conventional way of processing high TAN crude oil includes blending of the high TAN crude (1) with low TAN crude oils (2) to make the crude oil mixture (3) having low acidity levels to avoid equipment and pipeline corrosion. The mixed crude oil stream (3) is then routed to the crude desalter unit (4), where under the application of electric field, the salts and sediments are removed from the crude oil mixture. The desalted crude oil (5) is then sent to the Atmospheric Distillation Unit or also termed as Crude Distillation Unit (CDU) (6) where the lighter materials (7) such as naphtha, kerosene, straight run diesel are separated. These lighter hydrocarbon material are then routed to treatment or processing units (14) such as hydrotreater, isomerization, reformer, hydrogen generating unit. The heavy material (8) after separation of the lighter, exiting the CDU bottom is termed as reduced crude oil or long residue. The reduced crude oil is then sent to a vacuum distillation unit (VDU) (9) where the vacuum gasoil (10) are separated. The vacuum gasoil stream (10) is sent to a secondary processing unit (16) for further conversion. The heavier bottom material (11) exiting the vacuum distillation unit (9) is termed as vacuum residue or short residue. The vacuum residue stream (10) is then routed to the delayed coker unit (12) for thermal cracking. The lighter product material (13) exiting the delayed coker units are sent to product treatment units (14) and the heavy coker gasoil stream (15) is sent to the secondary processing units (16) for further conversion. The lighter products (20) from secondary conversion units are also sent to treatment units (14) for treatment. Products (17, 18, 19) are obtained from the process scheme.

(24) The process of present invention is exemplified in accordance to, but not limited to the FIG. 2, the neat high TAN crude oil (21) is routed to desalter unit (22) for desalting, where under the application of electric field, the salts and sediments are removed from the crude oil mixture. The desalted crude oil (23) is then routed to the pre-fractionator column (24) to remove the lighter hydrocarbon material (25) like naphtha boiling below 200 C. and the heavier boiling material boiling above 200 C. (26). Heavier boiling material (26) is then routed to the bottom section of fractionator column (27). In the fractionator column, the internal recycle component gets mixed with the heavier boiling stream (26) and is drawn out as secondary feed (39). The secondary feed (39) is then sent to a furnace (40) for heating to high temperature required for thermal cracking reactions as well as causing disintegration of acidic compounds. The hot feed (41) exiting the furnace is sent to one of the two reactor drums (43, 43), which is in feeding mode of operation. In the reactor drum, thermal cracking reactions takes place and the product vapors (44) are routed to the fractionator column (27) for fractionation into desired product cuts. The offgases with naphtha (35) is sent to the gas separation section (33), where the gasesous products (45) including fuel gas and LPG are separated from naphtha product (34). The light gasoil product (36) is withdrawn from the fractionator column (27) and sent to treater unit like hydrotreater for further treatment. The heavy gasoil stream (37) is sent to the secondary processing unit (30) which can be either a hydrocracker unit or fluid catalytic cracking unit for further conversion. The lighter hydrocarbon material (25) from the pre-fractionator column (24), naphtha (34) from gas separation section (33) and the naphtha (32) from the secondary unit (30) are sent to the naphtha/gasoline treatment section (28), to obtain the desired lighter product (29). The fuel oil (38) product withdrawn from the fractionator column (27) can be used as internal fuel oil or can also be sent for further catalytic conversion. Solid petroleum coke (29), which is formed in the reactor drums, can be used as a fuel grade coke for boilers or as anode grade coke for electrode manufacture etc. Conventional hydrocarbon products (33, 34) are produced from the process scheme. In the process scheme of the present invention, the major advantages include complete destruction of naphthenic acid compounds into harmless compounds which do not cause corrosion of equipment and pipelines downstream of the process.

(25) The present invention has several advantageous over conventional process. The advantages of the present invention include no requirement of CDU and VDU, no metallurgy changes in downstream units, complete TAN disintegration, removal of catalyst poisons as deposits in Coke, no impact on downstream unit conversions, and no or minimum use of costly corrosion inhibitors. Further, the scheme of the present invention is ideal for capacity expansion cases & grass root refineries for processing high acidic crude oil.

(26) In an embodiment of the present invention, the crude oil pre-fractionator operates at pressure in the range of 1-2 Kg/cm.sup.2 (g).

(27) In another feature of the present invention, top temperature of the pre-fractionator is in the range of 150 to 250 C., preferably in the range of 190 to 210 C. The process conditions are to be fine-tuned to enable separation of lighter boiling (<200 C.) naphtha range compounds from the crude.

(28) In an embodiment of the present invention, the reactor drums in the thermal cracking section of the process may be operated at a higher severity with desired operating temperature ranging from 470 to 520 C., preferably between 480 C. to 500 C.

(29) In another feature of the present invention, the reactor drums in the thermal cracking section operate at a desired operating pressure ranging from 0.5 to 5 Kg/cm.sup.2 (g), preferably between 0.6 to 3 Kg/cm.sup.2 (g). The residence time provided in rector drums is more than 10 hours.

(30) In yet another feature of the present invention, the furnace operates at a high temperature in the range of 470 C. to 520 C., preferably in the range of 480 C. to 500 C.

EXAMPLES

(31) The present invention is exemplified by following non-limiting examples.

Example 1

(32) A typical high TAN crude oil from India was arranged and detailed characterization was carried out to ascertain the physic-chemical characteristics. The properties are tabulated in Table-1.

(33) TABLE-US-00001 TABLE 1 Physio-chemical characteristics of crude oil Property Unit Value Gravity API 26.0 Sulfur wt % 0.079 Pour Point C. 21 Viscosity @ 40 C. Centistokes 59.7 Viscosity @ 60 C. Centistokes 25.2 Nitrogen, Total Weight ppm 496 Total Acid Number mg KOH/gm 2.09 Carbon Residue Wt % micro 4.6 Asphaltenes Wt % 0.38 Sediment Vol % 0 Water Vol % Trace Chlorides as NaCl lbs NaCl/1000 bbls 13.1 Reid Vapor Pressure psi 1.93

(34) Crude assay analysis was carried out to find the yields of various component streams w.r.t. various cut points like naphtha, kero etc. as shown in Table-2.

(35) TABLE-US-00002 TABLE 2 Crude assay data Yield, wt % Crude assay FG + LPG 0.7 LN (C5-95 C.) 2.3 HN (95-150 C.) 3.3 Kero (150-250 C.) 9.6 LGO (250-370 C.) 20.4 VGO (370-550 C.) 33 VR (550 C. +) 30.6

Example 2

(36) The high TAN crude oil sample of Example 1 was subjected to thermal cracking reaction conditions in a laboratory scale batch thermal cracker reactor unit. The experimental conditions of the unit are provided in Table-3.

(37) TABLE-US-00003 TABLE 3 Operating conditions of batch thermal cracker reactor unit Operating condition Unit RUN-1 RUN-2 Reactor temperature C. 485 490 Reactor pressure Kg/cm.sup.2(g) 1 1 Reaction time hrs 2 2

(38) The high TAN crude oil sample, of which properties are given in Table-1, was subjected to thermal treatment conditions as provided in Table-4. Two runs were carried out at different reactor temperatures. The liquid products from both runs were analyzed for TAN (mgKOH/g oil) and the results are provided in Table-4.

(39) TABLE-US-00004 TABLE 4 TAN analysis of liquid products from experiments Liquid product of Liquid product of Crude RUN-1 RUN-1 TAN, mg KOH/g 2.10 0.15 0.10

(40) It is evident from the Table-4 that the acidity of the crude oil is reduced from 2.1 mgKOH/g oil to very negligible levels of 0.1-0.15 mgKOH/g oil, which indicates that the TAN compounds are nearly completely disintegrated into harmless compounds. The liquid products after TAN reduction could be processed in the downstream units without any effect on the equipments. Also, the yield patterns from both experiments were compiled and compared in Table-5.

(41) TABLE-US-00005 TABLE 5 Comparison of yield pattern from experiments with crude assay data Yield, wt % Crude assay RUN-1 RUN-2 FG + LPG 0.7 8.1 7.4 LN (C5-95 C.) 2.3 2.7 2.4 HN (95-150 C.) 3.3 6.0 5.5 Kero (150-250 C.) 9.6 20.4 19.9 LGO (250-370 C.) 20.4 34.6 35.0 HGO (370-540 C.) 19.5 21.4 VGO (370-550 C.) 33 VR (550 C. +) 30.6 Coke 8.7 8.4

(42) It is evident from the Table-5 above that the yields obtained from thermal cracking of high TAN crude are comparable or superior to the yield pattern from conventional way of processing the same.

Example 3

(43) A pilot scale study using a semi-batch thermal cracking pilot plant was carried using the high TAN crude oil of Example 1 or Table-1. The process conditions employed in the pilot plant run are provided in Table-6.

(44) TABLE-US-00006 TABLE 6 Operating conditions of pilot plant Operating condition Unit Value Reactor temperature C. 490 Reactor pressure Kg/cm.sup.2(g) 1 Feed rate Kg/hr 8 Cycle time hrs 12

(45) The combined liquid product was collected and analyzed for TAN and the result is compared with feed in Table-7.

(46) TABLE-US-00007 TABLE 7 TAN analysis of liquid products from experiments Liquid product of Crude Pilot plant run TAN, mg KOH/g 2.10 0.42

(47) Table-7 above confirms the reduction of TAN content by thermal treatment process of present invention in pilot scale study, as well.

(48) Those of ordinary skill in the art will appreciate upon reading this specification, including the examples contained herein, that modifications and alterations to the composition and methodology for making the composition may be made within the scope of the invention and it is intended that the scope of the invention disclosed herein be limited only by the broadest interpretation of the appended claims to which the inventor is legally entitled.