MXPA95001180A - Ammonium hydroxides as mercapt depurers - Google Patents

Abstract

A method for the depuration of mercaptans in a hydrocarbon fluid is disclosed. According to the method, an effective mercaptan cleansing amount of an aqueous cleansing composition is added to the fluid. The composition comprises a quaternary ammonium hydroxide of the formula R1R2R3R4NOH. R1 and R2 are independently alkyl groups of one to about eighteen carbon atoms, aryl groups of six to about eighteen carbon atoms or alkylaryl groups of seven to about eighteen carbon atoms. R3 is an alkyl group of two to about eighteen carbon atoms, an aryl group of two to about eighteen carbon atoms or an alkylaryl group of four to about eighteen carbon atoms. R2 and R3 may be linked to form a heterocyclic ring including N and optionally an oxygen atom. R4 is - (CH2CH2O) nH, wherein n is an integer from one to about eighteen, or -CHR5CHR6Y, wherein R5 and R6 are independently, hydrogen, alkyl groups from one to about eighteen carbon atoms, aryl groups of six to about eighteen carbon atoms or alkylaryl groups from seven to about eighteen carbon atoms. And it's a non-acid group. Also disclosed are compositions and related methods

Description

AMMONIUM HYDROXIDES AS MERCAPTANO DEPURATORS,? BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the mercaptan demisters in hydrocarbon fluids and more particularly to the use of quaternary ammonium hydroxides as mercaptan scavengers. 2. Description of the Prior Art Hydrocarbon fluids, such as crude oil, crude oil emulsions, field condensates Petroleum products, petroleum residues, and often, refined fuels still contain a variety of mercaptans, including mercaptans with a relatively low molecular weight. Due to the volatility of mercaptans with a relatively low weight, (for example, CH.-SH methyl mercaptan, CE CH.sub.2 ethyl mercaptan and CH-CH-SH-SH propyl mercaptan) tend to fire in some places vapors, where their malodorous odors cause problems in the storage areas and around them, and through of the pipelines and in the shipping systems used to transport the hydrocarbons. To solve these problems attempts have been made using various additives. For example, it has been found that choline or choline hydroxide solves the evolution of hydrogen sulphide and the purification of mercaptans. For example, see US patents. No. 4,594,147 granted to Roof et al., No. 4,867,865 granted to Roof and No. 5,183,560 granted to Roof and collaborators. However, choline and choline hydroxide are not well suited for many uses and media such as in petrdleo -crudo. Although choline and choline hydroxide can purify mercaptans in such media, they also form a volatile and malodorous by-product with the sulfur compounds that occur naturally in such media. Therefore, the use of choline choline hydroxide to control the odors associated with light weight mersaptans is nullified by media such as crude oil. So the cited patents given to Roof and Roof and co-workers fail to address this problem instead of describing the use of choline or choline hydroxide in the more refined fuel oils. European application No. 0 538 819 A3 granted to < - _ *% Roof and co-workers describe the use of the oil-soluble quaternary ammonium compounds of the formula: for purifying various sulfur compounds, including the - mercaptans, of certain oils, especially heavy residual fuels of high ebollucidn. These compounds, prepared under anhydrous conditions, are those which are described herein as "internal ions"; that is, the positive charge on the nitrogen and the negative charge on the oxygen cause all the electrically neutral compounds, 5 without the presence of opposite ions, such as the halides. The European application stresses the importance of the oil solubility of these compounds, none should be more oil soluble than the choline base, and they are dispersed by means of oil that is more fully treated to effectively reduce the concentration of, the undesirable sulfur compounds. However, the compositions of the European patent application suffer from certain disadvantages. For example, compositions that are produced with high yields, and at low costs, and that more effectively reduce "mercaptan concentrations, are still desired." Therefore, despite the reports of these "techniques, the industry still is looking for other compositions and methods for a more effective and efficient depuration of the mercaptans with low molecular weight SHORT DESCRIPTION OF THE INVENTION The present invention, therefore, is directed to a novel method for debugging mercaptans in a hydrocarbon fluid According to the method, an effective amount of the mercaptan scavenger of an aqueous purification compound comprising a quaternary ammonium hydroxide is added to the fluid.The quaternary ammonium hydroxide can be reconstituted. 4 + - 1 2 present by the formula RRRRN OH R and R independently are alkyl groups of one to eighteen carbon atoms, aryl groups of six to eighteen carbon atoms or alkylaryl groups of seven to eighteen carbon atoms. 3 R is an alkyl group of two to eighteen carbon atoms, an aryl group of two to eighteen carbon atoms or 2-alkylaryl groups of seven to eighteen carbon atoms. R and The R 3 can be joined to form a heterocyclic ring that includes N and optionally an oxygen atom R corresponds to the formula - (CH 2 CH 20) H, wherein n is an integer from one to about three or more, or the formula -CHR 5CHR6Y, wherein R and R independently are hydrogen, alkyl groups of one to about eighteen carbon atoms, aryl groups of six to about eighteen carbon atoms and alkylaryl groups of seven to about eighteen. Reply They are preferably hydrogen, alkyl groups of one to about eighteen carbon atoms, aryl groups of six to about eighteen carbon atoms or alkylaryl groups of seven to about eighteen carbon atoms. The present invention is also directed to a novel method for the preparation of a quaternary ammonium hydroxide. According to the method, a tertiary amine f \ is reacted with ethylene oxide or propylene oxide, in the presence of water. The tertiary amine corresponds to the formula R 1 R 2 R 3 N, wherein R 1, R 2 and R 3 are defined as in the preceding paragraph, and R 2 and R 3 can be joined to form a heterocyclic ring including N and optionally a hydrogen atom. oxygen. The method produces a quaternary ammonium hydroxide of the formula R 1 R 2 R 3 R 4 N + OH -, wherein R 1, R 2 and R 3 are as defined above, and wherein m is 1, 2 d 3. Among the various advantages of this invention it can be seen that the method is provided to more effectively and efficiently purify mercaptans than by conventional methods; such a method is provided for selectively purifying the light mercaptans against the heavier weight mercaptans; the method is provided so that it does not have the tendency to generate new compositions with bad smell; and it is also provided for making a purifying composition useful in such a method. DETAILED DESCRIPTION OF THE PREFERRED MODALITIES In accordance with the present invention, it has been found that certain quaternary ammonium hydroxyls are surprisingly more preferred mercaptan deputants that selectively depress mercaptans with low weight, of preference. to the mercaptans of higher weight. The effectiveness of the hydroxides is especially surprising in view of the findings that the hydroxides are significantly more effective than the compounds that differ only by the opposite ion (that is, provided it is not hydroxide), and that in the preferred cases, the hydroxides are still more effective scavengers of the mercaptan than the corresponding internal ions (ie, R ^ R'O in + -i -zO where R_NR'OH OH is the preferred hydroxide). The selectivity of the hydroxides reduces the waste that can be found unnecessarily in the scrubbers of the higher weight mercaptans, and thus allows the purification of the less desirable mercaptans with quantities of relatively small hydroxyl. And still, the aforementioned European patent application emphasizes the importance of the solubility of the oil of its compounds instead of its effectiveness, a superior efficiency of hydroxyl has been found in the depuration of mercaptans in hydrocarbons, although The hydroxyls are expected to be significantly less soluble in the oil than their sorptive internal ions. Furthermore, it has been found that introducing oxygen, such as spraying the air-treated fluid, dramatically increases the purification activity. The quaternary ammonium hydroxide can be represented by the formula R1R2R3R4N + OH ~. R1 and R2 independently are alkyl groups of one to about eighteen carbon atoms, aryl groups of six to about eighteen carbon atoms or alkylaryl groups of seven to about eighteen carbon atoms. 3 R is an alkyl group of two to eighteen carbon atoms, an aryl group of two to about sixteen carbon atoms or alkylaryl groups of seven to about four-fourteen carbon atoms. R corresponds to the formula - tO - (CH2CH20) nH, where n is an integer from one to approximately three or more of the formula - (CH2CHO) m (CH2CH20) nH, where m CH3 and n are integers of zero to about eighteen (independently selected, except that m + n is approximately 15 years old), or the formula -CHR 5CHR6Y, wherein R and R independently are hydrogen, alkyl groups from one to about two-six sarbones, groups ^^ aryl of six to about seventeen atoms of sarbonate or alkylaryl groups from seven to about seventeen carbon atoms, and Y is a non-acidic group corresponding to the formula -OH, -SR d -NR R, wherein R and R independently are hydrogen, alkyl groups from one to about eighteen. carbon atoms, aryl groups of one to about one-tenth sarbone atoms or aryl-alkyl groups of seven to about eighteen sarbono atoms. Preferably, R is - (CH2CH20) nH d -CHR ^ CHR Y, 1 & 5 6 where n, R, R and Y are defined as above. 1 2 3 At the choline base, each of R, R and R is 1 2 methyl. It has now been found that when one of R, R and 3 5 R is larger than methyl, it can be taken to the depuration still in crude oil without volatility, nor is a depuration a bad odor that is a subprod of the trimethylamine generated. are the. Use of the choline base. Therefore, R has been designated as the radical having at least two sarbono atoms. In the preferred forms, R and R are diesiosho alkyl groups or fewer sarbono atoms and more preferable, lower alkyl groups of six sarbonuses or less, especially of three sarbonuses or less, and opsionally methyl group. More desirably, 3 R is a fatty group, such as from osho to about seventeenth sarbone atoms, eepesially from ten to about fourteen carbon atoms, such as group 3 coco-. However, alternatively, R may be a bensyl group or substituted aryl groups, for example, alkylbenzyl groups, such as methylbenzyl, or an alkyl group of at least two sarbon atoms may be even less desirable. In other less preferred embodiments, 2 3 R and R can be joined to form a heterocyclic ring that includes N and opsionally an oxygen atom. In the latter case, a morpholine can be formed. It has been found that the ring produstoe are less effetive than the other produtos and are more difficult to prepare by the oxyalkylation of a tertiary amine. 4 R, as noted, corresponds to the formula of - . 5 - (CH2CH20) H, where n is an integer of one to about diesiosho of the formula - (CH C C H H0) m (CH ~. CH ¿))) n H, in don CH3 of m and n are integers of zero to approximately eighteen (independently selected except that m + n is almost To Q approximately diesiosho), or the formula -CHR CHR Y, in gift N of R 5 and R 6 and Y are as defined above. It has been ensoned that the inslusion of such R groups in the quaternary compound significantly increases the performance of the compound as a mersaptan scavenger on the desorption of the quaternary tetra-alkyl compounds. In the preferred condition, R 4 corresponds to the formula -CHR 5 CHR 6 Y, wherein R 5 and R 6 are hydrogen, or Lower alkyls of at least six atoms of sarbon, especially hydrogen, and Y is -OH. However, when the quaternary compound is prepared by reacting a tertiary amine with an alkylene oxide to form a quaternary compound, wherein R is -CH2CH20H, the quaternary compounds are also formed wherein R. is the ether or the group of polyether - (CH2CH2 0) H. Thus, a composition which contains the quaternary compounds 4 where R is -CH 2 CH 2 OH, often also contains quaternary compounds wherein R 1 is an ether or a group of the polyether - (CH 2 CH 20) H. However, - generally, in the event that the quaternary compound is prepared by the oxyalkylation of a cross-linked amine, the amine is reacted with the alkylene oxide in an approximate molar ratio of 1: 1, so that while part of the amine remains unreacted, thus leaving part of the alkylene oxide available for the formation of the polyether, the chain formed by the ether and polyether is typically sorta; n is primarily one, two or three. The suaternary ammonium hydrides of this invention can be prepared by a variety of known techniques that will be readily apparent to those with experience in teasin. For example, the suaternary ammonium hydroxides can be prepared rapidly by the ion exchange techniques of the available quaternary ammonium halides, the quaternary ammonium halides can be passed through an ion exchange column to be extruded to the cell. an ion exchange resin, exchanging the halide ion for the OH ions (or Y ions, where Y is as defined above and not sorresponding to OH) from the solumn. So that according to this method 1 2 3 4 + - to produce the hydroxide, the halide R R R R N Z, where R, R, R, and R are as defined in the definition more broad z above and Z is a halide, put in sontaste are an ion intersession resin that has hydride ions to form the moiety R 1 R 2 R 3 R 4 N + OH. Alternatively, the quaternary ammonium hydroxides of this invention can be prepared by the oxyalkylazine of the tertiary amines in the presence of water. Tissues have been described for the oxyalkylation of the terrestrial amines, for example, in the European patent solidation mentioned above, but the European requirement * It is necessary that the reassumption be carried out under anhydrous sondisions. The anhydrous sondisions were necessary for the formation of the internal ions of the euro pea soliasity. However, the benefits of hydroxides have now been uncovered. Such compounds are formed by adding the oxyalkylase to the water presensia. And surprisingly it has been discovered that the reassumption carried out in the water presensia produces yields of the prodrug of ammonium hydroxide which are significantly higher than the yields of the internal ion. of quaternary ammonium causing the reaction to take place under anhydrous conditions. In addition, taking advantage of the reassessment in the water presensia allows the use of less oxide per amine than is necessary for the non-assumption reapplication of the European application of Roof et al-25 (ie, a molar ratio of 1: 1, in opposition to the formation of bubbles of the oxide through w '~ of the amine so-called by Roof and co-workers). Moreover, the nonassuous reassessment proceeds faster than the nonaqueous reassertion proceeds and thus the quaternary product can be formed in much less time. Where Y, R is a non-acidic group other than OH, a similar reassid can be carried out, for example, with an alkylene sulfide or alkylene imine instead of alkylene oxide. Thus, the inventor of the present invention has discovered that when the reaction of oxyalkylacid is carried out in the presence of water, the resulting quaternary ammonium hydroxides are not only more effective scavengers of mercaptan in certain preferred cases. that which are the internal ions that have been produced having a reassumption that takes to taste with absence of water, but also produce higher yields than those that the internal ions have had. 4 Therefore, more in detail, wherein R 20 of the quaternary ammonium hydroxide R 1 R 2 R 3 R 4 N + OH- is hydroxyethyl or hydroxypropyl, or in case R 4 is an ether or a polyether group as described above, the Hydroxide can be prepared by reacting a tertiary amine, such as in the form of R 1 R 2 R 3 N with alkylene oxide, in the presence of water. The alkylene oxide may be a propylene oxide, but ethylene oxide is preferred. In the less preferred cases where the quaternary ammonium compound is not a hydroxide, but that R corresponds to the formula of -CHR CHR Y, where R and R are defined as above and Y is a non-acid group corresponding with 7 7 8 the formula -SR or -NR R, an alkylene sulfide or alkylene imine, respectively, can be replaced by the alkylene oxide and the same procedures can be followed. ? R 1, R 2 and R 3 of the tertiary amine are as defined above. However, preferably R 1 is a methyl 2 and more preferably R is also a methyl. Although R 2 and R 3 can be joined to form a heterocyclic ring including N and optionally an oxygen atom, such as to form a morpholine derivative, said compositions have been found to be more difficult to undergo. oxyalkylation without the compensation of producing more powerful depurators, so that R 2 and R do not bind in the majority of the desirable configurations. R3 of preferensia is a fatty group of approximately six to twenty atoms of sarbon. The re-sorting is carried out in an aqueous solvent. For example, the solvent may comprise approximately 50% to 95% by weight of an alcohol, such as de-25 isopropyl or preferably methanol and approximately between 5% to 50% by weight of water. A solvent solution t ^ - typical, therefore can be learned, based on the weight, two parts of the solvent in relasidn are a part of water. The active ingredients may constitute approximately 70% by weight of the rearrangement mixture (the remainder 30% is the solvent). In a preferred preparation method, the tersary amine is stirred in the solvent and the system is pressurized with alkylene oxide added in a molar propulsion of about 1: 1 in relasid with the α-0 amine. The molar ratio is generally in the range of approximately 1: 1 to 1.5: 1 of alkylene oxide in relation to the amine. The reaction is typically carried out at an approximate temperature of 70 ° C, preferensia - approximately between 40 ° C and 50 ° C, is a sonorous agitation and its termination is indicated by decreasing the pressure to the atmosphere. The resulting mixture, in addition to the unreacted solvent, is a combination of the quaternary compounds, wherein R is the formulas -CH2CH2OH and - (CH2CH20) H, wherein n is as defined above, an amine without reacting , and the glisols formed from the reassidn of alkylene oxide and water. Other ammonium hydroxides suater 4 nano, where R corresponds to the formula - (CHIC | HO) m (CH "CH? .-, 0) nH CH3 or the formula CHR CHR Y, where m, n, R, R and Y are as defined above, and can be prepared by standard techniques, such as by injection or by simple emptying ^^ and can be dispersed throughout the fluid by agitation or other agitation. The additive is incorporated at a level sufficient to purify the mercaptans to a desired degree and will depend on the content of the mercaptans in the medium and the corresponding stoichiometry. However, typical additive levels may be in the order of about 100 to 10,000, preferably 500 to 5,000 ppm based on the weight of the medium to be treated. The medium can be any hydrocarbon fluid, preferably a liquid. For example, excellent results have been obtained for the treatment of crude oil, petroleum residues, and fuels such as kerosene. It will be recognized that while the fluids are referred to as hydrocarbon fluids, in some cases (eg, crude oil emulsions), the hydrocarbons may comprise less than half the fluid by weight. The product is particularly useful for the treatment of crude oil in which no additional malodorous compound is added as has been the use of soline for the treatment of petroleum. However, results superior to those achieved with the use of other sompositions, such as those of the internal ion of the aforementioned European patent application, have been shown in connection with a variety of hydrosarbon media.

In addition, it has been found that significantly greater degrees of purification result when the medium is first oxygenated, such as by aeration before the addition of the mercaptan scavenger. Although, the present inventor does not want to be subject to a particular theory, it is considered that the mechanism by which this debugging occurs is according to the following session of the reassessment, where R 1R2R3R4N + OH is the debugger and RSH is mersaptan: 1 2 3 4 + - - 1 2 3 4 + RRRRN PH + RSH ^ RS + H20 + RR ° R RSSR (disulfide) have seen improved results increasing, when the amount of oxygen is added by aeration or by forming air bubbles in the medium increasing up to 100% of the stoichiometry of this reaction scheme. Furthermore, with an amount of air greater than 100%, an improved debugging has not been found that is much greater than that associated with stoichiometric addition ff- at 100%. It can carry out an effective debugging ? At room temperature of the hydrocarbon fluid (eg, approximately 20 ° C for stored crude oil, residues or fuels), but the performance of the scrubber has been found to be improved at higher temperatures - approximately 50 ° C to 75 ° C. The debugger tends to decompose even at higher temperatures, approximately - ^ such as 100 ° C. However, decomposition at such temperatures occurs relatively slowly, while the time for the reaction between the scavenger and the mercaptans is relatively short, usually only requiring hours to substantially reduce the level of mersaptane. Thus, scrubbers at such high temperatures can also be used with good results. It has been found that the quaternary ammonium scavengers of this invention selectively react with the low molecular weight? -O-mercaptans without imparting to the system their particular odor. For example, it has been found more particularly that the scrubbers clean the methyl mercaptan in preference to the ethyl mercaptan, and the methyl mercaptan in preference to the n-propyl mercaptan, and the n-propyl mercaptan preferably to the n-butyl mersaptan, and so on. Also, it has been observed that the debuggers reasonably relegate are the linear mercaptans on the branched mercaptan JT. So, the scrubbers allow the removal of most of the volatile mersaptans, the are the largest contributors to odor problems, waste from the scrubber is limited in the solateral recesses with no less volatile mersaptans. The following examples discuss the preferred modes of research. Other modalities will be evident Within the scope of the claims of the present - to a person are experience in the interpretation by the sonatera, 5"application of the specification or practice of the invention as described herein. Specifics, together with the examples, are considered only 5 in an exemplary manner, the scope and spirit of the invention being indicated by the claims following the examples, In the examples, all the percentages are given based on the weight EXAMPLE 1 A tertiary amine was placed (ADMA WC Amine, Ethyl Corp., 77 g, 0.35 mol, methanol (92.4 g) and water (12.6 g, 0.70 mol) in a glass autoclave. adapted with cooling coils, a stirrer, a thermal well and an ethylene oxide supply tube.The reactor was sealed and the ethylene oxide (15.4 g, 0.35 mole) was added in one portion, with nitrogen to aid in the addition. tile, the (20 psi) and one container temperature of 20 ° C. After one hour, a maximum temperature of 26 ° C was reached. The pressure is measured at 2 1.12 kg / sm (16 psi) after 90 minutes. The produsto was analyzed by titulasión and contained 1.22 esg and ammonium ammonium hydroxide and 0.57 meq / g of the terrestrial amine. The relative yields are shown in Example 8. * EXAMPLE 2 The same expediency as followed in Example 1, except that the water was omitted, an internal salt compound was prepared as disclosed in the application. mentioned above granted to Roof and collaborators. Thus, 80.1 g (0.364 mole) of the amine was reacted in 96.1 g of methanol with 16.0 g (0.364 mole) of ethylene oxide. After 90 minutes, the product had 1.23 meq / g O of quaternary ammonium hydroxide and 0.72 meq / g of tertiary amine. The relative yields are shown in Example 8. EXAMPLE 3. Several superoxide ammonium hydroxides were prepared from the alkoxylated alkylamines and added to the 50 ° C crude oil samples which were 169.82 ppm of 1-propanethiol ( propyl mercaptan) and the consentrations of 1-propanothiol were measured. The results are reported in the following table, where each hydroxide of Alternating ammonium is identified by the tertiary amine and the alkylene oxide ("ALCOXIDE", either an ethylene oxide, referred to as EtO, or a propylene oxide referred to as PrO), the consentrasiones of the suaternary ammonium hydroxide ("CONTENT QUATERNARY ") and the unreacted amine (CON HAVE NON-REACTIONED AMINE ") in the samples is propounded in equivalents of one thousandth part per gram, and the concentration of 1-propanothiol in the sample after treatment as measured in accordance with ASTM D-3227 is given in ppm Table "% REDUCTION" refers to the percentage of reduction of 1-propanothiol that was achieved: TERINARY AMINE ALCOXAGE CONTENÍ CONTENT CONTENT% DE RE DO DO AMA DE 1-PROPA DUCCION TERNARIO SIN REAC- NOTICIÓN CIONAR Without additional compound 169.82 Methyl-morpholine EtO 2.04 0.96 127.71 25 Dimethylcoso EtO 1.23 0.61 119.86 29 2-hydroxyethylmorphine lino EtO 0, .54 2.34 126.49 26 Dime ilbencilo EtO 0, .812 1.624 88.26 48 Dimethylso PrO 0, .847 1,493 160.74 5 Meto-morpholine EtO 1, .334 1.66 75.38 56 Dimethyl ethanol EtO 3, .85 0.40 112.55 34 Dimethylcoco EtO 1, .26 1.17 110.19 35 EXAMPLE 4 20 The selactability of mercaptan was measured. 70% N- (2-hydroxyethyl) -N, N-dimethyl-N-coso ammonium hydroxide in a solution of isopropanol and raw petroleum water at 50 ° C by GC analysis (using a specific sulfur detector) ) approximately for two hours after • 25 of the addition of 1000 ppm of the hydroxide. A second step of the debugger was prepared and tested in the same way. The following table shows the amount of mersaptan (in ppm) .ps.of the crude oil for each of the various mercaptans (identified by the type of thiol) before and after the treatment and the reduction of the corresponding percentage of this mercaptan. 1 ° DEPURADOR 2 ° DEPURADOR MERCAPTANO CONTENT CONTENT CONTENT INITIAL AFTER %% EDE RE AFTER% RE READ OF TRADUCTION OF TRAILING TREATMENT 10 Methanethiol 91 21 77 52 43 Ethanethiol 85 32 62 58 32 2-Propanethiol 50 30 • 40 41 18 2-Methyl-2-Propa no thiol 7.3 5.4 26 6.7 8 1-Propanethiol 21 10 52 17 19 2-Butanethiol 45 32 29 41 9 EXAMPLE 5 mf The effectiveness of N- (2-hydroxyethyl) -N, N-dimethyl-N-coso ammonium hydroxide 20 was compared for the reduction of 1-propanethiol in kerosene fuel at 50 ° C are the corresponding salts with several opposite ions and with the corresponding internal salt (it is desir, without an opposite ion). The 1-propyl mersaptan (1-propanothiol) probe was measured 1 hour after the treatment according to ASTM D-3227.

The following results were obtained, where the content in the achieved content of 1-propanothiol. These results show an improvement better than 20% in the purification with the ammonium hydroxide of N- (2-hydroxyethyl) -N, N-dimethyl-N-coc in the scrubber's sontra are the internal salt of N- (2-hydroxyethyl) -N, N-dimethyl-N-soso ammonium (35% reductive of 1-propanothiol against 29% reduction of 1-propanothiol). 10 TIOL% REDUCTION CONTENT J COMPOSITION AFTER THE TRATAM. CIO WITHOUT ADDITIONAL COMPOSITION 260.7 N- (2-Hydroxy-ethyl-N, N-dimethyl-N-coco 169.7 ammonium hydroxide 35 N- (2-hydroxy-ethyl) -N, N-dimethyl-N-soso ammonium acetate 229.6 12 N- (2-hydroxy-ethyl) -N, N-dimethyl-N-coco ammonium chloride 259.7 '0 ßP N- (2-hydroxyethyl) -20 N, N-dimethyl-N-soso ammonium citrate 230.6 12 N- (2-hydroxy-ethyl) -N, N-dimethyl-N-soso ammonium bisulfate 259.9 0 N- (2-hydroxyethyl) -N, N-dimethyl-N-soso ammonium salt (without an opposite ion) 184.3 29 EXAMPLE 6 The effect of the presence of air was investigated by adding 3000 ppm of an N- (2-hydroxyethyl) -N, N-dimethyl-N-coco ammonium hydroxide solution to two samples of 5 oil field condensates at 50 ° C, one of which was sprayed with air before the addition of the additive. The concentrations of the various mercaptans in the feed and after the treatment were measured after eight hours of storage and are given in the next table in ppm, as in the percentage of reductions in yield ("% DE"). REDUCTION"). CONTENT CONTENT% OF RE-CONTENT% OF RE OF FOOD-AFTER DUCTION AFTER THE DUCTION OF TRAFFIC. MERCAPTANO TREATMENT (WITHOUT AIR) (WITH AIR) lno c - Methanethiol 15 12 20 2 87 Ethanethiol 94 40 57 16 83 2-Propanethiol 12 200 72 40 56 53 2-Meti1-2-pro panothiol 61 47 23 49 20 0o 1-Propanethiol 48 25 48 13 73 2-Butanethiol 159 108 32 92 42 2-Methyl-l-propa notiol 30 18 40 13 57 1-Butanediol 73 49 33 46 37 37 2-Methyl-3-butane thiol 21 17 19 17 19 EXAMPLE 7 The ammonium hydroxide solutions of N- (2-hydroxy-1) -N, N-dimethyl-N-coconut were added to the crude oil samples in test operations at room temperature from 50 ° C to 75 ° C. ° C. The initial mercaptan sonsension (0 min) was measured as the concentration of mercaptan at the five minutes, sixty minutes and 120 minutes after the Mf addition of the solution. The following table presents the results that provide the concentration of the additive solution and the concentrations of mercaptan ("RSH to min.") In ppm. 15 Ambient Temperature 50 ° C 75 ° C Additive Concentration 1000 2000 1000 2000 10002000 RSH at 0 min 743 743 727 727 757 757 RSH at 5 min 701 640 661 645 714 549 t RSH at 60 min 581 521 573 541 533 505 RSH at 120 min 518 517 458 434 420 354 EXAMPLE 8 The ladimethylcocoamine is reacted as deethylene oxide in two reactions carried out under identical conditions, except that one re-sorting was carried out under anhydrous conditions, while the other was carried out under the same conditions. out in the presence of water. The resulting yield of the preparations under these preparations in the presence of water) was measured at various times during the reaction and is presented in the following table in terms of milligrams of KOH per gram. The internal salt prepared under anhydrous condi tions is identified as "ANH" and the hydroxide prepared in the presence of water is identified as "WATER". 10 Performance at 30 minutes Yield at 60 min Yield at 90 minutes ANH WATER WATER WATER ANH WATER 57.3 65.0 59.4 67.6 63.1 68.1 EXAMPLE 9 15 Various quaternary compounds were prepared in the presence of water under anhydrous conditions by the ethoxylation of the tertiary amines. The concentrations of the resulting quaternary compound and the unreacted amine were "Measured at the end of the reaction and the% yield was calsed. The results are as follows, with the concentration of the quaternary compound ("QUATERNARY CONTENT") and the concentration of the unreacted amine ("CONTENT OF NON-REACTED AMATE") which are provided in thousandths equivalent per gram. - 2( AMINA WATER CONTENTS WHEN% REAM CONTENT WITHOUT REACTION C ONAR TERNARIO Dimethylsus • SI 1.21 0.56 68 Dimethylcocole NO 1.27 0.62 67 'Dimethylbenzyl SI 1.64 0.58 74 Dimethylbenzyl NO 1.73 0.97 64 Methylmorpholine SI 1.33 1.6 45 Methylmorpholine NO 1.45 1.87 44 Samples of the resulting compositions containing quaternary compounds were then added to the kerosene at 50 ° C containing ethanethiol. The additive composition was added to the kerosene at a concentration of 500 ppm of the composition and the sonotrans- test of ethanethiol was measured one hour after the addition of the composition, according to ASTM D-3227. The following results were obtained by the ethanothiol content, which is proportional in ppm. AMINA WATER CONTENT OF ETHANE% REDUCTION DIOL WITHOUT ADDITIONAL COMPOUND 241 Dimethylsoque SI 173 28.22 Dimethylcoccus NO 177 26.56 Dimethylbenzyl SI 201 16.60 Dimethylbenzyl NO 209 13.28 Methylmorpholine SI 219 9.13 Methylmorpholine NO 205 14.94 This procedure was repeated with different amounts selected from the quaternary compound in each composition. Sufficient co-option was added in each operation to achieve a concentration of 500 ppm of assets in each test. The results were the following . AMINA WATER CURRENT DOSE REDUCTION% CONTENT (ppm) ETANOTIOL CION without additional compound 241 J Dimethylcoccus SI 715 153 36.51 Dimethyl butyl NO 681 156 35.27 Dimethylbenzyl SI 527 199 17.43 Dimethylbenzyl NO 500 205 14.94 Methylmorpholine SI 650 214 11.20 Methylmorpholine NO 597 201 16.60 EXAMPLE 10 Further experiments were carried out with the amino hydroxide of N- (2-hydroxyethyl) -N, N-dimethyl-N-coco 20 to test the efesto oxygen. The hydroxide was added to a sonsentrasidn of 2000 ppm in each of the two samples of crude oil. Before the addition, one of the samples was sprayed with air to produce an oxygen level with a stoichiometric level of 75% based on 750 ppm of the total 25 mercaptans. The intrasial soncentrasions of the various mersaptans in the samples were measured and their sonsentrations were again measured after 1.5 hours of the addition.

The following results were obtained, with the consentrasiones given in ppm: MERCAPTANO CONTENT CONTENT 1 i% REDUC- CONTENT% INITIAL Hrs sin 02 CCION 1 hrs -REDUC are 02 CCION Methanethiol 97 69 28.87 15 84.54 Ethanethiol 75 56 25.33 22 70.67 2-Propanothiol 41 36 12.20 22 46.34 1-Propanothiol 17 14 17.65 6., 7 60.59 C_? 2-Butanethiol 37 35 5.41 24 35.14 2-Methyl-l-propa notiol 3.8 3.9 0 2.1 44.74 2-Methyl-3-buta-15 notiol 3.5 3.2 '8.57 2.6 25.71 2-Pentenothiol 16 15 6.25 11 31.25 3-Pentanothiol 7.7 7.4 3.90 5.9 23.38 Additional tests were carried out on the oxygen in-tV fluensia with the addition of 2000 ppm of the ammonium hydroxide of N- (2-hydroxyethyl) -N, N-dimethyl-N- coconut in crude oil at 50 ° C containing 200 ppm of 1-propanothiol. The test was conducted with smooth oil samples. No oxygen was added to one of the samples, oxygen was added at a stoichiometric level of 50% to the second sample, oxygen at a stoichiometric level of 100% was added to the sample, and oxygen at a stoichiometric level of 200% was added to the remaining sample. dioxide are the following results. OXYGEN ADDED% REDUCTION OF 1-PROPANE-% STYCHOMETRIC TIOL 0 16 50 28 100 51 10 200 57 EXAMPLE 11 Samples were prepared in hexane containing approximately 25 ppm of MeSH, 25 ppm of EtSH and 50 ppm of PrSH. Each of the two samples was tested with an equimolar amount (approximately 300 ppm) of the quaternary compound, one with the quaternary ammonium hydroxide (Petrolite product) and the other with the internal salt, the compounds that were prepared in the Examples 1 and 2, previous. Also an untreated preform was prepared. The samples were heated at 60-65 ° C for one hour, analyzed by gas chromatography, allowed to stand at room temperature overnight, and analyzed again. The results are shown in the following table.

Internal Salt, 1 hour 5 of salinity 78.7 54.3 49.8 55.2 OH Quaternary, 1 hour of salting 71.4 51.5 48.1 52.4 Internal salt, 20 hours 76.5 51.1 44.5 50.5 OH Quaternary, 20 10 hours 73.6 54.1 48.3 53.1 These results showed the nominal differences within the margin of experimental errors and even had the relative eficasia of the compositions. It is considered that the reduction of some values during the night was due to inaccuracies in the method, as opposed to some kind of decomposition. By virtue of the foregoing, it will be noted that various advantages of the invention are achieved and other advantages can be achieved. ? reach? 0 Several sambios can be made in the previous methods and sompositions without departing from the spirit of the invention, it is intended that all the content included in the previous rewriting will be interpreted in an illustrative sense and not in a limiting sense. 25

Claims (19)

1. NOVELTY OF THE INVENTION Having described the invention as above, we consider what is contained in the following: CLAIMS 1. A method for purifying mercaptans in a hydrocarbon fluid, which comprises adding to the fluid an effective amount of the mercaptan scavenger of a composition of aqueous depuration comprising the a-n-quaternary hydroxide of the formula R 1R2R3R4NOH, wherein R 1 and R 2 are independently selected from the group consisting of alkyl groups of one to about eighteen carbon atoms, aryl groups of six to about eighteen carbon atoms, and alkylaryl groups from seven to about seventeen carbon atoms, and R is selected from the group consisting of the alkyl groups of two to about eighteen carbon atoms, the aryl groups of six to about dieciosho atoms of sarbono and alkylaryl groups from seven to about eighteen atoms d carbon, however with the proviso that R 2 and R 3 can be joined to form a heterocyclic ring including N and optionally oxygen, and 4 R is selected from the group consisting of ~ (CH 2 C? LO) H wherein n is an integer from one to about an eighteen 5 6 5 6. carbon atoms, and -CHR CHR Y, wherein R and R xn- of the group consisting of sixteen carbon atoms, aryl groups of six to about eighteen carbon atoms and alkylaryl groups of seven to about eighteen carbon atoms; carbon, and Y is a non-acidic group selected from the group consisting of -OH, -SR and -NR R, wherein R 7 and R 8 are independently selected from the group consisting of hydrogen, alkyl groups of one at about eighteen carbon atoms, aryl groups from six to about eighteen carbon atoms and alkylaryl groups from seven to about sixteen atoms of sarbon.
2. 2. A method as described in claim 1, wherein R 2 and R 3 do not bind.
3. 3. A method as described in claim 2, wherein R4 is -CH2CH2OH.
4. 4. A method as described in claim 1 3, wherein R is methyl.
5. 5. A method as described in claim 20 3, wherein each R 1 and R 2 are methyl.
6. 6. A method as described in claim 3, wherein R is coconut.
7. 7. A method as described in claim 1, wherein the hydrosarbure fluid contains some relatively low molecular weight mercaptans and other relatively high molecular weight mercaptans, and the adipidation results in a reduction of mercaptans. with a relatively low weight than mercaptans with a relatively high molecular weight.
8. 8. A method as recited in claim 3, wherein the hydrocarbon fluid contains some relatively low molecular weight mercaptans and other mercaptans with a relatively high molecular weight, and the 0 addition of the depuration composition results in a pro - higher proportion of the mercaptans with relatively low molecular weight than the mercaptans are a relatively high molecular weight.
9. 9. A method as described in claim 1, wherein oxygen is also added to the hydrocarbon fluid.
10. 10. A method as described in claim 1, wherein the hydrocarbon fluid is crude oil.
11. 11. A method as described in claim 2, wherein the hydrocarbon fluid is crude oil.
12. 12. A method as described in claim 3, wherein the hydrosharbur fluid is petroleum syrup.
13. 13. A method as described in claim 5, wherein the hydrocarbon fluid is crude petroleum.
14. 14. A method for the preparation of a quaternary ammonium hydroxide comprising reacting in the presence of water,% & 1 !? 3"a tertiary amine of the formula R R R N, wherein R 1 and R 2 independently are selected from the group consisting of alkyl groups of one to about eighteen carbon atoms, aryl groups of six to about sixteen carbon atoms and alkylaryl groups of seven to about eighteen carbon atoms, and R is selected from the group consisting of alkyl groups of two to about eighteen carbon atoms, aryl groups f from six to about eighteen carbon atoms and alkylaryl groups from seven to about eighteen carbon atoms, however with the proviso that R 2 and R 3 can be joined to form a heterocyclic ring by including N and optionally an oxygen atom, with an alkylene oxide of two to three carbon atoms, to produce a quaternary ammonium hydroxide of the formula R1R2R3R4NOH, wherein R1, R2 and R3 are defined as above, and JR is - (CH2CiH0) mH, 'wherein m is 2 d 3 0 CH,
15. 15. A method as described in claim 14, wherein the alkylene oxide is ethylene oxide and m is 2.
16. 16. A method as disclosed in claim 15. , where R 2 and R3 do not join.
17. 17. A method as described in claim 1, wherein R is methyl.
18. 18. A method as described in claim 16, wherein R 1 and R 2 are each methyl.
19. 19. A method as described in claim 3, wherein R is coso. EXTRACT OF THE DISCLOSURE A method for the purification of a hydrocarbon fluid is disclosed. According to the effective quantity of mercaptan cleanser of an aqueous treatment composition is added to the fluid. The composition comprises a quaternary ammonium hydroxide of the formula R 1 R 2 R 3 R 4 N 4 H. R1 and R2 are, independently, alkyl groups of one to about eighteen carbon atoms, aryl groups of six to about eighteen carbon atoms, 10 carbon or alkylaryl groups of seven about eighteen carbon atoms. R3 is a two-alkyl group (Mr about sixteen carbon atoms, an aryl group of two to about sixteen carbon atoms or an alkylaryl group of four to about eighteen carbon atoms) 15 carbon. R2 and R3 may be linked to form a -heterocyclic ring including N and optionally an oxygen atom. R4 is - (CH2CH20) nH, wherein n is an integer from one to about eighteen, or -CHR5CHR6Y, wherein R5 and R6 are ? independently, hydrogen, alkyl groups from one to about 20 carbon atoms, aryl groups from six to about sixteen carbon atoms or alkylaryl groups from seven to about seventeen carbon atoms, and is a non-acidic group. disclose related compositions and methods.