text:
|Publication number
|Publication type
|Application number
|Publication date
|Mar 9, 1976
|Filing date
|Nov 23, 1973
|Priority date
|Jul 19, 1972
|Publication number
|Patrick H. Hess
|Original Assignee
|Chevron Research Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (7), Referenced by (10), Classifications (15)
|External Links: USPTO, USPTO Assignment, Espacenet
This is a division of application Ser. No. 273,256 filed July 19, 1972, now U.S. Pat. No. 3,850,249.
This invention relates to a novel method for the setting of an acid-settable liquid. More particularly, it relates to delaying the setting of an acid-settable liquid where the acid is released (generated) in situ in the liquid. Still more particularly, it relates to a new and improved method for treating a terrestrial zone or formation by introducing a homogeneous liquid mixture of an acid-settable liquid, an acid-releasing compound and a base into a terrestrial zone or formation, particularly a permeable zone or formation adjacent to the bore of an acid or gas well.
Acid-settable liquids are known and used in the art. Usually the liquid and a suitable acid are mixed and the liquid sets, gels or polymerizes. In the ordinary case the timing of the setting depends upon a precise adjustment of the acid concentration, and effective mixing of the reactants, otherwise the desired setting may occur too soon, only after a long time or not at all. In general, a treatment of an oil well by the introduction of a homogeneous mixture of an acid and an acid-settable liquid into a zone or formation adjacent to a well bore is relatively unsatisfactory because of the lack of practical control of the time factor. One proposal (U.S. Pat. No. 3,537,522) has been to introduce a mixture of an acid-releasing (AR) compound and a acid-settable liquid into a formation containing water. The interaction of the formation water and the AR compound is expected to produce the acid required to catalyse the desired setting of the liquid. Included among the disadvantages of this proposal is the limitation that it is only useful for a water containing formation, and it is subject to the vagaries as to the amount of water available in a formation, the adequacy of the mixing of the water and acid-settable liquid, and the like. In general, methods which require the introduction of acid-setting reaction components into a formation in stages are unsatisfactory in the absence of positive control means, effective mechanical mixing and the like, and these means are, in general, not available in many circumstances, for example in an earthen formation or zone, or in the treatment of a zone adjacent to a well bore. Other disadvantages experienced in the use, as known in the art, of acid-settable liquids for the treatment of earthen formations or zones include:
1. the problem of keeping the reactants separated until the desired encounter in the formation:
2. the problem of obtaining a timely encounter of the acid and acid-settable fluid in the formation;
3. the problem with flash-setting fluids such as furfuryl alcohol and the like in view of their extreme sensitivity to local fluctuation in pH; and
4. the relatively inefficient utilization of the reagents due to incomplete mixing of the fluid and catalyst in the formation.
Pursuant to this invention, the time of the setting of an acid-settable hydroxylic liquid or an acid-settable liquid containing an effective amount of a hydroxylic diluent is controlled, especially in the treatment of a terrestrial formation or zone with an acid-settable liquid, by the use of a delayed catalyst system which is dissolved in the acid-settable liquid. For each 100 parts of the liquid, the solution contains a minor amount of the catalyst system, usually an amount in the range from 2 to 20 parts.
The delayed catalyst system includes one or more compounds which release a strong acid, preferably a mineral acid, under solvolytic conditions at a temperature in the range from -10�C. to 175�C. It also contains one or more suitable bases capable of neutralizing a strong acid to form a salt. The amount of the base component, the moiety causing the delay of the acid catalysed setting of the liquid, must be less than the stoichiometric equivalent of the strong acid potentially available from the acid-releasing (AR) compound(s). Thus, for each potential equivalent of strong acid obtainable from the acid-releasing compound(s), the catalyst system should contain an amount of the base in the range from about 0.02 to 0.98 equivalent.
The use of a delayed catalyst system for the setting of an acid-settable liquid, as herein described, results in many advantages including:
1. it provides effective delay and control of the timing of the desired catalytic action;
2. it permits the introduction of an acid-settable liquid and the catalyst system as a unit into the subterranean zone as a one-stage operation;
3. it provides a method which can be used over a wide range of temperatures, particularly the elevated temperatures frequently encountered in subterranean zones;
4. in a particular embodiment it provides a catalyst system which can be prepared in advance, stored and conveniently transported to the field; and
5. it has other advantages which will become evident in the description to follow.
Throughout this description the term "parts" relates to parts by weight of the material under consideration.
Water incursion into a well bore via a permeable sand formation (zone) is a common problem in petroleum production. FIG. 1 illustrates this problem as encountered in the production zone of a Kern River, California well. A substantial water entry is experienced in the 695 to 715 foot level. The total depth of the well is 754 feet. Persuant to the method of the present invention the water incursion can be corrected. The rods, pump and tubing employed in producing the well are pulled. The well is then plugged with sand to about the 680 foot level and a 2 7/8 inch tubing delivery string fitted with a rubber cap packer (see FIG. 1) is run into the well to the 670 foot level. The string also has a pump seating nipple at the 427 foot level (static annulus liquid level). After the introduction of the delivery string of pipe and the packer, the annulus liquid level is checked, and if necessary, the annulus is refilled with liquid to the 420 foot level.
Before introducing the acid-settable liquid and dissolved catalyst system into the well bore via the delivery string, it is desirable to establish that a fluid can be pumped into the formation. The test is made by pumping water into the delivery string. When the ability to pump water into the zone is established, the pumping is discontinued.
For the treatment of the formation about 10 barrels of a furfuryl alcohol resin prepolymer-furfuryl alcohol mixture (an 80:20 volume ratio mix) is desirably used as the acid-setting liquid. Where the bottom hole temperature is moderate, for example about 60�C., and the formation porosity permits relatively easy introduction of the liquid into the formation, a convenient setting time for the liquid is about 2 hours. To achieve this timing about three weight percent (based upon the liquid) of a pyridine-α-trichlorotoluene delayed catalyst mixture is dissolved in the acid-setting fluid. The mole ratio of pyridine to the trichloride should be about 1 to 1. The 10 barrels of liquid are pumped through the delivery tube into the formation. A follow-up of about 1.25 barrels of water is pumped to displace the residual liquid from the delivery line and to introduce it into the formation. This is followed with a circulating plug that is pumped to the pump seating nipple with water. This circulating plug prevents overdisplacement of the treating liquid by the fluid head in the delivery tube. After about 2 hours at the formation temperature, the liquid commences to set and polymerization is completed after an additional period of about 2 hours. If desirable, the polymerized liquid may be given added time to cure by shutting-in the well. Before removing the delivery line, the formation seal should be tested. This is accomplished by retrieving the circulating plug with a wire line (not shown in the FIGURE) and attempting to pump water into the zone. In this test the surface pressure should not exceed a reasonable value, for example, it should be less than about 200 pounds per square inch. After the delivery line is removed, the well is returned to production.
The delayed catalyst system of the present method is, in general, useful as a timely source of strong acid for liquids which set or gel at a pH below 5 under the influence of a relatively strong (pKa less than 5) acid, and these acid-settable liquids are contemplated for use. Those liquids which respond to an acid catalyst at a pH below 3 are especialy contemplated for use in the present method. While known acid-settable liquids are in the main organic materials, acid-settable inorganic liquids can likewise be effectively catalysed by my method.
Organic liquids which set under the catalytic influence of a strong acid (pKa less than 5) are preferred for the treatment of a terrestrial zone or formation. These liquids usually contain one or more organic compounds (monomers), partially polymerized monomers (oligomers or prepolymers) or mixtures of monomers and oligomers which polymerize (gel and set up) when the pH of the liquid is reduced below 5, preferably below 3. The release of strong acid from the acid-releasing compound(s) involves the solvolytic action of a hydroxylic material as discussed below. Therefore, the liquid of itself must be:
1. an acid-settable hydroxylic liquid;
2. a nonhydroxylic acid-settable liquid which contains at least an effective amount of a hydroxylic acid-settable liquid; or
3. a nonhydroxylic acid-settable liquid which contains an effective amount of:
a. water;
b. one or more substantially neutral (i.e., exhibiting a pH in water or aqueous ethanol at 18�C. of about 7) and soluble organic compounds of the formula R(OH)n (n is 1, 2 or 3), in which R is an organic radical;
c. a mixture of water and the above neutral hydroxylic compounds; and
d. or the like.
An effective amount is one which provides at least 1 equivalent of hydroxyl group per equivalent of available strong acid from the acid-releasing compound.
Some acid-settable liquids are very reactive and may be designated as flash-setting (auto-accelerating) liquids. These are most preferred for use in the method of the invention. Representative liquids of this type are furfuryl alcohol, furfuryl alcohol-furfuryl alcohol oligomer mixtures, furfuryl alcohol prepolymers, and acid-setting liquids which contain a substantial percent (at least 20 weight percent) of furfuryl alcohol. These materials set readily after a suitable reduction in pH, assist in the generation of strong acid by solvolytic action and release a large amount of heat energy in polymerizing. The released heat energy in turn facilitates the desired setting of the liquid. My delayed catalyst system is particularly effective in controlling flash-setting, acid-settable liquids.
Representative acid-settable organic liquids satisfactory for use herein include furfuryl alcohol, methyl vinyl ketone, vinyl ethers, acrolein, butadiene, styrene, N-vinyl pyrrolidone, and mixtures of the foregoing; acid-settable mixtures such as urea-formaldehyde, phenol-formaldehyde, cresol-formaldehyde, melamine-formaldehyde, furfuryl alcohol-formaldehyde, furfuryl alcohol-furfuraldehyde, and the like mixtures, as known in the art; isoprene, and other acid-polymerizable polyolefinic hydrocarbons; and especially acid-polymerizable organic liquids which contain at least about 20 weight percent of furfuryl alcohol.
Representative acid-settable inorganic liquids satisfactory for use include aqueous and alcoholic silicates.
The delayed catalyst systems suitable for use in the catalysis of an acid-setting fluid contain one or more acid-releasing compounds, and it has now been found that the timing of the catalytic action of these compounds can be effectively controlled or delayed by the action of a base. Both the acid-releasing compound(s) and the base(s) should be dissolved, i.e., homogeneously distributed throughout the acid-setting liquid. For each equivalent of potential acid, an amount of the base in the range 0.02 to 0.98, preferably 0.05 to 0.95, equivalents, is usually effective for a deliberate delay of the setting time of an acid-settable liquid.
Several variables can be employed to modify the action of a delayed catalyst for an acid-settable liquid. These include:
1. the particular acid-releasing compound(s) chosen;
2. the base or bases employed;
3. the relative amounts of (1) and (2) employed; and
4. the polarity (dipole moment) of the liquid acid-settable mixture.
Items (1) and (2) are described more fully in the pertinent sections below.
Chemical aspects of the method of the invention are conveniently illustrated by reference to the curves of FIG. 2. These curves represent the estimated change in pH as a function of elapsed time of a representative mixture containing furfuryl alcohol and α-trichlorotoluene at a temperature of about 25�C., first, in the absence of a base, and then, in the presence of the indicated bases. The mole ratio of the trichloride to the base was 1 to 1.5 and the potential acid to base equivalence ratio was 2 to 1.
In the absence of a suitable base, Curve (1), the pH of the mixture decreases rapidly and reaches a value (about 2.5) sutiable for catalyzing the setting-up of an acid-settable liquid in a relatively short time, i.e., about 15 minutes. A fifteen minute interval is, in general, insufficient as a practical matter for the satisfactory placement of a mixture in a subterranean zone adjacent to a well bore at an ordinary depth, for example, a depth of about 2,000 to 5,000 ft.
When a base is added to the mixture, Curves (2), (3), and (4), the rate of the pH change with the time is markedly reduced and, consequently, the time available for use of such a mixture, for example by placement of the mixture in a subterranean zone, is increased to a practical range.
These curves illustrate that the pH leveling effect of the added base varies depending upon the strength of the base. Thus, where the liquid responds to a pH on the weakly acid side, for exaple in the range 3-5, a relatively strong base should be employed. Similarly, where the effective pH is below about 3, a wider range of bases, relatively weak as well as strong, can be employed for the control of a delayed catalyst system.
The length of the delay can be varied depending upon the acid-base equivalence ratio of the delayed catalyst system employed. In Table I below are listed data which illustrate the effect of changes in the acid-base equivalence ratio. In general, when the acid-base equivalence ratio is increased, the length of the time delay is shortened. As this ratio approaches 1, the delay becomes longer for a given temperature and where the ratio is essentially 1, substantially complete inhibition of the catalyst usually is experienced. Thus, depending upon the working time required for a convenient placement of the liquid in the subterranean zone, the method of the invention provides a useful "chemical clock" for control of the length of the time which will be available for the placement of the liquid in an earthen formation.
The generation of a strong acid from the acid-releasing compound involves the production of charged particles, ions.
TABLE I__________________________________________________________________________TRICHLOROTOLUENE(TCT)-PYRIDINE CATALYZEDFURFURYL ALCOHOL POLYMERIZATIONS EQUIVALENCE Gel Time, Hr:MinMOL RATIO, RATIO;TCT ACID TCTPYRIDINE BASE PERCENT 25�C. 60�C. 80�C. 100�C.__________________________________________________________________________1/0 ∞ 2 6:17 :17 -- :02 4 1:49 :11 -- -- 6 1:35 -- -- --1/0.25 12 2 6:02 -- -- -- 4 5:35 -- -- -- 6 6:44 -- -- --1/0.5 6 2 8:- 16: :33 -- -- 4 8:- 16: :28 -- -- 6 8:-16: :28 -- --1/1 3 2 22:50 1:18 :15 :07 4 20:22 1:14 :14 :07 6 21:09 1:15 :14 :061/1.5 2 2 -- 1:23 :23 -- 4 -- 1:31 :20 -- 6 -- 1:26 :20 --1/2 1.5 2 -- * :34 :10 4 -- 2:58 :36 :09 6 -- 3:05 :33 :071/2.5 1.2 2 -- 7:-21: :45 -- 4 -- 7:-21: :40 -- 6 -- 7:-21: :53 --1/3 1 2 -- * 1:15 :20 4 -- * 1:16 :19 6 -- * 1:23 :151/4 0.75 2 -- -- -- * 4 -- -- -- * 6 -- -- -- *__________________________________________________________________________ *No solid product after 24 hours at temperature.
Therefore, as a general consideration, the more polar the medium, the faster is the rate. Since water is a highly polar compound, the addition of water in minor amounts (0.1 to 5 weight percent) to hydroxy-substituted acid-settable organic liquids usually increases the acid-generation rate. Accordingly, the addition of a minor amount of water to such an acid-settable liquid affords a further means for controlling the setup time.
An organic compound which releases a strong acid under solvolysis conditions is, in general, satisfactory for use and is contemplated for us in the method of my invention provided that:
1. the compound of itself (prior to solvolysis) exhibits a substantially neutral pH, i.e., about 7 in aqueous ethanol at 18�C.;
2. the solvolysis rate (acid-releasing rate) of the compound is within the required range for suitable pH control; and
3. the compound is sufficiently soluble in the acid-settable liquid to provide the strong acid needed to reduce the pH to the required level.
The acid-releasing component of the mixture may be one or more compounds. Usually it is more convenient to employ a single acid-releasing compound.
By a strong acid, as used herein, is meant by definition an acid of the Bronsted-type which has a pKa (water at 18�C.) below 3. Strong acids having a pKa of less than 2 are preferred herein.
Acid-releasing compounds suitable for use in my invention generate a strong acid at a rate in the range 10- 3 to 10- 6 equivalent, preferably 10.sup.-4 to 10.sup.-5 equivalent per liter per minute at a temperature within the process range. Acid-releasing compounds which are free of acid halide substituent groups, i.e., free of sulfonyl and acyl groups, are a preferred class of compounds.
The generation in situ of an acid catalyst, as herein described, involves a reaction system which includes one or more hydroxyl-containing compounds and one or more compounds which are the source (precursors) of the acid anion. Thus, the reaction is a solvolytic generation of strong acid which may be illustrated in a simplified manner by the equation:
C.sub.6 H.sub.5 CCl.sub.3 + HOH .sup.k 1 {C.sub.6 H.sub.5 CCl.sub.2 OH} + HCl
In the above example the indicated solvolysis and subsequent interactions have been found to result in the timely production of three mols of hydrochloric acid per mol of the acid-releasing compound. Hence, α-trichlorotoluene has a molar potential of three equivalents of strong acid. As indicated in the equation above, the dissociation of the acid-releasing compound, here α-trichlorotoluene, is rate controlling, is a first order reaction, and for all practical purposes the rate depends upon the nature of and the concentration of the acid-releasing compound. It has been found that the addition of an appropriate amount of the acid-releasing compound and of a suitable base to an acid-settable liquid provides a means which can be used to effectively control the timing of the polymerization (acid-setting) of the acid-settable fluid.
Some acid-generating compounds also yield strong acid by reaction with a hydroxylic solvent or reagent in a reaction whose rate is a second-order reaction. These compounds are also satisfactory for use in combination with a suitable base as in a "chemical clock" system similar to the above-described method.
Prime considerations in the selection of strong acid-releasing (AR) compound for use in a delayed catalyst system include the temperature of the fluid at the point of use and the magnitude of the reaction rate constant for acid production for the acid-releasing compound at this operating temperature. Ordinarily, the operational temperature is the temperature prevailing in the zone or situs of use when the acid-settable fluid is to be set up. For example, depending upon the location and depth of a subterranean zone, the operational temperature may be as low as -10�C., or as high as 175�C., but usually is in the range from 0�C. to 150�C.
The magnitude of the solvolysis reaction constant for the AR compound at the temperature of use should be large enough to insure a useful rate of acid production, yet not so large as to impracticably reduce the working time for the placement of the fluid in the zone. In general, at the operational temperature the reaction constant, k1, for a satisfactory first-order AR compound is believed to be in the range 2 � 10- 2 to 2 � 10- 7 sec- 1, and preferably is in the range from 1 � 10- 4 to 1 � 10- 5 sec- 1.
The solvolytic displacement reactions which yield an acid are known in the art. The reaction constants are also known for a great many of these compounds, as are also the routine methods employed for determining these constants. A leading reference and exposition of this art is the review textbook, "Solvolytic Displacement Reactions" by A. Streitweiser, McGraw Hill Book Co. (1962). This text lists 811 references in the literature relating to this field of the chemical art. Another useful source containing rate constants is the National Bureau of Standards Circular 510, "Tables of Chemical Kinetics -- Homogeneous Reactions", U.S. Department of Commerce (1951).
Representative strong acid-generating reactions and reactants include those summarized by the equations:
C.sub.6 H.sub.5 CCl.sub.3 + 2 H.sub.2 O → C.sub.6 H.sub.5 CO.sub.2 H + 3 HCl (1)
OCOCH=CHCO + H.sub.2 O → HOOCCH=CHCOOH (2)
C.sub.6 H.sub.5 SO.sub.2 Cl + CH.sub.3 OH → C.sub.6 H.sub.5 SO.sub.3 CH.sub.3 + HCL (3)
(Cl.sub.2 HCCO).sub.2 O + H.sub.2 O → 2 Cl.sub.2 HCCO.sub.2 H (4)
p-CH.sub.3 C.sub.6 H.sub.4 SO.sub.3 CH.sub.2 CH.sub.3 + H.sub.2 O → p-CH.sub.3 C.sub.6 H.sub.4 SO.sub.3 H + CH.sub.3 CH.sub.2 OH (5)
CH.sub.3 COCl + CH.sub.3 OH → CH.sub.3 CO.sub.2 CH.sub.3 + HCl (6)
C.sub.6 H.sub.5 CHBr.sub.2 + H.sub.2 O → C.sub.6 H.sub.5 CHO + 2HBr (7)
C.sub.10 H.sub.7 CH.sub.2 Cl + CH.sub.3 CH.sub.2 OH → C.sub.10 H.sub.7 CH.sub.2 OCH.sub.2 CH.sub.3 + HCl (8)
(CH.sub.3).sub.3 CBr + H.sub.2 O → (CH.sub.3).sub.3 COH + HBr (9)
(CH.sub.3).sub.2 SO.sub.4 + H.sub.2 O → CH.sub.3 OSO.sub.3 H + CH.sub.3 OH (10)
representative classes of organic acid-releasing compounds suitable for use as components in the delayed acid-setting catalyst system of the invention include the organic chlorides, bromides and iodides, and the like, which satisfy the aforementioned pH, solubility, and solvolysis rate requirements; also, the acid anhydrides of strong acids, the esters of organic sulfonic acids, and the like, which likewise satisfy those requirements. The aforementioned halocompounds include representative subclasses such as the alkyl halides, the aralkyl halides, the cycloalkylalkyl halides, aryl sulfonyl halides, the acyl halides, the cycloalkyl halides, and the alkylcycloalkyl halides where the halogen atoms are chlorine, bromine or iodine.
As a practical matter and for reasons of cost, convenience and the like, the suitable organic acid-releasing compounds will, in general, have a carbon atom content of less than 21 carbon atoms, preferably less than 12.
Representative acid-releasing compounds useful as components of the delayed catalyst system of my invention include α-trichlorotoluene, t-butyl bromide, t-butyl iodide, benzene sulfonyl chloride and bromide, maleic anhydride, trichloroacetic acid anhydride, 1-pentanesulfonyl bromide, ethyl benzenesulfonate, diethyl sulfate, sec-butyl bromide, 3-iodohexane, β-cyclohexylethyl chloride, n-butyryl chloride, cyclohexyl bromide, 2-ethylcyclohexyl iodide, α-tribromotoluene, α,α-dichlorotoluene, α,α -dibromotoluene, o-tolyldichloromethane, 1-(α-trichloromethyl)-naphthalene, 4-(dibromomethyl)-biphenyl, p-(perchloromethyl)-toluene, o-(perchloromethyl)-toluene, 1,4-(perchloromethyl)-benzene, 1,4-(dichloromethyl)-benzene, α-chlorotoluene, α-bromotoluene, α-iodotoluene, α,α'-p-xylylene dibromide, α,α'-p-xylylene dichloride, benzhydril chloride and bromide, dichloroacetic anhydride, α-chloropropionic acid anhydride, p-t-butylbenzyl chloride and bromide, (CH3)3 CCH2 Br, (CH3)3 CCH2 CH2 Br, CH3 (CH2)2 CH2 Br, (CH3)3 CCH=CHCCH2 Br, CH3 OCH2 Cl, CH3 OCH2 Br, CH3 COOCH2 Cl, C6 H5 COCH2 Br, C6 H5 COOCH2 Cl, C6 H5 CCl2 CCl3, isopropyl benzenesulfonate, t-amyl chloride, α-phenylethyl chloride, p-methoxy-α-chlorotoluene, and the like acid-releasing organic compounds which release a strong acid under solvolytic reaction conditions at a useful rate at a temperature in the range from -10�C. to 175�C., preferably from 0�C. to 150�C.
Arylmethyl chlorides, bromides and iodides are especially preferred acid-releasing compounds for use in the instant invention, particularly the polyhalo analogues. The latter yield more than one equivalent of strong acid per mol. They may be represented by the formula AR[CH3 -y Xy ]n, where y is 1, 2 or 3 and n is 1 or 2, and AR is a benzene or a naphthalene ring and X is a halide such as chloride bromide, or iodide, or those compounds of the formula which are substituted by replacing 1 or 2 hydrogen atoms bonded to the aryl ring carbon atoms by 1 or 2 inert substituent groups, Y, such as a chloride, bromide, alkoxide, NaOSO2 --, KOSO2 --, NH4 OSO2 -- or alkyl group. Preferred carbon atom contents for these particular acid-releasing compounds are the same as disclosed above.
In those instances where the acid-settable liquid may be quite polar (have a high dipole moment), neutral organic acid-releasing compounds tend to have a low solubility and may not be satisfactorily distributed throughout the fluid. In this event, the sodium salt of a corresponding sulfonated derivative is desirably employed. For example, ammonium 2,4-di(trichloromethyl)benzene sulfonate is a useful source of a strong acid and is a salt which will have a reasonable solubility in a polar medium.
Except as noted below, organic and inorganic bases capable of neutralizing a strong acid under solvolytic conditions are, in general, suitable for use in the method of my invention. Thus, salt-forming bases, in general, are contemplated for use. As in the case of the other components of the catalyst system, the base should be homogeneously distributed in the acid-settable fluid. Better results can therefore be achieved when the components are present as solutes in the fluid.
Since the generated acid is a strong acid, the range of bases suitable for neutralizing the acid is extensive. For example, bases in general which have a pKb (determined in water or aqueous ethanol at 18�C.), which is less than 13.5 are satisfactory. These include inorganic and organic bases. Prime factors relating to the selection of the base for my delayed catalyst system include:
1. the solubility of the base in the acid-settable fluid; and
2. the pH which should be maintained prior to the drop to the level required for catalysis.
The base should be soluble to an extent necessary for the sufficient delay of the pH drop. And where the acid-settable liquid sets under the influence of a weakly acidic pH (3-5), a strong base (pKb<6) is desirably employed.
Organic and inorganic bases noted above are suitable for use as components in the delayed catalyst system of my method except in the case where the AR compound is an acid halide (acyl and sulfonyl). In this exceptional case, pyridine and the like nucleophilic aromatic heterocyclic nitrogen bases and aryl amines are not satisfactory.
Representative classes of bases suitable for employment, except as noted above, include alkali metal hydroxides, alkali metal salts of weak acids (pKa in water at 18�C. above 5), alkali metal alkoxides, organic nitrogen bases, i.e., primary, secondary, and tertiary amines, and the like.
Representative bases suitable herein, except as noted above, include sodium hydroxide, potassium hydroxide, sodium butoxide, sodium acetate, pyridine, piperidine, triethylamine, diethylamine, sodium ethoxide, cyclohexylamine, N,N-dimethylaniline, di-n-butylamine, aniline, quinoline, isobutylamine, di-(2-ethylhexyl)amine, 4,4'-diaminobenzophenone, 4,4'-diamino diphenyl ether, diisopropyl amine, hexamethylene diamine, ethylene diamine, ethanolamine, diethanolamine, triethanolamine, ispropylamine, octylamine, sodium benzoate, and the like compounds. Organic nitrogen bases, in general, are preferred for use as the base component of a delayed latent catalyst system. Of these, the pyridine-type nitrogen bases in admixture with an aryl halomethyl-type AR compound (see discussion above for formulation) yield catalyst mixtures having excellent shelf lives and are, therefore, especially useful herein. Pyridine-type bases include pyridine, quinoline and isoquinoline and these compounds in which 1, 2 or 3 of the hydrogen atoms attached to the carbon atoms of the heterocyclic ring are replaced by 1, 2 and 3 inert substituent groups such as chloride, bromide, alkyl (C1 -C10), and phenyl. These are conveniently described by the formula (ARN)(X)n, where ARN represents pyridine, quinoline or isoquinoline less n hydrogen atoms, X is an inert substitutent group, and n is 1, 2 or 3.
Other representative pyridine-type bases suitable for use in the invention include the crude and refined coal tar fractions from coking which contain so-called pyridine crude bases, picolines and the like.
As a practical matter and for reasons of cost, convenience and the like, the organic bases used in the method should have a carbon atom content of less than 21, preferably less than 12.
The amount of the catalyst system (AR compound plus base) desirably included in the acid-settable fluid varies depending in the main upon the acid potential (equivalent weight) of the AR compound and the pH needed for an effective setting of the fluid. At a pH of 5 the solvated hydrogen ion concentration is 10- 5 mol per liter, and at a pH of 2, it is 10- 2 mol per liter. Hence, the solvolysis of only a correspondingly small amount of the AR compound is necessary to provide these amounts of strong acid. Aside from a cost factor, the presence of a substantial excess of the AR compound, as a rule, is advantageous. By reference to FIG. 3, it is evident that there is no marked variation in the set time for the acid-settable fluid over a wide concentration range for the present delayed catalysts. This circumstance is a particular and practical advantage of the method herein because the man in the field need only use ordinary means for measuring and introducing the catalyst into the fluid.
FIG. 3 demonstrates that the prime concern re the catalyst requirement is that the addition of at least the minimum satisfactory amount be made. In general, a satisfactory amount of the delayed catalyst is in the range 2 to 20 parts per 100 parts of the acid-settable fluid, preferably 3 to 6 parts.
The placement of the present acid-settable fluids in a subterranean zone, for example in a zone surrounding a well bore, is readily accomplished by ordinary methods. However, the one-step integral nature of the present fluids and method usually makes possible the employment of simplified and more convenient procedures. Spacer fluids, for example, are not required for the separation of reactive chemicals. The time available for the placement can be delayed to provide a convenient and safe rate of introduction.
In one method, a suitably sized pipe string is lowered into the well bore with the bottom of the tubing being positioned for delivery of fluid into the bore adjacent to the treatment zone. The fluid is then forced out of the bore and into the formation by displacement with other liquids or a suitable inert gas.
Ordinarily the zone and well bore environs will be substantially free of strong acid or base. Consequently, no pretreatment will be needed. Should there be a residue of strong acid in the zone or well bore, as from an acid treatment, then a neutralizing preflush should precede the placement of the consolidation liquid mixture. For example, a prewash using dilute aqueous ammonia is a convenient means for neutralization of the acid. A follow-up water or hydrocarbon preflush may be desirable. If the zone to be treated (consolidated or plugged) is a carbonate formation, the introduction of an acid-setting liquid containing a relatively larger amount of the acid-releasing compound is usually desirable. Alternatively, it may be more economical to pacify the carbonate formation by ordinary methods, for example, as known in the art, by the introduction into the formation of an aqueous calcium chloride preflush.
The acid-setting liquid is usually pumped into the well bore or formation. Accordingly, it should have a viscosity in the range suitable for convenient pumping, i.e., a pumpable liquid. Preferably, the liquid should have a viscosity in the range 1 to 300 centipoise. Although the use of a fluid having a viscosity in the upper portion of the range is less convenient to pump, nevertheless, the use of a fluid having a relatively high viscosity is often preferable because plug flow is better, undesirable channeling of the fluid in the zone may be minimized, and the fluid is more likely to stay in place after pumping ceases.
Ordinarily, commercially available acid-settable liquids have a suitable viscosity or the viscosity can be readily reduced, for example by the addition of furfuryl alcohol, or of some other suitable diluent, monomer or oligomer, or of a minor amount of water, methanol, benzene or the like.
After the acid-settable liquid is introduced into the terrestrial zone or formation, it must remain in place until the setting occurs. Thus, depending upon the particular liquid employed, it must be maintained in place for a period of from 1 to 24 hours, preferably 2 to 6 hours.
The following examples further illustrate, but not by way of limitation, the invention.
The use of a variety of representative bases for preparing a delayed acid catalyst system are illustrated in these examples. The acid-settable liquid employed was a mixture of 80 parts of a commercial resin and 20 parts of furfuryl alcohol. The resin was a liquid composed of partially polymerized furfuryl alcohol, i.e., furfuryl alcohol oligomers, which were capable of further polymerization with a strong acid catalyst to form a solid, furfuryl alcohol polymer.
Based upon 100 parts of the acid-settable liquid, 5 parts of acid-releasing (AR) compound were used and the amount of the base included was sufficient for the neutralization of one-fourth of the total acid available from the AR compound. The AR compounds, bases used, and results for the temperatures indicated were as follows:Benzenesulfonyl Chloride, 25�C.EX. NO. BASE GEL TIME, MINS.______________________________________1 None 602 Triethylamine 673 Triethanolamine 954 Tri-n-butylamine 765 Cyclohexylamine 125______________________________________α-Chlorotoluene, 93�C.EX. NO. BASE GEL TIME, MINS.______________________________________6 None 417 Triethylamine 728 Triethanolamine 2189 Tri-n-butylamine 8710 Cyclohexylamine 215______________________________________α-Chlorotoluene, 115�C. CATALYST GEL TIMEEX. NO. WT. % BASE MINS.______________________________________11 4 Triethanolamine 7412 6 " 7613 8 " 6314 10 " 55______________________________________
In these examples the catalyzed solutions remained predominantly unchanged until the reaction time approached. Then the solutions turned from clear to blue-green to black. Reaction occurred rapidly with total conversion of the liquid to solid.
The foregoing examples demonstrate the delay of free-acid generation from suitable low temperature AR compound, benzenesulfonyl chloride, and from a relatively high temperature AR compound, benzyl chloride, by a number of representative nitrogen bases. These systems are especially suitable for use in plugging voids or relatively open zones in an earthen formation.
In the manner described above in Examples 1-14, gel times were determined for furfuryl alcohol using the indicated AR compound with and without pyridine base. Based upon the furfuryl alcohol, the weight percent of the AR compound used together with the temperatures used and with the result obtained are listed in Table II.
TABLE II__________________________________________________________________________CHLOROTOLUENES AS LATENT CATALYSTS AND DELAYEDLATENT CATALYSTS FOR FURFURYL ALCOHOLCATALYST, CATALYST, Gel Time, Hr:Min.EX. MOL RATIO WEIGHTNO. α-TCT/PY PERCENT 25�C. 60�C. 80�C. 100�C.__________________________________________________________________________15 1/0 2 6:17 :17 -- :02 4 1:47 :11 -- -- 6 1:35 -- -- --16 1/1 2 22:50 1:18 :15 :07 4 20:22 1:14 :14 :07 6 21:09 1:15 :14 :0617 1/2 2 -- * :34 :10 4 -- 2:58 :36 :09 6 -- 3:05 :33 :0718 1/3 2 -- * :75 :20 4 -- * :76 :19 6 -- * :83 :15 α-DICHLORO- TOLUENE/PY19 1/0 2 * 4:-24: :09 -- 4 * 4:-24: :06 -- 6 : :13 :04 --20 1/1 2 -- * * :20 4 -- * 1:32 :30 6 -- 24: 1:20 :2921 1/2 2 -- -- * 4: 4 -- -- 21:-28: 1:45 6 -- -- 21:-28: 4: α-CHLORO- TOLUENE/PY22 1/0 2 * * -- 31/2:** 4 * * -- 31/2: 6 * * -- 31/2:__________________________________________________________________________ *No solid product formed in 24 hours at temperature. **Solid product, but no obvious gel point.
In these examples α-trichlorotoluene (TCT) and pyridine were mixed in a molar ratio of 1 to 1. Portions of this mixture were then added to furfuryl alcohol (FA) or to a furfuryl alcohol-water mixture, as noted in the Table below, and the gel times at 60�C. for the mixtures were determined.
TABLE III______________________________________EX. Wt. FA TCT ADDED, GEL TIME,NO. Wt. H.sub.2 O Wt. % MIN.______________________________________23 100/0 2 4124 100/0 4 5325 100/0 6 5626 90/10 2 1727 90/10 4 1628 90/10 6 15______________________________________
Examples 23-28 demonstrate that the addition of water to an acid-settable organic liquid is a useful means for reducing the delay of a delayed catalyst system. Water also improves the leveling effect of the delayed catalyst system, i.e., there was little or no change of gel times over a range of catalyst concentrations.
The conditions in a loose porous earthen formation were simulated for laboratory tests by filling test tubes with sand and filling the interstices of the sand with the acid-settable fluid. In each example, 5 weight percent of the indicated AR compound was used and the acid-settable liquids were mixtures of furfuryl alcohol and formaldehyde (formalin) having the mol ratios as noted in Table IV.
TABLE IV__________________________________________________________________________MOL RATIO MOL RATIO REACTION TEMPERATURE, �C.EX. FURFURYL ALCOHOL CATALYSTNO. TO FORMALDEHYDE TO PYRIDINE 25 40 60 80 100__________________________________________________________________________ α-TRICHLOROTOLUENE29 1/1 1/0 8<t<19 hr 1 hr 34 min 4 min 1 min -- 1/1 -- 2 hr 32 min 14 min 2 min -- 1/2 -- 6.5<t<22.5 hr 1 hr 18 min 4 min -- 1/3 -- -- 4 hr 25 min 2 hr 5 min30 2/1 1/0 8<t<19 hr 1 hr 41 min 4 min 1 min -- 1/1 -- 2 hr 30 min 16 min 3 min -- 1/2 -- 6.5<t<22.5 hr 1 hr 52 min 5 min -- 1/3 -- -- 3 hr 13 min 1 hr 30 6 min31 3/1 1/0 8<t<19 hr 1 hr 43 min 5 min 2 min -- 1/1 -- 2 hr 48 min 38 min 4 min -- 1/2 -- 6.5<t<22.5 hr 1 hr 51 min 6 min -- 1/3 -- -- 6 hr 56 min 1 hr 21 8 min32 4/1 1/0 8<t<19 hr 2 hr 25 min 6 min 2 min -- 1/1 -- 2 hr 50 min 51 min 6 min -- 1/2 -- 6.5< t<22.5 hr 1 hr 50 min 6 min -- 1/3 -- -- 6 hr 24 min 2 hr 9 8__________________________________________________________________________ min α-CHLOROTOLUENE33 2/1 1/0 -- -- -- -- 28 min 2/1 -- -- -- -- 1 hr 11 min 1/1 -- -- -- -- 1 hr 58 min34 3/1 1/0 -- -- -- -- 30 min 2/1 -- -- -- -- 1 hr 28 min 1/1 -- -- -- -- 3 hr 20__________________________________________________________________________ min -- Reaction not performed.
The resulting polymer impregnated sands were hard, stable solids. For reactions above 80�C., α-trichlorotoluene was unsatisfactory. The rate of acid-generation at this temperature, i.e., the solvolysis rate, for the trichloride was inconveniently fast. The rate for α-chlorotoluene is satisfactory at high temperatures and hence it was used for the examples at 100�C. These examples demonstrate that delayed catalysts are useful for the setting of an acid-settable fluid in an earthen formation.
The conditions in a stable permeable earthen formation were simulated in a laboratory test using cores of Boise sandstone. Each core was 3 inches long and 1 inch in diameter and was cut parallel to the bedding plane. Prior to use, they were extracted with toluene, dried in a vacuum oven at 125�C. and under a vacuum of 29 in. of mercury. The dried cores were vacuum saturated with deionized water and then encased in either an aluminum or monel tube using a suitable adhesive. The initial permeabilities for the cores were measured at 10 psi using deionized water.
Core plugging tests were conducted at 25�, 40�, 60�, 80�, 100� and 120�C. The plugging behavior of a given solution at each temperature was investigated by using a suite of four cores. Initially, the cores were mounted in potted core holders, placed in an oven, and allowed to reach the desired temperature. The cores and core holders were then removed from the oven and 15 ml of plugging solution were injected into each core. The cores were then shut in and replaced in the oven. After one, two, and three hours, and overnight, a core was removed from the core holder, the ends of the core were cleaned and/or faced off as necessary, and replaced in the core holders. Finally, the plugged permeabilities were measured using deionized water at room temperature and 100 psi. All permeability measurements and plugging injections were made by flowing in the same direction.
Table V is a summary of these examples in which five percent of the AR compound and the indicated acid-settable fluid was used. The AR compound was α-trichlorotoluene or α-chlorotoluene as noted.
TABLE V__________________________________________________________________________EX. REACTION MOL RATIO: MOL RATIO SHUT-IN K.sub.I ** K.sub.F *** %NO. TEMPERATURE FURFURYL ALCOHOL CATALYST TIME md md Shut-Off__________________________________________________________________________ Formaldehyde Pyridine35 25�C. 2/1 No Pyridine 69 hr 1126.8 6.85 99.4 69 hr 1278.8 12.1 99.136 40�C. 3/1 No Pyridine 1 1103.7 107.7 90.2 2 852.6 0.1 100.0 3 878.9 22.1 97.4 19 1034.0 3.4 99.737 60�C. 2/1 1/2 1 735.2 116.1 84.2 2 759.3 29.7 96.1 3 1285.8 84.9 98.9 19 853.8 4.4 99.538 80�C. 1/1 1/3 1 1165.9 688.1 41.0 2 1156.6 11.0 99.1 3 738.1 30.5 95.9 19 1425.0 0.1 100.039 100�C. 2/1 *1/1 1 774.7 676.9 12.6 2 1039.4 116.9 88.8 3 1226.3 436.7 63.8 19 1082.7 23.7 97.840 120�C. 3/1 *1/1 1 1170.6 437.8 62.6 2 1171.7 212.9 81.8 3 1113.2 39.7 96.4__________________________________________________________________________ *α -chlorotoluene catalyst **Initial permeability ***Final permeability
Examples 35-40 demonstrate that stable porous earth formations can be effectively sealed or plugged by the use of an acid-generating catalyst. They also demonstrate that, in general, a 95 percent and higher reduction in permeability can be achieved in a period of 2-3 hours.
In order to simulate conditions in the field where aqueous brine or hydrocarbons are present in the formation, cores that were initially saturated with these materials were also tested. These were run under similar conditions at 60�C. The permeability was measured after three hours and overnight shut-in periods. The permeability reduction of brine-saturated cores averaged 92%, or slightly less than most cores that were initially saturated with deionized water, but this is still satisfactory performance. The diesel oil saturated cores both exhibited 100% shut-off. The process is thus relatively unaffected by extraneous fluid saturations.
In order to check the durability of plugs formed by the one-step furfuryl alcohol process, selected plugged cores were put into 21/2% brine solution at 93�C. for static brine aging. Cores that had been plugged at 40�, 60�, 80� and 100�C., and that were shut-in for three hours or longer, were used in this test. Because the cores were potted, their exposure to the aging environment was limited, but they were nonetheless subjected to 93�C. heat for the aging period. The aged cores were faced off before each permeability measurement in order to eliminate effects of corrosion products in the aging fluid that could act to plug them. α-Trichlorotoluene (TCT) or α-chlorotoluene (CT) were the AR compounds used and pyridine (PY) was the inhibitor. Table VI summarizes the aging data.
TABLE VI__________________________________________________________________________CORE AGING RESULTS PROCESS RUN SHUT IN % AGING % AGING % AGING %EX. IDENTIFICATION TEMP. TIME SHUT TIME, SHUT TIME, SHUT TIME, SHUTNO. MOL RATIOS �C. HR. K.sub.I K.sub.F OFF DAYS OFF DAYS OFF DAYS OFF__________________________________________________________________________ F.A./ TCT/ H.sub.2 C=O PYR41 2/1 -- 25 69 1126.8 6.9 99.4 21 99.9 51 99.9 -- -- 2/1 -- 25 69 1278.8 12.1 99.1 21 99.8 51 99.7 -- --42 1/1 -- 40 3 1258.3 34.8 97.2 21 97.0 51 96.9 -- -- 1/1 -- 40 69 1137.3 25.6 97.8 21 97.0 51 97.3 -- --43 2/1 1/2 60 3 1183.1 44.0 96.3 26 95.6 56 96.9 -- -- 2/1 1/2 60 44 1305.2 19.4 98.5 24 98.1 54 99.2 -- --44 3/1 1/3 80 19 1218.9 24.3 98.0 20 98.1 42 97.1 79 97.1 1/1 1/3 80 19 592.4 72.0 87.8 20 96.4 42 **74.2 79 76.645 2/1 1/0* 100 3 952.2 37.6 96.1 18 96.9 48 96.4 83 96.1 1/1* 100 19 1082.7 23.7 97.8 18 97.8 48 96.9 83 96.9__________________________________________________________________________CORES INITIALLY SATURATED WITH DIESEL OIL46 2/1 1/2 60 3 740.2 0.0 100.0 17 100.0 39 100.0 76 100.0 2/1 1/2 60 19 619.3 0.6 99.9 17 100.0 39 100.0 76 100.0__________________________________________________________________________CORES INITIALLY SATURATED WITH 10% BRINE47 2/1 1/2 60 3 497.2 34.6 93.1 17 94.6 39 93.0 76 91.9 2/1 1/2 60 19 488.2 44.5 91.2 17 93.0 39 91.3 76 91.5__________________________________________________________________________ *Solution catalyzed with α-chlorotoluene **Core fractured during aging
The foregoing Examples 41-47 demonstrated that the static aging of the plugged cores showed an average of 1% permeability return after about 8 weeks in the aging tanks. There was no apparent difference in the durability of plugs with long or short shut-in times, or those plugs formed in oil or brine saturated cores. These examples demonstrate that the use of delayed acid-generating catalysts with acid-settable liquids is an effective method for plugging stable porous earthen formations.
Under comparable conditions, furfuryl alcohol, furfuryl alcohol resin, urea-formaldehyde resin, and phenolic resin were polymerized at 60�C. The delayed catalyst was α-trichlorotoluene (TCT) and pyridine (PY) at a 1 to 1 mol ratio. The results are listed in Table VII. The furfuryl alcohol was of commercial grade. The resins were typical acid-settable, commercially available, partially polymerized resins.
TABLE VII______________________________________ACID-SETTABLE RESIN POLYMERIZATIONSEX. TCT TCT GEL TIMENO. RESIN TYPE PYR PERCENT 60�C., MIN.______________________________________48 Furfuryl Alcohol 1/0 4 11 1/1 4.8 65 1/1 6.2 70 1/1 7.7 7049 Furfuryl Alcohol Resin 1/0 4 18 1/1 4.8 114 1/1 6.2 110 1/1 7.7 12050 Urea-Formaldehyde Resin 1/0 4 7 1/1 4.8 13 1/1 6.2 12 1/1 7.7 1551 Phenolic Resin 1/0 4 9 1/1 4.8 13 1/1 6.2 11 1/1 7.7 11______________________________________
Examples 48-51 and the other examples above demonstrate that acid-settable liquids, that is liquids which set under the influence of a strong acid, are effectively polymerized under the influence of a delayed acid catalyst. These examples and the other examples above further demonstrate that the method of the present invention is a useful means for delaying or controlling the time of setting of an acid-settable liquid which is set by means of a latent acid-releasing compound.
Examples 52-57 illustrate the effect of dilution upon the gelling or setting up time of an acid-settable liquid catalysed by a representative latent catalyst system. In these examples, the AR compound was α-trichlorotoluene (TCT). The determinations were made at 25�C., using the diluents and concentrations and results as noted in Table VIII below:
The above examples demonstrate a further degree of freedom in the controlling of the gelating or setting time of an acid-settable liquid as herein. Similar results obtain when a delayed catalyst, i.e., when a base is added as herein described, is employed. Thus, the setting-up time of the liquid can be further delayed for a delayed catalyst system by dilution with inert organic liquids (note methanol, as described above, furnishes a proton for strong acid generation where no other hydroxylic agent is present). Usually for an impermeable consolidation of a formation, the degree of dilution should not exceed about 50 volume percent, preferably should not exceed 30 volume percent; otherwise, the dilution may be by as much as 70 volume percent.
The shelf life of two typical α-trichlorotoluene-pyridine (TCT/PY) delayed latent catalyst mixtures were determined for mixtures prepared and placed in storage under ambient temperature conditions, i.e., about a 22�C. average temperature. After 1 year the aged composition and freshly prepared control catalyst mixtures were tested as delayed latent catalysts (5 parts-weight) for the setting of a typical furfuryl alcohol-furfuryl alcohol prepolymer mixture (95 parts-weight) with the results as follows:
TCT/PY TIME TOMIXTURE MOL RATIO SET, MIN.______________________________________Control Mix 1:1 16Aged Mix 1:1 16Control Mix 1:2 33Aged Mix 1:2 35______________________________________
These comparative data demonstrate that delayed latent catalyst mixtures in which an α-trichloromethyl substituted aromatic compound is the acid-releasing component and a pyridine-type organic nitrogen component is the delaying agent have excellent shelf lives. These mixtures may be compounded, stored and conveniently used simply by the addition of a portion of the mix to the acid-setting liquid, mixing the combined portions well, and introducing the resulting mixture into a terrestrial zone or formation or as desired. The relative amounts of those novel catalyst systems which are added to the acid-setting liquid may vary over a range (see examples in preceding sections) and can be conveniently carried out in the field.
In addition to being useful in effecting the setting (polymerizing) of an acid-settable liquid in the usual difficult circumstances encountered in a terrestrial zone, and particularly where the use is in a well bore environment, the delayed latent catalyst system herein provides useful improvements, in general, in the setting of an acid-settable liquid by a strong acid. Representative improvements include the use as a catalyst in the impregnation of solids such as wood, fiber glass cloth, felt, burlap, and the like porous materials with an acid-settable liquid containing a delayed latent catalyst of the invention. It also includes the use of a delayed catalyst for setting of acid-settable liquids as adhesive for glass sheeting, and as a martar when a mixture of the liquid, catalyst and sand is applied to common bricks, cinder blocks, and the like earthen materials. Principle elements of the improvements reside in the controlled delay of the setting of the liquid and in the convenient unitary aspect of the working mixture, catalyst and acid-settable liquid. The following examples illustrate further useful aspects of the invention.
A solid homopolymer of furfuryl alcohol was prepared using a delayed catalyst obtained by mixing 3 mols of pyridine with 4 mols of α-chlorotoluene. A mixture of 97 parts of the alcohol and 3 parts of the catalyst was maintained at 180�F. for about 9 hours. The controlled catalysis permitted a slow homogeneous polymerization of the acid-settable alcohol without localized hot spots, voids and the like problems. The cured product was an ebony black solid having the following characteristics:
Compressive Strength (ASTM No. D-695-63T), psi 15,700Tensile Strength (ASTM No. D-638-61T), psi 28,000Izod Impact (ASTM No. D-256-56), ft.lbs/inch 0.17Shear Impact (ASTM No. D-732-46), psi 5,050Specific Gravity, g/ml 1.27
This example demonstrates that the delayed latent catalyst of my invention is useful for the effective control of acid-settable liquids whose polymerizations are ordinarily very vigorous and highly exothermic. It further illustrates that the present method is useful for the production of engineering plastics from furfuryl alcohol. Similar useful results are obtained when acid-settable liquids comprising copolymers such as phenolformaldehyde, urea-formaldehyde, melamine-formaldehyde and the like mixed monomeric acid-settable liquids are set using a homogeneous mixture of the liquid and a delayed latent catalyst as herein. Variations, such as the addition of a filler-like asbestos, glass cloth, glass fibers, etc. to the monomer or comonomer mixtures, are also effectively handled.
A section of fiber glass cloth was spread out on a wooden surface and impregnated with a commercially available acid-settable liquid. The latter contained about 80 volume percent of a furfuryl alcohol oligomeric mixture and 20 volume percent of furfuryl alcohol. The delayed catalyst was an equimolar mixture of α-trichlorotoluene and pyridine. Five parts by weight of the catalyst were mixed with 95 parts of the liquid and the mixture was applied to the supported cloth. After about 17 hours at 110�C., the polymerization and cure of the supported glass cloth was completed. The adherence of the polymerized liquid to the glass and wood was excellent.
A mortar was made using the acid-settable liquid described in the preceding example. The delayed catalyst was a 4 to 1 molar mixture of benzenesulfonyl chloride and cyclohexyl amine. Five parts (weight) of the catalyst was mixed with 95 parts of the liquid. The mortar was prepared by mixing the following:
Nevada No. 130 sand, g. 115Acid-settable liquid and catalyst, g. 50
The mixture was then placed between common red bricks. After 24 hours at the ambient temperature, the bricks were effectively bonded together.
This example and Examples 29-34 demonstrate that the delayed latent catalyst, as herein, is useful for the preparation of sand molds in which an acid-settable liquid is the bonding agent. The control (delay) in the setting time provided by the instant catalyst system simplifies and improves the preparation of sand molds.
A block of ordinary sugar pine wood was impregnated with a mixture of furfuryl alcohol (95 parts-weight) and a delayed latent catalyst (5 parts) by immersion of the wood in the mixture for 15 minutes. The catalyst was an equimolar mixture of α-trichlorotoluene and pyridine. After 24 hours at 110�C., the acid-settable liquid in the impregnated wood had polymerized and cured.
The above Examples 59-62 demonstrate that a mixture of a suitable organic acid-releasing compound, as described above, and a suitable base, also as described above, is an effective delayed latent catalyst for the setting, in general, of acid-settable liquids which are set by the action of a strong acid.
The delayed latent catalyst system herein is also useful for effecting a permeable consolidation in an unconsolidated terrestrial formation and the like with an acid-settable liquid. This is illustrated in the following examples.
Nevada 135 sand was charged to a 60-inch Hassler cell. The sand and cell was maintained at 150�F. and a mixture of an acid-settable liquid (95 parts-weight) and a delayed latent catalyst (α-trichlorotoluene-pyridine; equimolar mixture; 5 parts) was injected into the sand. The liquid was a commerciaL furfuryl alcohol resin. After the injection of the liquid, the excess liquid was removed from the sand and permeability was established by injecting an inert fluid, kerosene, into the sand. The cell was then shut in. The residual acid-settable liquid adhering to the sand set under the generated catalytic influence of the delayed catalyst. The consolidated sand averaged 450 md permeability and 6600 psi compressive strength. In conventional practice and prior to the present discovery an additional stage is required because the catalyst must be separately introduced into the unconsolidated material after the permeability flush. In addition to the disadvantageous requirement of an additional operational stage, the conventional method suffers from the usual problems inherent in a multistage method for the introduction and contacting of reactants in a well bore and its surrounding formations.
Unconsolidated sand, as in the previous example, was charged to a Hassler cell. A mixture of a commercially available acid-settable phenolic resin in 2-propanol (50 weight percent solution) and containing 5 parts of an equimolar mixture of α-trichlorotoluene and pyridine per 95 parts of the resin was injected into the sand. The cell and its contents were maintained at 150�F. for about 18 hours. The resulting consolidated sand averaged 120 md permeability and a compressive strength of 1220 psi.
In the manner of Example 64, sand was consolidated except that a furfuryl alcohol resin (80% furfuryl alcohol oligomer and 20% furfuryl alcohol monomer) was substituted for the phenolic resin. The consolidation averaged a 160 md permeability and a compressive strength of 700 psi.
Examples 63-65 demonstrate that the delayed latent catalyst system herein is an effective catalyst for the consolidation of unconsolidated earthen formations, especially by the overflush and by the phase separation methods in which an acid-settable liquid is the bonding agent. They also establish that the acid-settable liquid and catalyst combination, as herein, are useful in the installation of precoated sand packs, and prepacked liners in wells, especially oil wells.
Other advantages for the method herein include its use in connection with the plugging of a section of a well bore, the plugging of a vug, and the plugging of a thief zone.
In view of the above examples, acid-settable liquids, and especially furfuryl alcohol-type liquid and liquid oligomeric mixtures, are useful for the treatment of or bonding of wood, paper, glass, ceramics, coal, coke, nut shells, sand, soil, and the like. Accordingly, the method herein is useful for controlling the setting of acid-settable liquids in their use as soil stabilizers, grouting agents, and bonding agents for wood and coal fines, and for sandtype foundry castings, molds and the like.
Another of the many advantageous aspects of the delayed catalyst systems herein is the absence of any appreciable change in viscosity of the liquid during the extended working time obtained from the presence of the base component. This circumstance is especially useful because it eliminates variation in the viscosity parameter, which can be, and often is, a severe process burden.
It will be readily appreciated from the above disclosure and examples that variations can be made therein and equivalents may be substituted without going beyond the purview of the invention or exceeding the scope of the claims.
|Cited Patent
|Filing date
|Publication date
|Feb 27, 1942
|Apr 23, 1946
|Gen Electric
|Resinous products from furfuryl alcohol and process of making the same
|Nov 29, 1944
|May 31, 1949
|Haveg Corp
|Method of making furfuryl alcohol resinous products and the product
|Jul 12, 1947
|Feb 28, 1950
|Haveg Corp
|Process of making a furfuryl alcohol resinous product
|Feb 25, 1963
|Oct 5, 1965
|Halliburton Co
|Sand consolidation method
|Apr 25, 1968
|Aug 3, 1971
|Haveg Industries Inc
|Refractory heat insulating sleeve
|May 5, 1969
|Oct 24, 1972
|Ameron Inc
|Acid catalyst system for furan resins of filler containing acid salts
|Jan 7, 1972
|Sep 18, 1973
|Halliburton Co
|Internally catalyzed well consolidation method
|Citing Patent
|Filing date
|Publication date
|Aug 25, 1975
|Apr 5, 1977
|Chevron Research Company
|Method for delaying the setting of an acid-settable liquid in a terrestrial zone
|May 5, 1981
|Nov 30, 1982
|The United States Of America As Represented By The United States Department Of Energy
|Quick setting water-compatible furfuryl alcohol polymer concretes
|Jul 2, 1979
|Dec 3, 1985
|The Dow Chemical Company
|Process for cementing geothermal wells
|Oct 18, 1984
|May 19, 1987
|Cities Service Oil And Gas Corporation
|Gel for retarding water flow
|Aug 1, 1988
|Jul 3, 1990
|Cities Service Oil And Gas Corporation
|Gel for retarding water flow
|Feb 1, 2002
|Mar 7, 2006
|Wood Polymer Technologies Asa
|Furan polymer impregnated wood
|Mar 2, 2010
|Jun 12, 2012
|Kebony AB
|Furan polymer impregnated wood, method for preparing the polymer and uses thereof
|Feb 1, 2002
|Dec 19, 2002
|Schneider Marc H.
|Furan polymer impregnated wood
|Dec 16, 2005
|May 4, 2006
|Wood Polymer Technologies Asa
|Furan polymer impregnated wood
|Mar 2, 2010
|Feb 3, 2011
|Schneider Marc H
|Furan polymer impregnated wood, method for preparing the polymer and uses thereof
|U.S. Classification
|523/130, 524/803, 526/270, 528/232, 528/230, 166/295
|International Classification
|Cooperative Classification
|European Classification


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If there's anything that Harry and Marv deserve credit for, it's being persistent, especially after encountering Buzz's tarantula, getting clobbered by paint cans, dealing with a face full of feathers, and stepping on ornaments in bare feet. Kevin eventually asks them, "You guys give up or ya thirsty for more?" Wear this t-shirt to scare off your own neighborhood Wet Bandits.
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Look at walls of the Fortress of Ghosts
That has never been captured before
Look at sullen towers, sockets of windows,
At the gloomy air of walls made of stone
For the last time
Look at her majestic silhouette
Towering over the ancient oaks
She was the guardian of this land
But soon her yards
And nearby fields will be full of blood
Since our gods have forgotten
about their favourite people
It was too late
When we saw the hostile hordes
There had been something vicious
in the air for a long time
Insane old men
were shouting out their prophecies
But no one
wanted to believe them
Until now. Until this moment
And now
In front of us
There is the legion
Of warriors in full armour
The enemy began a long siege of the Black Fortress
But its seasoned defenders turned out to be invincible
Afterwards the invader found the only effective way
He decided to make them starve
The time passed but brave warriors were invariably invincible
The invader attacked defenders a few more times
But after every raid the invaders were coming back terrified
Saying they don't want to be gobbled by spectres...
Dark silhouettes of naked warriors carrying enormous swords
were seen coming out of the mist
They were massacring the enemies roaring hoarsely,
cutting them into pieces
Afterwards they were greedily drinking blood running down their swords
Stuck in the hostile warriors' bodies
And here came the end
There are too few of us to resist any longer
We will not dishonour our land by giving up
Let's put the fortress on fire
And when the smoke reaches our enemy
The People of Mists will be there too
They say that spectres lead mists
But it is mists that will lead us
We will go at dusk
To seek death in the enemy's camp...
Lyrics submitted by Bloodmouth
The Fall of Black Fortress song meanings
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Wick Chair by Karl Malmvall & Jesper StahlSeptember 13, 2016
While many people may see a wicker basket as a good receptacle for storing fruit and vegetables, Swedish designers Karl Malmvall and Jesper Stahl used it as... Full Story
Sink Into the KERMAN Sofa by e15August 29, 2016
A sofa needn't be boring, and with the KERMAN sofa that's never the case. Designed by German-based design firm e15, this multi-functional piece of furnishing... Full Story
Siro+ Chair for WoodnotesAugust 26, 2016
Designers Raffaella Mangiarotti and Ilkka Suppanen teamed up to create the Siro+ Chair for Finnish brand Woodnotes. Both comfortable and functional, it can be... Full Story
NEOCON 2016: 'Laura' by Davis FurnitureJune 29, 2016
One of our favourite finds of this year's NEOCON, here's an in depth look at Davis Furniture's new series. 25 year Davis design veteran Wolfgang... Full Story
Woodieful Multipurpose Stool Launched Through KickstarterMay 19, 2016
The Woodieful chair is design with intention and on a mission. Furniture today needs to be multi functional, and the Woodieful stool covers so much more than... Full Story
Mad for m.a.d.'s Design Forward FurnitureMay 11, 2016
Generally when people think of Asian based manufacturing, design copies or poorly made 'inspired by' furniture comes to mind. Matt Cole and Dan Given set out... Full Story
Jasper Morrison's New Supernormal Collection For VitraMay 05, 2016
Jasper Morrison, together with his longtime collaborator, Japanese designer Naoto Fukasawa, coined the term 'supernormal' to describe how design should... Full Story
Stua Launches Cosy New Collection for 2016April 28, 2016
Barcelona based Home-Vice team created a singular installation for Stua for Salone di Mobile 2016. Themed the "Swiss Warm Home", the project evokes... Full Story
Blu Dot Is Spot On With Field Lounge ChairApril 19, 2016
Born in Minneapolis, Blu Dot has been a favourite of the of American contract market nearly since it's beginning in 1997. Straight forward, durable... Full Story
New Fukasawa And Morrison Launches for MaruniApril 11, 2016
Japanese manufacturer Maruni has grown leaps and bounds in recent years. Already well-established in Japan as a high quality wooden furniture manufacturer,... Full Story
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Henry is a great friend from my time at First Burleson. I worked with him packing boxes for See You At The Pole too. He drove through Bellville on his way to see his Mom. Abby snapped this quick shot:
And yes, I shared a Dr Pepper with him. Imperial Pure Cane Sugar only btw.


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Don't work hard, work smarter. We've all heard the saying, but translating idioms into practice tend to involve more than the initial intuitive understanding.
The surest way to generate passive streams of income to grow wealth is always changing, just like the market. There is no one answer – if you want your money to work for you, it's a matter of opportune timing, perseverance and patience. Opportune timing is all about tapping into the market today and finding the exceptional deal.
There are always traditional routes to turtle your way to financial independence. You might be grey-haired and dusty by the time your mortgage is paid and you have some savings but at least you got there (still an achievement in our day and age). Tradition has its place in financial matters because we all like security when it comes to our hard earned cash. The question is: how do you define security?
Real Estate vs. Stocks
Real estate is just that – it is a real asset. From a finance perspective, even currency is at the mercy of the market to some degree. Interest on money in a bank account is good today, but the actual value of your end plan might fluctuate. Stocks, well, there is no control over your stock value. It's nice to own a few stocks and if you are able to play the stock market to get a small profit percentage return, you're doing well. It's a great portfolio diversification but not really the best way to generate steady, consistent returns. If you've had success in stocks lately, big congrats to you, because you must have a hell of an eye for detail and patience for research to generate any smidgen of returns nowadays. But, you'd do a lot more for your money if you looked into the U.S. Real Estate market (don't worry stock addicts; there are plenty of fund opportunities for you).
Top 3 Reasons to Invest in the U.S. Real Estate Market:
- Market research indicates a projected rise in U.S. real estate property values over the next five years (while current property is being low-balled due to foreclosures).
- Rental streams of income can tide you over until selling at a later date and earn you consistent monthly income if you do your due diligence.
- Rental units in the U.S. are in demand, creating healthy rental rates and projecting increases in your rental income.
The opportune timing on this one is now. The word is out and Canadian positioning is primed to build wealth. The cautionary note here is: remember to perform your due diligence and get the expert advice you need to take the guesswork out of the equation. We've been investing in U.S. real estate and I promise you, there is a method to the madness but the clock is ticking.


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Nowadays, organizations prefer to provide unique badges as their employee identity and this permits them to access their office area as well. For some organizations, badges are the tool that can be applied to operate their in and out mechanism. No matter what the purpose it is used for, an appropriate badge holder can offer you the flexibility and convenience to utilize their badge properly.
A secure way of accessing
The badge is one of those things that are used on a regular basis and even more than a few times in a day. So, this should be easily accessible and must be safe. By providing stretchable
badge holders to their employees, an organization can make the task of accessing for the employees simple enough. The item is designed such a way that it can be attached to any part of your clothing and it can be easily pulled out too. This offers the flexibility to use this as required and get to the back after the job is done. This convenient accessing process can also offer safety to the badge.
Clear visibility of identity
Throughout the working hours, while interacting with the customers and other individuals, there should be a clear visibility of the identity of the employees. For this, the badge should be well-placed as this can be noticed by the other persons. This is actually beneficial for the company image.
Get rid of the neck hangings
Actually, hanging the identity card around the neck has become an older concept and this may not be acceptable for a large number of employees. They always prefer to go with the contemporary and smart look that always goes with their corporate image. For these professionals, the badge reel is the best option that provides them a great flexibility of using their identity badge without facing the reason of irritation hanging around their neck. This neck hanging option can also be the reason of any injury and such risks are not associated with the retractable badge holder.
So, here are so many reasons that can highlight the importance of having a stretchable batch holder with you but now the question is from where you can get this. Custom Lanyards is the most popular source in Canada that can offer you these personalized ID accessories. They have the best quality items to offer you. If you like to provide your employees the full flexibility with their identity badge, this source has no other alternative.


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Sunday, April 27, 2014
We're bored with special effects. Now what?
Drew McWeeny of HitFix takes a stab at this problem in a recent column on what he calls "casual magic." McWeeny believes that visual effects have become truly spectacular and allow impossible events to unfold onscreen, but that this has contributed to our increasing fatigue with big-budget films. Even the truly spectacular special effects and scenery no longer wow audiences. Our threshold for what will amaze us is constantly moving up, and anything below that is considered boring. It's not just that special effects are dull now; worse, they're obligatory. We pay $15 for movie tickets, and we're expecting a sensory barrage.
McWeeny is understandably upset with this jadedness, but he suggests a solution. If outlandish and impossible worlds are our new baseline, the author suggests that we explore those to their fullest and stop creating films about superheroes or the battle of good and evil. We have reached an unprecedented point at which filmmakers can depict seemingly anything they want, and if that is now our bare minimum requirement for seeing a movie on the big screen, the next generation of blockbusters should explore those impossible ideas. More Inception and less Spider-Man, basically.
It's not exactly groundbreaking to argue that special effects should be used to more exciting ends, but it's always spiriting to hear a major movie critic tackle our increasingly apathy to media. Maybe there'll be something worth writing home about this summer. After all, summer movie season starts on Friday!
Thursday, April 24, 2014
Love DC theaters? Support the Avalon's annual fundraiser this Sunday!
With the sad news that Filmfest DC may be entering its last year, we've reached a critical moment for DC film culture. Many of us probably take for granted that we live in a city that our city is home to independent theaters, several film festivals, and the AFI Silver. Once in a while, it's important to head out and support these cultural institutions.
One such opportunity is coming up this weekend to support the Avalon Theater, small non-profit theater in Chevy Chase. The Avalon is a historic theater that, admittedly, has been through a lot in the last 91 years. Originally built to show silent films, the Avalon has had a bumpy time transitioning through the sound era and now into the digital projection era, with much of their facility needing constant remodeling or being stripped down by leasers for other use. At the brink of demolition about a decade ago, the Avalon Theater Project acquired the building and began a lengthy restoration process. That process continues today: last year, the Avalon remodeled its lobby and reinstalled its elevator.
This Sunday, April 27th, at 5pm, the Avalon will host its annual fundraiser to help renovate the theater's second screening room. This year's feature event is a screening of Herblock: The Black & the White, a documentary about the influential editorial cartoonist Hebert Block. The screening will be accompanied by a panel discussion led by Judy Woodruff and Washington Post cartoonist Tom Toles. This is sort of a big deal!
Make no mistake: this is a very pricey event. But your ticket will be going to a great cause. If you can't make or afford to go to this weekend's event, look for one of the other many exciting film screenings coming to the Avalon in the next few weeks, including a Q&A with Kevin Spacey. It's a lovely little theater that needs support more than ever now.
Wednesday, April 23, 2014
Director Michael Glawogger dies unexpectedly, leaves behind great works on globalization
died today of malaria while filming on location in Liberia. He died far too young and early into his career, but he leaves us with a number of quality films exploring hazardous products of globalization, from slum living to prostitution.
It's difficult to mourn properly a filmmaker whose career had only yet begun, but Glawogger's untimely death should not overshadow the significance of his completed works. We have two of the director's films in our collection – Whores' Glory and Workingman's Death – and we highly recommend watching them.
It is unclear if Glawogger's final project will see the light of day, but we have no doubt that he leaves a body of work that will enter, as the chief of the Austrian Film Institute puts it, "the canon of world cinema."
It's difficult to mourn properly a filmmaker whose career had only yet begun, but Glawogger's untimely death should not overshadow the significance of his completed works. We have two of the director's films in our collection – Whores' Glory and Workingman's Death – and we highly recommend watching them.
It is unclear if Glawogger's final project will see the light of day, but we have no doubt that he leaves a body of work that will enter, as the chief of the Austrian Film Institute puts it, "the canon of world cinema."
Thursday, April 17, 2014
Film festival season begins! Union Market kicks off annual drive-thru this Friday
DC outdoor film festivals spring up almost immediately once the weather gets nice out. Usually we have to wait until May or June for the first movie screenings, but this year, at least one is starting early. This is great news if you won't be in DC over summer break!
Starting tomorrow, for the next few Fridays, the Union Market near the NoMA Metro stop will be hosting a crowd-pleasing drive-thru film series. The first film in the festival's line-up is National Lampoon's Vacation, possibly the definitive summer vacation movie. After that, it's Diner, a James Bond film, and a Frozen singalong. (We suspect people will really like that last one.)
Doors open at 6pm tomorrow evening, and the film begins at 8pm (when it's reasonably dark out). Food and unspecified "pre-show activities" will be available for early birds. If you don't have a car, don't be scared away by the drive-thru nature of this festival; pedestrians are welcome too!
Stay tuned for the inevitable summer onslaught of outdoor film screenings. For now, this is a great option for people sick of staying indoors at this time of year. Get thee to the big screen!
Wednesday, April 16, 2014
Celebrate Emancipation Day with a look at DC history
In honor of a very DC holiday, we want to celebrate a few very DC films in our collection. You may be familiar with our Washington, DC Pinterest board, which features movies that take place in DC, but we also want to highlight our Washington, DC filmography. This filmography contains a large number of documentaries from our collection that deal with DC culture, and we can think of no better way to celebrate Emancipation Day then looking back on the unique history of this city.
If you're in the library today, stop by Media Services and ask what DC films we have available. We hope you enjoy this local holiday, and we hope you weren't planning on getting a driver's license today!
Monday, April 14, 2014
See Let's Be Cops TONIGHT!
We're a little last minute on this one, but if you're looking for something to do this evening, consider seeing a new movie!
We have advance passes to see Let's Be Cops, an upcoming action-comedy starring some very funny people. The ensemble includes Jake Johnson from New Girl, Damon Wayans Jr. from Happy Endings, Rob Riggle of The Daily Show, and Keegan-Michael Key from Key and Peele. These are all very funny people, and we're very excited about the idea of them all in a cop movie.
The screening goes down tonight at the AMC Loews 14 in Georgetown at 7pm. (Again, a little last minute, but maybe you're heading down there!) If you want a ticket, follow this link here and print one out! We also have a few print copies left in Media Services, so feel free to visit us in person too.
Again, this is happening TONIGHT at 7pm! We hope to see you there!
(As always, remember that this pass is not necessarily a guarantee that you will get into a screening.)
Sunday, April 13, 2014
How much food do The Goonies eat? Analysis says: a lot
One of the most fun things about movies, television, and really any entertainment medium is the way in way people break them down and uncover all sorts of weird trivia. Just like when someone recently figured out when Ice Cube had a "Good Day," people across the Internet are always figuring out unusual facts about pop culture. This time, it's The Goonies.
An enterprising blogger from Bon Appétit (AU's former food service provider) has calculated how much Chunk eats over the course of The Goonies. Needless to say, it's not healthy. Over the course of the film, he consumes (or is implied to consume) close to 3,000 calories, and he has over 20 food-related moments. That leaves only about 5 minutes to breathe between each time Chunk shows up with some food. That's impressive commitment to a one-off character trait.
There's really not too much academic about this factoid, but we love seeing people break down movies like this. We're sure someone out there could write a terrific essay about The Goonies and its thematic use of food. Maybe Chunk has been the key to the movie all along!
Thursday, April 10, 2014
Welcome to Television Bubble Month!
Deciding whether to bring back a television series for another season is a harrowing process, one that often elicits letter-writing campaigns and grassroots attempts to keep beloved but unsuccessful shows from getting the axe. This year is no different; popular but iffy shows like Hannibal and The Mindy Project could go either way.
In honor of this sort of scary and expectant season, we'd like to celebrate a number of shows that were canceled before their time. Some have seen a revival in movie form or an additional season, but these are classic cases of the television bubble bursting. Come check out these shows from the library, and be warned that your favorite struggling series might be next to join this list!
Freaks and Geeks, The Complete Series – HU DVD 3441
Arrested Development, The Complete Series – HU DVD 4871 - 4873
Firefly, The Complete Series – HU DVD 5301
(Revived in Serenity – HU DVD 5317)
Deadwood, The Complete Series – HU DVD 7101 - 7129
Pushing Daises, Season 1 – HU DVD 10251
Carnivale, Season 1 – HU DVD 10287
Sports Night, The Complete Series – HU DVD 10611 - 10612
Twin Peaks, The Complete Series – HU DVD 14069 - 14070
(Revived in Twin Peaks: Fire Walk with Me – HU DVD 5760)
Luck, Season 1 – HU DVD 14098
Tuesday, April 08, 2014
The tool for the job
Excel 2013: Managing and Analyzing Data. Two hours of tips so you can hit that nail on the head - sorting and filtering data, creating subtotals, and advanced analytics.
As a current AU student, faculty or staff, you have access to all of Lynda.com's tutorials and resources. First, go to www.american.edu/lynda and log in with your AU credentials. Enjoy.
Monday, April 07, 2014
Looking back on ten decades of Mickey Rooney
Rooney began his acting career in the 1920s and achieved international fame in the dozens of movies in which he appeared across the 1930s and 1940s. He was a song-and-dance man who acted in tandem with other famous faces, especially and notably his collaboration with Judy Garland. Even after his career highs, Rooney regularly star in films through the end of his life. To today's viewers, he is perhaps best known for his appearance in Night at the Museum (at age 85!) and his unfortunate, much-criticized turn as Mr. Yunioshi in Breakfast at Tiffany's.
Mickey Rooney may not hold the same iconic status of the other superstars of his era, but make no mistake: he was a legend of his time. We have a number of his most successful films in our collection, including a number of documentaries and compilations about the era and his work.
Quicksand – HU DVD 203
Breakfast at Tiffany's – HU DVD 501*
National Velvet – HU DVD 5483
That's Entertainment! – HU DVD 5671
That's Entertainment, Part II – HU DVD 5672
That's Entertainment! III – HU DVD 5673
Golden Age of Television. Disc 3 – HU DVD 7093
Babe: Pig in the City – HU DVD 7222
Babes in Arms – HU DVD 7871
Strike Up the Band – HU DVD 7872
Babes on Broadway – HU DVD 7873
Girl Crazy – HU DVD 7874
Mickey Rooney & Judy Garland Collection, Bonus Disc – HU DVD 7875
Beach Blanket Bingo – HU DVD 10337
Beast of the City – HU DVD 11071
When the World Breaks – Streaming video
Sunday, April 06, 2014
Bon voyage to Todd Chappell
We wanted to take a break from our normal programming to wish a fond farewell to our colleague Todd Chappell. Todd has been with the AU Library and Media Services since 2010, and his tenure as New Media Center Coordinator led to a customer service boom. Todd is departing the AU Library to further his career in web development, and we wish the best of luck on his new adventures.
In deference to Todd's sensibilities, we present a 23-minute montage of 80s cartoon intros. Godspeed, Mr. Chappell!
In deference to Todd's sensibilities, we present a 23-minute montage of 80s cartoon intros. Godspeed, Mr. Chappell!
Wednesday, April 02, 2014
Same as it ever was? Neurological study explains why we miss film goofs
Spotting continuity errors can be both one of the most fun and one of the most annoying parts of the film-watching experience. Sometimes, odd mistakes and slip-ups are amusing and add an extra wrinkle to the appreciation of the film's craftsmanship (Black Dynamite, HU DVD 8479, is based almost entirely around these sort of mistakes). But finding too many noticeable errors can potentially ruin an otherwise great movie. It's understandable if some people don't want to know what their favorite films got wrong.
As it turns out, our brain doesn't want us to find that out either. Last week, UC Berkeley released a fascinating study on our perception of visual change and continuity fields. Essentially, human brains are wired to smooth over discontinuous images and stimuli, allowing us to perceive that objects are changing. If a person smiles, for instance, you understand that their face has simply moved and was not instantly replaced.
This has an unusual side effect when we watch movies. Our brain automatically smooths over small changes between takes and scenes, so long as the image appears largely similar, we won't call foul. We've let our brains tune us out of seemingly huge goofs, like Julia Roberts eating a pancake in Pretty Woman (above). Way to let us down, lizard brain!
Tuesday, April 01, 2014
Learn about the AU's Cinema Studies program TODAY!
If you have been interested in pursuing degrees in literature or film, you may want to stop by the Cinema Studies information session today at 5pm! Swing by the Battelle-Tomkins Atrium at 5pm to learn about what this program offers and have a few cookies.
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The Australian future of General Motors' most upmarket North American brand was confirmed by GM's newly-appointed director of luxury brands in the Asia/Pacific region, Australian Peter Ruefli, at the motor show in Sydney last week. Ruefli also has responsibility for overseeing the Saab brand here.
Ruefli told Drive that "ultimately it will happen, but Australia is not the most important market".
He stressed that a launch here would have to wait until the new range of Cadillac models, which will be developed for right-hand drive markets, were released.
GM is planning a rash of new models during 2002/2003, with the next-generation Catera, which will be about the same size as a Commodore, and the Evoq roadster (pictured) due about then.
The Evoq will take on models such as Jaguar's XK8 as a sporty flagship from late 2002. To be built alongside the Corvette in Kentucky, the car, which will use aluminium to minimise weight, will drive the rear wheels through a 4.6-litre V8.
It will showcase Cadillac technology with a five-speed automatic transmission, active suspension, run-flat tyres and an anti-skid system to be standard equipment.
The company plans to fit its infra-red night vision system, while the car's instruments have been designed by Italian jewellery maker, Bvlgari. The car will come with a folding hardtop roof, expected to be similar to that on the Benz SLK.
Ruefli said that while details had yet to be finalised, Cadillacs are expected to be sold through Saab dealers, either in separate or clearly-branded Cadillac showrooms.
The move points to a more cosy relationship between Saab Automobile - which is owned by GM but has been run as a stand-alone company - and GM.
"Globally Saab and GM will develop many synergies, with many of the back-office functions such as computer systems and finance coming together."
It is even possible that Saab will share office space with Holden at Fishermens Bend.
Ruefli will be in charge of developing this sharing arrangement, with his experience of similar moves in Japan and Korea being useful.
The move to import Cadillac will not be welcomed by all at Holden, with some believing that it may threaten sales of the Statesman/Caprice models.


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N672 North Ave Ashippun - MLS: 1541784 - Houses
|Call Me Today at 414-339-1686 or Send Me an E-mail.
MLS Property Search
N672 North Ave, Ashippun, Wisconsin 53066-9315
Ashippun Single-Family
Click on a Thumbnail Image to Enlarge
List Price: $259,000
Property Type: Single-Family
MLS Number: 1541784
County: Dodge
Bedrooms: 3
Bathrooms: Full 2
Taxes: $4,052.58
Tax Year: 2016
Description: 3 BR/2BA Ranch sits on a .48 acre lot in a beautiful subdivision located in the Town of Ashippun. Open concept floor plan with vaulted ceilings and fireplace. Master bedroom features a master bath and 2 walk in closets. Convenient first floor laundry/utility room.Deep 3 car attached garage.Full basement awaits your rec room ideas. Desireable Oconomowoc school district.
Garage Type: Attached
GA Spaces: 3
Year Built: 2005
Zoning: Residential
School District: Oconomowoc Area
Flood Plain: No
Appliances Included: Disposal, Microwave, Oven/Range
Garage/Parking: Electric Door Opener
Heating/Cooling: Natural Gas
Heating/Cooling Type: Central Air, Forced Air
Misc. Interior: Gas Fireplace
Style: 1 Story
Listing Courtesy of: Milwaukee Executive Realty, LLC
Copyright 2017 MetroMLS - All Rights Reserved.
Information is supplied by seller and other third parties and has not been verified.
IDX information is provided exclusively for consumers' personal, non-commercial use and that it may not be used for any purpose other than to identify prospective properties consumers may be interested in purchasing.
Request a Showing / Information Request N672 North Ave, Ashippun, Wisconsin 53066-9315 – Milwaukee Executive Realty
Like this page? Please give it a Google +1 vote.
MLS Property Search | Find Out Your Buying Power | Request a Comparative Market Analysis | Milwaukee Condos
Chris Haines, Milwaukee Executive Realty, LLC


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Opposition picks up on BJP after LK Advani's Emergency remark
Delhi Chief Minister Arvind Kejriwal reacted to BJP veteran LK Advani's remarks on Emergency saying "Advani ji is correct in saying that emergency can't be ruled out. Is Delhi their first experiment?." Aam Aadmi Party leader Ashutosh on Thursday claimed that a recent interview given by veteran Bharatiya Janata Party leader L.K. Advani was indicative of his dissatisfaction with the current leadership of the party.
Opposition parties, including the Congress and AAP, on Thursday attacked the Narendra Modi government after veteran BJP leader LK Advani's remarks that forces that can crush democracy were stronger at present and a repeat of an Emergency-like situation cannot be ruled out. Advani made the remarks in an interview to the Indian Express daily.
Congress spokesperson Sanjay Jha, tweeted: "A totalitarian system is gradually overwhelming India; Advani Ji's warnings confirm our worst apprehensions."
Bihar Chief Minister Nitish Kumar, of the Janata Dal-United, said Advani was a veteran leader and there is need to give attention to his fear and worry. "The BJP leader is right to a large extent in his remarks that at the present point of time, the forces that can crush democracy, notwithstanding the constitutional and legal safeguards, are stronger," he told media persons in Patna.


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Jim Weisman leads BioEnterprise's efforts in serving and developing start-up healthcare software and service opportunities including the newly formed H.I.T. Accelerator. He brings almost 20 years of experience in general management, having worked in senior management at PepsiCo and Macy's as well as consulting to major financial institutions while with the First Manhattan Consulting Group. Weisman served on the management team of HealthSync, a start-up company developing marketplaces for defined-contribution based corporate sponsored health insurance. He has worked with Glengary Ventures, a fund focused on technology based companies, and provided consulting and executive management services to early-stage companies in the biotech and satellite communications industries.
Weisman received his B.S. in Economics from The Wharton School at the University of Pennsylvania and his Executive MBA from Case Weatherhead School of Management.


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Chairman & CEO
Managing Director
Senior Advisor
Senior Associate
Social Media Administrator
Stella received her Master's degree in Journalism from Marshall University. While attending graduate school, she interned in State Education Department, Communications Office, and Center for International Programs at Marshall University. Her experience also includes working as an English Instructor at a University in China.
In her spare time, Stella enjoys spending time with her friends and exploring the city.
Focus Area
- Public Relations
- Marketing
- Social Media
- Graphic & Editorial Design
- Branding
- Christian Entrepreneurship Program
Contact Info
645 Martinsville Road, Suite 202, Basking Ridge, NJ 07920
(908) 202-1351


text: As we stated in our weekly market update the AUSUSD was facing a major overhead resistance level at 0.8027 and to look for possible shorting opportunities. The Aussie dollar is now at a much lower level and anyone watching out for this trade could have made a 100+ pip profit. I maintain a bearish outlook on the AUDUSD until the resistance level is broken.


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I personally have many WordPress site on localhost to try stuff, can be plugins, and even copied my live sites to localhosts too.And if you want to explore WordPress before sign up in a webhosting company, I really recommend you to do this in your local computer first. Click this link, if you want to know I move a WP site to a new server in same domain.After you are comfortable enough with … [Read more...]
Tips To Move WordPress to New Server Using Same Domain
I always wanted to post a tutorial to move WordPress to new server same domain a long time ago, but for some reasons I haven't done it.So in this tutorial, we are going to move WordPress to new server using same domain. I am using wpdemoblog.com which is currently hosted in HostGator (for the demo purpose only) to BlueHost. Obviously, you can replace wpdemoblog.com with your domain … [Read more...]