CA2294952C - Thermal process for reducing total acid number of crude oil - Google Patents
Thermal process for reducing total acid number of crude oil Download PDFInfo
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- CA2294952C CA2294952C CA002294952A CA2294952A CA2294952C CA 2294952 C CA2294952 C CA 2294952C CA 002294952 A CA002294952 A CA 002294952A CA 2294952 A CA2294952 A CA 2294952A CA 2294952 C CA2294952 C CA 2294952C
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
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Abstract
TAN containing oils, e.g., crudes, are treated by flashing to remove substantially all of the water therefrom, thermally treating the recovered liquid to reduce the naphthenic acid content thereof, and re-combining light gases recovered from the flashing step with the treated liquid.
Description
THERMAL PROCESS 1~OR REDUCING TOTAL ACID NUMBER OF
CRUDE OIL
FIELD OF THE INV'ENTIO:IV
This invention :relates to the treatment of crude oil, including heavy cruder, for reducing ~'he total acid number (TAN) of the oil.
BACKGROUND OF' THE IrIVENTION
The value of crude oils is often dependent on the corrosiW ty of the oil, and corrosivity is mainly a function of the total acid number of the oil.
TA.N, in tour, is heavily dependent, although not completely so, on the naphthenic acid conc~entratioa of the oil. Consequently, cruder having a relatively high TAN, e.g., Z2 have a significantly lower market value, on a per cubic meter basis, than crudea having a relatively lower TAlV'. For example, high TAN etudes are often hl~ended off with lower TAN erodes rather than being processed separatelythrough refineries, thereby avoiding excessive corrosion in refinery equipment. frocessi~ng of high TAN cruder can also necessitate the use of expensive alloys ire primanr equipment, e.g., pipestills, thereby minimizing corrosivity effects of the etudes. Both methods for handling high TAN cruder are expensive and cans lead to excessive storage Facilities or upsets in the refinery. Consequently, there remains a need for handling high TA~'~1 etudes that is not disruptive of refinery operations and avoids excessive costs, SUMMARY OF THEf TION
In accordance with this invention, TAN containing oils, e.g., cruder, extra heavy oils, bitumens, kerogens, are pretreated by flashing og vapors including light gases, water, and Light hydrocarbons, subjecting the r4maining liquid phase to a thermal treatment wherein naphtheaic acids ate decomposed and TAN is redw~ed, followed by recombining at least a portion of the hydrocarbon vapour recovc;red from the flash with the treated liquid.
AMENDED SHEET
_2_ The thermal tre;atmeat of this invention a not to be confused with visbreaking which is essentially a treatment of heavy oils or whole crudes at temperatures in excess of the temperatures of the thermal treatment disclosed herein:
TAN reductions in accordance with this invention are preferably on the order of at least 70°lg more preferably at least about 80°!0, still more preferably at Least about 90%r.
In the practice of this invention the oil to be treated may or may not be subjected to desalting prior to the flashing of the light materials.
Desalting is generally preferred with oils having in excess of 5.7g of salt per cubic meter of oil and more lrreferably when the salt level exceeds 11.4g of salt per cubic meter of oil. Desalting is a common process and will be well known to those skilled in the a~-t of refLaing.
In many ruses, particularly where heavy erodes, e.g., Bachaquern, Morichal, Cerro Negro, Zuae~, or Cameo-1-Bare, alI Venezuelan heavy erodes, and cases involving hitumens, the crude or heavy oil is diluted with naphtha to provide ease of traas;portation, e.g., pumpability. Tn the flashing step, the diluent will be vaporized along with C4- gases (e.g., light-ends), water, and anything else that wilt be vaporized at the flashing conditions of about 121.1 to 371.1°C, and pressures ranging from atmospheric to about 1.82 MPa. The extent of the flash step is largely detertr~ined by removing substantially all of the water present in the oil, e.g., to levels of less than about 0.5 wt°%, preferably less ;han about 0.1 wt°/a. The flashed hydrocarb~5ns, e.g., light gases, naphtha diluent, or light hydrocarbons are recovered from the flash and maintained for later combining of at least a portion thereof and substantially all, with the product of the thermal treatment.
BRIEF DESCRIPTIt3N OF T'HE DRAWINGS
Figure 1 is a schematic flow plan illustrating the process of this invention.
AMENDED SHEET
Figure 2 shows the effect of water on TAN conversion, where the abscissa is reaction time (min.) at 385°C and the ordinate is product TAN/feed TAN.
Curve A was at 0.17 MPa HZO, curve B at 0.10 MPa HZO, and curve C at below 1.38 KPa HZU.
Figure 3 is similar to Figure 2; curve A bring at 0.17 MPa H20, curve B at 1.3 8 KPa.
The thermal treating process described herein is distinguished from Visbreaking (a thermal treating p~roccss j by temperature and overall severity of the operation, as well as by operation at conditions that maintain water partial pressure in the reaction zone below a certain Level. For purposes of this invention we define severity in terms of equivalent seconds at 4b8.3'C, using the following equation:
Ossa.3~ - 60 x e:cp ~ ~ 1 - 1 8.319 , 468.3 +273 T°C r 373 Where: 8ass,~~C = Equiv seconds at 468.3°C for 1 min. operation at T°C
Ea = Activation energy in J/g-mole (.~ J'oule) (221,900 J/g-male typical for Visbrealdng) Visbreaking is typically carried out in one of two configurations, a coil reactor ti~at is contained within a fi~rnac;e or in a "soaker reactoz''.
The former operates at temperatures in the range of about 454_.1-4&7.8°C
with a coil outlet pressure of up to about 7 MPa or above. The soaker reactor operates at as average temperature in the range of about 437.8°C at pressures ranging from about 0.31 to 3.45 MPa. Thermal treatment seventies for both of these visbrealdng processes fall in the range of about 100-200 equivalent seconds at 468.3°C. Them is no specification on water partial pressure in Visbrealdng.
dperation at Visbrealdng sevesities is neither needed nor desired for the practice of the present process where the objective is to destroy carboxylic acids (e.g., naphthenic acids) with minimal cracking of the oil.
The process of this invention comprises the following steps:
prcflash to remove any water that is present in the feed, mild thermal treating in a purged low-pressure reactor of two or more stages and a final step wherein light hydrocarbons rbat are recovered from either thermal treating or tom the pre-flash are recombined with the reactor effluent to obtain a low T.~1N
upgraded crude oil. The thermal treating reactor operates at 343.3-426.7°C, preferably 357.2 - 412.8°C and most preferably from 3?l.l-398.9°C. Pressure is maintauncd below about 0.79 MPa, preferably lfelow about 0.45 MPa. Reaction severity falls in the range of 10 to about 80 equivalent secoads at 468.3°C, preferably from about 20 to 60 equivalent seconds. At a treaunent temperature of 385°C, for example, reaction time will fail in the range of 17-134 miautes.
Turning to Figure 1, crude from an available source, wliether diluted for transportation purposes, or not, in line 10 is processed through desalter 12, cooled and flashed in flash drum 14 from which diluent, if any, water and light hydrocarbons, including gases are recovered in line 15. The flashed crude, rceovcred in line 16 is heated in furnace 18 and injected into a staged bubble column 22 via Iine 19. A purge gas, as described below,, is preferably injected into column 22 via line 21 and engages in counter current contact with the flashed crude. The purge gas, along with auy light hydrocarbons forming via cracking in the bubble column, is recovered in line 23, condensed in condenser 26 from which feel gas is recovered for re-use in line 27. Condensed light hydrocarbons are recovered in line 28 and recombined with the treated crude fraction in line 29 to form an upgraded crude.
In prefeaed embodiments of this invention, at least a portion of the light h~drocatbons, stripped of water and. preferably stripped of dilueat, if any, recovered in line 1~ is recombined with the treated crude by Line 17 or lint 17a;
and a portion of the recovered hydrocarbons from line 15 or line 28 or both is combusted in furnace 18 through line Z5.
As illustrated in examples to follow, control of water partial pressure in the thermal reaction zone is important to the success of the present process. Water has been diseovercd to act as a powerful inhibitor fcr the thermal decomposition of naphthenic acids (WO 96/25471).
Moreover, we have found that inhibition of TAN conversion also inhibits viscosity reduction. Consequently, water (steam) partial pressure in the reaction zone is held below about 68.9 KPa, preferably below about 34.5 KPa and most .5-ably below about I3 .8 KFa. Thus, the need for removal of bulk water from the feed. Additionally, since water is produced by decomposition of carboxylic acids, the reaction zone must: be purged with inert gas (e.g. methane) to control water partial pressure. Carbon dioxide, also an inhibitor for acid decomposition is formed in the process and is purged from the reactor alang with water.
Purge rate is chosen consistent with pressure and level of water in the reaction zone, will generally fall in the range of 8.91-89.1 SCM/cubic rrzeter oil (SCM =
standard cubic meter's). Suitable purge gases include non-oxidizing gases, such a_s ni~agen, methane, well-head gas (fuel gas j hydrogen and carbon monoxide.
The th~rrmal treatment process of this invention is designed to mitumize cracking o:f the hyclrocarbons, yet maximize the decomposition of naphthenic acids. Nevertheless, during the th~:rmal treatment some cracking of the oil will occur anti small amounts of light hydrocarbon gases, i.e., butanes and lighter, will he obtained along with HBO, CO, and C02that arise from decomposition of the; acids. The yield of hydrocarbon gases is low at the mild severities used, and swill ran8;e from about O.S to 2.0 wt% based oa feed.
Thermal treatment is taken, for this invention in its ncnnal meaning and for purposes of this invention ado includes the absence of any catalyst for promoting the conversion of naphthenic acids, the absence of any material added to react with or complex with naphthenic acids, and the absence of absorbents for naphthenic acids, i.e., the absence of any material used for the purpose of removing naphthenic acids.
The thc;rmal treatment is carried out to reduce significantly the oil's TAN, e.g., to levels of less than about 2.0 mg KDHIg oil, preferably less than about l .5 mg KnH/g oil, more preferably less ilum about 1.0 mg KOHIg oil, and still more preferably less than. about 0.5 mg 1COH~g nit as measured by ASTM D-b64.
The oils that can be effectively treated by this process include whole or topped cruder, crude fractions boiling above about 204.4°C, atmospheric residua .and vacccum gas oils, e.g., boiling at about 343.3°C+, e.g., 343.3-565.6°(:.
AMENDED SHEET
During; the therrmal treatment, any cracked hydrocarbons and light gases can be separately recovered and at least a portion thereof may be re-combined with the tireated oil. in a preferred embodiment, a portion of the C4-materials produced in the treatment or a portion of the hydrocarbons produced and recovered from the flash. step, preferably minor portions thereof; c.g., less than 50%, preferabh,r less them 40%, more preferably less than 25°Jo, is combusted to pmvid.e pre-heat for heating the liquid to be thermally treated or to provide heat for the treating zone.
Upon :recovery of the liquid product, and preferably the liquid product plus at least a portion of the hydrocarbons recovered as vapors from the treating zone, i.e., crocked piroducts or light hydrocarbons, or both, the vaporous hydrocarbons, or at :least a p~5rtion thereof recovered from the flash step are also recombined with the treated licguid. Of course, the vaporous hydrocarbons recovered from the treating step may be recombined with the liquid before or after recombination with vap~oraus hydrocarbons from the flashing step.
The ~uial recornbiued product may then be further processed in a refinery without feaa~ of corrosion due to naphthenic acids, either in the pipe stills or in downstream units where various streams ~e.g. distillates) from the pipestills are processed.
A snail fraction of the carboxylic acid components of the feed can volatilize under thermal upgrader conditions and emerge from the reactor as part of the volatile hydrocarbon stream. The yield of this strew, its boiling range and acid (TAN) content will vary with conditions used in the thermal upgrader.
This stream can com.pri5e materials with boiling points up to a temperature close to that used in the thermal upgrader, e.g.37I. i-385~'C. The yield can range from about S to 20 wt% of feed or more and TAN numbers caa range from 1 to 3 or above. Thus, under some conditions, it may prove advantageous to further process the volatile hydrocarbon stream, or a portion thereof, to destroy the TAN
prior to back blendiry this stream with the thermal upgrader liquid effluent"
In one embodiment thi<.> treamxcnt can be hydrotreatment in accordance with the procedure in W 0196/06899 based on PCT/NO95/00142. This process essentially includes treating the recovered fractions in the presence of hydrogen ~,N~ENDED SHL.bE
and a catalyst comprised of nickel or cobalt and molybdenum at temperatures of about I00-300°C anal pressw~es of about 0.1-5 MPa, preferably 200-245°C and 2-3 MP'a, and hydrogen treat rates of 53.4-890.5 SC:vI/cubic meter oil, preferably 89.1-356.2 SCM/cubic meter oil.
The reactor system for the thermal process is _'esigned to provide liquid residence time; at t#le chosen process temperature adequate to achieve the desired conversion and achieve rapid mass transfer to remove the inhibiting products of the reaction water and carbon dioxide. Suitable reactor systems would include mechanically stirred and jet stirred gas-liquid reactors, bubble columns, a-ickle bed reactors (loosely packed fot enhanced mass transfer), membrane reactors, ~~tc., etc. either staged or upstaged.
A pref:rred reactor system for the thermal process is a continuous flow bubble column where tt~e purge gas or stripping gas is bubbled up through the liquid to be ireata:d which flows continuously through the column. The liquid may flow upward, producing cocurrent contact, downward, producing countercurrent contact or crossflow. Generally, countercurrent contact is preferred since it is more e~.cient in stripping the products of ~e therm l reaction from the liquid phase.
More preferred, the bubble column may be empty of internals, yet more preferred bafliE:d, or even further preferred, a separately staged system may be used. It is advantageous t~o have a staged system to achieve high levels of conversion, and the conversion increases with the number of stages in an asymptotic fashion. An empity column basically acts as a single stage in one vessel and has the advantage that it is simple, and that there are no internals to foul with contaminants that nay be in the feed andlor trace reaction products that may be sticky. The haled column gives a multistage reactor in one vessel and has rather simple internals to effect staging. The baffles may be disk and doughnut type or segmented ~aad may or may not have holes for passage of gas vertically through the columr,~ Generally, the baffled single vessel reactor will give more than one stage but less than the number of compartments produced by the baffling since Borne back mixing is always present in such systems.
.. n. ",-_..
~,11J~.'sn~'' . ,. ..
_g_ A still more preferred configuration is a separately staged system which gives the number of stages equal to the number of separate vessels, For operational convents:nce in te;ims of flow of gas (and liquid in the case of countercurrent contact), the <.~tages may be stacked vertically. Any number of stages may be used F~ccordin~; to the design of the process, at least two stages are preferred for the levs;l of conversion desired.
Examples Two arudes from Venezuela were used in the following experiments. Properties ane ;given in Table 1. Prior to use the feeds were subjected to a pre-flesh at 121°C to remove bulk water.
-,. _,_ ~,. : ,,_:: ° , .t _ .g.
TABLE i Source Zuata Cam o-1-Bare Feed Water Content, wt% 1.3 ! 3.8 SS 1.?+C Btms. G(~D)wt~ SO 50.5 V1SCOS1 , Kinematic, CSt (c~ 50535 22701 Total Acid Ntunber (TAN (mg KOHlg 4.5 2.4 Crude S ecific Gravi 1.5.6C/lsi.6C 1.OI6 1.002 Tol. E uiv. 1~ 27 ~LicmCon Carbon, wt'~o 15.2 14.9 H tune insoL, wt% 11.1 1 I.8 Sulfur, wt% 4.2 3.6 Ni, m 100 84 V, m 412 330 Example 1 Dry rluata feed was treated in a stirred autoclave reactor at 385°C
0.31 MPa for 60 rniinutes. 7Che reactor was swept with argon, 67.7 SCMlcubic meter oil, during the course of the thermal treatment to remove volatile products, including water anct carbon oxides that resulted from decornpos~tion of carboxylic acids (e.g., naphthenic acids). The reactor purge or sweep was su~cient to hold water partial pressure below 6.89 KPa. Ln this manner, TA~~T
was reduced by 90a~o and viscosity was reduced by 9G.5%.
Example 2 The p~roceduria of Example 1 were repeated except that the autOClaVe was S~ale:C~. ThlS OpeTatlon SlInulateS COndItI0IIS 1I1 a GOII
YIS~rCaICeT
reactor wherein products of decomposition are in contact, under pressure, with the feed. In this mode of operation, the partial pressure of water in the autoclave reactor reached a maximum of 55.8 KPa (calculated value based on moles of acid decolnposed).. The resultant reduction in TAN was 80.6% and viscosity was reduced 91.8°,~0.
AMENDED SHEET
- i0 -Exam le Ex le 2 Max Press., MPa 0.308 1.20 Partial Press., KPa CO 8.96 10.5 C02 0.689 8.96 I~20 4.83 55.8 H2S 19.3 244 C4- 44.8 576 TAN Conv. % 94.2 50.6 Relative R~~te 1.0 0.4 Viscosi , c;~t 40'C 1767 4115 Example 3 Experimeats were carried out with dried Zuata feed to further demonstrate and to quantify 'the effect of water on TAN and Viscosity reduction under mild thermal treating conditions. The procedures of Example 1 were repeated except that water was fed to the reactor along with sweep gas to simulate operation ~~ith feed that had not been dried, i.e., not subjected to the pre-flash step of the present iinvention.
In one set of experiments, TAN conversion was measured as a fimction of increasing reaction severity, while purge the reactor with inert gas to hold water partial pressure' below about 1.38 KPa. In a second set of experiments within the same range of reaction seventies, water was fed to the reactor along with inert sweep gas to sirnulat~ operation with a feed that contained 2.6 wt% bulk water. Water partial pressure was approximately Q.1 MPa in this series of runs. b~ a third set of experi-menu, water was added to attain a partial press~xre of 0.17-0.19 MPa in the reactor.
AMENDED SHEET
TAN reductions was suppressed with water present (Figure 2).
Viscosity reduction was also suppressed.
Example 4 The e~~eriments of Example 3 were repeated with the Cameo-1-Bare feed (Table 1). With eater present in. the thermal treating reactor at 0.17 MPa, TAN conversion was inhibited relative to operation with a dry feed wherein water parti~~l pressure was less than 1.38 KPa (Figure 3). Viscosity reduction was also inhibited 'by the presence of water.
w, ~ cy,~ ~'= :' ~,;:~~,_ , _.
CRUDE OIL
FIELD OF THE INV'ENTIO:IV
This invention :relates to the treatment of crude oil, including heavy cruder, for reducing ~'he total acid number (TAN) of the oil.
BACKGROUND OF' THE IrIVENTION
The value of crude oils is often dependent on the corrosiW ty of the oil, and corrosivity is mainly a function of the total acid number of the oil.
TA.N, in tour, is heavily dependent, although not completely so, on the naphthenic acid conc~entratioa of the oil. Consequently, cruder having a relatively high TAN, e.g., Z2 have a significantly lower market value, on a per cubic meter basis, than crudea having a relatively lower TAlV'. For example, high TAN etudes are often hl~ended off with lower TAN erodes rather than being processed separatelythrough refineries, thereby avoiding excessive corrosion in refinery equipment. frocessi~ng of high TAN cruder can also necessitate the use of expensive alloys ire primanr equipment, e.g., pipestills, thereby minimizing corrosivity effects of the etudes. Both methods for handling high TAN cruder are expensive and cans lead to excessive storage Facilities or upsets in the refinery. Consequently, there remains a need for handling high TA~'~1 etudes that is not disruptive of refinery operations and avoids excessive costs, SUMMARY OF THEf TION
In accordance with this invention, TAN containing oils, e.g., cruder, extra heavy oils, bitumens, kerogens, are pretreated by flashing og vapors including light gases, water, and Light hydrocarbons, subjecting the r4maining liquid phase to a thermal treatment wherein naphtheaic acids ate decomposed and TAN is redw~ed, followed by recombining at least a portion of the hydrocarbon vapour recovc;red from the flash with the treated liquid.
AMENDED SHEET
_2_ The thermal tre;atmeat of this invention a not to be confused with visbreaking which is essentially a treatment of heavy oils or whole crudes at temperatures in excess of the temperatures of the thermal treatment disclosed herein:
TAN reductions in accordance with this invention are preferably on the order of at least 70°lg more preferably at least about 80°!0, still more preferably at Least about 90%r.
In the practice of this invention the oil to be treated may or may not be subjected to desalting prior to the flashing of the light materials.
Desalting is generally preferred with oils having in excess of 5.7g of salt per cubic meter of oil and more lrreferably when the salt level exceeds 11.4g of salt per cubic meter of oil. Desalting is a common process and will be well known to those skilled in the a~-t of refLaing.
In many ruses, particularly where heavy erodes, e.g., Bachaquern, Morichal, Cerro Negro, Zuae~, or Cameo-1-Bare, alI Venezuelan heavy erodes, and cases involving hitumens, the crude or heavy oil is diluted with naphtha to provide ease of traas;portation, e.g., pumpability. Tn the flashing step, the diluent will be vaporized along with C4- gases (e.g., light-ends), water, and anything else that wilt be vaporized at the flashing conditions of about 121.1 to 371.1°C, and pressures ranging from atmospheric to about 1.82 MPa. The extent of the flash step is largely detertr~ined by removing substantially all of the water present in the oil, e.g., to levels of less than about 0.5 wt°%, preferably less ;han about 0.1 wt°/a. The flashed hydrocarb~5ns, e.g., light gases, naphtha diluent, or light hydrocarbons are recovered from the flash and maintained for later combining of at least a portion thereof and substantially all, with the product of the thermal treatment.
BRIEF DESCRIPTIt3N OF T'HE DRAWINGS
Figure 1 is a schematic flow plan illustrating the process of this invention.
AMENDED SHEET
Figure 2 shows the effect of water on TAN conversion, where the abscissa is reaction time (min.) at 385°C and the ordinate is product TAN/feed TAN.
Curve A was at 0.17 MPa HZO, curve B at 0.10 MPa HZO, and curve C at below 1.38 KPa HZU.
Figure 3 is similar to Figure 2; curve A bring at 0.17 MPa H20, curve B at 1.3 8 KPa.
The thermal treating process described herein is distinguished from Visbreaking (a thermal treating p~roccss j by temperature and overall severity of the operation, as well as by operation at conditions that maintain water partial pressure in the reaction zone below a certain Level. For purposes of this invention we define severity in terms of equivalent seconds at 4b8.3'C, using the following equation:
Ossa.3~ - 60 x e:cp ~ ~ 1 - 1 8.319 , 468.3 +273 T°C r 373 Where: 8ass,~~C = Equiv seconds at 468.3°C for 1 min. operation at T°C
Ea = Activation energy in J/g-mole (.~ J'oule) (221,900 J/g-male typical for Visbrealdng) Visbreaking is typically carried out in one of two configurations, a coil reactor ti~at is contained within a fi~rnac;e or in a "soaker reactoz''.
The former operates at temperatures in the range of about 454_.1-4&7.8°C
with a coil outlet pressure of up to about 7 MPa or above. The soaker reactor operates at as average temperature in the range of about 437.8°C at pressures ranging from about 0.31 to 3.45 MPa. Thermal treatment seventies for both of these visbrealdng processes fall in the range of about 100-200 equivalent seconds at 468.3°C. Them is no specification on water partial pressure in Visbrealdng.
dperation at Visbrealdng sevesities is neither needed nor desired for the practice of the present process where the objective is to destroy carboxylic acids (e.g., naphthenic acids) with minimal cracking of the oil.
The process of this invention comprises the following steps:
prcflash to remove any water that is present in the feed, mild thermal treating in a purged low-pressure reactor of two or more stages and a final step wherein light hydrocarbons rbat are recovered from either thermal treating or tom the pre-flash are recombined with the reactor effluent to obtain a low T.~1N
upgraded crude oil. The thermal treating reactor operates at 343.3-426.7°C, preferably 357.2 - 412.8°C and most preferably from 3?l.l-398.9°C. Pressure is maintauncd below about 0.79 MPa, preferably lfelow about 0.45 MPa. Reaction severity falls in the range of 10 to about 80 equivalent secoads at 468.3°C, preferably from about 20 to 60 equivalent seconds. At a treaunent temperature of 385°C, for example, reaction time will fail in the range of 17-134 miautes.
Turning to Figure 1, crude from an available source, wliether diluted for transportation purposes, or not, in line 10 is processed through desalter 12, cooled and flashed in flash drum 14 from which diluent, if any, water and light hydrocarbons, including gases are recovered in line 15. The flashed crude, rceovcred in line 16 is heated in furnace 18 and injected into a staged bubble column 22 via Iine 19. A purge gas, as described below,, is preferably injected into column 22 via line 21 and engages in counter current contact with the flashed crude. The purge gas, along with auy light hydrocarbons forming via cracking in the bubble column, is recovered in line 23, condensed in condenser 26 from which feel gas is recovered for re-use in line 27. Condensed light hydrocarbons are recovered in line 28 and recombined with the treated crude fraction in line 29 to form an upgraded crude.
In prefeaed embodiments of this invention, at least a portion of the light h~drocatbons, stripped of water and. preferably stripped of dilueat, if any, recovered in line 1~ is recombined with the treated crude by Line 17 or lint 17a;
and a portion of the recovered hydrocarbons from line 15 or line 28 or both is combusted in furnace 18 through line Z5.
As illustrated in examples to follow, control of water partial pressure in the thermal reaction zone is important to the success of the present process. Water has been diseovercd to act as a powerful inhibitor fcr the thermal decomposition of naphthenic acids (WO 96/25471).
Moreover, we have found that inhibition of TAN conversion also inhibits viscosity reduction. Consequently, water (steam) partial pressure in the reaction zone is held below about 68.9 KPa, preferably below about 34.5 KPa and most .5-ably below about I3 .8 KFa. Thus, the need for removal of bulk water from the feed. Additionally, since water is produced by decomposition of carboxylic acids, the reaction zone must: be purged with inert gas (e.g. methane) to control water partial pressure. Carbon dioxide, also an inhibitor for acid decomposition is formed in the process and is purged from the reactor alang with water.
Purge rate is chosen consistent with pressure and level of water in the reaction zone, will generally fall in the range of 8.91-89.1 SCM/cubic rrzeter oil (SCM =
standard cubic meter's). Suitable purge gases include non-oxidizing gases, such a_s ni~agen, methane, well-head gas (fuel gas j hydrogen and carbon monoxide.
The th~rrmal treatment process of this invention is designed to mitumize cracking o:f the hyclrocarbons, yet maximize the decomposition of naphthenic acids. Nevertheless, during the th~:rmal treatment some cracking of the oil will occur anti small amounts of light hydrocarbon gases, i.e., butanes and lighter, will he obtained along with HBO, CO, and C02that arise from decomposition of the; acids. The yield of hydrocarbon gases is low at the mild severities used, and swill ran8;e from about O.S to 2.0 wt% based oa feed.
Thermal treatment is taken, for this invention in its ncnnal meaning and for purposes of this invention ado includes the absence of any catalyst for promoting the conversion of naphthenic acids, the absence of any material added to react with or complex with naphthenic acids, and the absence of absorbents for naphthenic acids, i.e., the absence of any material used for the purpose of removing naphthenic acids.
The thc;rmal treatment is carried out to reduce significantly the oil's TAN, e.g., to levels of less than about 2.0 mg KDHIg oil, preferably less than about l .5 mg KnH/g oil, more preferably less ilum about 1.0 mg KOHIg oil, and still more preferably less than. about 0.5 mg 1COH~g nit as measured by ASTM D-b64.
The oils that can be effectively treated by this process include whole or topped cruder, crude fractions boiling above about 204.4°C, atmospheric residua .and vacccum gas oils, e.g., boiling at about 343.3°C+, e.g., 343.3-565.6°(:.
AMENDED SHEET
During; the therrmal treatment, any cracked hydrocarbons and light gases can be separately recovered and at least a portion thereof may be re-combined with the tireated oil. in a preferred embodiment, a portion of the C4-materials produced in the treatment or a portion of the hydrocarbons produced and recovered from the flash. step, preferably minor portions thereof; c.g., less than 50%, preferabh,r less them 40%, more preferably less than 25°Jo, is combusted to pmvid.e pre-heat for heating the liquid to be thermally treated or to provide heat for the treating zone.
Upon :recovery of the liquid product, and preferably the liquid product plus at least a portion of the hydrocarbons recovered as vapors from the treating zone, i.e., crocked piroducts or light hydrocarbons, or both, the vaporous hydrocarbons, or at :least a p~5rtion thereof recovered from the flash step are also recombined with the treated licguid. Of course, the vaporous hydrocarbons recovered from the treating step may be recombined with the liquid before or after recombination with vap~oraus hydrocarbons from the flashing step.
The ~uial recornbiued product may then be further processed in a refinery without feaa~ of corrosion due to naphthenic acids, either in the pipe stills or in downstream units where various streams ~e.g. distillates) from the pipestills are processed.
A snail fraction of the carboxylic acid components of the feed can volatilize under thermal upgrader conditions and emerge from the reactor as part of the volatile hydrocarbon stream. The yield of this strew, its boiling range and acid (TAN) content will vary with conditions used in the thermal upgrader.
This stream can com.pri5e materials with boiling points up to a temperature close to that used in the thermal upgrader, e.g.37I. i-385~'C. The yield can range from about S to 20 wt% of feed or more and TAN numbers caa range from 1 to 3 or above. Thus, under some conditions, it may prove advantageous to further process the volatile hydrocarbon stream, or a portion thereof, to destroy the TAN
prior to back blendiry this stream with the thermal upgrader liquid effluent"
In one embodiment thi<.> treamxcnt can be hydrotreatment in accordance with the procedure in W 0196/06899 based on PCT/NO95/00142. This process essentially includes treating the recovered fractions in the presence of hydrogen ~,N~ENDED SHL.bE
and a catalyst comprised of nickel or cobalt and molybdenum at temperatures of about I00-300°C anal pressw~es of about 0.1-5 MPa, preferably 200-245°C and 2-3 MP'a, and hydrogen treat rates of 53.4-890.5 SC:vI/cubic meter oil, preferably 89.1-356.2 SCM/cubic meter oil.
The reactor system for the thermal process is _'esigned to provide liquid residence time; at t#le chosen process temperature adequate to achieve the desired conversion and achieve rapid mass transfer to remove the inhibiting products of the reaction water and carbon dioxide. Suitable reactor systems would include mechanically stirred and jet stirred gas-liquid reactors, bubble columns, a-ickle bed reactors (loosely packed fot enhanced mass transfer), membrane reactors, ~~tc., etc. either staged or upstaged.
A pref:rred reactor system for the thermal process is a continuous flow bubble column where tt~e purge gas or stripping gas is bubbled up through the liquid to be ireata:d which flows continuously through the column. The liquid may flow upward, producing cocurrent contact, downward, producing countercurrent contact or crossflow. Generally, countercurrent contact is preferred since it is more e~.cient in stripping the products of ~e therm l reaction from the liquid phase.
More preferred, the bubble column may be empty of internals, yet more preferred bafliE:d, or even further preferred, a separately staged system may be used. It is advantageous t~o have a staged system to achieve high levels of conversion, and the conversion increases with the number of stages in an asymptotic fashion. An empity column basically acts as a single stage in one vessel and has the advantage that it is simple, and that there are no internals to foul with contaminants that nay be in the feed andlor trace reaction products that may be sticky. The haled column gives a multistage reactor in one vessel and has rather simple internals to effect staging. The baffles may be disk and doughnut type or segmented ~aad may or may not have holes for passage of gas vertically through the columr,~ Generally, the baffled single vessel reactor will give more than one stage but less than the number of compartments produced by the baffling since Borne back mixing is always present in such systems.
.. n. ",-_..
~,11J~.'sn~'' . ,. ..
_g_ A still more preferred configuration is a separately staged system which gives the number of stages equal to the number of separate vessels, For operational convents:nce in te;ims of flow of gas (and liquid in the case of countercurrent contact), the <.~tages may be stacked vertically. Any number of stages may be used F~ccordin~; to the design of the process, at least two stages are preferred for the levs;l of conversion desired.
Examples Two arudes from Venezuela were used in the following experiments. Properties ane ;given in Table 1. Prior to use the feeds were subjected to a pre-flesh at 121°C to remove bulk water.
-,. _,_ ~,. : ,,_:: ° , .t _ .g.
TABLE i Source Zuata Cam o-1-Bare Feed Water Content, wt% 1.3 ! 3.8 SS 1.?+C Btms. G(~D)wt~ SO 50.5 V1SCOS1 , Kinematic, CSt (c~ 50535 22701 Total Acid Ntunber (TAN (mg KOHlg 4.5 2.4 Crude S ecific Gravi 1.5.6C/lsi.6C 1.OI6 1.002 Tol. E uiv. 1~ 27 ~LicmCon Carbon, wt'~o 15.2 14.9 H tune insoL, wt% 11.1 1 I.8 Sulfur, wt% 4.2 3.6 Ni, m 100 84 V, m 412 330 Example 1 Dry rluata feed was treated in a stirred autoclave reactor at 385°C
0.31 MPa for 60 rniinutes. 7Che reactor was swept with argon, 67.7 SCMlcubic meter oil, during the course of the thermal treatment to remove volatile products, including water anct carbon oxides that resulted from decornpos~tion of carboxylic acids (e.g., naphthenic acids). The reactor purge or sweep was su~cient to hold water partial pressure below 6.89 KPa. Ln this manner, TA~~T
was reduced by 90a~o and viscosity was reduced by 9G.5%.
Example 2 The p~roceduria of Example 1 were repeated except that the autOClaVe was S~ale:C~. ThlS OpeTatlon SlInulateS COndItI0IIS 1I1 a GOII
YIS~rCaICeT
reactor wherein products of decomposition are in contact, under pressure, with the feed. In this mode of operation, the partial pressure of water in the autoclave reactor reached a maximum of 55.8 KPa (calculated value based on moles of acid decolnposed).. The resultant reduction in TAN was 80.6% and viscosity was reduced 91.8°,~0.
AMENDED SHEET
- i0 -Exam le Ex le 2 Max Press., MPa 0.308 1.20 Partial Press., KPa CO 8.96 10.5 C02 0.689 8.96 I~20 4.83 55.8 H2S 19.3 244 C4- 44.8 576 TAN Conv. % 94.2 50.6 Relative R~~te 1.0 0.4 Viscosi , c;~t 40'C 1767 4115 Example 3 Experimeats were carried out with dried Zuata feed to further demonstrate and to quantify 'the effect of water on TAN and Viscosity reduction under mild thermal treating conditions. The procedures of Example 1 were repeated except that water was fed to the reactor along with sweep gas to simulate operation ~~ith feed that had not been dried, i.e., not subjected to the pre-flash step of the present iinvention.
In one set of experiments, TAN conversion was measured as a fimction of increasing reaction severity, while purge the reactor with inert gas to hold water partial pressure' below about 1.38 KPa. In a second set of experiments within the same range of reaction seventies, water was fed to the reactor along with inert sweep gas to sirnulat~ operation with a feed that contained 2.6 wt% bulk water. Water partial pressure was approximately Q.1 MPa in this series of runs. b~ a third set of experi-menu, water was added to attain a partial press~xre of 0.17-0.19 MPa in the reactor.
AMENDED SHEET
TAN reductions was suppressed with water present (Figure 2).
Viscosity reduction was also suppressed.
Example 4 The e~~eriments of Example 3 were repeated with the Cameo-1-Bare feed (Table 1). With eater present in. the thermal treating reactor at 0.17 MPa, TAN conversion was inhibited relative to operation with a dry feed wherein water parti~~l pressure was less than 1.38 KPa (Figure 3). Viscosity reduction was also inhibited 'by the presence of water.
w, ~ cy,~ ~'= :' ~,;:~~,_ , _.
Claims (11)
1. A process for reducing the total acid number (TAN) of TAN
and water containing oils comprising: (a) flashing the oil and removing there-from substantially all of the water; (b) separately recovering liquid and hydrocarbon gases; (c) thermally treating the liquid in a reaction zone in which the water partial pressure is maintained below about 69 KPa, (d) combining at least a portion of the recovered hydrocarbon gases with the treated liquid
and water containing oils comprising: (a) flashing the oil and removing there-from substantially all of the water; (b) separately recovering liquid and hydrocarbon gases; (c) thermally treating the liquid in a reaction zone in which the water partial pressure is maintained below about 69 KPa, (d) combining at least a portion of the recovered hydrocarbon gases with the treated liquid
2. The process of claim 1 wherein the oil is subjected to desalting prior to step (a).
3. The process of claim 1 wherein the treated liquid has a TAN
<= 2.0 mg KOH/gm oil.
<= 2.0 mg KOH/gm oil.
4. The process of claim 1 wherein the water content of the oil after step (a) is less than about 0.5 wt%.
5. The process of claim 1 wherein a portion of the hydrocarbon gases recovered in claim 1 is combusted.
6. The process of claim 5 wherein the hydrocarbon gases are combusted for preheating the liquid recovered in step (b).
7. The process of claim 5 wherein the hydrocarbon gases are combusted to provide heat for the thermal treatment of the liquid recovered in step (b).
8. The process of claim 1 wherein the thermal treatment is effected at temperatures of 343.3-426.7°C.
9. The process of claim 1 wherein the flash temperature of step (a) ranges from about 121.1-371.1°C.
10. The process of claim 1 wherein a purge gas is injected into the thermal treating reacting zone to maintain a water partial pressure therein of less than about 69 KPa.
11. The process of claim 1 wherein the reaction zone is a two stage bubble column.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/920,549 | 1997-08-29 | ||
| US08/920,549 US6086751A (en) | 1997-08-29 | 1997-08-29 | Thermal process for reducing total acid number of crude oil |
| PCT/US1998/018050 WO1999010452A1 (en) | 1997-08-29 | 1998-08-28 | Thermal process for reducing total acid number of crude oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2294952A1 CA2294952A1 (en) | 1999-03-04 |
| CA2294952C true CA2294952C (en) | 2005-06-14 |
Family
ID=25443933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002294952A Expired - Lifetime CA2294952C (en) | 1997-08-29 | 1998-08-28 | Thermal process for reducing total acid number of crude oil |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6086751A (en) |
| EP (1) | EP1062298B1 (en) |
| AU (1) | AU735810B2 (en) |
| CA (1) | CA2294952C (en) |
| DE (1) | DE69804025T2 (en) |
| DK (1) | DK1062298T3 (en) |
| ES (1) | ES2172912T3 (en) |
| WO (1) | WO1999010452A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4112702A1 (en) | 2021-06-29 | 2023-01-04 | Indian Oil Corporation Limited | Pre-treatment process for conversion of residual oils in a delayed coker unit |
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|---|---|---|---|---|
| BR0202552B1 (en) * | 2002-07-05 | 2012-10-30 | process of reducing naphthenic acidity in petroleum. | |
| US20100098602A1 (en) * | 2003-12-19 | 2010-04-22 | Opinder Kishan Bhan | Systems, methods, and catalysts for producing a crude product |
| US7591941B2 (en) | 2003-12-19 | 2009-09-22 | Shell Oil Company | Systems, methods, and catalysts for producing a crude product |
| US7745369B2 (en) | 2003-12-19 | 2010-06-29 | Shell Oil Company | Method and catalyst for producing a crude product with minimal hydrogen uptake |
| CA2455011C (en) * | 2004-01-09 | 2011-04-05 | Suncor Energy Inc. | Bituminous froth inline steam injection processing |
| CA2455149C (en) * | 2004-01-22 | 2006-04-11 | Suncor Energy Inc. | In-line hydrotreatment process for low tan synthetic crude oil production from oil sand |
| US7435760B2 (en) * | 2004-05-14 | 2008-10-14 | Battelle Memorial Institute | Method of generating hydrocarbon reagents from diesel, natural gas and other logistical fuels |
| EP1950267A1 (en) * | 2004-05-14 | 2008-07-30 | Battelle Memorial Institute | Method of generating hydrocarbon reagents from diesel, natural gas and other logistical fuels |
| US20060043003A1 (en) * | 2004-08-26 | 2006-03-02 | Petroleo Brasileiro S.A. - Petrobras | Process for reducing the acidity of hydrocarbon mixtures |
| CN1814704A (en) * | 2005-01-31 | 2006-08-09 | 中国石油化工股份有限公司 | Method for deeply removing petroleum acids from acid-contained raw oil |
| CN100363467C (en) * | 2005-03-03 | 2008-01-23 | 中国石油化工股份有限公司 | A method for processing high acid value crude oil |
| BRPI0609416A2 (en) | 2005-04-11 | 2011-10-11 | Shell Int Research | method to produce a gross product |
| US20090007996A1 (en) * | 2005-05-12 | 2009-01-08 | Battelle Memorial Institute | Method for Vibrating a Substrate During Material Formation |
| BRPI0503793B1 (en) * | 2005-09-15 | 2014-12-30 | Petroleo Brasileiro Sa | ACIDITY REDUCTION PROCESS FOR HYDROCARBON MIXTURES |
| US8277639B2 (en) * | 2005-09-20 | 2012-10-02 | Exxonmobil Chemical Patents Inc. | Steam cracking of high TAN crudes |
| GB2446867A (en) * | 2007-02-21 | 2008-08-27 | Oil Plus Ltd | Method for determining Total Acid Number (TAN) |
| BRPI0905232A2 (en) * | 2009-12-30 | 2011-08-23 | Petroleo Brasileiro Sa | process for reducing naphthenic acidity and simultaneously increasing heavy oil api |
| KR101898289B1 (en) | 2011-01-10 | 2018-09-13 | 에스케이이노베이션 주식회사 | Method for reducing organic acid in a hydrocarbon oil |
| CN102643671B (en) * | 2011-02-17 | 2015-03-18 | 中国石油化工股份有限公司 | Processing method of heavy oil raw material |
| US8911616B2 (en) | 2011-04-26 | 2014-12-16 | Uop Llc | Hydrotreating process and controlling a temperature thereof |
| JP6072790B2 (en) | 2011-07-29 | 2017-02-01 | サウジ アラビアン オイル カンパニー | Method for reducing total acid number in petroleum refinery feedstock |
| US9238780B2 (en) | 2012-02-17 | 2016-01-19 | Reliance Industries Limited | Solvent extraction process for removal of naphthenic acids and calcium from low asphaltic crude oil |
| WO2014124517A1 (en) | 2013-02-15 | 2014-08-21 | Rival Technologies Inc. | Method of upgrading heavy crude oil |
| US20140325896A1 (en) * | 2013-05-02 | 2014-11-06 | Shell Oil Company | Process for converting a biomass material |
| US9751072B2 (en) * | 2014-03-18 | 2017-09-05 | Quanta, Associates, L.P. | Treatment of heavy crude oil and diluent |
| CN113322098A (en) * | 2020-08-19 | 2021-08-31 | 中国石油天然气股份有限公司 | Method for reducing acid value of high-acid crude oil and marine fuel oil |
| CN114106874A (en) * | 2020-08-27 | 2022-03-01 | 中国石油天然气股份有限公司 | Method and device for pyrolysis deacidification of high-acid crude oil or high-acid residual oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1953353A (en) * | 1930-08-19 | 1934-04-03 | Associated Oil Company | Process of treating hydrocarbon oils |
| US2040104A (en) * | 1931-02-27 | 1936-05-12 | Barrett Co | Tar treatment |
| US2227811A (en) * | 1938-05-23 | 1941-01-07 | Shell Dev | Process for removing naphthenic acids from hydrocarbon oils |
| CA1307489C (en) * | 1989-04-07 | 1992-09-15 | Stephen V. Krynski | Crude oil emulsion treating apparatus |
| US5250175A (en) * | 1989-11-29 | 1993-10-05 | Seaview Thermal Systems | Process for recovery and treatment of hazardous and non-hazardous components from a waste stream |
| US5820750A (en) * | 1995-02-17 | 1998-10-13 | Exxon Research And Engineering Company | Thermal decomposition of naphthenic acids |
| DK0809683T3 (en) * | 1995-02-17 | 2002-03-04 | Exxonmobil Res & Eng Co | Thermal decomposition of naphthenic acids |
-
1997
- 1997-08-29 US US08/920,549 patent/US6086751A/en not_active Expired - Lifetime
-
1998
- 1998-08-28 CA CA002294952A patent/CA2294952C/en not_active Expired - Lifetime
- 1998-08-28 EP EP98942323A patent/EP1062298B1/en not_active Expired - Lifetime
- 1998-08-28 AU AU90406/98A patent/AU735810B2/en not_active Ceased
- 1998-08-28 WO PCT/US1998/018050 patent/WO1999010452A1/en not_active Ceased
- 1998-08-28 ES ES98942323T patent/ES2172912T3/en not_active Expired - Lifetime
- 1998-08-28 DE DE69804025T patent/DE69804025T2/en not_active Expired - Lifetime
- 1998-08-28 DK DK98942323T patent/DK1062298T3/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4112702A1 (en) | 2021-06-29 | 2023-01-04 | Indian Oil Corporation Limited | Pre-treatment process for conversion of residual oils in a delayed coker unit |
| US11661556B2 (en) | 2021-06-29 | 2023-05-30 | Indian Oil Corporation Limited | Pre-treatment process for conversion of residual oils in a Delayed Coker Unit |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2172912T3 (en) | 2002-10-01 |
| EP1062298B1 (en) | 2002-02-27 |
| DE69804025D1 (en) | 2002-04-04 |
| AU9040698A (en) | 1999-03-16 |
| US6086751A (en) | 2000-07-11 |
| WO1999010452A1 (en) | 1999-03-04 |
| DK1062298T3 (en) | 2002-04-02 |
| AU735810B2 (en) | 2001-07-19 |
| CA2294952A1 (en) | 1999-03-04 |
| DE69804025T2 (en) | 2002-08-14 |
| EP1062298A1 (en) | 2000-12-27 |
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