US2300554A - Process for breaking petroleum emulsions - Google Patents

Description

Patented Nov. 3, 1942 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Dei., a corporation of Delaware No Drawing. Application May 12, 1941, Serial No. 393,130

4 Claims. (Cl. 252-334) 'in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

"Another object of our invention is to provide aneconomical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsiflcation and subsequent demulsification under the conditions just mentioned is of significant value in removing impuritiies, particularly inorganic salts from pipe line l.

The process, which constitutes our present invention, consists in subjecting a petroleum emulsion of the water-in-oil type to the action of a' demulsifier or demulsifying agent, thereby causing the emulsion to break and separate into its component parts of oil and water or brine, when the emulsion is permitted to remain in a quiescent state after treatment, or is subjected to other equivalent separatory procedure. The demulsifying agent employed in our process comprises a chemical compound consisting of the.

salt of a basic amine. The amine salts intended to be used as the demulsifier of our process are of the kind exemplified by salts derived from diacetone amine, triacetone amine, etc. They are derivatives of the water-soluble type of petroleum sulfonic acid, commonly known as green acids. Petroleum sulfonic acids are produced from a wide variety of petroleum distillates or petroleum fractions, and in some instances they.

are produced from the crude petroleum itself. when produced from crude petroleum itself it is customary to use crude oil of the naphthenic type, crude oil of the paraflin type, crude oil of the asphaltic type and mixtures of said three diil'erent types of crude oil.

The art of refining crude petroleum or various fractions, using sulfuric acid of various strengths, as well as monohydrate and fuming acid, is a well known procedure. In such conventional refining procedure, petroleum sulfonic acids have mahogany acids also show limited ydrophilic been produced as by-products. For instance. in

removing the olefinic components, it has been common practice to use sulfuric acid so as to polymerize the olefines or convert them into sulfonic acids which are subsequently removed. Likewise, in the production of white oil, or highly refined lubricating oils, it has been customary to treat with fuming sulfuric acid, so as to eliminate certain undesirable components.

In recent years, certain mineral oil fractions have been treated with sulfuric acid with the primary object of producing petroleum sulfonic acids, and in such procedure the petroleum sulfonic acids represented the primary products of reaction rather than concomitant by-products.

Petroleum sulfonic acid, regardless of whether derived as the principal product of reaction or as a by-product, can be divided into two general products, to wit, green acid or acids and mahogany acid or acids. The green acids are characterized by being water-soluble or dispersible. In other words, they form either true solutions or sols. For purpose of convenience, they will be herein referred to as water-soluble, without any effort to indicate whether the solution is molecular or colloidal in nature. The green acids, as indicated by their name, frequently give an aqueous solution having a dark green or greyappearance. They generally appear as a component of the acid draw-oft, and do not remain behind dissolved in the oil fraction which has been subjected to sulfuric acid treatment. The green acids are not soluble in oil, even when substantially anhydrous, and certainly are not soluble in oil when they contain as much as I5% of water. Similarly, their salts obtained by neutralizing the green acids with a strong solution of caustic soda, caustic potash, or ammonia, are not oil-soluble. For convenience of classification. the ammonium salt will be considered as an alkali salt.

In contradistinction to the hydrophile green acids, there occurs as in the manufacture of medicinal white oil, the oil-soluble type or the mahogany acids. These mahogany acids are characterized by being soluble in oil, especially when anhydrous, and being soluble in oil, even if they contain some dissolved water. Some of the properties to the extent that either some water can be dissolved in the acids, or they, in turn, may dissolve to some extent in water. In some instances their salts. such as the sodium, ammonium, or potassium salt, will dissolve in water to give a colloidal sol. However, regardless of the presence of any hydrophilic properties whatketone, methyl normal amyl ketone, etc. Thus, referring to the previous formula'for triacetone amine, it is obvious that instead of an amine having nine carbon atoms, one may obtain comparable ketone amines in which amyl groups, for example, appear at least twice, as a. substituent for a hydrogen atom of a methyl group, with the re- The utility of the mahogany acids in various arts has been enhanced by increasing their wa-- ter-solubility; for instance, converting the mahogany acids into hydroxy alkylamine salts. 0n the other hand, as far as we are aware, no valuable product of commerce has resulted from decreasing the water solubility of the mahogany acids by the addition of some oil-soluble basic amine, such as, for example, triamylamine. The triamylaminesalts of mahogany acids, for example, are completely devoid of any solubility in water which the alkalisalts may have exhibited and show, as would be expected, an increased solubility in hydrophobe solvents.

Green acids are hydrophile in character, as previously stated. Their hydrophile character has been increased by neutralization with materials such as triethanolamine and the like. Such green acid salts, having enhanced water solubility, as compared with the ordinary alkali salts, have found application in certain arts.

We have found that if green acids, i. e., the

' oil-insoluble type, are neutralized with a ketone amine of the kind hereinafter described, the resulting product has pronounced value as a demulsifler for oil field emulsions of the water-inoil type, either when used alone, or when used in coniunuction with other compatibleand well known demulsifying agents. The ketone amines, particularly acetone amines, most suitable for neutralizing the green acids to give compounds of the kind herein contemplated, are best illustrated by 'diacetone amine and triacetone amine. The structural formula for diacetone amine is as follows:

(cubic-ornament) Similarly, the formula for triacetone amine is as follows:

NH 0 t (CH3): 'CH:

These compounds are obtained by the action of ammonia on mesityl oxide and phorone. The structural formula for mesityl oxide is asfollows:

CHa

- cm I The structural formula for phorone is as follows:

Insofar that the reactions leading to the formation of mesityl oxide and phorone are dependent primarily on the presence of an alphahydrogen atom, it becomes obvious that either by direct or indirect methods one can obtain alkylzted or substituted ketone amines which may be considered as derivatives of other available keton-ra, such as, for example, methyl isobutyl sult that such amines may contain as many as seventeen carbon atoms. Similarly, other ketone amines illustrate a variation in carbon atom content from nine to seventeen carbon atoms.

The manufacture of the demulsifier employed in our process contemplates nothing more nor less than neutralizing the selected petroleum sulfonic acid with a suitable amineuntil neutral to litmus. indicator, or to some other suitable indicator. For purposes of convenience we prefer that the selected petroleum sulfonic acid contain'not over 15% of water. It is, of course, understood that the conventional procedure employing double decomposition instead of direct neutralization can be employed in the manufacture of our new material or composition of matter.

'We are aware that at least in a number of instances, comparable amines are obtainable by the use of an amine other than a tertiary amine to replace ammonia as a reactant iii-combination with mesityl oxide, phorone, etc. In such compounds the amlno nitrogen atom or atoms of the ketone amines above described, are replaced by suitable hydrocarbon radicals, such as alkyl radicals, aralkyl radicals, alicyclic radicals, etc.. as for example, when amylamine; cyclohexylamine, benzylamine, etc. replace ammonia as a reactant.

In order to designate the amines of the kind herein contemplated as reactants, they will be referred to as the class consisting of diacetone amine, triacetone amine, carbonatom linked alkylated diacetone amines containing not over seventeen carbon atoms, and carbon atom linked alkylated triacetone amines containing not over seventeen carbon atoms.v Referencetothefactthat the alkylation is carbon atom linked is intended to eliminate from present consideration alkylated derivatives of 'diacetone amine, triacetone amine, and the like, in which the alkyl group or groups substituted in the compound or compounds replace an amino hydrogen atom, and thus are nitrogen linked.

It may bewell to point out that hydrophile non-hydrophobe petroleum sulfonic acid or acids of the green acid type vary somewhat; for instance, the molecular weightmay vary within the range of 350-500, or thereabouts. Natural- 13, these petroleum sulfonic acids may carry some polymerized olefines, free hydrocarbons, or the like, or may even carry a bit of naphthenic acids which represent carboxylated non-sulfonated petroleum acids. As previously stated, these materials are well-known commercial products and areavailable in the open market, either in the form of the acid itself, or in the form of a salt.

The amines 'above described may properly be referred to as-basic, inasmuch as the basicity is in the neighborhood of that of ammonia. This is obvious, insofar that no amino hydrogen atom has been replaced by an aryl group, an acyl moisture content is not over 15%.

enteen carbon atoms. Whether-or-not a-waterinsoluble salt is produced, depends, in part, on the molecular weight, and as has been previously indicated, this property may show some variation.

'Althoughjit .is believed, in view or what has been said previously, that no furtherdscription is required in regard to themanufacturep! the ,Greenacids are obtained-from lubricating, cii distillate having an s. U. viscosit Hat 150 F. of about 400 seconds. The procedure employed in obtaining such green, acids is that described in U. S. Patent No. 2,188,770, dated January 30,1940, to Robertson. The material so obtained 'contains'iconsiderable moisture and is preferably dehydrated to' the point where the Thesulfonic acid isthen neutralizedtoI-litmus indicator with diacetone amine.

Example 2 The same procedure is followed as in Example 1, but instead, the green acids are obtained from Gulf Coast transformer oil extract in the manner described in U. S. Patent No. 2,203,443, dated June 4, 1940, to Ross and Mitchell.

Example 3 The same procedure is followed asin Example 2, except that California 65 Baybolt viscosity Edeleanu extract is employed instead of Gulf Coast transformer Edeleanu extract employed in Example 2.

Example 4 The same procedure is followed as in Example 1, except that the product is made from aGuli' Coast naphthene type crude, preferably of the kind which has little or no low boiling fraction, 1. e., the kind which, on a straight run distillation, gives little or no gasoline.

Example 5 The same procedure is followed as in Examples 1-4, inclusive, except that triacetone amine is employed instead of diacetone amine.

Example 6 alcohol, denaturedalcohol, propyl alcohol, butyl alcohol, hexyl alcohol, ocetyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petro leum, etc., may be employed as diluents. Similarly. the material or materials employed as the demulsifying agent oi our process may be admixed wlth one or more of the solvents customarily used in connection with conventional materialsmay be used alone, or in admixture with other suitable well known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in anoil -"solubleform, or in a form exhibiting both oil and-water solubility. Sometimes they may be used in a form which exhibits relatively limited oil solubility. However, since such reagents are sometimesused in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water isnot significant, becausesaid reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials employed as the demulsifying agent of our We desire to point out that the superiority of the reagent or demulsifying agent contemplated in our process is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available-demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned: butwe have found that such a demulsifying agent has commercial value, as it will economically break or resolve oil field emulsions in. a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.

In practising our process, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various ways, or by any'of the various apparatus now generally used. to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone or in combinationwith other demulsifying procedure, such as the electrical dehydration process.

The demulsifi'er herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, i. e., bringing the demulsifler in contact with the fluids of the well at the bottom of the well, or at some point prior to their emergence. This particular type of application is decidedly feasible when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1..A process for resolving petroleum emulsions of the water-in-oil type, characterized bysubiecting the emulsion to the action of a demulsifier comprising a chemical compound, consisting of the salt of a basic amine; said amine salt bein obtained. from a water-soluble, non-hydrophobe petroleum sulfonic acid of the green acid type, and a ketone amine selected from the class consisting of diacetone amine, triacetone amine, carbon atom linked alkylated diacetone amines containing not over 17 carbon atoms, and carbon atom linked alkylated triacetone amines containing not over 1'7 carbon atoms.

2. A process for resolving petroleum emulsions of the water-in-oiltype, characterized by subjectinr the emulsion to the action of a demulsifler comprising-a chemical compound, consisting of demulsifying agents. Moreover, said material or the salt of a basic amine; said amine salt being obtained from a water-soluble, non-hydrophobe petroleum sulionic acid of the green acid type. and a ketone amine selected from. the class con sisting of diacetone amine, triacetone amine, carbon atom linked alkylateddiacetone amines containing not over 17 carbon atoms, and carbon atom linked aliq'lated triacetone amines containing not over 17 carbon atoms; said green acid being obtained from a naphthene type crude.

3. A process for resolving petroleum emulsions of the water-in-oil type, characterized by subject ing the emulsion to the action of a demulsifler comprising a chemical compound, consisting of the salt of a basic amine; saiol amine salt bein obtained from a water-soluble, non-hydrophobe petroleum sulfonic acid of the greeen acid type, and a ketone M 1 50, selected from the class consisting of diacetcne amine, triacetone amine, car= bon atom linked allzylated diacetone amines conthe salt of a basic amine; said amine salt bein taming not over liicarbon atoms, and carbon 2o obtained from a water-soluble, non-hydrophobe petroleum. sulfonic acid of the green acid type, and a ketone amine selected from the class consisting of diacetone amine, triacetone amine, carbon atom linked alkylated diaOetone amines containing not over 17 carbon atoms, and carbon atom linked allsylated triacetone amines containing not over 17 carbon atoms; said green acid being obtained from an asphaltic crude.

MJELWIN DE GROOTE. IBERD KEISER.