USRE23360E

USRE23360E - Art of extracting oil from

Info

Publication number: USRE23360E
Authority: US
Publication date: 1951-04-24

Description

Reissued Apr. 24, 1951 ART OF EXTRACTING OIL FROM THE EARTH Ernst Berl, deceased, late of Pittsburgh, Pa., by Walter G. Berl, executor, Pittsburgh, Pa.

No Drawing. Original No. 2,267,548, dated December 2.3, 1941, Serial No. 61,804, January 31,

1941, Serial No. 78,890

Matter enclosed in heavy brackets I: Ii appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

8 Claims.

The present invention relates to the art of extracting oil from the earth. It has been well known that, heretofore, the extraction of oil from the earth has been very incomplete. Tests have demonstrated that considerable quantities of crude oil remained in the mother rock, such as limestone, sandstone, and the like. In some instances, it has been found that about 20% to about 70% of oil remained in the rocks in the earth. The residual oil left in the earth has been considered lost for all practical purposes. Various proposals have been made to avoid the losses which have been experienced in the past. Of these proposals, mention may be made of the attempts to pump or force water down wells surrounding the oil well which has been undergoing pumping. In some cases, salt or soda has been added to the water. In a few isolated cases, some results were obtained, but in most cases the results have been unfavorable. None of the attempts [as far as I am aware] as far as it is known has been wholly satisfactory, particularly when carried into practice on an industrial scale.

[I have] I t has been discovered that the aforesaid losses of oil remaining in the mother rock can be reduced and that considerable improvements in the yields can be effected from oil wells.

It is an object of the present invention to overcome the unfavorable conditions in the exploitation and recovery of oil from the earth and to utilize an aqueous solution containing substances possessing stronger wetting properties than water for removing oil from the mother rock.

A further object of the present invention is to pump aqueous solutions containing wetting agents possessing some solubility in oil into the earth adjacent to the well to release from the mother rock residual oil locked therein.

The invention likewise contemplates the provision of a process of utilizing capillary active substances to effect the removal of imprisoned oil and of utilizing aqueous solutions of the aforesaid substances containing the so-called polar groups.

Other advantages and objects of the invention will become apparent from the following description.

Broadly stated, the invention comprises releasing the oil and freeing it from the surrounding rocks to enable the oil to flow together in a mass or pool from which it may be removed to the surface of the earth. It has been found that capillarity phenomena cause the adhesion of oil to the surfaces of the walls of mother rock. By

Application for reissue February 28,

utilizing a watery solution containing an organic oil soluble and water soluble wetting agent and by pumping this solution into a region containing imprisoned oil, the walls of the rock and even the capillary spaces are moistened and Wetted by the wetting solutions and the bond between the oil and the mother rock is disrupted. It is believed that the wetting substance forms a film over the surface of the rock which enables the oil to form droplets and globules and to collect together in a mass. In this manner, the oil is freed from the mother rock, even the capillary spaces, and the oil can then be easily separated from the rock and removed from the interior of the earth.

In carrying the present invention into practice, [I have] it has been found that aqueous solutions containing wetting substances, especially capillary-active substances, are effective to release the imprisoned oil from the mother rock and to enable the thus-released oil to run together and to be collected and removed from its native environment. [As a result of extensive experiments, I have discovered that aqueous solutions containing so-called water-soluble tar acids and/or salts thereof have given satisfactory results. In addition] [substances] Substances [having similar constitution] containing socalled polar groups, such as OH, NHz, COOH, [SO3H, CSSH] and their combinations associated with straight chain hydrocarbons, aromatic ring compounds, etc., etc., are within the purview of the present invention. Thus, satisfactory results have been given by free fatty acids, such as oleic acid, palmitic acid, stearic acid, etc. which contain long carbon chains. [and/or their salts, such as oleates, palmitates, stearates, etc. which are known as soaps] Other examples of oil-- liberating agents are phenols or aromatic amino compounds, etc., such as aniline and its homologues, amino phenols, [phenol-sulfonic acids, amido sulfonic acids,] alcohols with long carbon chains, [alcohol sulfonates, xanthogenates] and/or combinations thereof. Aqueous solutions of suitable organic dyestuffs may be advantageously used as oil-liberating agents. For instance, basic dyestuffs, such as crystal violet and methylene blue, or acid dyestuffs (in weak acid solutions, if necessary), such as cloth red and alizarin yellow. [As further examples of oil-liberating agents, mention may be made of substances used in flotation. A fairly complete list of these flotation agents may be found in Taggarts Handbook of Ore Dressing (1927 edition, pages 830 to 839).]

In contrast to the foregoing, if water is used in accordance; with. the .priorart teachings in place of the aqueous solutions mentioned herein; been observed that an emulsion of the oil with water formed and that an incomplete removal of the oil occurs.

For the purpose of giving those skilled in the. art a better understanding of. the inventiomthe following illustrative examples are given.

[Example No. 1]

[A diluted solution, say about -0.114%.- oftan. alkaline salt, such, for instancey a sodium -salt of the so-called tar acids may be used as the oil-liberating agent for removal of crude. oil ad.- herin to hydrophile rocks, such as sandstone, limestone; dolomite, etc. The so-ca-lled watersoluble tar acids may be made, for: instance; according to U. S. Patent No. 1,812,316 or made byadding to 'waterrsoluble taracid of theacid wash inpetroleum. refining, the alkaline wash liquids: from the purification of crude oil. tracitions. For the. same purpose, water solutions of free tar..aci.ds or/and their acid salts, may also be. .used, especially infithe. case'of acid. rock like sandstone. In this manner, a substantially com.- pleteremovaLofthe oil, even in .the fine capil'-. laries may be. effected].

Efcample: No. 1 h

.10 [In contrast to. the foregoing, ifj'water is used in accordancewithprior art teachings in place, of theaqueous solutionsmentioned herein, it has been observed'that an emulsion of "the oil? with wateriormedand that anincompleteremoval of the oil'occursJ'f Inapplying my solution. ofoileliberating agents... it is, preferred. to pump. anaqueous solution containing the same'intothe earthsurrounding the oilwell through one or. more pipes. For instance, 40 it is preferred to usefour pipes surrounding the oil well, pr.eferably in the fiirmof a quadrangle.

Example No. 2.

Example-"No; 4

Aqueous solution of alkaline salts, of [ethyl or amyl xanthogenates or. alkaline saltsofv higher alcohol sulionates or of. benzol sulfonic acids or their homologues orlamino phenols [or aromatic amino sulfoniCacidsJQor/and the corresponding,

free. compounds. may beusedfor. thepurpose of.

liberating and removing oil., One may also use for the same purpose aqueous solutions of, amino phenols and amino phenolates, amido carbonic. acidsor/and their saltsjandmixtures of the substances mentioned in-this example orinthe fore-.-- goingexamples. Excellent result haveibeenob tained: by their use.

Example N0. 5

A diluted aqueous solution ofmethylviolet or methylene blue has been found to give satisfact'oryresults: for the liberation. and :removal of oil.

Example No- 6 the:.- following; groups; mam: beeincludediz.

=NH, =S, -SH, CSN-,: and CSNH. [For best results,v sodium salts. of. water. soluble. acid tars and alcohol sulfonates arepreferrecL]- Certain.

advantages may be. obtained in. using suchsubstances which. will. give soluble calcium salts .becausev thegreatest part off'mother rock which contain oil are. formedof limestone or dolomite.

When aqueous. solution of 'a substance. which. produces aninsoluble calciumsaltiare used, capil-- Iariesand fi'nefissures tendftobecome clogged and certain diflicultiestowardthe liberation and. free fiow of voiliare.encountered.

Wli'at'is claimed. is:

1. The processotextracting oil'Ifiomthe earth in regions adjacent tomoth'er rocks, .which comprises introducing. intosuch. regions. [aI'an oil freeing water solutionhaving, no substantial. destructive effect upon saidTmotherv rocks,,said solutz'tm haviiiga wetting eflfectcn saidbiZ-b'caring. mother rocks, andfcompri's'ing, an organic oil soluble andwater soluble substance containing a polar groupv and free from [sulfonic] "sulfur-containing' acid groups in the molecule.

2; The process of extracting oil'from'the earth in regionsadjacent to mother rocks which comprises introducing into said regions .an oil-freeing wettingagent'comprising, a water solution of an oil solub'let and water solub'le aromatic compound 2 free from" sulfur-containing acid'groups in the molecule; saidco'mpoun'dbeing a member of the group'consisting'of aniline; amino phenols, amino phenolates; and'phenols: [hand amino carbonic. acids} [3; The process'of' extracting. oil from the earth in regions adjacentto'motherrocksLwhich comprises intro'ducingdnto'sald regions an oil-freeingagent comprisinga water solution of an arcmatic dyestufi" of "the group consisting. of basic and acid ofjbenzener naphthalene, anthracene andthioanthracene compounds] [4; The'processof extracting oil from the earth. inregions adjacent to mother rocks which comprises introducing. into. said regions,. an oil-freeing agentcomprisinga water solution of a salt of a thiocarboxylic acid' having not more than six carbon atoms]- 51 Theprocess offemtracting oil. from the earthv in regions adjacent to mother rocks whichcomprises .introducinainto. said regions. an oilfreeing wetting, agent; comprising a. water solution at aniline.

6. The. process .ojextracting-oil .jrom the earth in.regions.ad7'acent.tomother rocks which comprises. introducing, into said regions .an. oil-freeing. wetting ayent comprising a.water solution of anoil-soluble and'tvater-soluble phenolic compound free from sulfur-containing acid groups in the molecule.

7. The process of extracting oil from the earth in regions adjacent to mother rocks which comprises introducing into said regions an oil-freeing wetting agent comprising a water solution of an oil-soluble and water-soluble amino phenol compound free from sulfur-containing acid groups in the molecule.

8. The process of extracting oil from the earth in regions adjacent to mother rocks which comprises introducing into said regions an oil-freeing wetting agent comprising a water solution of an oil-soluble and water-soluble amino phenolate free from sulfur-containing acid groups in the molecule.

9. The process of claim 1, wherein said substance is an aromatic dyestufi.

10. The process of extracting oil from the earth in regions adjacent to mother rocks which comprises introducing into said regions an oil-freeing wetting agent comprising a water solution of methylene blue.

WALTER G. BERL, Executor of the Last Will and Testament of Ernst Berl, Deceased.

REFERENCES CITED The following references are of record in the file of this patent or the original patent:

UNITED STATES PATENTS Number Name Date 1,734,990 Ackerman Nov. 12, 1929 1,822,271 Goggeshall Sept. 8, 1931 1,823,439 De Groote Sept. 15, 1931 1,823,440 De Groote Sept. 15, 1931 1,829,705 Walker Oct. 27, 1931 1,861,176 De Groote May 31, 1932 1,877,504 Grebe et a1 Sept. 13, 1932 1,894,759 De Groote Jan. 17, 1933 1,911,446 Grebe et al May 30, 1933 2,024,119 Viette et a1 Dec. 10, 1935 2,024,718 Chamberlain Dec. 17, 1935 2,032,825 Ambrose Mar. 3, 1936 FOREIGN PATENTS Number Country Date 163,519 Great Britain May 26, 1921 OTHER REFERENCES The EiI-ect of Flooding Oil Sands with Alkaline Solutions, by R. C. Beckstrom and F. M. Van Tuyl, published in American Association of Petroleum Geologists Bulletin, vol. II, January-June, 1927, pages 223-235.

The Separation of Oil Sands by Physical Methods, by Werner Grunder, Chemical Abstracts, vol. 24, pages 5988 and 5989, October-December 1930.