US20130025857A1 - Preserving oil gravity - Google Patents
Preserving oil gravity Download PDFInfo
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- US20130025857A1 US20130025857A1 US13/136,237 US201113136237A US2013025857A1 US 20130025857 A1 US20130025857 A1 US 20130025857A1 US 201113136237 A US201113136237 A US 201113136237A US 2013025857 A1 US2013025857 A1 US 2013025857A1
- Authority
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- United States
- Prior art keywords
- high gravity
- gel
- oil
- hydrocarbons
- gravity oil
- Prior art date
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- 230000005484 gravity Effects 0.000 title claims abstract description 45
- 238000003860 storage Methods 0.000 claims abstract description 37
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 30
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 30
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- -1 phosphate ester Chemical class 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010452 phosphate Substances 0.000 claims abstract description 13
- 239000004971 Cross linker Substances 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 42
- 235000019198 oils Nutrition 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000003345 natural gas Substances 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 4
- 239000008158 vegetable oil Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000005690 diesters Chemical class 0.000 claims description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims 1
- 238000007792 addition Methods 0.000 claims 1
- 239000010775 animal oil Substances 0.000 claims 1
- 239000003129 oil well Substances 0.000 claims 1
- 239000000499 gel Substances 0.000 abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 7
- 150000001298 alcohols Chemical class 0.000 abstract description 5
- 230000009969 flowable effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000003349 gelling agent Substances 0.000 description 9
- 235000021317 phosphate Nutrition 0.000 description 7
- 239000012530 fluid Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 241000124008 Mammalia Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical class C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 1
- ZUGAOYSWHHGDJY-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-aluminabicyclo[3.3.2]decane-3,7,10-trione Chemical compound [Al+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZUGAOYSWHHGDJY-UHFFFAOYSA-K 0.000 description 1
- 241001133760 Acoelorraphe Species 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- 244000020518 Carthamus tinctorius Species 0.000 description 1
- 235000003255 Carthamus tinctorius Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 241000282898 Sus scrofa Species 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000004426 flaxseed Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/007—Use of gas-solvents or gas-sorbents in vessels for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]
Definitions
- the invention relates to the conservation of volatile organics in oil and gas, and/or condensates and distillates from produced oil and gas, in storage vessels generally, but most usefully as they are recovered from the earth.
- the loss of volatile organics during storage of high gravity oil is minimized by forming a flowable or pumpable gel in the high gravity oil, (and/or condensates and distillates), as they are introduced to a storage vessel.
- the gel-former may comprise a phosphate ester of one or more low molecular weight alcohols, and a crosslinker including a source of iron or aluminum.
- the gels are flowable and pumpable, they can be broken after transportation from the production site or at another desirable time, returning the hydrocarbon product to its original properties.
- the American Petroleum Institute's system of classifying crude oils includes designations by gravity, relating the oil to the density of water.
- a high gravity oil is one which contains a high concentration of volatile, low molecular weight hydrocarbons, and a lower gravity oil will contain fewer such components.
- Liquid storage is also commonly provided for liquid components removed from natural gas, sometimes known as “condensates and distillates.” Although in the liquid phase at the time of removal from the produced gas, they tend to include significant concentrations of readily volatilized light hydrocarbons, which are especially vulnerable to loss.
- Some tanks and other storage vessels are equipped with special seals, pressure controls, or vents made to suppress emissions not only during static storage conditions, but also when the tanks are being filled or when the contents are being removed, and otherwise when there may be a degree of turbulence in them.
- Variations in head space when the vessels are low or near filled are of course important factors in volatilization, as are variations in temperature, which affect vapor pressures.
- a high gravity oil is defined as one having a gravity of 33° API or higher, including an API value higher than 60°, regardless of whether it is a crude oil or is derived from natural gas; for example, a condensate (I consider “condensate” and “distillate” to be interchangeable for my purposes) from natural gas.
- a weak gel I mean one which is flowable and pumpable, so that the normal passage from well to storage, including whatever equipment or treatment steps are between, will not be unduly retarded by a suddenly induced high viscosity.
- a strong gel is not necessary to retard emissions in storage, and would require further treatment to remove from the storage vessel.
- My weak gel is substantially formed in the conduit prior to introduction to the storage vessel.
- Hydrocarbon gels are commonly used for fracturing fluids, the gelling agents having been found to be excellent aids for suspending propping agents.
- Virtually any gelling agent useful in a hydrocarbon fracturing fluid may be used in my invention.
- Well known gelling agents have two basic components—a phosphorous-containing gelling agent, and a crosslinking agent including a source of polyvalent metal; by a polyvalent metal, I mean iron or aluminum.
- I may use any known gelling agent for hydrocarbons used in fracturing fluids.
- Burnham uses the term “pumpable” as desirable for gelled fracturing fluids. He describes a class of aluminum oxaalkyl phosphates useful for the purpose.
- a common orthophosphate diester may be expresses as HPO 4 RR′ where R is a straight or branched chain alkyl, aryl, alkoxy, or alkaryl group having about 6 to about 18 carbon atoms and R′ is hydrogen or an aryl, alkaryl, alkoxy, or alkyl group having up to about 18 carbon atoms.
- R is a straight or branched chain alkyl, aryl, alkoxy, or alkaryl group having about 6 to about 18 carbon atoms and R′ is hydrogen or an aryl, alkaryl, alkoxy, or alkyl group having up to about 18 carbon atoms.
- More complicated phosphorous-containing gelling agents are described by Jones et al in U.S. Pat. No. 5,990,053 and U.S. Pat. No. 6,147,034. Generally, they are two-component systems, one providing a phosphorous-containing gelling agent and the other providing a polyvalent metal, typically aluminum or iron. But see also Taylor et al U.S. Pat. No. 7,534,745, who utilize as the phosphorous-containing gelling agent various organophosphonic acid esters and organophosphinic acid esters, again together with a polyvalent metal.
- any orthophosphate diester of the formula HPO 4 RR′ where R is a straight or branched chain alkyl, aryl, alkoxy, or alkaryl group having about 6 to about 18 carbon atoms and R′ is hydrogen or an aryl, alkaryl, alkoxy, or alkyl group having up to about 18 carbon atoms may be used as the phosphorous-containing material
- I can use a product of the reaction of orthophosphoric acid (PO 4 ) with an excess of a mixture of C 2 to C 6 alcohols to maximize the formation of diesters.
- any known aluminum crosslinker may be used, such as sodium aluminate or polyaluminum chloride
- any of the iron crosslinkers mentioned in the above patents or used commercially in formation fracturing may be applied.
- I may use an iron solution such as ferric sulfate dispersed with a mixture of imidazolines, amides and alkanolamides derived from primarily vegetable oils and dimethylaminopropylamine and diethanolamine.
- Vegetable oils include but are not limited to, coconut, palm kernel, palm, soya, safflower, sunflower, linseed, tall oil, rapeseed(high and low euric), and blown versions of the above, or oxidized oil versions.
- Other non vegetable oils as tallow of swine, sheep(including lanolin), and beef or other mammals, as well as aquatic species of fish, mammals, encompassing many water living species.
- the crosslinking composition may contain a coconut(food grade) diethanolamide.
- the properties of this well known emulsifier in the cosmetic and detergent-market is also used in the oilfield, typically having a TAV of about 137 from diethanolamine, as the amine equivalent weight of the amide is infinity.
- Stabilizers for the crosslinking composition can be cellosolves, glycerin and/or ethanols.
- the storage vessel is discharged into a sales line, transmission line, or other pipeline of some length, the user may wish to break the gel just prior to beginning discharge in order not to unnecessarily consume energy in pumping because of the viscosity of the gel, even though it is a weak gel.
- the storage vessel is discharged into a truck, it may be more efficient to wait until the truck arrives at its destination; the benefits of high gravity preservation will thereby be obtained while the truck holds the weakly gelled hydrocarbons.
- the gel can be broken in either case by adding a small amount of aminoalcohols, and especially in the form of hexahydro triazines, aminoalcohol(reactions of glycidyl ethers and secondary amines).
- Addition of the gel breaker can be made either to the holding vessel or truck or directly to a pipe or other conduit. Addition can be “batch” or substantially continuous if the material is flowing, and may be coordinated with a stabilizer or other system where light ends are deliberately separated.
- My gels containing butanes, pentanes, and other C5s to C8s exhibit Reid Vapor pressure of ⁇ 2 psi, while ungelled hydrocarbon liquids and vapors have Reid vapor pressures of 3 to 8 psi or even higher.
- My method will frequently provide a Reid vapor pressure is a hydrocarbon storage vessel at least two Reid vapor pressure units lower than it would be without my invention.
- My invention includes inhibiting volatilization of light hydrocarbons from a liquid mixture of hydrocarbons in a storage vessel comprising, (1) prior to placing said liquid mixture of hydrocarbons in said storage vessel, adding to said liquid mixture (a) a phosphorous-containing gel former and (b) a source of polyvalent metal crosslinking agent in an amount effective to form a pumpable gel comprising said liquid mixture of hydrocarbons, and (b) pumping said pumpable gel into said storage vessel.
- My invention also includes a method of storing and transporting newly produced high gravity oil comprising (a) converting said high gravity oil to a weak gel, (b) placing said weak gel in a storage vessel, (c) storing said weal gel in said storage vessel, (d) breaking said weak gel to render said high gravity oil substantially free of said weak gel, and (e) transporting said high gravity oil to a new location.
- my invention includes a method of storing newly produced high gravity oil to inhibit a reduction in its high gravity by vapor loss comprising (a) adding to said newly produced high gravity oil 0.001 to 0.02 parts by volume phosphate ester of C 2 -C 6 alcohol per cubic meter of high gravity oil, (2) adding to said newly produced high gravity oil containing said phosphate ester 0.001 to 0.02 parts by volume of a crosslinker for said phosphate, thereby forming a pumpable gel, and (c) introducing said newly produced high gravity oil in the form of said pumpable gel to a storage vessel.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Colloid Chemistry (AREA)
Abstract
Description
- The invention relates to the conservation of volatile organics in oil and gas, and/or condensates and distillates from produced oil and gas, in storage vessels generally, but most usefully as they are recovered from the earth. The loss of volatile organics during storage of high gravity oil is minimized by forming a flowable or pumpable gel in the high gravity oil, (and/or condensates and distillates), as they are introduced to a storage vessel. The gel-former may comprise a phosphate ester of one or more low molecular weight alcohols, and a crosslinker including a source of iron or aluminum. Although the gels are flowable and pumpable, they can be broken after transportation from the production site or at another desirable time, returning the hydrocarbon product to its original properties.
- The American Petroleum Institute's system of classifying crude oils includes designations by gravity, relating the oil to the density of water. By this system, a high gravity oil is one which contains a high concentration of volatile, low molecular weight hydrocarbons, and a lower gravity oil will contain fewer such components.
- When a high gravity oil is recovered from the ground and placed in a tank or other vessel not equipped with a special seal or vent designed to contain or minimize vapor emissions, substantial losses of light hydrocarbons can be incurred simply from evaporation and volatilization. This not only represents an economic loss but also is environmentally undesirable; moreover, some of the volatile components—for example, benzene, toluene and xylene in the atmosphere—could be hazardous for nearby workers.
- Liquid storage is also commonly provided for liquid components removed from natural gas, sometimes known as “condensates and distillates.” Although in the liquid phase at the time of removal from the produced gas, they tend to include significant concentrations of readily volatilized light hydrocarbons, which are especially vulnerable to loss.
- Some tanks and other storage vessels are equipped with special seals, pressure controls, or vents made to suppress emissions not only during static storage conditions, but also when the tanks are being filled or when the contents are being removed, and otherwise when there may be a degree of turbulence in them. Variations in head space when the vessels are low or near filled are of course important factors in volatilization, as are variations in temperature, which affect vapor pressures. Numerous storage tanks in the field—in the vicinity of producing wells—are not equipped with the expensive vents necessary to adjust to such variations. A simple way of inhibiting volatilization in such storage vessels is needed.
- Although this invention is applicable to lower gravity oils, it is most useful for high gravity oils, designated 33° API or higher, and is well suited for oils in the range of 40-45° API. Perhaps the most beneficial use is with respect to “condensates and distillates,” typically produced with natural gas, and sometimes described as “natural gas liquids,” having API gravities of 45° to 60°. For my purposes in this application, a high gravity oil is defined as one having a gravity of 33° API or higher, including an API value higher than 60°, regardless of whether it is a crude oil or is derived from natural gas; for example, a condensate (I consider “condensate” and “distillate” to be interchangeable for my purposes) from natural gas.
- I are able to preserve the high gravity rating of high gravity oils and condensates in storage by forming a weak gel in the high gravity oil or condensate as it is conducted from the producing well to the storage tank, it being understood that other steps, such as filtration, may be practiced also during transport. By a weak gel I mean one which is flowable and pumpable, so that the normal passage from well to storage, including whatever equipment or treatment steps are between, will not be unduly retarded by a suddenly induced high viscosity. A strong gel is not necessary to retard emissions in storage, and would require further treatment to remove from the storage vessel. My weak gel is substantially formed in the conduit prior to introduction to the storage vessel.
- Hydrocarbon gels are commonly used for fracturing fluids, the gelling agents having been found to be excellent aids for suspending propping agents. Virtually any gelling agent useful in a hydrocarbon fracturing fluid may be used in my invention. Well known gelling agents have two basic components—a phosphorous-containing gelling agent, and a crosslinking agent including a source of polyvalent metal; by a polyvalent metal, I mean iron or aluminum.
- I may use any known gelling agent for hydrocarbons used in fracturing fluids.
- Generally I may use any of the combinations of phosphorous-containing gelling agents and crosslinkers containing a source of polyvalent metal described in the following patents, all of which are incorporated herein specifically in their entirety:
-
- Monroe U.S. Pat. No. 3,505,374, describing gels made with a reaction product of Fe3O4 and an alkyl oleyl diester of orthophosphoric acid. Other diesters of phosphoric acid may be used.
- Crawford U.S. Pat. No. 3,757,864 uses aluminum salts of alkyl aliphatic orthophosphate diesters as friction reducers in flowing hydrocarbons.
- Griffin, in U.S. Pat. No. 4,153,649, lists, in just a few lines of column 1, eighteen US patents said to describe organic phosphoric acid esters used to thicken organic liquids, and summarizes his invention in claim 1 as an organic phosphate ester composition having as a property the ability to increase the viscosity of kerosene when admixed in kerosene with sodium aluminate, said composition being prepared by the process which comprises the reaction of: [A] a pentavalent phosphorus compound selected from the group consisting of P2O5 and a mixture of P2O5 with polyphosphoric acid; [B]. a hydroxy ether of the formula ROR1OH wherein R is a C1 to C6 alkyl group, R1 is a C2 or C3 alkylene group and the total carbon atoms of R and R1 range from 3 to about 8; and [C]. when the total carbon atoms of R and R1 and is 3 or 4, a long chain substantially unsubstituted monohydric aliphatic alcohol containing at least 5 carbon atoms, but when the total carbon atoms of R and R1 is 5 to 8, an alcohol selected from the group consisting of a long chain substantially unsubstituted monohydric aliphatic alcohol containing at least 5 carbon atoms, a short chain substantially unsubstituted monohydric aliphatic alcohol containing from 1 to 4 carbon atoms and a mixture of said alcohols, the individual mole ratios of the hydroxy ether, the long chain alcohol and the short chain alcohol to total P2O5 being within the ranges of 0.4:1 to 4.5:1; 0:1 to 4.0:1 and 0:1 to 5.0:1 respectively, said reaction being conducted at temperature ranging from about 70.degree. to about 90.degree. C. for a period of time of from about 1.5 to about 6 hours, and said pentavalent phosphorus compound, hydroxy ether, and alcohol or alcohols being provided in molar ratios and admixed in a sequence effective to provide a reaction product suitable for use in increasing the viscosity of kerosene. See also Griffin's U.S. Pat. Nos. 4,174,2283 and 4,152,289 disclosing additional aluminum salts of phosphate esters useful for gelling fracturing fluids.
- In U.S. Pat. No. 4,316,810; Burnham uses the term “pumpable” as desirable for gelled fracturing fluids. He describes a class of aluminum oxaalkyl phosphates useful for the purpose.
- As indicated in Smith & Persinski U.S. Pat. No. 5,571,315 and related patents, a common orthophosphate diester may be expresses as HPO4RR′ where R is a straight or branched chain alkyl, aryl, alkoxy, or alkaryl group having about 6 to about 18 carbon atoms and R′ is hydrogen or an aryl, alkaryl, alkoxy, or alkyl group having up to about 18 carbon atoms. These phosphates are combined with ferric aluminum citrate to make gels in hydrocarbon based fracturing fluids.
- More complicated phosphorous-containing gelling agents are described by Jones et al in U.S. Pat. No. 5,990,053 and U.S. Pat. No. 6,147,034. Generally, they are two-component systems, one providing a phosphorous-containing gelling agent and the other providing a polyvalent metal, typically aluminum or iron. But see also Taylor et al U.S. Pat. No. 7,534,745, who utilize as the phosphorous-containing gelling agent various organophosphonic acid esters and organophosphinic acid esters, again together with a polyvalent metal.
- For my purposes, while any orthophosphate diester of the formula HPO4RR′ where R is a straight or branched chain alkyl, aryl, alkoxy, or alkaryl group having about 6 to about 18 carbon atoms and R′ is hydrogen or an aryl, alkaryl, alkoxy, or alkyl group having up to about 18 carbon atoms may be used as the phosphorous-containing material, I can use a product of the reaction of orthophosphoric acid (PO4) with an excess of a mixture of C2 to C6 alcohols to maximize the formation of diesters.
- For the crosslinker, while any known aluminum crosslinker may be used, such as sodium aluminate or polyaluminum chloride, any of the iron crosslinkers mentioned in the above patents or used commercially in formation fracturing may be applied. For example, I may use an iron solution such as ferric sulfate dispersed with a mixture of imidazolines, amides and alkanolamides derived from primarily vegetable oils and dimethylaminopropylamine and diethanolamine. Vegetable oils include but are not limited to, coconut, palm kernel, palm, soya, safflower, sunflower, linseed, tall oil, rapeseed(high and low euric), and blown versions of the above, or oxidized oil versions. Other non vegetable oils, as tallow of swine, sheep(including lanolin), and beef or other mammals, as well as aquatic species of fish, mammals, encompassing many water living species.
- The crosslinking composition may contain a coconut(food grade) diethanolamide. The properties of this well known emulsifier in the cosmetic and detergent-market is also used in the oilfield, typically having a TAV of about 137 from diethanolamine, as the amine equivalent weight of the amide is infinity. Stabilizers for the crosslinking composition can be cellosolves, glycerin and/or ethanols.
- If the storage vessel is discharged into a sales line, transmission line, or other pipeline of some length, the user may wish to break the gel just prior to beginning discharge in order not to unnecessarily consume energy in pumping because of the viscosity of the gel, even though it is a weak gel. If the storage vessel is discharged into a truck, it may be more efficient to wait until the truck arrives at its destination; the benefits of high gravity preservation will thereby be obtained while the truck holds the weakly gelled hydrocarbons. The gel can be broken in either case by adding a small amount of aminoalcohols, and especially in the form of hexahydro triazines, aminoalcohol(reactions of glycidyl ethers and secondary amines). Addition of the gel breaker can be made either to the holding vessel or truck or directly to a pipe or other conduit. Addition can be “batch” or substantially continuous if the material is flowing, and may be coordinated with a stabilizer or other system where light ends are deliberately separated.
- While viscosity is objectively measurable and useful in evaluating my gels, it should be observed that our invention is not simply a matter of increasing the viscosity of the stored hydrocarbons, since it is normally desirable to break the gel on termination of storage. In other words, I do not use polymeric viscosifiers that cannot be readily broken down to restore the original viscosity of the hydrocarbons. Moreover, crosslinked gels are more efficient at suppressing emissions than are linear polymers because they inhibit the formation of bubbles below the surface of the stored hydrocarbons, while linear polymers may only temporarily divert the ascent of small bubbles to the surface. A crosslinked network on or near the liquid surface also physically alters the phase interface, resulting in vapor pressure effects favorable to retention of the lighter components of the stored material. My gels containing butanes, pentanes, and other C5s to C8s exhibit Reid Vapor pressure of <2 psi, while ungelled hydrocarbon liquids and vapors have Reid vapor pressures of 3 to 8 psi or even higher. My method will frequently provide a Reid vapor pressure is a hydrocarbon storage vessel at least two Reid vapor pressure units lower than it would be without my invention.
- My invention includes inhibiting volatilization of light hydrocarbons from a liquid mixture of hydrocarbons in a storage vessel comprising, (1) prior to placing said liquid mixture of hydrocarbons in said storage vessel, adding to said liquid mixture (a) a phosphorous-containing gel former and (b) a source of polyvalent metal crosslinking agent in an amount effective to form a pumpable gel comprising said liquid mixture of hydrocarbons, and (b) pumping said pumpable gel into said storage vessel.
- My invention also includes a method of storing and transporting newly produced high gravity oil comprising (a) converting said high gravity oil to a weak gel, (b) placing said weak gel in a storage vessel, (c) storing said weal gel in said storage vessel, (d) breaking said weak gel to render said high gravity oil substantially free of said weak gel, and (e) transporting said high gravity oil to a new location.
- In another aspect, my invention includes a method of storing newly produced high gravity oil to inhibit a reduction in its high gravity by vapor loss comprising (a) adding to said newly produced high gravity oil 0.001 to 0.02 parts by volume phosphate ester of C2-C6 alcohol per cubic meter of high gravity oil, (2) adding to said newly produced high gravity oil containing said phosphate ester 0.001 to 0.02 parts by volume of a crosslinker for said phosphate, thereby forming a pumpable gel, and (c) introducing said newly produced high gravity oil in the form of said pumpable gel to a storage vessel.
Claims (20)
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US13/136,237 US20130025857A1 (en) | 2011-07-27 | 2011-07-27 | Preserving oil gravity |
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US13/136,237 US20130025857A1 (en) | 2011-07-27 | 2011-07-27 | Preserving oil gravity |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3505374A (en) * | 1968-01-30 | 1970-04-07 | Dow Chemical Co | Gelling agents for hydrocarbons |
US3652242A (en) * | 1970-02-02 | 1972-03-28 | Mobil Oil Corp | Liquid hydrocarbon fuels containing alkylamine salts |
US4153649A (en) * | 1976-02-09 | 1979-05-08 | The Dow Chemical Company | Phosphate ester-type reaction product and method of preparing same |
US5276248A (en) * | 1991-09-09 | 1994-01-04 | Cassella Aktiengesellschaft | Process for the storage and transportation of liquid hydrocarbons |
US6250391B1 (en) * | 1999-01-29 | 2001-06-26 | Glenn C. Proudfoot | Producing hydrocarbons from well with underground reservoir |
US7066262B2 (en) * | 2004-08-18 | 2006-06-27 | Halliburton Energy Services, Inc. | Gelled liquid hydrocarbon treatment fluids having reduced phosphorus volatility and their associated methods of use and preparation |
US7875759B2 (en) * | 2004-11-04 | 2011-01-25 | Rafael Bin Mohd Shamsudin | Process for extracting natural gas liquids from natural gas |
-
2011
- 2011-07-27 US US13/136,237 patent/US20130025857A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3505374A (en) * | 1968-01-30 | 1970-04-07 | Dow Chemical Co | Gelling agents for hydrocarbons |
US3652242A (en) * | 1970-02-02 | 1972-03-28 | Mobil Oil Corp | Liquid hydrocarbon fuels containing alkylamine salts |
US4153649A (en) * | 1976-02-09 | 1979-05-08 | The Dow Chemical Company | Phosphate ester-type reaction product and method of preparing same |
US5276248A (en) * | 1991-09-09 | 1994-01-04 | Cassella Aktiengesellschaft | Process for the storage and transportation of liquid hydrocarbons |
US6250391B1 (en) * | 1999-01-29 | 2001-06-26 | Glenn C. Proudfoot | Producing hydrocarbons from well with underground reservoir |
US7066262B2 (en) * | 2004-08-18 | 2006-06-27 | Halliburton Energy Services, Inc. | Gelled liquid hydrocarbon treatment fluids having reduced phosphorus volatility and their associated methods of use and preparation |
US7875759B2 (en) * | 2004-11-04 | 2011-01-25 | Rafael Bin Mohd Shamsudin | Process for extracting natural gas liquids from natural gas |
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