CA2512822C - Gel assisted separation method and dewatering/desalting hydrocarbon oils - Google Patents
Gel assisted separation method and dewatering/desalting hydrocarbon oils Download PDFInfo
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- CA2512822C CA2512822C CA2512822A CA2512822A CA2512822C CA 2512822 C CA2512822 C CA 2512822C CA 2512822 A CA2512822 A CA 2512822A CA 2512822 A CA2512822 A CA 2512822A CA 2512822 C CA2512822 C CA 2512822C
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 152
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 123
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 120
- 239000003921 oil Substances 0.000 title claims description 133
- 238000000926 separation method Methods 0.000 title claims description 24
- 238000011033 desalting Methods 0.000 title claims description 15
- 238000000034 method Methods 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 239000010779 crude oil Substances 0.000 claims description 47
- 150000003839 salts Chemical class 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 230000001351 cycling effect Effects 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000005608 naphthenic acid group Chemical group 0.000 claims description 12
- 238000011282 treatment Methods 0.000 claims description 11
- -1 hydrocarbons compounds Chemical class 0.000 claims description 10
- 239000003245 coal Substances 0.000 claims description 9
- 239000000571 coke Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol group Chemical group [C@@H]1(CC[C@H]2[C@@H]3CC=C4C[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C)[C@H](C)CCCC(C)C HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229920005610 lignin Polymers 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical class [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 235000011148 calcium chloride Nutrition 0.000 claims description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- LKVLGPGMWVYUQI-UHFFFAOYSA-L calcium;naphthalene-2-carboxylate Chemical class [Ca+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 LKVLGPGMWVYUQI-UHFFFAOYSA-L 0.000 claims 2
- 235000019198 oils Nutrition 0.000 description 91
- 239000000499 gel Substances 0.000 description 66
- 235000002639 sodium chloride Nutrition 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 230000005686 electrostatic field Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000019476 oil-water mixture Nutrition 0.000 description 2
- 230000003534 oscillatory effect Effects 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 210000000707 wrist Anatomy 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000000196 viscometry Methods 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/02—Non-metals
-
- 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
- C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
-
- 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
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A method for separating polar hydrocarbon compounds from a hydrocarbon oil containing polar hydrocarbon compounds comprising the steps of: a) forming a gel in the hydrocarbon oil, and thereafter b) separating the gel from the hydrocarbon oil to produce a separated gel and a separated hydrocarbon oil.
Description
~ 1 GEL ASSISTED SEPARATION METHOD AND
DEWATERING/DESALTING HYDROCARBON OILS
FIELD OF THE INVENTION
[0001] The invention relates to separating polar hydrocarbons from hydrocarbon oils.The invention also relates to desalting and/or dewatering s hydrocarbon oils.
BACKGROUND
DEWATERING/DESALTING HYDROCARBON OILS
FIELD OF THE INVENTION
[0001] The invention relates to separating polar hydrocarbons from hydrocarbon oils.The invention also relates to desalting and/or dewatering s hydrocarbon oils.
BACKGROUND
[0002] Hydrocarbon oils, particularly heavy crude oils, contain polar io hydrocarbon compounds such as naphthenic acids, nitrogen and sulfur containing hydrocarbon compounds and pose problems in refining. There is a need to upgrade such hydrocrabon oils. Separation of polar hydrocarbon compounds such as naphthenic acids, nitrogen and sulfur containing hydrocarbon compounds from crude oils results in upgrading. The present ~s invention addresses this need.
[0003] Hydrocarbon oils, particularly crude oils when produced comprise varying amounts of water and inorganic salts like halogens, sulfates and carbonates of Group I and Group II elements of The Periodic Table of Elements.
20 ( The Periodic Table of Elements is the common long form of the periodic table;
Advanced Inorganic Chemistry by F.A Cotton and G. Wilkinson Interscience Publishers, 1962) Removal of water from produced crude oils is termed dewatering and salt removal is termed desalting. Often, the process of dewatering also desalts the crude oil since water-soluble salts are removed with 25 the water.
20 ( The Periodic Table of Elements is the common long form of the periodic table;
Advanced Inorganic Chemistry by F.A Cotton and G. Wilkinson Interscience Publishers, 1962) Removal of water from produced crude oils is termed dewatering and salt removal is termed desalting. Often, the process of dewatering also desalts the crude oil since water-soluble salts are removed with 25 the water.
[0004] Dewatering the produced crude oil is desired at crude oil production facilities as it impacts the value of crude oil and its economic transportation. The presence of salts, especially chlorides of Group I and Group II elements of The Periodic Table of Elements, corrode oil processing equipment. In order to mitigate the effects of corrosion, it is advantageous to reduce the salt concentration to the range of 1 to 5 ppm or less and water content to about 0.25 to 1 wt% by weight of the crude oil prior to transportation and processing of the oil.
[0005] Among the crude oil dewatering and/or desalting methods in use today, electrostatic separation methods are commonly used. Heavy crude oils ~o containing high concentrations of asphaltenes, resins, waxes, and napthenic acids are difficult to dewater and desalt and usually require longer processing times, higher process operation temperatures and higher concentrations of demulsifier chemicals to effect the desired dewatering and desalting. As a result of these processing requirements for heavy crude oils the process throughput is lowered 1s and costs for dewatering and desalting increased. Consequently, there is a need for improved crude oil dewatering and/or desalting methods that improve the efficiency of dewatering andJor desalting especially with heavy crude oils containing asphaltenes and naphthenic acids. The present invention also addresses this need.
SUMMARY OF THE INVENTION
SUMMARY OF THE INVENTION
[0006] In one embodiment is a method for separating polar hydrocarbon compounds from a hydrocarbon oil containing polar hydrocarbon compounds 2s comprising the steps of:
a) forming a gel in the hydrocarbon oil, and thereafter b) separating the gel from the hydrocarbon oil to produce a separated gel and a separated hydrocarbon oil.
a) forming a gel in the hydrocarbon oil, and thereafter b) separating the gel from the hydrocarbon oil to produce a separated gel and a separated hydrocarbon oil.
[0007] In another embodiment is a method for dewatering and/or desalting a s hydrocarbon oil containing water and salt comprising the steps of:
a) forming a gel in the hydrocarbon oil, b) separating the gel from the hydrocarbon oil to produce a io separated gel and a separated hydrocarbon oil, and thereafter c) separating water and salt from the separated hydrocarbon oil to provide a dewatered and desalted hydrocarbon oil.
is DETAILED DESCRIPTION OF THE PRFERRED EMBODIMENTS
a) forming a gel in the hydrocarbon oil, b) separating the gel from the hydrocarbon oil to produce a io separated gel and a separated hydrocarbon oil, and thereafter c) separating water and salt from the separated hydrocarbon oil to provide a dewatered and desalted hydrocarbon oil.
is DETAILED DESCRIPTION OF THE PRFERRED EMBODIMENTS
[0008] The gel separation method of the instant invention is useful for hydrocarbon oils comprising polar hydrocarbon compounds. It is particularly useful for crude oils that contain polar hydrocarbon compounds such as 2o naphthenic acids, asphaltenes and metalloprophyrins. Separation of the polar hydrocarbon compounds from the crude oil results in a upgraded crude oil.
Preferred hydrocarbon oils are hydrocarbon oils selected from the group consisting of crude oil, crude oil distillate , crude oil residuum or mixtures thereof.
Preferred hydrocarbon oils are hydrocarbon oils selected from the group consisting of crude oil, crude oil distillate , crude oil residuum or mixtures thereof.
[0009] The desalting and/or dewatering method of the instant invention is useful for hydrocarbon oils comprising salts, water and mixtures thereof. It is particularly useful for heavy and waxy crude oils that are generally difficult to dewater and/or desalt. The salts present in the hydrocarbon oil are inorganic salts including halogens, sulfates and carbonates of Group I and Group II elements of The Periodic Table of Elements. The concentration of the salts can vary from about 0.001 to lOwt% based on the weight of the hydrocarbon oil. The process is s effective for both water-soluble and water insoluble salts that are suspended in the hydrocarbon oil. The water content of the hydrocarbon oil-water mixture can vary in the range of 0.5 wt% to 20 wt% based on the weight of the hydrocarbon-water mixture. The hydrocarbon oil required to be dewatered and/or desalted can be a crude oil, crude oil distillate, and crude oil residuum obtained from ~o distillation or mixtures thereof. Generally the water of the hydrocarbon oil is in a form wherein the water is dispersed as droplets in the hydrocarbon oil. In this form of occurrence the hydrocarbon oil -water mixture is generally a water-in oil emulsion.
~5 [0010] The gel of the invention is a complex fluid comprising hydrocarbon oil, water, water soluble salts such as sodium, potassium and calcium chlorides, water insoluble salts such as calcium carbonate and calcium sulfate, organic carbonaceous solids like coal and coke, crude oil derived compounds such as asphaltenes, naphthenic acids, naphthenic acids salts such as sodium and calcium 2o naphthenates, organo sulfur compounds, organo nitrogen containing compounds and metalloporphyrins. The crude oil derived compounds in the gel are polar hydrocarbon compounds, preferably surface active polar hydrocarbon compounds, and more preferably surface active polar hydrocarbon compounds that are surface active at a hydrocarbon - water interface. Surface activity of the 25 polar hydrocarbon compounds can be determined using known tensiometric techniques such as hydrocarbon /water interfacial tension by one of ordinary skill in the art of interfacial science.
[0011] The gel has physical properties suitable for separation from the hydrocarbon oil from which it is formed. Preferably the density of the gel is greater than that of the hydrocarbon oil at the temperature the method is conducted. More preferably the density is greater than that of the hydrocarbon oil and less than that of water at the temperature the method is conducted. The density of the gel being greater than that of the hydrocarbon oil and less than that of water allows easy separation of the gel from the hydrocarbon oil. The gel is preferably viscoleastic. Viscoelastic properties of materials is known to one of ordinary skill in the art of theology. By virtue of its viscoelastic nature the gel io has an elastic modulus and a viscous modulus. The elastic modulus and viscous modulus of the viscoelastic gel can be measured by one of ordinary skill in the art of fluid theology using oscillatory visometry techniques. Preferably the viscous modulus of the gel is at least two times that of the hydrocarbon oil from which it is formed at a given temperature. Preferably the elastic modulus of the is gel is at least two times that of the hydrocarbon oil from which it is formed at a given temperature.
[0012] The first step of the method is to form a gel in a hydrocarbon oil. To form the gel, a variety of methods can be employed. One non-limiting example 2o includes adding gel forming agents including but not limited to lignin, cellulose, coke fines, coal fines, synthetic cross linked polymers, cholesteryl and cholestanyl derived gellation compounds and oxidized alkyl aromatic hydrocarbons and water. Water is a preferred gel-forming agent. The amount of gel forming agent to be added can vary in the range of 0.01 to 20 wt% based on 25 the weight of the hydrocarbon oil. When water is the gel forming agent it is preferred to add water also the range of 0.01 to 20 wt% based on the weight of the hydrocarbon oil. More preferrably water is in the range of 0.01 to 10 wt%
based on the weight of the hydrocarbon oil. Water addition can be in one lot or in aliquots. After addition of the gel forming agent the hydrocarbon oil is mixed and allowed to stand for a period of time and at a temperature sufficient to promote gel formation. Mixing can be conducted during or after addition of the gel forming agent. The preferred temperature of addition and mixing is in the range of about IS°C to about 85°C and preferred period of time of addition and mixing is in the range of 5 minutes to 10 days.
[0013] Another example of forming a gel from a hydrocarbon oil is to subject the hydrocarbon oil to temperature cycles i.e., increase and decrease the io temperature of the hydrocarbon oil in a temperature range several times.
Preferrably the temperature cycling is in the temperature range of 10 °
C to 90 ° C
at atmospheric pressure and the number of cycles is at least 2 and the total time period of cycling is from 5 minutes to 10 days. In another example a hydrocarbon oil is subject to pressure cycles in a suitable pressure range. A pressure in the is range of 14 psia ( 96.46 kPa) to 150 psia ( 1033.5 kPa) is preferred. The hydrocarbon oil can be subject to both temperature and pressure cycles at the same time. In yet another example the hydrocarbon oil can be subject to electrostatic fields. Preferably the electrostatic field is at potentials ranging from about 10,000 volts to about 40,000 volts, A.C. or D.C. Voltage gradients in the 2o electrostatic field range from about 500 volts per inch to about 5,000 volts per inch, preferably ranging from about 500 to about 1,000 volts per inch.
Residence times in the electrostatic fields range from about 0.5 to about 120 minutes, preferably from about 0.5 to about 15 minutes. In yet another example the hydrocarbon oil can be subject to shear cycling i.e., subject the hydrocarbon oil 2s to shearing forces of varying intensities. This can be accomplished for example by subjecting the hydrocarbon oil to turbulent force field followed by a quiescent force field. The hydrocarbon oil can also be subject to sonic treatment cycles. In this embodiment the hydrocarbon oil is subject to cycles of ultrasonic waves by turning on and turning off the ultrasonicator alternately for a period of time sufficient to form the gel. The temperature, pressure, electrostatic, sonic and shear treatments can be conducted on the hydrocarbon oil or on the hydrocarbon oil treated with gel forming agents. For example, one can treat the hydrocarbon oil with water and then subject it to the temperature, pressure, electrostatic, sonic or shear treatments to promote gel formation.
(0014] The amount of gel formed in the hydrocarbon oil is an amount sufficient to extract at least 1 weight percent of polar hydrocarbon compounds in ~o the starting hydrocarbon oil, preferably at least 1 weight percent surface active polar hydrocarbon compounds, and more preferably at least 1 weight percent surface active polar hydrocarbon compounds that are surface active at a hydrocarbon - water interface. Preferably the surface active polar hydrocarbon compounds are nitrogen, oxygen , sulfur and metals containing surface active is compounds of the hydrocarbon oil. The total amount of polar hydrocarbon compounds of the hydrocarbon oil can be measured by one of ordinary skill in the art of organic compound analyses. Preferably, the amount of gel that is formed is in the range of 0.5 to 20wt% based on the initial weight of the hydrocarbon oil. More preferrably the the amount of gel that is formed is in the 2o range of 0.5 to lOwt% based on the initial weight of the hydrocarbon oil.
[0015] The second step of the method comprises separating the gel from the hydrocarbon oil to produce a separated gel and a separated hydrocarbon oil.
This separation can be accomplished by methods known to one of ordinary skill 2s in the art of separations. The system for separation can be considered as a liquid -viscoelastic gel system. Because of the favorable density and viscoelastic properties of the formed gel the preferred separation method is gravity settling followed by removal of the top oil phase. Centrifugation or hydrocyclone _g_ techniques can also be employed to increase the rate of separation of the gel from the treated oil. Suitable centrifugal force fields can be applied for the separation.
Suitable filtration methods can also be employed. For example, for gels formed from crude oils one can use a mineral or rock bed such as a gravel bed as a s filtration medium to filter off or separate the gel from the oil. Other filtration media such as membrane filters can also be used. After gel formation and separation, the separated hydrocarbon oil contains polar hydrocarbon compounds that are at least 1 wt% less than the starting hydrocarbon.
~o [0016] The last step of the method for dewatering and desalting is separating water and salt from the separated hydrocarbon oil. Methods known for separating water and salt from the hydrocarbons oils can be employed. These include methods such as electrostatic separation, centrifugation and hydrocyclone treatment. Electrostatic separation is the preferred method to ~s separate the water and salts from the separated hydrocarbon oil. Preferably demulsifier chemicals known to one of ordinary skill in the art of dewatering and desalting hydrocarbon oils are added to the separated hydrocarbon oil and subject to electrostatic treatment to provide the dewatered desalted oil.
20 [0017] The following non-limiting examples illustrate one embodiment of the invention.
Step - 1: Gel Formation 25 [0018] 100 grams of a crude oil from Canada was used. To the crude oil was added 1 wt% water based on the weight of the crude oil. The crude oil was subject to temperature cycling by heating the crude oil to 60°C and holding the temperature at 60°C for 30 minutes. The sample was then cooled to 25°C. The heating and cooling was conducted five times. The sample was then allowed to gravity settle for 5 days.
[0019] After 5 days a gel layer was observed to settle at the bottom of the s jar containing the temperature cycled oil. The amount of gel formed was Swt%
based on the initial weight of the crude oil. A bright light source held in front or behind the jar containing the oil was sufficient to detect the gel layer.
Step - 2: Separation of Oil and Gel io [0020] The oil residing on top of the gel was carefully siphoned off to provide the separated oil (denoted , sample-1). The gel was at the bottom of the jar and is the separated gel (denoted , gel sample -G).
~5 Step - 3: Separation of water and salts from the separated oiI
(electrostatic treatment [0021] Two samples were examined. Sample-1 was the separated oil (obtained from step 2) and Sample-2 untreated Canadian crude oil.
Water (5 wt% ) was added to samples 1 and 2 and both samples shaken for 5 minutes on a wrist shaker. A phenol formaldehyde ethoxylated alcohol demulsifier formulation sold by BASF Corporation as Pluradyne DB7946 was added to both samples at a treat rate of 100 ppm based on the weight of crude oil and the mixture shaken on a wrist shaker for an additional 10 minutes. Both samples were subject to electrostatic demulsification by applying 830 volts/square inch AC current to the samples at 60C for 1 hour. After completion of the procedure the samples were examined and amount of water separating out recorded. The samples were also analyzed for sodium content by Inductively Coupled Plasma (ICP) analyses. Sample -2 did not demulsify under the conditions of the experiment and no water was observed to split out at the bottom of the demulsifier vessel. In Sample-1, 97% dewatering and 80% reduction in salt content was observed. Thus, formation and separation of the gel results in effective dewatering and desalting whereas the untreated crude oil does not demulsify under the same conditions.
Analyses of the separated gel [0022] The separated gel ( gel sample -G) from step 2 was subject to rheological analyses using oscillatory viscometry. A Haake viscometer in the oscillating mode was used and analyses conducted at 25°C. The separated gel ( gel sample -G) had a viscous modulus of 32.5 Pascal and an elastic modulus of 4.4 Pascal. In contrast, the separated oil (sample-2) had a viscous modulus of 7.7 Pascal an elastic modulus of 0.7 Pascal. Thus the formed gel has a significantly higher elastic and viscous modulus compared to the crude oil.
[0023] Next, the gel phase was subject to component analysis. The gel was found to contain 95% oil and 5% water. The oil and water from the separated gel o was analyzed. The oil of the gel (Gel Oil) was itself observed to have a micro-concarbon residue (MCCR), naphthenic acid (TAN), basic nitrogen and sulfur level higher than the separated oil (sample-2) obtained from step -2.
Additionally, the surface activity of the oil from the gel was an order of magnitude higher than the surface activity of the separated oil. This is evident in ~s the oil/water interfacial tension { IFr (o/w) } values. Thus, in the method of the invention the gel extracts the most surface active sulfur, nitrogen and naphthenic acid compounds. Results of the analyses are shown in Table-1..
~5 [0010] The gel of the invention is a complex fluid comprising hydrocarbon oil, water, water soluble salts such as sodium, potassium and calcium chlorides, water insoluble salts such as calcium carbonate and calcium sulfate, organic carbonaceous solids like coal and coke, crude oil derived compounds such as asphaltenes, naphthenic acids, naphthenic acids salts such as sodium and calcium 2o naphthenates, organo sulfur compounds, organo nitrogen containing compounds and metalloporphyrins. The crude oil derived compounds in the gel are polar hydrocarbon compounds, preferably surface active polar hydrocarbon compounds, and more preferably surface active polar hydrocarbon compounds that are surface active at a hydrocarbon - water interface. Surface activity of the 25 polar hydrocarbon compounds can be determined using known tensiometric techniques such as hydrocarbon /water interfacial tension by one of ordinary skill in the art of interfacial science.
[0011] The gel has physical properties suitable for separation from the hydrocarbon oil from which it is formed. Preferably the density of the gel is greater than that of the hydrocarbon oil at the temperature the method is conducted. More preferably the density is greater than that of the hydrocarbon oil and less than that of water at the temperature the method is conducted. The density of the gel being greater than that of the hydrocarbon oil and less than that of water allows easy separation of the gel from the hydrocarbon oil. The gel is preferably viscoleastic. Viscoelastic properties of materials is known to one of ordinary skill in the art of theology. By virtue of its viscoelastic nature the gel io has an elastic modulus and a viscous modulus. The elastic modulus and viscous modulus of the viscoelastic gel can be measured by one of ordinary skill in the art of fluid theology using oscillatory visometry techniques. Preferably the viscous modulus of the gel is at least two times that of the hydrocarbon oil from which it is formed at a given temperature. Preferably the elastic modulus of the is gel is at least two times that of the hydrocarbon oil from which it is formed at a given temperature.
[0012] The first step of the method is to form a gel in a hydrocarbon oil. To form the gel, a variety of methods can be employed. One non-limiting example 2o includes adding gel forming agents including but not limited to lignin, cellulose, coke fines, coal fines, synthetic cross linked polymers, cholesteryl and cholestanyl derived gellation compounds and oxidized alkyl aromatic hydrocarbons and water. Water is a preferred gel-forming agent. The amount of gel forming agent to be added can vary in the range of 0.01 to 20 wt% based on 25 the weight of the hydrocarbon oil. When water is the gel forming agent it is preferred to add water also the range of 0.01 to 20 wt% based on the weight of the hydrocarbon oil. More preferrably water is in the range of 0.01 to 10 wt%
based on the weight of the hydrocarbon oil. Water addition can be in one lot or in aliquots. After addition of the gel forming agent the hydrocarbon oil is mixed and allowed to stand for a period of time and at a temperature sufficient to promote gel formation. Mixing can be conducted during or after addition of the gel forming agent. The preferred temperature of addition and mixing is in the range of about IS°C to about 85°C and preferred period of time of addition and mixing is in the range of 5 minutes to 10 days.
[0013] Another example of forming a gel from a hydrocarbon oil is to subject the hydrocarbon oil to temperature cycles i.e., increase and decrease the io temperature of the hydrocarbon oil in a temperature range several times.
Preferrably the temperature cycling is in the temperature range of 10 °
C to 90 ° C
at atmospheric pressure and the number of cycles is at least 2 and the total time period of cycling is from 5 minutes to 10 days. In another example a hydrocarbon oil is subject to pressure cycles in a suitable pressure range. A pressure in the is range of 14 psia ( 96.46 kPa) to 150 psia ( 1033.5 kPa) is preferred. The hydrocarbon oil can be subject to both temperature and pressure cycles at the same time. In yet another example the hydrocarbon oil can be subject to electrostatic fields. Preferably the electrostatic field is at potentials ranging from about 10,000 volts to about 40,000 volts, A.C. or D.C. Voltage gradients in the 2o electrostatic field range from about 500 volts per inch to about 5,000 volts per inch, preferably ranging from about 500 to about 1,000 volts per inch.
Residence times in the electrostatic fields range from about 0.5 to about 120 minutes, preferably from about 0.5 to about 15 minutes. In yet another example the hydrocarbon oil can be subject to shear cycling i.e., subject the hydrocarbon oil 2s to shearing forces of varying intensities. This can be accomplished for example by subjecting the hydrocarbon oil to turbulent force field followed by a quiescent force field. The hydrocarbon oil can also be subject to sonic treatment cycles. In this embodiment the hydrocarbon oil is subject to cycles of ultrasonic waves by turning on and turning off the ultrasonicator alternately for a period of time sufficient to form the gel. The temperature, pressure, electrostatic, sonic and shear treatments can be conducted on the hydrocarbon oil or on the hydrocarbon oil treated with gel forming agents. For example, one can treat the hydrocarbon oil with water and then subject it to the temperature, pressure, electrostatic, sonic or shear treatments to promote gel formation.
(0014] The amount of gel formed in the hydrocarbon oil is an amount sufficient to extract at least 1 weight percent of polar hydrocarbon compounds in ~o the starting hydrocarbon oil, preferably at least 1 weight percent surface active polar hydrocarbon compounds, and more preferably at least 1 weight percent surface active polar hydrocarbon compounds that are surface active at a hydrocarbon - water interface. Preferably the surface active polar hydrocarbon compounds are nitrogen, oxygen , sulfur and metals containing surface active is compounds of the hydrocarbon oil. The total amount of polar hydrocarbon compounds of the hydrocarbon oil can be measured by one of ordinary skill in the art of organic compound analyses. Preferably, the amount of gel that is formed is in the range of 0.5 to 20wt% based on the initial weight of the hydrocarbon oil. More preferrably the the amount of gel that is formed is in the 2o range of 0.5 to lOwt% based on the initial weight of the hydrocarbon oil.
[0015] The second step of the method comprises separating the gel from the hydrocarbon oil to produce a separated gel and a separated hydrocarbon oil.
This separation can be accomplished by methods known to one of ordinary skill 2s in the art of separations. The system for separation can be considered as a liquid -viscoelastic gel system. Because of the favorable density and viscoelastic properties of the formed gel the preferred separation method is gravity settling followed by removal of the top oil phase. Centrifugation or hydrocyclone _g_ techniques can also be employed to increase the rate of separation of the gel from the treated oil. Suitable centrifugal force fields can be applied for the separation.
Suitable filtration methods can also be employed. For example, for gels formed from crude oils one can use a mineral or rock bed such as a gravel bed as a s filtration medium to filter off or separate the gel from the oil. Other filtration media such as membrane filters can also be used. After gel formation and separation, the separated hydrocarbon oil contains polar hydrocarbon compounds that are at least 1 wt% less than the starting hydrocarbon.
~o [0016] The last step of the method for dewatering and desalting is separating water and salt from the separated hydrocarbon oil. Methods known for separating water and salt from the hydrocarbons oils can be employed. These include methods such as electrostatic separation, centrifugation and hydrocyclone treatment. Electrostatic separation is the preferred method to ~s separate the water and salts from the separated hydrocarbon oil. Preferably demulsifier chemicals known to one of ordinary skill in the art of dewatering and desalting hydrocarbon oils are added to the separated hydrocarbon oil and subject to electrostatic treatment to provide the dewatered desalted oil.
20 [0017] The following non-limiting examples illustrate one embodiment of the invention.
Step - 1: Gel Formation 25 [0018] 100 grams of a crude oil from Canada was used. To the crude oil was added 1 wt% water based on the weight of the crude oil. The crude oil was subject to temperature cycling by heating the crude oil to 60°C and holding the temperature at 60°C for 30 minutes. The sample was then cooled to 25°C. The heating and cooling was conducted five times. The sample was then allowed to gravity settle for 5 days.
[0019] After 5 days a gel layer was observed to settle at the bottom of the s jar containing the temperature cycled oil. The amount of gel formed was Swt%
based on the initial weight of the crude oil. A bright light source held in front or behind the jar containing the oil was sufficient to detect the gel layer.
Step - 2: Separation of Oil and Gel io [0020] The oil residing on top of the gel was carefully siphoned off to provide the separated oil (denoted , sample-1). The gel was at the bottom of the jar and is the separated gel (denoted , gel sample -G).
~5 Step - 3: Separation of water and salts from the separated oiI
(electrostatic treatment [0021] Two samples were examined. Sample-1 was the separated oil (obtained from step 2) and Sample-2 untreated Canadian crude oil.
Water (5 wt% ) was added to samples 1 and 2 and both samples shaken for 5 minutes on a wrist shaker. A phenol formaldehyde ethoxylated alcohol demulsifier formulation sold by BASF Corporation as Pluradyne DB7946 was added to both samples at a treat rate of 100 ppm based on the weight of crude oil and the mixture shaken on a wrist shaker for an additional 10 minutes. Both samples were subject to electrostatic demulsification by applying 830 volts/square inch AC current to the samples at 60C for 1 hour. After completion of the procedure the samples were examined and amount of water separating out recorded. The samples were also analyzed for sodium content by Inductively Coupled Plasma (ICP) analyses. Sample -2 did not demulsify under the conditions of the experiment and no water was observed to split out at the bottom of the demulsifier vessel. In Sample-1, 97% dewatering and 80% reduction in salt content was observed. Thus, formation and separation of the gel results in effective dewatering and desalting whereas the untreated crude oil does not demulsify under the same conditions.
Analyses of the separated gel [0022] The separated gel ( gel sample -G) from step 2 was subject to rheological analyses using oscillatory viscometry. A Haake viscometer in the oscillating mode was used and analyses conducted at 25°C. The separated gel ( gel sample -G) had a viscous modulus of 32.5 Pascal and an elastic modulus of 4.4 Pascal. In contrast, the separated oil (sample-2) had a viscous modulus of 7.7 Pascal an elastic modulus of 0.7 Pascal. Thus the formed gel has a significantly higher elastic and viscous modulus compared to the crude oil.
[0023] Next, the gel phase was subject to component analysis. The gel was found to contain 95% oil and 5% water. The oil and water from the separated gel o was analyzed. The oil of the gel (Gel Oil) was itself observed to have a micro-concarbon residue (MCCR), naphthenic acid (TAN), basic nitrogen and sulfur level higher than the separated oil (sample-2) obtained from step -2.
Additionally, the surface activity of the oil from the gel was an order of magnitude higher than the surface activity of the separated oil. This is evident in ~s the oil/water interfacial tension { IFr (o/w) } values. Thus, in the method of the invention the gel extracts the most surface active sulfur, nitrogen and naphthenic acid compounds. Results of the analyses are shown in Table-1..
Table-1 Oil S (1o) Total N Basic TAN MCCR IFT (o/w) N
(ppm) (ppm) dynes/cm Separated Oil 3.0 3800 960 0.99 6 20 Gel Oil 4.0 4700 1200 1.82 13 2
(ppm) (ppm) dynes/cm Separated Oil 3.0 3800 960 0.99 6 20 Gel Oil 4.0 4700 1200 1.82 13 2
Claims (31)
1. A method for separating polar hydrocarbon compounds from a hydrocarbon oil comprising polar hydrocarbon compounds comprising the steps of:
a) adding a gel forming agent comprising water to the hydrocarbon oil;
b) subjecting the hydrocarbon oil and the gel forming agent comprising water to a process selected from the group consisting of temperature cycling, pressure cycling, shear cycling, sonic cycling, and combinations thereof to form a gel comprising at least a portion of the polar cydrocarbon compounds, wherein the gel is formed without using a resin;
c) separating the gel from the hydrocarbon oil to produce a separated gel comprising water, water soluble salt, and water insoluble salts, and a separated hydrocarbon oil, said separation of the gel from the hydrocarbon oil is by a process selected from the group consisting of gravity settling, centrifugation, hydrocyclone treatment, filtration, and combinations thereof.
a) adding a gel forming agent comprising water to the hydrocarbon oil;
b) subjecting the hydrocarbon oil and the gel forming agent comprising water to a process selected from the group consisting of temperature cycling, pressure cycling, shear cycling, sonic cycling, and combinations thereof to form a gel comprising at least a portion of the polar cydrocarbon compounds, wherein the gel is formed without using a resin;
c) separating the gel from the hydrocarbon oil to produce a separated gel comprising water, water soluble salt, and water insoluble salts, and a separated hydrocarbon oil, said separation of the gel from the hydrocarbon oil is by a process selected from the group consisting of gravity settling, centrifugation, hydrocyclone treatment, filtration, and combinations thereof.
2. The method of claim 1 wherein said separated hydrocarbon oil comprises said polar hydrocarbon compounds that are at least 1 wt% less than in the hydrocarbon oil.
3. The method of claim 1 wherein said hydrocarbon oil is selected from the group consisting of crude oil, crude oil distillate , crude oil residuum and mixtures thereof.
4. The method of claim 1 wherein said gel has a density greater than the density of the hydrocarbon oil at the temperature at which step b) is conducted.
5. The method of claim 1 wherein the amount of gel formed in the hydrocarbon oil is in the range of 0.5 to 20wt% based on the weight of the hydrocarbon oil.
6. The method of claim 1 wherein said water is in the range of 0.01 to 10wt%
based on the weight of the hydrocarbon oil.
based on the weight of the hydrocarbon oil.
7. The method of claim 1 wherein said temperature cycling is in the temperature range of 10°C to 90°C at atmospheric pressure, the number of cycles is at least 2, and the total time period of cycling is from 5 minutes to 10 days.
8. A method for dewatering and/or desalting a hydrocarbon oil comprising polar hydrocarbon compounds, water and salt comprising the steps of:
a) adding a gel forming agent comprising water to the hydrocarbon oil;
b) subjecting the hydrocarbon oil and the gel forming agent comprising water to a process selected from the group consisting of temperature cycling, pressure cycling, shear cycling, sonic cycling, and combinations thereof to form a gel comprising at least a portion of the polar hydrocarbon compounds, wherein the gel is formed without using a resin;
c) separating the gel from the hydrocarbon oil to produce a separated gel comprising water, water soluble salt, and water insoluble salts, and a separated hydrocarbon oil, said separation of the gel from the hydrocarbon oil is by a process selected from the group consisting of gravity settling, centrifugation, hydrocyclone treatment, filtration, and combinations thereof, and thereafter;
d) further separating water and salt from the separated hydrocarbon oil to provide a dewatered and desalted hydrocarbon oil.
a) adding a gel forming agent comprising water to the hydrocarbon oil;
b) subjecting the hydrocarbon oil and the gel forming agent comprising water to a process selected from the group consisting of temperature cycling, pressure cycling, shear cycling, sonic cycling, and combinations thereof to form a gel comprising at least a portion of the polar hydrocarbon compounds, wherein the gel is formed without using a resin;
c) separating the gel from the hydrocarbon oil to produce a separated gel comprising water, water soluble salt, and water insoluble salts, and a separated hydrocarbon oil, said separation of the gel from the hydrocarbon oil is by a process selected from the group consisting of gravity settling, centrifugation, hydrocyclone treatment, filtration, and combinations thereof, and thereafter;
d) further separating water and salt from the separated hydrocarbon oil to provide a dewatered and desalted hydrocarbon oil.
9. The method of claim 8 wherein said separation of water and salt from the separated hydrocarbon oil in step d) is by electrostatic treatment.
10. The method of claim 8 wherein said hydrocarbon oil is selected from the group consisting of crude oil, crude oil distillate, crude oil residuum and mixtures thereof.
11. The method of claim 8 wherein said hydrocarbon oil comprises asphaltenes and naphthenic acids.
12. The method of claim 8 wherein said gel is viscoelastic.
13. The method of claim 8 wherein said gel has a density greater than the density of the hydrocarbon oil at the temperature at which step b) is conducted.
14. The method of claim 8 wherein said gel has a density greater than the density of the hydrocarbon oil and lower than the density of water at the temperature at which step b) is conducted.
15. The method of claim 8 wherein the amount of gel formed in the hydrocarbon oil is an amount sufficient to extract at least 1 wt% of the polar hydrocarbons compounds from the hydrocarbon oil.
16. The method of claim 8 wherein the amount of gel formed in the hydrocarbon oil is in the range of 0.5 to 20wt% based on the weight of the hydrocarbon oil.
17. The method of claim 8 wherein said water is in the range of 0.01 to 10wt%
based on the weight of the hydrocarbon oil.
based on the weight of the hydrocarbon oil.
18. The method of claim 8 wherein said temperature cycling is in the temperature range of 10°C to 90°C at atmospheric pressure, the number of cycles is at least 2, and the total time period of cycling is from 5 minutes to 10 days.
19. The method of claim 1 wherein the water soluble salts are selected from the group consisting of sodium, potassium, calcium chlorides and any combination thereof and the water insoluble salts are selected from the group consisting of calcium carbonate, calcium sulfate and any combination thereof and wherein the gel further comprises crude oil derived compounds selected from the group consisting of asphaltenes, naphthenic acids, naphthenic acids salts such as sodium and calcium naphthenates, organo sulfur compounds, organo nitrogen containing compounds and any combination thereof and organic carbonaceous solids selected from the group consisting of coal, coke, and any combination thereof.
20. The method of claim 1 wherein the hydrocarbon oil comprises surface active polar hydrocarbon compounds that are surface active at a hydrocarbon water interface.
21. The method of claim 8 wherein the water soluble salts are selected from the group consisting of sodium, potassium, calcium chlorides and any combination thereof and the water insoluble salts are selected from the group consisting of calcium carbonate, calcium sulfate and any combination thereof and wherein the gel further comprises crude oil derived compounds selected from the group consisting of asphaltenes, naphthenic acids, naphthenic acids salts such as sodium and calcium naphthenates, organo sulfur compounds, organo nitrogen containing compounds and any combination thereof and organic carbonaceous solids selected from the group consisting of coal, coke, and any combination thereof.
22. The method of claim 8 wherein the hydrocarbon oil comprises surface active polar hydrocarbon compounds that are surface active at a hydrocarbon water interface.
23. The method of claim 8 further comprising adding a demulsifier chemical to the separated hydrocarbon oil and subjecting the separated hydrocarbon oil to electrostatic treatment to provide the dewatered desalted oil.
24. The method of claim 1 further comprising injecting the separated gel in a hydrocarbon reservoir.
25. The method of claim 8 further comprising injecting the separated gel in a hydrocarbon reservoir.
26. A method for recovering crude oil from a subterranean environment comprising the steps of:
a) adding a gel forming agent comprising water to a hydrocarbon oil comprising polar hydrocarbon compounds;
b) subjecting the hydrocarbon oil and the gel forming agent comprising water to a process selected from the group consisting of temperature cycling, pressure cycling, shear cycling, sonic cycling, and combinations thereof to form a gel comprising at least a portion of the polar hydrocarbon compounds, wherein the gel is formed without using a resin;
c) separating the gel from the hydrocarbon oil to produce a separated gel comprising water, water soluble salts, and water insoluble salts, and a separated hydrocarbon oil, said separation of the gel from the hydrocarbon oil being by a process selected from the group consisting of gravity settling, centrifugation, hydrocyclone treatment, filtration, and combinations thereof; and d) thereafter injecting the separated gel into the subterranean environment and recovering crude oil from said environment.
a) adding a gel forming agent comprising water to a hydrocarbon oil comprising polar hydrocarbon compounds;
b) subjecting the hydrocarbon oil and the gel forming agent comprising water to a process selected from the group consisting of temperature cycling, pressure cycling, shear cycling, sonic cycling, and combinations thereof to form a gel comprising at least a portion of the polar hydrocarbon compounds, wherein the gel is formed without using a resin;
c) separating the gel from the hydrocarbon oil to produce a separated gel comprising water, water soluble salts, and water insoluble salts, and a separated hydrocarbon oil, said separation of the gel from the hydrocarbon oil being by a process selected from the group consisting of gravity settling, centrifugation, hydrocyclone treatment, filtration, and combinations thereof; and d) thereafter injecting the separated gel into the subterranean environment and recovering crude oil from said environment.
27. The method of claim 1 wherein the gel forming agent further comprises another gel forming agent selected from the group consisting of lignin, cellulose, coke fines, coal fines, cholesteryl and cholestanyl derived gellation compounds and oxidized alkyl aromatic hydrocarbons, and any combination thereof.
28. The method of claim 8 wherein the gel forming agent further comprises another gel forming agent selected from the group consisting of lignin, cellulose, coke fines, coal fines, cholesteryl and cholestanyl derived gellation compounds and oxidized alkyl aromatic hydrocarbons, and any combination thereof.
29. The method of claim 26 wherein the gel forming agent further comprises another gel forming agent selected from the group consisting of lignin, cellulose, coke fines, coal fines, cholesteryl and cholestanyl derived gellation compounds and oxidized alkyl aromatic hydrocarbons, and any combination thereof.
30. The method of claim 1 wherein the gel forming agent consists essentially of water and optionally one or more of lignin, cellulose, coke fines, coal fines, cholesteryl and cholestanyl derived gellation compounds, and oxidized alkyl aromatic hydrocarbons.
31. The method of claim 8 wherein the gel forming agent consists essentially of water and optionally one or more of lignin, cellulose, coke fines, coal fines, cholesteryl and cholestanyl derived gellation compounds, and oxidized alkyl aromatic hydrocarbons.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59089104P | 2004-07-23 | 2004-07-23 | |
| US60/590,891 | 2004-07-23 | ||
| US11/173,975 US20060016727A1 (en) | 2004-07-23 | 2005-07-01 | Gel assisted separation method and dewatering/desalting hydrocarbon oils |
| US11/173,975 | 2005-07-01 |
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|---|---|
| CA2512822A1 CA2512822A1 (en) | 2006-01-23 |
| CA2512822C true CA2512822C (en) | 2013-05-21 |
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| CA2512822A Expired - Fee Related CA2512822C (en) | 2004-07-23 | 2005-07-21 | Gel assisted separation method and dewatering/desalting hydrocarbon oils |
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| Country | Link |
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| CA (1) | CA2512822C (en) |
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| US8709233B2 (en) * | 2006-08-31 | 2014-04-29 | Exxonmobil Chemical Patents Inc. | Disposition of steam cracked tar |
| US7897828B2 (en) * | 2007-08-28 | 2011-03-01 | Exxonmobile Research And Engineering Company | Process for separating a heavy oil feedstream into improved products |
| US8864996B2 (en) * | 2007-08-28 | 2014-10-21 | Exxonmobil Research And Engineering Company | Reduction of conradson carbon residue and average boiling points utilizing high pressure ultrafiltration |
| US7871510B2 (en) * | 2007-08-28 | 2011-01-18 | Exxonmobil Research & Engineering Co. | Production of an enhanced resid coker feed using ultrafiltration |
| US8177965B2 (en) * | 2007-08-28 | 2012-05-15 | Exxonmobil Research And Engineering Company | Enhancement of saturates content in heavy hydrocarbons utilizing ultrafiltration |
| US7815790B2 (en) | 2007-08-28 | 2010-10-19 | Exxonmobil Research And Engineering Company | Upgrade of visbroken residua products by ultrafiltration |
| US7867379B2 (en) * | 2007-08-28 | 2011-01-11 | Exxonmobil Research And Engineering Company | Production of an upgraded stream from steam cracker tar by ultrafiltration |
| US7736493B2 (en) * | 2007-08-28 | 2010-06-15 | Exxonmobil Research And Engineering Company | Deasphalter unit throughput increase via resid membrane feed preparation |
| CA2911610C (en) * | 2014-11-13 | 2017-12-12 | Weatherford Technology Holdings, Llc | Oil/bitumen emulsion separation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2182145A (en) * | 1937-01-26 | 1939-12-05 | Petrolite Corp | Process and apparatus for treating oil |
| FR2229440B1 (en) * | 1973-05-17 | 1977-07-29 | Inst Francais Du Petrole | |
| US4737265A (en) * | 1983-12-06 | 1988-04-12 | Exxon Research & Engineering Co. | Water based demulsifier formulation and process for its use in dewatering and desalting crude hydrocarbon oils |
| US5219471A (en) * | 1991-11-12 | 1993-06-15 | Amoco Corporation | Removal of metals and water-insoluble materials from desalter emulsions |
| US7125912B2 (en) * | 2001-10-09 | 2006-10-24 | Simax Technologies, Inc. | Doped sol-gel materials and method of manufacture utilizing reduced mixing temperatures |
-
2005
- 2005-07-01 US US11/173,975 patent/US20060016727A1/en not_active Abandoned
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| CA2512822A1 (en) | 2006-01-23 |
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