text:
|Publication number
|Publication type
|Application number
|Publication date
|Aug 30, 1988
|Filing date
|Jul 31, 1986
|Priority date
|Jul 31, 1986
|Fee status
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|Publication number
|Athanasios Karydas, Thomas W. Cooke, Robert A. Falk
|Original Assignee
|Ciba-Geigy Corporation
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|Patent Citations (38), Non-Patent Citations (39), Referenced by (43), Classifications (20), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
[Rf)n R']m Z
[(Rf)n R']m Z
The present invention relates to an improved method of transporting hydrocarbon crude oils containing paraffin wax, asphaltenes, or mixtures thereof, and compositions for use in such method. More particularly, the present invention relates to the introduction into low water hydrocarbon crude oils contaminated with paraffin wax, asphaltenes, or mixtures thereof, and which oils are normally susceptible to deposition by such contaminants, of an effective deposition inhibiting amount of an oil soluble organic compound having at least one oleophobic and hydrophobic fluoroaliphatic group. The present invention also relates to crude oil compositions contaminated with deposition susceptible paraffins, asphaltenes, or mixtures thereof, and containing an effective deposition inhibiting amount of such oleophobic and hydrophobic fluoroaliphatic group containing oil soluble organic compounds.
Crude oils are complex mixtures comprising hydrocarbons of widely varying molecular weights, i.e. from the very simple low molecular weight species including methane, propane, octane and the like to those complex structures whose molecular weights approach 100,000. In addition, sulfur, oxygen and nitrogen containing compounds may characteristically be present. Further, the hydrocarbyl constituents may comprise saturated and unsaturated aliphatic species and those having aromatic character.
By a variety of fractionation procedures crude oils can be separated into various classes, the most common of which is boiling range. The mixtures which are in the lower boiling ranges generally consist of materials of relatively simple structures. The mixtures which are in the high boiling point ranges comprise substances which, with the exception of paraffins, are so complex that broad terms are applied to them such as resins and asphaltenes. Resins are poorly characterized but are known to be highly aromatic in character and are generally thought to be high molecular weight polynuclear aromatic hydrocarbons which melt over a wide, elevated temperature range. Asphaltenes are even more complex chemically--some of which suffer thermal decomposition before melting. They are high molecular weight polymers in colloidal suspension. Resins and asphaltenes characteristically contain sulfur, nitrogen or oxygen-containing compounds. Paraffins are linear or branched chain hydrocarbons in the range of C18 H38 to C60 H122 and are usually waxy solids with widely varying melting points. Paraffins generally have limited, temperature-dependent, solubility in produced crude oils. This poor solubility creates a considerable problem for the oil producer.
The problem is aggravated by the very nature of oil production, as crude oil is generally removed from a high pressure or high temperature environment and then is subjected to atmospheric pressure and low temperatures.
The paraffin is usually soluble in crude petroleum under "down-hole" conditions. Ordinarily, as the petroleum is brought to the surface, its temperature is reduced and the crude is subjected to a diminished pressure. As the crude leaves the wellhead at the reduced pressure, dissolved gases, which act as natural solubilizers for paraffin, tend to come out of solution. These two factors, the decrease in temperature and the loss of dissolved gases, decrease the ability of the remaining crude to keep the paraffin solution. As a result, wax crystals may precipitate on any appropriate surface.
When the petroleum waxes precipitate, they cause a myriad of problems for the oil producer. The precipitated waxy solids can create flow restrictions by depositing or accumulating downhole on tubing, rods, and sub-surface pumps; and aboveground in valves, piping, separators, and storage tanks. These troublesome deposits are combinations of an array of molecular weight hydrocarbons and adsorbed impurities.
Since any given crude always contains a mixture of alkanes (saturated hydrocarbons) of different molecular weights, different solubilities and different melting points, the associated paraffin deposits will vary in content depending on the deposition conditions. The major influences on the quantity of the deposit, as well as its composition, are the bulk oil and pipe surface temperatures, the temperature gradient between the oil and surface, and the flow rate of the oil.
Important factors determining the amount and rate of deposition of wax include the pipe surface and bulk oil temperatures relative to the cloud point of the crude. The cloud point of a crude is generally defined as the temperature at which wax crystallization begins. If the temperature of both the pipe and the oil flowing through it are above the cloud point, little or no waxy deposition will occur. If, however, the temperature of the inside surface of the pipe falls below the cloud point of the oil and the bulk of the flowing crude oil is at a higher temperature, wax will characteristically be deposited on the pipe surface. If the pipe surface is only slightly cooler than the cloud point of the oil, and the oil is much warmer, a lesser amount of waxy deposit will form, generally composed of the highest molecular weights, highest melting, hardest waxes in the crude. If the pipe surface temperature is much lower than the bulk oil temperature, a greater quantity of softer, lower melting deposit will usually accumulate.
If the gradient is reversed and the pipe wall is warmer than the oil flowing past, little or no deposition will occur, even if the temperature of the pipe and the oil are both below the oil's cloud point.
The flow rate of a crude past a deposition surface may also influence the composition of the deposits. A high flow rate tends to selectively remove the lower melting, softer fractions from the growing deposit, resulting in the formation of a hard dense deposit of high melting wax. A very low flow rate allows the inclusion of low melting, softer waxes and even of oil fractions in the waxy deposits. The net deposit is generally a very soft, low melting deposit.
Because of the diverse conditions that exist in a production system, it is not uncommon for several of the conditions for deposition to be present in the same system. This can result in different types of deposits forming in different locations within the same system. Soft, low melting deposits may form downhole while hard, higher melting deposits may form downstream of a choke or a valve in the pipeline leaving the well.
There are many methods of handling paraffin deposition. These can be divided into 3 categories: mechanical, thermal, and chemical.
A widely used mechanical treatment involves running a scraper that mechanically cuts the deposit from the tubing. Wirelining the tubing and "pigging" the flowlines are two examples.
Thermal treatment normally consists of minimizing heat losses and the addition of external heat to the system. Insulation of flowlines and maintaining a higher pressure in the flow lines that minimizes cooling through dissolved gas expansion are two examples of minimizing heat losses. Procedures such as steaming the flowlines, installing bottomhole heaters, and circulation of hot oil or hot water are examples of the application of heat in an effort to melt or increase the solubility of the deposit.
Chemical control generally falls into one of two classes: (1) using a solvent to dissolve the deposit once it has formed and (2) inhibiting wax crystal growth or inhibiting its adherence to the tubing wall.
Solvents used for dissolving paraffin deposits generally have a high aromatic content. A variety of solvents, including relatively low wax crude oils, are heated when used to increase the wax solution capacity of the solvents. Unfortunately, this procedure can be prohibitively expensive, particularly where such solvents are not readily available.
Typical paraffin inhibitors include certain known copolymers capable of crystal distortion or modification during the wax deposition process. Because the use of such copolymers involve a cocrystallization mechanism, it is necessary to have the copolymer in solution above the cloud-point temperature of the crude. This cocrystallization mechanism prevents or interferes with the molecular diffusion mechanism of deposition, and is believed to modify the crystal structure of the precipitated waxes into small, highly branched structures with low cohesive properties. Three popular crystal modifiers are copolymers in these groups: (1) Group A--copolymers of ethylene vinyl acetate, (2) Group B--copolymers of C12 through C30 methacrylates, and (3) Group C--copolymers of olefin/maleic anhydride esters.
Products of this type are commercially available under the trade names Shellswim�, Waxstock� and Marchon�. Some are described in U.S. Pat. No. 3,776,247 and British Pat. Nos. 1,161,188 and 1,154,966. However, not all waxy crudes are beneficially affected by treatment with such substances, possibly because the ability of any particular conventional popular copolymer to cocrystallize will vary depending on the particular crude oil treated.
Asphaltenes may also precipitate from crude oils, likewise creating a myriad of problems for the oil producer.
Asphaltenes are aromatic-base hydrocarbons of amorphous structure. They are present in crude oils in the form of colloidally dispersed particles. The central part of the asphaltene micelle generally consists of high molecular weight compounds surrounded and peptized by lower weight neutral resins and aromatic hydrocarbons.
Any action of chemical, electrical or mechanical nature that depeptizes the asphaltene micelle may lead to flocculation and precipitation of the asphaltenes from the crude oil. The addition of low-surface-tension liquids--i.e. below 24 mN/m [24 dyne/cm] at 25� C., such as gasoline, pentane, hexane, petroleum naphtha, etc. may precipitate asphaltenes. The addition of HCl during acidizing also tends to cause the formation of precipitated asphalticacid sludges. The flow of crude oil through porous media may also result in the precipitation of asphaltenes because of the neutralization of their charge by the streaming potential.
Asphaltene deposits are characteristically hard, brittle, dark black, dry solids, similar in appearance to coal and other bitumens. These deposits are very difficult to remove from a system because typical thermal methods of hot oil or water treatment are generally totally ineffective. The deposition of these materials also constricts or blocks the passage of crude oil causing reduced efficiency of production. Prevention or removal can be attempted chemically through the use of aromatic solvents, solvent accelerators, or the resinous components of crudes. Here again, such procedures can be prohibitively expensive and may not be effective.
Other approaches that have been suggested to inhibit or prevent asphaltene and paraffin deposits include the use of aqueous surfactant solutions to form low viscosity oil-in-water emulsions as shown in U.S. Pat. Nos. 3,943,954, 4,265,264, 4,429,554 and 4,239,052. Such emulsions generally contain a rather high percentage of water, for example 10-40% water, which must be removed. Removal is not always easy and yields large volumes of water contaminated with oil. High treating temperatures are required for separation of the water and this results in additional expenditures. Also, corrosion problems, freezing problems, and emulsion inversion into highly viscous water-in-oil emulsions problems may be associated with such aqueous emulsions, depending upon the nature of the field conditions, local climate, and the like.
Inhibition of paraffin and asphaltene deposition by crude oils is achieved by the addition to such oils of an effective amount of paraffin and asphaltene deposition inhibitors which are oil soluble organic compounds having at least one oleophobic and hydrophobic fluoroaliphatic group.
One embodiment of the present invention relates to a method of inhibiting paraffin wax or asphaltene deposition from a low water hydrocarbon crude oil contaminated with such paraffin wax or asphaltene or mixtures thereof by contacting said oil with an effective deposition inhibiting amount of an oil soluble organic compound having at least one oleophobic and hydrophobic fluoroaliphatic group, said group having between about 4 to about 20 carbon atoms.
Preferably, the fluoroaliphatic group-containing oil soluble organic compound is added to the pipeline or well bore of the wax or asphaltene contaminated hydrocarbon crude oil. In order to insure rapid and efficient dissolution and dispersion of the fluoroaliphatic oil soluble organic compound, the deposition inhibitor may conveniently be added to the crude oil as a solution or semiliquid by dilution of the deposition inhibitor in a liquid organic oil soluble carrier.
Advantageously, useful fluoroaliphatic oil soluble organic compounds are those exhibiting a solubility in the crude oil to be treated of at least 10 ppm by weight at 80� C.; which are sufficiently oleophobic such that a steel coupon treated with the fluoroaliphatic compound gives a contact angle with hexadecane of fifteen degrees or more; and wherein the fluorine content is generally between about 1 and about 70 weight percent of the fluoroaliphatic compound. Useful guides in selecting highly preferred fluoroaliphatic compounds useful in deposition inhibition are found in the laboratory screening techniques for paraffin and asphaltene deposition inhibition tests described hereinafter.
An alternate embodiment of the present invention relates to antideposition stabilized crude oil compositions containing in the dissolved and dispersed state an effective wax and asphaltene deposition amount of the fluoroaliphatic oil soluble compound.
These and other objects of the present invention are apparent from the following specific disclosures.
Generally, suitable oil soluble organic compounds containing at least one oleophobic and hydrophobic fluoroaliphatic group can be represented by the formula
[(Rf)n R']m Z (I)
Rf is an inert, stable, oleophobic and hydrophobic fluoroaliphatic group having about 4 to about 20 carbon atoms;
n is an integer from 1 to 3;
R' is a direct bond or an organic linking group having a valency of n+1 and is covalently bonded to both Rf and Z;
m is an integer of from 1 to about 5000; and
Z is a hydrocarbyl containing residue having a valency of m and being sufficiently oleophilic so as to impart an oil solubility to said compounds of at least 10 parts by weight per million parts of hydrocarbon crude oil.
Suitable Rf groups include straight or branched chain perfluoroalkyl having 4 to 20 carbon atoms, perfluoroalkoxy substituted perfluoroalkyl having a total of 4 to 20 carbon atoms, omega-hydro perfluoroalkyl of 4 to 20 carbon atoms, or perfluoroalkenyl of 4 to 20 carbon atoms. If desired, the Rf group may be a mixture of such moieties.
The integer n is preferably 1 or 2.
Where n is 1, R' may be a direct bond or a divalent organic linking group. The nature of the divalent organic linking group R', when present, is not critical as long as it performs the essential function of bonding the fluoroaliphatic group, Rf, to the oleophilic organic radical Z.
In one sub-embodiment, R' is an organic divalent linking group which covalently bonds the Rf group to the group Z.
Thus, R' may, for example, be a divalent group, R� , selected from the following:
--C1 -C8 alkylene--,
--C1 -C8 alkylene--R1 --C1 -C8 alkylene--,
--C1 -C8 alkylene--R1 --,
--R1 --C1 -C8 alkylene--,
--R1 --C1 -C8 alkylene--R1 '--,
--R1 --phenylene--,
--R1 --phenylene--R1 '--,
--R1 --phenylene--C1 -C8 alkylene--, or
--phenylene--R1 --,
wherein, in each case, said alkylene and phenylene are independently unsubstituted or substituted by hydroxy, halo, nitro, carboxy C1 -C6 alkoxy, amino, C1 -C6 alkanoyl, C1 -C6 carbalkoxy, C1 -C6 alkanoyloxy or C1 -C6 alkanoylamino. The alkylene moiety may be straight or branched chain or contain cyclic alkylene moieites, such as cycloalkylene or norbornylene.
R1 and R1 ' independently represent: ##STR1## --O--, where R2 is hydrogen, C1 -C6 alkyl or C1 -C6 alkyl substituted by: C1 -C6 alkoxy, halo, hydroxy, carboxy, C1 -C6 carbalkoxy, C1 -C6 alkanoyloxy or C1 -C6 alkanoylamino. Also, if desired, the amino group --N(R2)--, above, may be in quaternized form, for example of the formula ##STR2## wherein a is 1, R3 is hydrogen or C1 -C6 alkyl which is unsubstituted or substituted by hydroxy, C1 -C6 alkoxy, C1 -C6 alkanoyloxy or C1 -C6 carbalkoxy and X is an anion, such as halo, sulfato, lower alkylsulfato such as methylsulfato, lower alkyl-sulfonyloxy such as methylsulfonyloxy, lower alkanoyloxy such as acetoxy or the like.
As an alternate sub-embodiment, R', while being covalently bonded to both Rf and Z may contain an ionic bridging group as an integral part of the chain linking Rf to Z.
Thus, for example, R' may be selected from the following:
--(--Ra ')s Q.sup.⊕⊖ T(Rb ')t
--(--Ra ')s T.sup.⊖⊕ Q(Rb ')t
Ra ' is --C1 -C8 alkylene--, --phenylene--, --C1 C8 alkylene--R1 --C1 -C8 alkylene--, --R1 -C8 alkylene--, --R1 --phenylene--or --R1 --phenylene--C1 -C8 alkylene--;
Rb ' is --C1 -C8 alkylene, --phenylene--, --C1 -C8 alkylene--R1 --C1 -C8 alkylene--, --C1 -C8 alkylene--R1 --, --phenylene--R1 -- or --C1 -C8 alkylene--phenylene--R1 --; s and t are independently 0 or 1; T is an anionic group, Rf is as defined above and Q is a cationic group and wherein said alkylene and phenylene unsubstituted or substituted by hydroxy, halo, nitro, carboxy, C1 -C6 alkoxy, amino, C1 -C6 alkanoyl, C1 -C6 carbalkoxy, C1 -C6 alkanoyloxy or C1 -C6 alkanoylamino.
Suitable anionic groups for T include carboxy, sulfoxy, sulfato, phosphono, and phenolic hydroxy. Suitable cationic groups for Q include amino and alkylated amino, such as those of the formula ##STR3## where each R2 and R3 are as defined above.
Where n is 2 and m is 1, R' is an organic trivalent group. Suitable such groups include those of the formula: ##STR4## wherein R1 and R2 are defined above; u, v and w are independently 1 or 0 and R0 is alkanetriyl, arenetriyl or aralkanetriyl of up to 18 carbon atoms which may be interrupted by one or more hetero atoms, and as oxygen, sulfur or imino.
The oleophilic organic radical Z can vary widely and is, in general, not critical, as long as the group performs the essential function of conferring the requisite oil solubility to the compound.
For example, suitable oleophilic organic radicals, when m is 1 include, without limitation, conventional hydrophobic-oleophilic higher alkyl or alkenyl of 6-24 carbon atoms which are unsubstituted or substituted e.g. by chloro, bromo, alkoxy of up to 18 carbon atoms, nitro, alkanoyl of up to 18 carbon atoms, alkylmercapto of up to 18 carbon atoms, amino, C1 -C18 alkylamino, or di--C1 -C18 alkylamino; an aryl group, such as phenyl or naphthyl, the phenyl and naphthyl moiety of which is unsubstituted or substituted by alkyl of up to 20 carbon atoms, alkoxy of up to 20 carbon atoms, alkanoyl of up to 20 carbon atoms, alkanoyloxy of up to 20 carbon atoms or mono- or di-alkylamino of up to 20 carbon atoms; mono- or di--C6 -C24 --alkylamino--C2 -C7 -- alkylene; alkoxyalkylene of 4-20 carbon atoms which is unsubstituted or substituted by one or two C6 -C24 carbalkoxy or C6 -C24 carbamoyl groups; poly--C6 -C24 alkoxy-higher alkyl or alkenyl of 6-24 carbon atoms; a heterocyclic group such as piperidino, piperazino, azepino, N-pyridinium, morpholino, benztriazolyl, triazinyl, pyrrolidino, furanyl, tetrahydrofuranyl and the like, which are unsubstituted or substituted e.g. by halo, alkoxy of up to 18 carbon atoms, nitro, alkanoyl of up to 18 carbon atoms, alkylmercapto of up to 18 carbon atoms, amino or alkylamino of up to 18 carbon atoms; poly--C2 -C3 alkoxy-phenyl, the phenyl group of which is unsubstituted or substituted by alkyl of up to 20 carbon atoms; a group of the formula --(CH2 CH2 CH2 CH2 O)g H and g is 2-80; a group of the formula ##STR5## wherein b is 2-40, c is 2-80, and d is 2-40; a group of the formula ##STR6## wherein each e is 3-20, and each f is 3-20 and A is an anion; a group of the formula ##STR7## where p is 1-15 and q is 1-15 and R" is alkyl of 6 to 22 carbon atoms or alkanoyl of 6 to 22 carbon atoms; or a group of the formula ##STR8## where Ro, b, c and d are as defined above.
Also, where m is 2 or 3, Z represents an oleophilic organic divalent or trivalent radical. Suitable such radicals include those wherein Z is an oleophilic di- or trivalent aliphatic, carbocyclic, heterocyclic or aromatic group. For example, when m is 2, Z may represent an oleophilic polyalkyleneoxy containing group, the terminal members of which are covalently bonded to R'; an arylene group, such as phenylene or naphthalene which are unsubstituted or substituted, e.g. by alkyl up to 20 carbon atoms, alkoxy of up to 20 carbon atoms, alkanoyloxy of up to 20 carbon atoms, alkanoylamino of up to 20 carbon atoms, halo, amino or alkylamino of up to 20 carbon atoms, or the like; an alkylene or alkenylene group of up to 20 carbon atoms which is unsubstituted or substituted, e.g. by alkoxy of up to 20 carbon atoms, alkylamino of up to 20 carbon atoms, alkanoyl of up to 20 carbon atoms, alkanoylamino of up to 20 carbon atoms, or alkanoyloxy of up to 20 carbon atoms; a heterocyclic group, such as N, N'-piperazinylene, triazinylene, or the like.
An alternate group of oil soluble compounds according to formula I are those wherein the Rf group is pendant to an oleophilic polymer backbone.
Suitable oleophilic polymer backbones are those derived from condensation polymers and addition polymers.
For example, the group Z may contain condensation units of the formula:
(O-R3 -OCONH-D-NHCO)m
wherein R3 is an aliphatic triradical or tetraradical of 2-50 carbon atoms which is covalently bonded to the (Rf)n R' groups and is selected from the group consisting of branched or straight chain alkylene, alkylenethioalkylene, alkyleneoxyalkylene or alkyleneiminoalkylene; and D, together with the --NHCO groups to which it is attached, is the organic divalent radical of a diisocyanate.
In a preferred subembodiment, D is alkylene of 2 to 16 carbon atoms; cycloaliphatic of 6 to 24 carbon atoms; phenylene that is unsubstituted or substituted by lower alkyl, lower alkoxy or chloro; diphenylene; phenyleneoxyphenyl, phenylene (lower alkylene) phenylene, or naphthylene, where the aromatic ring is otherwise unsubstituted or substituted by lower alkyl, lower alkoxy or chloro. In an alternate embodiment, up to about 85 percent of the [(Rf)n R']m R3 groups may be replaced by the biradical of a bis(2-aminopropyl) ether of a polyethylene oxide; an aliphatic polyol of up to 18 carbon atoms; a di- or polyalkoxylated aliphatic or aromatic tertiary amine of up to 18 carbon atoms; a lower alkylene polyether; or a hydroxyterminated polyester having a hydroxyl number from 40 to 500.
Suitable preferred condensation polymers and their preparations are described, inter alia, in U.S. Pat. Nos. 3,935,277, 4,001,305, 4,046,944 and 4,054,592.
Suitable oleophilic polymer backbones derived from addition polymers comprising the group Z include those wherein up to about 5000 groups of the formula (Rf)nR'-- are attached to an oleophilic hydrocarbyl containing polymeric backbone. Suitable polymers include those wherein the addition polymer contains up to about 5000 units of the formula ##STR9## wherein Rf, n and R' are defined above, and Ra is hydrogen or lower alkyl. Preferably Ra is hydrogen or methyl.
Such addition polymers are generally prepared, by methods known in the art, e.g. in U.S. Pat. Nos. 3,282,905, 3,491,169 and 4,060,681, by homo- or co-polymerizing the corresponding monomer of the formula ##STR10## wherein Rf, n, R', and Ra are defined above, optionally with polymerizable vinylic comonomers.
Suitable comonomers include:
Ethylene and chloro, fluoro- and cyano- derivatives of ethylene such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, acrylonitrile, methacrylonitrile, tetrafluoroethylene, trifluorochloroethylene, hexafluoropropylene; acrylate and methacrylate monomers, particularly those with 1 to 12 or 18 carbon atoms in the ester groups such as n-propyl methacrylate, 2-methyl cyclohexyl methacrylate, methyl methacrylate, t-butyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 3-methyl-1-pentyl acrylate, octyl acrylate, tetradecyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, and phenyl acrylate; dienes particularly 1, 3-butadiene, isoprene, and chlorprene, 2-fluoro-butadiene, 1,1,3-trifluorobutadiene, 1,1,2,3-tetrafluoro butadiene, 1,1,2-trifluoro-3,4-dichlorobutadiene and tri- and pentafluoro butadiene and isoprene; nitrogen-vinyl monomers such as vinyl pyridine, N-vinylimides, amides, vinyl succinimide, vinyl pyrrolidone, N-vinyl carbazole and the like;
styrene and related monomers which copolymerize readily with the novel esters of this invention such as o-methylstyrene, p-methylstyrene, 3,4-dimethyl styrene, 2,4,6-trimethyl styrene, m-ethyl styrene, 2,5-diethyl styrene;
vinyl esters, e.g. vinyl acetate, vinyl esters of substituted acids, such as for example, vinyl methoxyacetate, vinyl trimethylacetate, vinyl isobutyrate, isopropenyl butyrate, vinyl lactate, vinyl caprylate, vinyl pelargonate, vinyl myristate, vinyl oleate and vinyl linoleate; vinyl esters of aromatic acids, such as vinyl benzoate;
alkyl vinylethers, such as methyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, 2-methoxy ethyl vinyl ether, n-propyl vinyl ether, t-butyl vinyl ether, isoamyl vinyl ether, n-hexyl vinyl ether, 2-ethylbutyl vinyl ether, diisopropylmethyl vinyl ether, 1-methyl-heptyl vinyl ether, n-decyl vinyl ether, n-tetradecyl vinyl ether, and n-octadecyl vinyl ether.
Propylene, butylene and isobutylene are preferred α-olefins useful as comonomers with the novel fluoro monomers of the present invention with straight and branched chain α-olefins useful with up to 18 carbon atoms in the side chain.
Suitable candidate compounds of the formula I containing one or more inert stable oleophobic and hydrophobic fluoroaliphatic groups, Rf, and an oleophilic hydrocarbyl containing residue, represent a well known class of compounds widely described in the literature.
For example, compounds of the formula I wherein n and m are 1 are described in U.S. Pat. Nos. 4,460,791; 4,302,378; 3,575,899; 3,575,890; 4,202,706; 3,346,612; 3,575,899; 3,989,725; 4,243,658; 4,107,055; 3,993,744; 4,293,441; 4,107,055; 3,839,343; JP No. 77/88,592; Ger. Offen. Nos. 1,966,931; 2,245,722; JP No. 60/181,141; EP No. 140,525; JP No. 53/31582; CH No. 549,551; EP No. 74,057; FR No. 2,530,623; Ger. Offen. No. 2,357,780; JP No. 58/70806; Ger. Offen. No. 2,344,889; U.S. Pat. Nos. 3,575,890; 3,681,329; Ger. Offen. No. 2,559,189; U.S. Pat. Nos. 3,708,537; 3,838,165; 3,398,182 Ger. Offen. Nos. 2,016,423; 2,753, 095, 2,941,473; 3,233,830; JP Nos. 45/38,759; 51/144,730; Ger. Offen. Nos. 3,856,616; 2,744,044; JP No. 60/151,378; Ger. Offen. No. 1,956,198; and GB No. 1,106,641.
Compounds of the formula I wherein n is 2 or 3, or m is 2 to 4 are described, for example, in U.S. Pat. No. 4,219,625; Ger. Offen. No. 2,154,574; Ger. Offen. No. 2,628,776; Text. Res. J., 47 (8), 551-61 (1977); U.S. Pat. Nos. 4,268,598; 3,828,098; Ger. Offen. Nos. 1,938,544; 2,017,399; 2,628,776; 1,956,198; JP No. 47/16279; Ger. Offen. Nos. 1,938,545; 1,916,651; U.S. Pat. Nos. 3,492,374; 4,195,105; Ger. Offen. No. 2,009,781; U.S. Pat. No. 4,001,305; and GB No. 1,296,426.
Compounds where n is 1 to 3 and m is in excess of 4, up to for example about 500, are described, inter alia, in U.S. Pat. Nos. 3,935,277; 2,732,370; 2,828,025; 2,592,069; 2,436,144; 4,011,305; 4,046,944; 4,054,592; 4,557,837; 3,282,905, 3,491,169; and 4,060,681.
In a preferred embodiment of the invention, highly suitable candidate oil soluble organic compounds, containing at least one oleophobic and hydrophobic group, of formula I useful as antideposition agents in crude oils contaminated with paraffin wax, asphaltenes, or mixtures thereof, contain 1-70% fluorine and have a solubility in crude oil of at least 10 ppm at 80� C. and are advantageously screened for efficacy using simple laboratory techniques a described hereinafter.
For example, in screening oil soluble candidate compounds of formula I for paraffin antideposition properties, it has been found that those compounds repeatedly applied to the surface of steel coupons from e.g. a 5% by weight solution of candidate compound in a suitable volatile inert solvent, such as xylene, toluene, isopropyl acetate, methylene chloride, ethanol, water or miscible mixtures thereof, and air dried after each application, which render the metal coupon sufficiently oleophobic such that hexadecane exhibits a contact angle with the treated coupon of fifteen degrees or more, are characteristically suitable for use in the instant invention.
A second screening technique for oil soluble candidate compounds of formula I for paraffin deposition involves the determination of the comparative deposition reduction in the paraffin contaminated crude oil to be treated by comparing the wax deposition of a treated oil, containing from 10 to 500 parts by weight of the compound of formula I per million parts oil, with a crude oil identical to the treated oil but without the fluorochemical candidate, in respect to the amount of residue retained on the walls of standard laboratory beakers in accordance with the Beaker Method more fully described hereinafter. While 100 ml Pyrex beakers are employed, the test may be run using, e.g. degreased stainless steel 100 ml beakers. Under the test conditions, those compounds in which the treated crude oil composition exhibits reduction in total beaker weight gain due to residual oil on the beaker surface have characteristically been found to be highly preferred.
An alternate and generally efficient laboratory technique for screening preferred oil soluble candidate compounds of formula I for paraffin antideposition properties in the paraffin contaminated crude oil to be treated is the Static Cold Finger Method, described hereinafter. In this test 500 parts by weight of fluorochemical are added per million parts of crude oil. Depending upon the solubility of the fluorochemical under the test conditions, it is recognized that lesser amounts may be employed, to a minimum of about 10 parts by weight of fluorochemical per million parts crude oil, in the event that the candidate possesses but limited solubility. Those treated crude oil compositions exhibiting a reduction in the percent decrease in weight gain of the cold finger coil of at least 10% vis-a-vis crude oil not containing the fluorochemical candidate qualifies such candidate as characteristically suitable for use in the instant invention. Preferred compounds generally inhibit paraffin deposition of crude oils in this method by percent decrease in weight gain of the coil of at least 20%, most preferably at least 40%.
A convenient laboratory screening technique for oil soluble candidate compounds of formula I for asphaltene deposition inhibition is the Asphaltene Deposition test described hereinafter, wherein a crude oil contaminated with deposition susceptible amounts of asphaltene is treated by dissolving 10 to 200 parts per million by weight of compound of formula I to such oil and comparing the amount of asphaltene precipitate occassionaled by the addition of hexane as compared to an otherwise identical control sample of crude oil not containing the candidate. Preferably, 200 parts per million by weight of candidate compound is employed per part crude oil. It has been found that under the best conditions, those compounds which significantly inhibited the precipitation of asphaltene, e.g. at least 10 percent decrease by weight of asphaltenes collected on the filter paper, preferably at least 20% and most preferably 50%, characteristically result in the compound of highly suitable for use as an asphaltene inhibitor in the instant invention.
It is to be understood that for purposes of easily and efficiently dispersing and dissolving the fluorochemical in the crude oil to be treated, it is generally advantageous to first dissolve or disperse the fluorochemical of formula I in a suitable solvent which is generally compatable with the crude oil in the amounts employed. Suitable solvents vary widely but include, inter alia, conventional organic solvents such as toluene, xylene, cumene, aliphatic and or aromatic oil fractions, petroleum ether, isopropyl acetate, methylene chloride, alkanols and the like.
In the following test descriptions and examples, all temperatures are given in degrees Centigrade and all parts are given in parts by weight unless otherwise indicated. The examples are for illustrative purposes only and are not intended to limit the scope of the invention.
Crude oil A is paraffinic; originating from Utah, it has a pour point of 31� C., a paraffin content of 22%, and a cloud point of 50� C. Its water content is 0.4%, it is black, and it has API gravity of 35�.
Crude oil B is paraffinic; originating from Utah, it has a pour point of 45� C., a paraffin content of 35%, and a cloud point of 66� C. Its water content is 0.05%, it is yellow and it has an API gravity of 42�.
Crude oil C is paraffinic; originating from Utah, it has a pour point of 35� C., a paraffin content of 25% and a cloud point of 57� C. Its water content is 0.05%, it is black and it has an API gravity of 36�.
Crude oil D is asphaltenic from off shore Italy; it has a viscosity of 39,500 cP at 25� C. Its estimated asphaltene content is 9% and it has an API gravity of 14�.
Degreased steel coupons (SAE 1010 1/2"�3"�1/8") are dipped for one minute in a 5% solution of fluorochemical in a suitable solvent, then are removed and air-dried for one minute. The procedure is repeated five times and the coupons are air-dried for at least 30 minutes. Contact angles with hexadecane are determined using a Raume-Hart contact angle goniometer. Hexadecane is used as a testing liquid due to its structural resemblance to paraffin wax and ease of handling. The contact angle of hexadecane with untreated steel coupons is zero degrees; for a fluorochemical to be considered effective the contact angle for the coated coupon should be at least fifteen degrees.
One hundred grams of crude oil are placed in an eight ounce bottle and heated to a temperature 10� C. higher than its cloud point for five minutes. Seven 100 ml beakers are pre-weighed and left standing at room temperature. The crude oil is poured into the first beaker. After the first beaker is filled,its contents are immediately transferred to the second beaker and the first beaker is put upside down. The procedure is repeated five times and the contents of the seventh beaker are transferred to the bottle and the beaker is placed upside down. The total weight gain of the seven beakers is determined. Potential paraffin deposition inhibitors are added to a new sample of oil during the heating stage and the procedure is repeated. Deposition inhibition is expressed as % decrease in beaker weight gain.
A method similar to the one described by Hunt (Journal of Petroleum Technology, 1962, pp 1259-1269) is used: Nine hundred ml of a high paraffin crude oil are placed in a 1 liter vessel and heated with gentle agitation to a temperature 10� C. below its cloud point. A pre-weighed stainless steel coil of 0.25 inch outer diameter and a total surface area of 26 square inches is immersed in the oil for 45 minutes. Water circulating through the coil maintains its temperature 15� C. below the cloud point of the crude oil. The coil is removed and the weight gain due to paraffin deposition is recorded. Potential paraffin deposition inhibitors are added to a new sample of crude oil and the procedure is repeated. Deposition inhibition is expressed as percent decrease in weight gain of the coil.
As mentioned earlier, addition of low surface tension hydrocarbons depeptizes the asphaltene micelle and causes asphaltene deposition: Fifty grams of low gravity asphaltic crude are mixed with 50 grams of hexane and the mixture is heated at 50� C. with gentle agitation for fifteen minutes. The diluted oil is then filtered through a Whatman #2 filter paper and the asphaltene deposit collected is air dried and weighed. Potential asphaltene deposition inhibitors are added to a new sample of crude oil and the procedure is repeated. Deposition inhibition is expressed as percent decrease of asphaltenes collected on the filter paper.
Hexadexane contact angles for compounds of the formula ##STR11## were determined employing the procedure previously described. Steel coupons were coated using tolulene solutions.
______________________________________ ContactExam- Angle,ple # Rf a b Degrees1______________________________________1 C6 F13 11 16 34 � 12 2% C4 F9, 38% C6 F13, 35% C8 F17 11 16 40 � 1 20% C10 F21, 5% C12 F253 C6 F13 6 56 25 � 14 2% C4 F9, 38% C6 F13, 35% C8 F17 6 56 25 � 1 20% C10 F21, 5% C12 F255 C6 F13 5 21 32 � 16 C6 F13 12 21 33 � 17 C6 F13 3 30 25 � 18 C6 F13 10 30 31 � 19 C6 F13 5 39 25 � 110 C6 F13 22 39 39 � 1______________________________________ 1 Average of at least four measurements.
All contact angles are greater than fifteen degrees indicating that the tested compounds are useful as deposition inibitors. Since many of the above compounds are soluble in hexadecane the angle may decrease as the coating dissolves in hexadecane; therefore only initial angles should be considered.
Hexadecane contact angles were determined for come commercial fluorochemicals. Steel coupons were coated using toluene solutions.
______________________________________Exam-ple # Trade Name, Source Contact Angle, Degrees1______________________________________11 Fluorad � FC 430, 3M Co.3 40 � 112 Fluorad � FC 740, 3M Co.3 .sup. 45 � 3213 Fluorad � FC 742, 3M Co.3 64 � 2______________________________________ 1 Average of at least four measurements. 2 The angle rapidly decreases to about 20 degrees. 3 Listed as fluorinated alkyl esters.
The above contact angles indicate that the compounds of the examples are useful as paraffin deposition inhibitors. The rapid contact angle decrease (from 45� to 20�) for the FC 740 coated coupon is attributed to the dissolution of FC 740 in hexadecane.
The efficiency of compounds of the formula ##STR12## as paraffin desposition inhibitors was determined by the previously described static cold finger method.
Crude A was used and it was held at 40� C. The water circulating through the coil was at 35� C. and treating level of inhibitor in crude oil was 500 ppm.
______________________________________Example # a b % Inhibition______________________________________14 5 21 7915 11 21 6516 3 30 7717 10 30 3718 5 39 6519 22 39 2520 6 56 6521 19 30 76______________________________________
The above examples demonstrate dramatic decreases in paraffin deposition. It should be noted that this is a static evaluation and even greater decreases may be observed in a dynamic system where precipitated paraffins are carried by the flowing crude oil.
A mixture of 1.58 g benzotriazole (0.0131 mole), 7.0 g ##STR13## and 34.24 g toluene, is heated to reflux (110�-111 C.) for 10.25 hours. Then 0.02 g boron trifluoride etherate are added and the reaction mixture is heated under reflux for 45 minutes. Removal of the toluene affords a product containing a mix of two isomers with the following structures I and II, as determined by 13 C-NMR , ##STR14##
Analysis: Calculated (percent): C, 37.0; H, 2.8; N, 6.7; F, 45.3. Found (percent): C, 37.3; H, 2.8; N, 6.7; F, 43.6.
A mixture of 26.8 g (0.05 moles) of 3-(1,1,2,2-tetrahydroperfluorodecanethio)-1,2-epoxypropane was reacted with 14.9 g (0.05 moles) of octadecyldimethylamine and 3.35 g (0.055 moles) of acetic acid in 179 grams toluene at 50�-60� for 18 hours.
The clear reaction product has the structure C8 F17 CH2 CH2 SCH2 CH(OH)CH2 N+ (CH3)2 C18 H37 O2 - CCH3 and is soluble at a 20% concentration in toluene to 0� C.
The product was coated on a coupon of cold rolled mild steel SAE 1010 and contact angle measurements were run. For hexadecane the angle was 50� (untreated steel=0�, i.e. it wets completely). Its surface tension in toluene at 1% was 26.0 dynes/cm (toluene=28.2).
A 300 ml, 3-neck reaction flask equipped with stirrer, nitrogen inlet, condenser and thermometer was charged with 30 g (0.03 mol) (Rf)2 -diol* and 35 g methylethyl ketone (MEK) which had been dried over molecular sieves. After all diol had dissolved, 4.4 g, 3,3,4-trimethyl hexane-1,6-diisocyanate (TMDI) (0.02 mol) were added followed by 0.01 g triethylamine. The mixture was heated to reflux for three hours, after which time free--NCO groups were not detected by IR. Then another 4.4 g TMDI were added, dissolved in 4.4 g MEK followed after 1/2 hour by 4.5 g bis-2-aminopropyl ether of polyethylene glycol of MW 900 (BAPG-900) (0.05 mol) and 8.8 g TMDI together with 54 g MEK. The mixture was kept at reflux for 4 more hours at which time no--NCO was detectable by IR. Heating was discontinued and 93 g water were slowly added under vigorous stirring. A yellowish, slightly turbid solution resulted, whose solids content was adjusted to 25%.
Methyl ethyl ketone (600 g) was charged to a 2 l flask fitted with a stirrer, thermometer, nitrogen inlet and a condenser protected with a drying tube. 2,3-Bis(1,1,2,2-tetrahydroperfluoroalkylthio) butane-1,4-diol (600 g; 0.571 mole)* was added together with a 1:1 mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylenediisosycanate (80.16 g; 0.381 mole). All reagents were rinsed in with an additional 50 g MEK. The solution was heated to boiling and 50 g solvent was removed by distillation to effect azeotropic drying of all materials. Then dibutyltindilaurate (0.692 g; 1.14�10-3 mole; 2 mole % based on diol) was added as a catalyst and the solution was heated under reflux for 6 hours, when the reaction was judged to be complete by the absence of the N═C═O infrared band at 2270 cm-1. The solution was cooled to room temperature (25�) and diluted with MEK to a total of 2042 g (331/3 % solids). A portion of the above material was taken to dryness. A quantitative recovery of a resinous material was obtained. Elemental analysis showed 52.8% F (theory: 53.4% F). Infrared bannds at 3460 cm-1 (O-H str.), 3340 cm-1 (N-H str.) and 1705 cm-1 (C═) str.) confirmed the structure of the hydroxy-terminated urethane prepolymer.
The hydroxy-terminated prepolymer (53.7 g solution, 17.9 g solids) was treated further at 75� with dimer acid derived diisocyanate (6.0 g; 0.01 mole) (DDI, HENKEL Company) for two hours, then the urethane chain was completed by the additon of trimethylhexamethylene diisocyanate (2,2,4 and 2,4,4 isomer mixture) (1.05 g; 0.005 mole) and N-methyldiethanolamine (1.19 g; 0.01 mole). Reaction was complete in three hours, as shown by the disappearance of the N═C═O band (2270 cm-1) in the infrared spectrum. Hexadecane contact angle on steel coupons was 73�1 degrees.
The efficiency of the compounds whose preparation is described in examples 22-25 as paraffin deposition inhibitors was determined by the previously described static cold finger method. Crude A was used and it was held at 40� C. The water circulating through the coil was at 35� C. and treating level of inhibitor in crude oil was 500 ppm.
______________________________________Example # Compound Described in Example % Inhibition______________________________________26 22 6527 23 7628 24 7629 25 51______________________________________
Potential paraffin deposition inhibitors were evaluated using the previously described beaker method. Testing levels of inhibitor in crude oil were 500 ppm.
______________________________________Example # Inhibitor Crude Oil % Inhibition______________________________________30 Compound F1 C 9.731 Compound G2 C 19.432 Compound G B 4.133 Fluorad � FC 740 B 3.2______________________________________ 1 Compound F: ##STR17## 2 Compound G: ##STR18##
A comparison of example 30 with example 20 reveals that although 65% inhibition was recorded by the coil method, the beaker method yielded only 9.7% inhibition for the same compound. This is an indication of the severity of the beaker method and any inhibition recorded using this method is an indication of the usefulness for a compound.
__________________________________________________________________________Example # Fluorochemical Reference__________________________________________________________________________50 ##STR19## Jpn. Kokai Tokkyo Koho JP 58/7080651 ##STR20##52 ##STR21## U.S. Pat. No. 3,575,899.53 ##STR22## Japan. Kokai JP 51/14473054 Poly[oxy(methyl-1,2-ethanediyl)], Japan. Kokai JP 51/151126 ω-[(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl) oxy]-ω'-hydroxy-α,α'-[(methyl- phenylene)bis(iminocarbonyl)]bis- (9CI)__________________________________________________________________________
The fluorinated addition polymers described in the following examples exhibit usefulness as paraffin deposition inhibitors. Addition of 1% dodecyl mercaptan to the monomer mixture yields polymers having low enough molecular weight to be oil soluble.
__________________________________________________________________________Ex-am-pleRf Monomer Parts Comonomer Parts__________________________________________________________________________55 C8 F17 SO2 N(CH3)CH2 CH2 OOCCHCH2 80 Octadecyl acrylate 2056 C6 F13 C2 H4 OOCC(CH3)CH2 65 Tridecyl methacrylate 3557 C6 F13 C2 H4 SC2 H4 OOCCHCH2 70 CH 2CHCOO(CH2 CH2 O)6 (CH(CH3)CH2 O)56 (CH2 CH2 O) 6H 3058 C8 F17 C2 H4 OOCC(CH3)CH2 40 Decyl methacrylate 6059 C8 F17 C2 H4 N(CH3)C2 H4 OOCC(CH.sub.3)CH2 45 3,5,5-Trimethylhexyl methacrylate 5560 C2 F5 C6 F10 CH2 OOCCHCH2 60 C22 H45 OOC(CH3)CH2 4061 C7 F15 CH2 OOCCHCH2 90 Decyl acrylate 1062 C7 F15 CON(CH3 )C2 H4 OOCCHCH2 50 Lauryl methacrylate 5063 (CF3)2 CF(CF2)6 CH2 CH(OH)CH2 OOCCH2 CH 2CH 2 60 2,6,8-Trimethyl-4-nonyl methacrylate 4064 (CF3)2 CFOC2 F4 C2 H4 OOCCHCH2 35 Lauryl acrylate 6565 C8 F17 C2 H4 SO2 N(C3 H7)C2H4 OOCCHCH2 70 Tridecyl acrylate 3066 C7 F15 C2 H4 CONHC4 H8 OOCCHCH2 50 Stearyl methacrylate 50 ##STR23## 80 Stearyl acrylate 2068 C7 F15 COOCH2 C(CH3)2 CH2 OOCC(CH3)CH2 75 Octadecyl acrylate 2569 C8 F17 SO2 N(C2 H5)C4 H8 OOCCHCH.sub.2 10 Lauryl methacrylate 9070 (C3 F7)2 C6 H3 SO2 N(CH3)C2H4 OOCCHCH2 60 2,6,8-trimethyl-4-nonyl methacrylate 40 ##STR24## 40 Decyl methacrylate 6072 C6 F17 CFCHCH2 N(CH3)C2 H4 OOCCHCH2 50 C22 H45 OOC(CH3)CH2 5073 C8 F17 SO2 N(C4 H9)C2 H4 OCOCHCH.sub.2 35 Stearyl acrylate 6574 C8 F17 SO2 N(C2 H5)C2 H4 OCOCH(CH.sub.3)CH2 50 Tridecyl methacrylate 50__________________________________________________________________________
In the foregoing Examples 55-74, the monomers and dodecyl mercaptan are dissolved in tetrahydrofuran, an azo initiator, azo-bis (isobutrylnitrile), is added in an amount of about 0.1% by weight based on the amount of monomer, and the solutions are placed in ampules which are evacuated and sealed, and the polymerization conducted at 100� C. overnight in an agitating bath.
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|Minnesota Mining And Manufacturing Company
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|Bayer Aktiengesellschaft
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|Citing Patent
|Filing date
|Publication date
|Jan 19, 1988
|Oct 24, 1989
|Ciba-Geigy Corporation
|Use of organic fluorochemical compounds with oleophobic and hydrophobic groups in asphaltenic crude oils as viscosity reducing agents
|Jul 17, 1989
|Mar 5, 1991
|Ciba-Geigy Corporation
|Use of organic fluorochemical compounds with oleophobic and hydrophobic groups in crude oils as antideposition agents, and compositions thereof
|Sep 5, 1990
|Aug 18, 1992
|Shell Oil Company
|Method of inhibiting asphalt precipitation in an oil production well
|Jul 5, 1996
|Oct 13, 1998
|Mosbach; Klaus
|Stabilizers, polymers, and emulsions useful for molecular imprinting technology
|Jul 5, 1996
|Sep 28, 1999
|Mosbach; Klaus
|Supports useful for molecular imprinting technology
|Aug 22, 2007
|Sep 8, 2009
|Board Of Regents, The University Of Texas System
|Compositions and methods for improving the productivity of hydrocarbon producing wells using a non-ionic fluorinated polymeric surfactant
|Aug 4, 2008
|Aug 10, 2010
|Board Of Regents, The University Of Texas System
|Use of fluorocarbon surfactants to improve the productivity of gas and gas condensate wells
|Jun 30, 2010
|Dec 21, 2010
|Board Of Regents, The University Of Texas System
|Use of fluorocarbon surfactants to improve the productivity of gas and gas condensate wells
|Dec 30, 2007
|Oct 25, 2011
|Board Of Regents, The University Of Texas System
|Method for treating a fractured formation with a non-ionic fluorinated polymeric surfactant
|Dec 30, 2007
|Mar 20, 2012
|Board Of Regents, The University Of Texas
|Compositions and methods for treating a water blocked well using a nonionic fluorinated surfactant
|Nov 25, 2008
|Sep 11, 2012
|Board Of Regents, The University Of Texas System
|Methods for improving the productivity of oil producing wells
|Dec 30, 2007
|Mar 26, 2013
|3M Innovative Properties Company
|Method for treating a hydrocarbon-bearing formation with a fluid followed by a nonionic fluorinated polymeric surfactant
|Dec 18, 2008
|Apr 16, 2013
|3M Innovative Properties Company
|Fluorinated polymer compositions and methods for treating hydrocarbon-bearing formations using the same
|Dec 17, 2009
|Jan 14, 2014
|3M Innovative Properties Company
|Method of contacting hydrocarbon-bearing formations with fluorinated ether compositions
|Dec 18, 2008
|Mar 25, 2014
|3M Innovative Properties Company
|Methods for treating hydrocarbon-bearing formations with fluorinated polymer compositions
|Apr 27, 2009
|Apr 22, 2014
|3M Innovative Properties Company
|Methods for treating hydrocarbon-bearing formations having brine
|Jul 2, 2010
|Sep 16, 2014
|3M Innovative Properties Company
|Methods for treating carbonate hydrocarbon-bearing formations with fluorinated amphoteric compounds
|Dec 14, 2009
|Jun 16, 2015
|3M Innovative Properties Company
|Method of contacting hydrocarbon-bearing formations with fluorinated phosphate and phosphonate compositions
|Jul 15, 2009
|Dec 1, 2015
|3M Innovative Properties Company
|Cationic fluorinated polymer compositions and methods for treating hydrocarbon-bearing formations using the same
|Dec 30, 2007
|May 31, 2016
|Board Of Regents, The University Of Texas System
|Method for treating a formation with a solvent
|Dec 21, 2011
|Nov 22, 2016
|3M Innovative Properties Company
|Method for treating hydrocarbon-bearing formations with fluorinated amine
|Mar 5, 2014
|Feb 21, 2017
|Ecolab Usa Inc.
|Method of assessing asphaltene inhibitor efficiency
|Dec 20, 2011
|Apr 18, 2017
|3M Innovative Properties Company
|Methods for treating carbonate hydrocarbon-bearing formations with fluorinated amine oxides
|Jan 13, 2012
|Jul 11, 2017
|3M Innovative Properties Company
|Methods for treating siliciclastic hydrocarbon-bearing formations with fluorinated amine oxides
|Dec 19, 2003
|Jun 1, 2006
|Basf Aktiengesellschaft
|Hydrophobic-hydrophilic compounds for treating metallic surfaces
|Feb 22, 2006
|Aug 23, 2007
|Kies Jonathan K
|System and method for creating an ad hoc group in a push-to-talk system
|Mar 27, 2006
|Sep 27, 2007
|Pope Gary A
|Use of fluorocarbon surfactants to improve the productivity of gas and gas condensate wells
|Aug 23, 2006
|Feb 28, 2008
|Pope Gary A
|Method of obtaining a treatment composition for improving the productivity of hydrocarbon producing wells
|Aug 23, 2006
|Feb 28, 2008
|Pope Gary A
|Compositions and method for improving the productivity of hydrocarbon producing wells
|Aug 22, 2007
|Feb 28, 2008
|Board Of Regents, The University Of Texas System
|Compositions and methods for improving the productivity of hydrocarbon producing wells
|Aug 4, 2008
|Mar 5, 2009
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|Use of fluorocarbon surfactants to improve the productivity of gas and gas condensate wells
|Dec 30, 2007
|Jun 3, 2010
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|Method for Treating a Fractured Formation
|Dec 30, 2007
|Jul 1, 2010
|Board Of Regents, The University Of Texas System
|Compositions and Methods for Treating a Water Blocked Well
|Dec 30, 2007
|Jul 22, 2010
|Board Of Regents, The University Of Texas System
|Method and System for Treating Hydrocarbon Formations
|Dec 30, 2007
|Sep 9, 2010
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|Compositions and Methods for Treating a Water Blocked Well
|Aug 22, 2007
|Oct 28, 2010
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|Dec 18, 2008
|Oct 28, 2010
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|Methods for treating hydrocarbon-bearing formations with fluorinated polymer compositions
|Dec 30, 2007
|Nov 4, 2010
|Pope Gary A
|Method for Treating a Hydrocarbon Formation
|Dec 18, 2008
|Nov 18, 2010
|Moore George G I
|Fluorinated polymer compositions and methods for treating hydrocarbon-bearing formations using the same
|Nov 25, 2008
|Dec 23, 2010
|Board Of Regents, The University Of Texas System
|Methods for improving the productivity of oil producing wells
|Apr 27, 2009
|Mar 10, 2011
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|Methods for treating hydrocarbon-bearing formations having brine
|Jul 15, 2009
|Jul 21, 2011
|Baran Jr Jimmie R
|Cationic fluorinated polymer compositions and methods for treating hydrocarbon-bearing formations using the same
|Mar 5, 2014
|Sep 25, 2014
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|Method of assessing asphaltene inhibitor efficiency
|U.S. Classification
|507/90, 507/205, 507/930, 166/304, 507/931
|International Classification
|Cooperative Classification
|European Classification
|Jun 19, 1987
Owner name: CIBA-GEIGY CORPORATION, 444 SAW MILL RIVER ROAD, A
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Effective date: 19860730
|Jan 13, 1992
|Fee payment
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|Feb 5, 1996
|Fee payment
Year of fee payment: 8
|Mar 17, 1997
Owner name: CIBA SPECIALTY CHEMICALS CORPORATION, NEW YORK
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CIBA-GEIGY CORPORATION;REEL/FRAME:008447/0985
Effective date: 19961227
|Jan 24, 2000
|Fee payment
Year of fee payment: 12


text:
8/24/2017Harlem Arts Alliance and Lower Manhattan Cultural Council Special Meeting - Grant Info Session
8/26/2017Percy Sutton Harlem & Run & Walk
The Mama Foundation for the Arts proudly presents ALIVE!, a musical celebration of a generation featuring a full company of performers who are age 55 and over; at The Dempsey Theater in Harlem. Conceived and written by Vy Higginsen and Ken Wydro, and directed by Mr. Wydro.
Member Survey
Workshop Survey
Harlem Arts Alliance229 West 135 StreetNew York, NY 10030Phone: (347) 735-4280Email Us »

subset: commoncrawl


text: Viewing Best of 2014 - 77 of 39 Let's Get Physics Y'all with Megan Amram, Nick Offerman, Rich Fulcher, and Steve Agee 'Science for Her' by Megan Amram is available Nov. 4. Order it at: AMAZON: ... more »'Science for Her' by Megan Amram is available Nov. 4. Order it at: AMAZON: http://www.amazon.com/Science-For-Her-Megan-Amram/dp/1476757887/ ITUNES: https://itunes.apple.com/cz/book/science...for-her!/id837624505?mt=11%20%20%20 « less Nick OffermanFunny Or Die March 05, 2015 190k Views Order 'Science For Her' More Info Full Credits Megan Amram Actor/Writer Nick Offerman Actor Rich Fulcher Actor Steve Agee Actor Payman Benz Director/Editor Funny Or Die Uploader Aaron Ulrich Gaffer Matt Sweeney Key Grip Tricia Robertson Production Designer Rick Mader Art Director Jordy Scheinberg - Wardrobe Stylist Wardrobe Stylist BoTown Sound Sound Mixer Ally Hord Producer Additional Credits Starring - Megan Amram, Nick Offerman, Rich Fulcher and Steve AgeeWritten by Megan AmramDirected by Payman BenzMusic - Ring The AlarmComposer - Matthew ComptonDirector of Photography - Chris Darnell1st AC - Ray LeeGaffer - Aaron UlrichKey Grip - Matt SweeneySwing - Mike BlevinsProduction Designer - Tricia RobertsonArt Director - Rick MaderBuilder - Tom Gerhardt & Correy DoyleArt PA - Kate StaplesWardrobe Stylist - Jordy ScheinbergMake Up Artist - Brenna HaukedahlMake Up Asst - Daniella RotellaSound Mixer - BoTown SoundProduction Assistant - Troy GuthrieUnit Production Manager - Jacob GellerEditor - Payman BenzProducer - Ally Hord & Sean Boyle Stats & Data 3,910Funny2,753Die 190,669 Views March 05, 2015 Published Category Sketch Music Tags physics women feminism megan amram nick offerman rich fulcher steve agee science education textbooks books music video parody physical fat gross ugly dudes sexy little girl baby sexism feminism newton's laws apple gravity exercise gym kale alcohol texting Transcript > HELLO LADIES. CAN I GET A WHA-WHAT. MY SCIENCE TEXT BOOK FOR GIRLS, "SCIENCE FOR HER", COMES OUT NOVEMBER 4TH. EVERYONE KNOWS, WOMEN'S BRAINS AREN'T BIOLOGICALLY CONSTRUCTED TO UNDERSTAND SCIENTIFIC CONCEPTS, AND WOMEN'S TINY HANDS AREN'T BIOLOGICALLY CONSTRUCTED TO TURN THE LARGE HEAVY COVERS OF MOST SCIENCE TEXT BOOKS. THAT'S WHY I'VE WRITTEN A BOOK THAT MAKES SCIENCE FUN AND EASY FOR WOMEN OF ALL SIZES. EXCEPT PLUS SIZES. SO WHY SHOULD CARE ABOUT SCIENCE GALS? WELL, LET ME PUT INTO TERMS YOU CAN ACTUALLY UNDERSTAND. COME ON OUT HERE BOYS. (music plays) I'm teaching all the facts that I know you'll like About these fixes and science (inaudible) to get it right You're just a sexy little girl (I'm a baby) Your brain is just a cute little bumble bee Compared to a man's big pumpkin (brains) That's why I'll teach you girlier things Like how to make biological clock get a potato Let's get physics y'all physics y'all I wanna get physics y'all Let's get into physics y'all Let me here some Newton's laws Some Newton's laws Let me here some Newton's laws Let's get physics y'all physics y'all I wanna get physics y'all Let's get into physics y'all Teach me how a babies made A babies made How the heck are babies made Let's get physics y'all physics y'all I wanna get physics y'all Let's get into physics y'all Teach me why does kale's (inaudible) Why kale's (inaudible) Why is Kale a science name (music stops) (sound from the exercising machine is heard) > WHY WON'T SANDRA TEXT ME BACK? IS IT BECAUSE I DRINK SO MUCH CAMPAIGN? WHAT? OH... WELL, HAVE FUN YOU SEXY LITTLE, BABY SEXY GIRLS AND ORDER MY SCIENCE TEXTBOOK, "SCIENCE FOR HER" OUT NOVEMBER 4TH. SCIENCE-NARA SUCKERS. I'M SO HUNGRY. OWW... DON'T WORRY LADIES. IT'S MY CHEAT DAY. IT'S SO GOOD. Up Next: Will Ferrell Screams at Derek Jeter for Four Straight Minutes AUTOPLAY Up Next In: 10 Will Ferrell Screams at Derek Jeter for Four Straight Minutes Amazon's New Product Revealed Are You On Ello? Comcast Doesn't Give A F*CK Follow Browse Related Comments Best of 2014 80+ more View All ▶ Videos Recommended by FOD Staff 9+ more View All ▶ Megan Amram 10+ more View All ▶ Nick Offerman 9+ more View All ▶ Rich Fulcher 10+ more View All ▶ Steve Agee 50+ more View All ▶ Payman Benz 4360+ more View All ▶ Funny Or Die 170+ more View All ▶ Aaron Ulrich 340+ more View All ▶ Matt Sweeney 130+ more View All ▶ Tricia Robertson 10+ more View All ▶ Rick Mader 70+ more View All ▶ Jordy Scheinberg - Wardrobe Stylist 620+ more View All ▶ BoTown Sound 190+ more View All ▶ Ally Hord Vaguely Related Pics & Words Advertisement Tags: physics women feminism megan amram nick offerman Nick Offerman Funny Or Die Advertisement


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Earlier this month you may have noticed that the Swimwear365 team disappeared for a few days, armed with over 100 bikinis, swimsuits and tankinis. We travelled for hours to get to one very special hot tropical destination, with white sandy beaches, high dunes and soaring temperatures… we had landed in Manchester. Swapping sunny Ibiza … Continue reading Behind the scenes with Swimwear365
Styling Your Shape With Swimwear
It's starting to feel as though Spring is starting to peek its way through the gloom of winter, the days are getting (slightly) longer. The weather's not quite as dire (for now), the Easter break is nearly upon us and for some of us, thoughts turn to a holiday in the Sun – which means … Continue reading Styling Your Shape With Swimwear


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Hitman episode 6 arrives tomorrow for all platforms and to top off the first season of Hitman, Agent 47 is headed to Hokkaido, Japan!
Last week, the official Hitman YouTube channel released the first of seven "countdown" videos to build excitement for the season finale. Today they released the last one which gives us some new footage for the upcoming level.
47's final mission for the season has him taking out two targets in a hyper-exclusive hospital. The location will be a mix of traditional Japanese beauty and cutting edge technology. And we can clearly see that in the teaser video as we see clips of advanced surgical equipment juxtaposed with traditional Japanese attire and weapons.
Hitman Episode 6 Unlock Times
According to their official blog, the new episode will launch worldwide for all platforms on October 31, 15:00 CET. Players should be aware that by 11:00AM CET, the servers will be down for maintenance to prepare for episode 6.
During this down time, there will be a 5-8GB patch for the game, depending on the platform. This patch is in addition to the actual episode. All in all, the entire download should be 12-14GB, so be ready for that.
Read More: Hitman Episode 6 Japan: Finale is 'Toughest Challenge'; Release Date & Plot Here
Season Finale
As with all locations, Hokkaido will come with 20 mastery levels. Attached to these levels are six new weapon/gear unlocks for 47. One of these unlocks is the new Sieger 300 Sniper Rifle which comes with three levels of zoom and a suppressor.
There will also be 70+ new challenges and seven achievements/trophies tied to Hokkaido. And of course, it comes with the new story mission "Situs Inversus" along with seven guided Opportunities.
Along with Hokkaido and all the goodies attached to it, the October 31 patch will also include some general game play fixes. Most of them are quality of life changes to the UI, inventory, and Contracts mode. The patch will also fix some game play issues and bugs such as 47 getting stuck in the environment or NPCs not acting properly.
A full list of changes can be found on their official blog.
The Road Ahead
As previously mentioned, Hitman Episode 6 will mark the season finale for the first season of the game. As of now, there has been no official statement or news regarding when the next season will start. Likewise, there's no news if a separate season pass will be required to gain access to the next season.
For the time being, Io has revealed their update plans for the month of November which includes three new Elusive Targets and several new Contracts, so there's still a lot to look forward to even after the finale. The official dates and information can be found in the image below.


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Solar Companies Reviews in
Payette, ID
The average rating for solar companies in Payette
Best solar companies in Payette, Idaho displaying solar power system cost and offering online solar quotes
Nampa, IDGet live pricing
2017 top rated solar companies based on consumer reviews score in Payette, Idaho
Most reviewed solar companies in Payette, Idaho
Services: Residential Solar Electric, Commercial Solar Electric, Wind Turbines, Storage
Excellent Solar, some hiccups delay production after install
IWS is a well known and respected local company in SLC, UT. I got an estimate 5 years ago, but deferred and got the system installed May 1st. IWS was great even though the installation had a couple of minor complicating factors. They obliged my request to have extra underground conduit installed ... read more
Services: Residential Solar Electric, Commercial Solar Electric
Auric has been everything as advertised so far.
Office location: Boise, ID 83709
This winter I came home to a tag on my door from Auric solar. I had been looking into solar panels for my house since it is electric only, but have never been able to come up with down payment for them. One of Auric''s big selling points for me was the fact that they use your tax write-off for the d... read more
Great Customer Service
Skyline Solar has been a great company to work with. They have answered all our questions and are friendly and honest. They have great customer service and did a great job. read more
Enter your address to find out what tax credits
and other solar incentives your property is eligible for
My solar install
If you are planning on solar panels, this is the only place to go! They are fast and efficient. If you have any questions or need help with anything they are right there to help you.
Brian Adams is probably the best, most reliable, considerate, honest person I have ever worked with.
I love... read more
Services: Residential Solar Electric, Commercial Solar Electric
Calculate your savings and ROI from
"buying solar panels for your home"
Back to list of Cities in Payette, Idaho
Back to list of Counties in Idaho
Payette covers the following zip codes:
Please note: when you click on the zip code the company listing will also show companies that have an office in that county, and not just those that service this specific zip code. The number shown above only includes those that specifically have an office in or service that zip code.


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Good evening
Find Your Voice... Call us on 020 7434 2040 or email firstname.lastname@example.com
Attentive, charismatic, authoritative & intelligent.
A star of the stage.
Nominated for an Evening Standard Award in 2013 for 'Best Actor'.
Brought up in Essex.
John Heffernan leads the cast of Saint George and The Dragon at The National Theatre.
Opening on the 4th October 2017.
Don Gilet, John Heffernan, Simone Lahbib and Alastair Mackenzie star in this gripping new murder mystery.
Set against Loch Ness and starring four fantastic Sue Terry Voices.
Sundays at 9pm on ITV.
Thriller, based on an operation to capture terrorists in Kenya. John Heffernan plays Major Harold Webb. In cinemas now!
Drama set within the fictional realms of Charles Dickens' critically acclaimed novels. John plays Jaggers. Fridays 8:30pm on BBC1.


text: " Assessment | Biopsychology | Comparative | Cognitive | Developmental | Language | Individual... Utilization reviews Pages in category "Utilization reviews" This category contains only the following page. U Utilization reviews Retrieved from "http://psychology.wikia.com/wiki/Category:Utilization_reviews?oldid=155118" Ad blocker interference detected! Wikia is a free-to-use site that makes money from advertising. We have a modified experience for viewers using ad blockers Wikia is not accessible if you've made further modifications. Remove the custom ad blocker rule(s) and the page will load as expected. Categories: Healthcare utilization Add category Cancel Save


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Sold Out
Bathe like royalty with our own exclusive bath bomb scent!
Ingredients: Mango Fragrance Oil, Indian Sandlewood Fragrance Oil, Olive Oil and Blood Orange Essential Oil.
Girly bling ring inside
*Bath bombs sold individually unless stated as part of a set.
Copyright © 2017 Belle & Blush • Shopify Theme by Underground Media • Powered by Shopify
Join Our Mailing List


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When you purchase a digital subscription to Cake Central Magazine, you will get an instant and automatic download of the most recent issue.
Chocolate cake with white and milk chocolage ganche filling, covered with fondant, decorations fondant, toys supplied by client. Rainbow is a giant gingerbread cookie covered with dark chocolate and fondant.
50Th Birthday Cakes
Mini Square Birthday Cakes
Jasmine, Strawberry Shortcake, Smurfette Birthday Cakes
(if this is a private computer)
Yes please, register now!


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Mai multe idei de la Naty
jeff your drunk go home xD
don't hug me i'm scared:
Slender PhD : Jeff the Killer by Alloween.deviantart.com on @DeviantArt
The only way jeff can drink soda xD
Imma come back alive and tell yall a story
Wow, I didn't know that Jeff was into romance...
I do... but other times it terrifies me
A conversation with Life and Death.
it would be better if they phrased it like this: Hush little baby, don't say a word and nevermind that noise you heard It's just the beast under neath your bed in your closet and in your head.
Cool right after that photo shoot there all gonna try to kill each other


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Elms Farm Blog
Windmills and Watermills to visit in Lincolnshire
Around 800 windmills were grinding flour in Lincolnshire up to a century ago. Since then times have changed and the ones that are left have been turned into tourist attractions and we have an interesting and varied selection that you can visit. Read More »
Local Cheeses made in Lincolnshire
If you are a cheese lover Lincolnshire is a great place to visit. Blessed with three of its own local cheeses and two wonderful cheese shops you could spend almost all your time in our wonderful county indulging your passion. Read More »
Bird Watching in Lincolnshire
Lincolnshire is a great place for birdwatching and near Boston we have the RSPB at Frampton Marsh and Freiston Shore as well as Gibralter Point near Skegness, which is run by the Lincolnshire Wildlife Trust. Read More »
10 Good Reasons to Visit Woodhall Spa
JUBILEE PARK is a beautiful park in the heart of Woodhall. It has a lovely childrens play area which is open all the year round. The open air heated swimming pool and paddling pool is open from May to September and on a warm day you can spend all day there relaxing on the grass around the pool. There is a little shop and café so you don't even have to take a picnic. There is also tennis, bowls, putting and croquet.
Jubilee Park, 78 Stixwould Rd, Woodhall Spa, Lincs LN10 6QH tel:01526 353478
www.jubileeparkwoodhallspa.co.uk E: email@example.com Read More »
A day out at Skegness Aquarium
Skegness Aquarium only opened last year and is a great addition to the attractions that Skegness has to offer. Ideal for a wet or chilly day you can spend hours having fun and learning all about the creatures who live under the sea. Read More »
Blog Archive
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- July 2011


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Tired of bad science, outrageous supernatural claims and out of control conspiracy theories? Me too.
This is a discussion group for all things related to skepticism of the supernatural, conspiracy theories, out-of-control conspiracy theorists, bad science, psychic charlatans and similar subjects.
If you want to bring attention to something that's is ripe with logical fallacies or makes wild claims with little to no evidence, this is the place to do it.
I'm tired of the world being led around by the nose by fakes and superstitious paranoids. If you'd like to share articles and discuss a fact and reason based view of the world, please join the group and share what you have to say.


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My URBAN NIGHTMARES collection is this week's Kindle Countdown! Just $.99 through Aug. 1. Also available as an audiobook.
My URBAN NIGHTMARES collection is this week's Kindle Countdown! Just $.99 through Aug. 1. Also available as an audiobook.
A book I edited - FORBIDDEN TEXTS - will be just $.99 via Kindle Countdown from July 21 through midnight July 27. (July 22 to July 28 in the U.K. (and not dollars but pence, of course. ;-)
Zombie Apocademia!
I was pleasantly surprised to find that a quote from my Lovecraftian zombie tale "Under an Invisible Shadow" has turned up as the epigraph for a chapter in Zombie Generation: Essays on the Living Dead in Modern Culture.
Go buy the book to see the quote! Go buy my story in my collection Worlds Come Undone!
And I suppose this is as good a place as any to announce that ... well, I've been threatening to turn this short story - which was previously published in first a Lovecraftian anthology and then a zombie anthology - into a full-blown novel.
And actually I'm going to do even more than that!
I'll keep you posted here!
July 14th, 2015
Sword and Zombie: Vol. 1 will be just $.99 via a Kindle Countdown from July 15 through July 21. (99 p. in the U.K. from July 16 through July 22.)
These are zombie tales in medieval sword and sorcery settings.
The book features a new "Bigfoot" story from Eric S. Brown!
Also included are a novella by G. W. Thomas and stories by William Meikle and Rebecca L. Brown.
This chapbook is also available as part of the TERROR X 3 boxed set!
I'll have two Kindle Countdowns going here in the first full week of July.
The first - and shorter of the two - is WRITE ANYWAY! This book's jam-packed with essays, story prompts and journaling ideas to bust writer's block wide open! I've been teaching writing to community college students for more than twenty years, insisting to them that I don't believe in writer's block and giving them all sorts of tips and tricks to keep the pen flowing. Now I'm sharing these tactics with you!
This sale will run only run June 6 thru June 9!
The other sale is on DARK HIGHWAYS, a collection of five top-notch horror tales which take place on the highways and byways of the great American road. I edited the thing and, yes, I slipped a tale of my own in there, but you'll want to check out Mike Arnzen's literally "Damned Potholes" as well as John Burke's "Black Trailer" and Lorelei Shannon's haunted hearse that makes Christine look like Herbie the Love Bug! And, oh yeah, my oft-times writing accomplice C. Dennis Moore has a twisted time-looping tale in there too!
This sale will run June 7 through midnight, June 13.
My U2 Souvenirs
The U2 concert I went to in Chicago last week was one of the best of my life - and I've been to my share of concerts.
As a closer, the band barely sang or played "One", letting the audience carry it. Singing along on that one acapella with 30,000+ other people or, say, the chorus to "Bad" or "Pride (in the Name of Love)" is simply unforgettable. Hard to imagine more positivity in one place, no matter what you think of Bono and his bully pulpit activism. (Personally, I'm all for the guy. You got a platform, go out there and use it and do some good in the world, dammit!)
This is on top of the incredible video and stage setup for this year's Innocence + Experience Tour - I could go into it, but I'm sure you can read about it elsewhere, if you're interested.
I'll buy merch from the indie bands I see didn't buy a $40 U2 shirt, because I figure U2 doesn't exactly need more of my money or my promotion. Then again, concert shirts are a form of connection - I wore one of my Hold Steady shirts and at the end of the concert, after the house lights came on, I was suddenly the lifelong best friend of these drunk fortyish guys who proclaimed The Steady the best band in the world - "even better than U2!" - and were basically inviting me to move into their homes because of mutual admiration of Craig Finn & Co.
Anyway, the picture above is of my only souvenirs of the show, which consist of my ticket and three scraps of confetti dropped on the crowd. Turns out the confetti was chopped up pages of high-falutin' literature! I got Dante's Divine Comedy, Psalm 44, and Alice in Wonderland. Is that awesome or what?
David Bain - Writer.
August 2017


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Paper Organizing In The Office – 6 Tips to Gain Control
Way back when as computers were first introduced we were told that these marvellous machines were going to save a lot of trees with the paper that was about to be saved. That hasn't happened yet, has it? We are creatures that like to be able to look and feel what we have created so…… Continue Reading


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Have Mercedes Questions? Ask a Mechanic for Answers ASAP
Hello and thank you for your question,The Data link connector is located on the left side of the instrument panel. See the enclosed diagram . I have marked it for you. Copy and paste the link to your browser to open and view it.https://dl.dropboxusercontent.com/u/104923897/DCL%20Feb%203.pdf


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This article contains heavy SPOILERS. Continue at your own risk, or use the icons above (if any) to switch to another version of the page without spoilers.
- Manga
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The Mid-East Allied Forces (中東連合 Chūtō Rengō?) is a nation consisting of a coalition of various territories. They are enemies of Marley who were at war with their nation for four years after the warriors' failure to capture the Founding Titan, though the Allies eventually lost the war and presumably lost autonomy of their nation.
While little can be said of the climate or exact location of the Mid-East Allied Forces, it is said that the nation was located on a peninsula.[1]
The Mid-East Allied Forces are superior in some instances to their enemy nation of Marley.
Being the defender in the battle of Fort Slava, the Allies make use of water-cooled machine guns and heavy artillery installed on the fort's towers to fend off the Marleyan assault. Additionally, its troops are well sheltered in concrete bunkers.
The Allies were acutely aware of the threat that Titans pose. For example, Allied soldiers were willing to fire on a seemingly unarmed and surrendering Gabi, simply because they suspected that she was an Eldian and might turn into a Titan in any moment. Perhaps the best example that illustrates the Allies' concern of that threat was the anti-Titan artillery which it developed. Designed solely for the purpose of fighting Titans, it fires 100mm armor-piercing shells which are capable of destroying even the Nine Titans. The guns are fitted on an armored train, which moves on a railway network built around the fort to ensure rapid deployment of the guns.
The Allies presumably had a strong naval force before the battle of Fort Slava, as warrior cadet Udo mentioned that it took four years for the Marleyan navy to control the sea with almost half of its fleet lost.
Marley arc
After Marley lost the Colossus Titan and the Female Titan during the Paradis Island Operation, the Mid-East Allied Forces took advantage of their enemy's weakened military capabilities and declared war on Marley. Over the course of four years, the Mid-East Allied Forces gradually lost their advantage against the enemy, losing control of the seas by the time of the battle of Fort Slava. The Allies' navy, however, dealt significant damage to the Marley navy in their naval battles.
At some point before or during the war, the Allies develop the anti-Titan artillery, a heavy cannon designed to kill any Titan in a single shot, even one of the Nine Titans.
After four years, the Allies make a final stand at Fort Slava, a fortress equipped with heavy machine gun defenses and anti-Titan artillery overlooking their last naval station. Commander Magath of the Marley military leads a siege against the fort alongside an 800-man unit of warrior cadets, with their warriors kept on standby, as Magath is unable to use them due to the anti-Titan defenses implemented by the Allies. However, when cadet Gabi destroys the armored train carrying artillery around the fort, the Allied soldiers are attacked by the Jaw Titan and Cart Titan, the Titans of Porco Galliard and Pieck. Soon afterwards, once the outer defenses of the fort are destroyed, a zeppelin overhead carrying Zeke Yeager and Reiner Braun releases dozens of parachuting Eldians above the fort which Zeke turns into Titans using his Titan powers, raining devastation down upon the Allies. When all the Titans are killed, Reiner's Armored Titan and Zeke's Beast Titan finish off the remaining artillery guns, and Zeke tosses spare rounds at the fleet in the nearby bay, destroying the last of the Allies' fleet and ensuring victory for Marley.
A peace treaty is signed after the Allies' defeat at Fort Slava, and the Mid-East Allied Forces presumably lose their autonomy following the war. However, other nations opposed to Marley praise the Allied Forces for their success with the anti-Titan artillery, signalling the coming of the age when mankind has overcome the power of the Titans. Survivors of the battle of Fort Slava are later sent home traumatized to serve as a reminder of the Eldians' demonic nature.
- Given the fact that the Mid-East Allied Forces are said to be located on a peninsula that lost its political autonomy,[1] it is possible that the nation is located either on the peninsula resembling a mirrored Arabian Peninsula or the peninsula resembling a mirrored India in the southeastern region of Marley as displayed on the map in Chapter 93.[2]
- Their uniforms resemble that of Ottoman Empire during World War I.
- ↑ 1.0 1.1 Attack on Titan manga: Chapter 93 (p. 1)
- ↑ Attack on Titan manga: Chapter 93 (p. 4)


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The 2013 MINI Coupe S or MINI Cooper John Cooper Works are among several models in this lineup that can be seen as bona fide performance cars; but it's easy to forget that the Cooper family is mostly a family of light, compact, economical four-cylinder hatchbacks.
On that matter, the MINI Cooper models are surprisingly efficient, scoring 29/37 mpg city/highway in base form with the manual transmission. Opt for the automatic and you'll only lose 1 mpg in both city and highway numbers.
The 2013 MINI Cooper is even more fuel-efficient than it looks--although green shoppers will probably want to skip the JCW.
The John Cooper Works is the most powerful model in the range, but it still earns 25/33 mpg. Cooper S may be the best compromise from a gas mileage versus performance standpoint, as they get 27/35 mpg with the manual and 26/34 mpg with the automatic.


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Fight results in lengthy suspensions
ETOBICOKE, Ontario - A jockeys' room altercation prior to the running of the fourth race at Woodbine on Nov. 11 has resulted in lengthy suspensions for riders Patrick Husbands and Constant Montpellier.
On Saturday, Husbands was fined $5,000 and suspended 60 calendar days for hitting Montpellier with his helmet during the incident.
"He used his helmet as a weapon, attacking another rider," said Richard Grubb, senior steward for the Ontario Racing Commission here at Woodbine.
Montpellier, who later was found to have suffered a concussion, was fined $5,000 and suspended for 150 calendar days after the stewards ruled he had attempted to retaliate on the racetrack following the fourth race.
"After the race, pulling up, Mr. Montpellier went after Mr. Husbands with his horse, endangering him and two other riders," said Grubb.
"We believe it was premeditated. He'd made the threat in the jockeys' room and he carried it out."
Husbands, winner of four consecutive Sovereign Awards as Canada's outstanding rider from 1999 through 2002, is the second-leading rider at the current meeting. He had 115 wins heading into Saturday's card.
Montpellier, the Sovereign Award winner as Canada's outstanding apprentice in 1993, has not ridden since Nov. 11. His 50 winners puts him 11th in the standings heading into the weekend.
The suspensions, which will begin Monday, continue through Dec. 10 - the final day of the 2006 Woodbine meeting - and resume with the opening of the 2007 meeting on March 31.
Husbands's suspension will run through May 8 and Montpellier's through Aug. 6.
Both riders have the right to appeal the suspensions in hearings before the Ontario Racing Commission head office.


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Piers Morgan thought the firestorm over Mitt Romney's "binders" comment was "facile and silly," but he apparently didn't get the CNN memo.
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