US2828267A - Process for breaking petroleum emulsions - Google Patents

Process for breaking petroleum emulsions Download PDF

Info

Publication number
US2828267A
US2828267A US526330A US52633055A US2828267A US 2828267 A US2828267 A US 2828267A US 526330 A US526330 A US 526330A US 52633055 A US52633055 A US 52633055A US 2828267 A US2828267 A US 2828267A
Authority
US
United States
Prior art keywords
weight
foots
phenol
oil
demulsifier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US526330A
Inventor
Groote Melvin De
Smith Alvin Howard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Baker Petrolite LLC
Original Assignee
Petrolite Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petrolite Corp filed Critical Petrolite Corp
Priority to US526330A priority Critical patent/US2828267A/en
Application granted granted Critical
Publication of US2828267A publication Critical patent/US2828267A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00Dewatering or demulsification of hydrocarbon oils
    • C10G33/04Dewatering or demulsification of hydrocarbon oils with chemical means

Definitions

  • the present invention relates to processes or procedures particularly adapted for preventing, breaking, or resolving petroleum emulsions of the water-in-oil type, and particularly petroleum emulsions.
  • Our invention provides an economical and rapid process that are commonly'referred to as cut oil, roily oil,
  • emulsified oil etc., and which comprises fin'e droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.
  • the present invention is concerned with a process for breaking petroleum emulsions of the water-'i'n-oil type characterized by subjecting theemulsion to the action of a demulsifying agent comprising a mixture of at least I 60% by weight and not over 90% by weight of (A) a conventional aromatic solvent-soluble non-ionic demulsifier, and at least 10% by weight and not over 40% by weight of-(B) ammonium salts obtained by monosulfonation and neutralization of a sulfonatable mixture consisting of (a) nonyl phenol foots characterized by a dinonyl phenol to nonly phenol ratio within the range of 2:1
  • dodecyl benzene bottoms consisting essentially of didodecyl benzene and other polyalkylated benzenes.
  • bottoms will be referred to by customary trade name, to wit, alkyl'ate detergent i
  • alkyl'ate detergent i There is produced a large amount of aproduct Which is essentially monododecyl benzene. This product is frequently referred to as detergent alkylate The reason isthat the product is subjected to monosulfonation followed by neutralization to give one of the most important commercial synthetic detergents.
  • alkylation of benzene there is produced some dialkylated, and possibly even trialkylated, benzene.
  • dodecyl benzene foots consist essentially of didodecyl benzene and other polyalkylated benzenes. It is possible that in some instances there is introduced into the aromatic nucleus a fewer number of carbon atoms, for instance, 6 or 8.
  • detergent alkylate foots can be sulfonated by the use of oleum, sulfur trioxide, or the like, in the same manner as is employed in the sulfonation of dodecyl benzene or more highly alkylated benzenes including keryl benzene.
  • Nonyl phenol foots consisting largely of dinonyl phenol and sometimes referred to as dinonyl phenol crude or as nonyl phenol bottoms has been available only recently as a commercial product. The reason is as follows: Nonyl phenol is finding substantial use in the form of its ethylene oxide addition product as a synthetic detergent.
  • the nonyl phenol used for this purpose is preferably colorless and free from dinonyl phenol. In the alkylation of phenol to produce the nonyl phenol there is invariably produced some dinonyl phenol. The nonyl phenol is removed by distillation.
  • nonyl phenol bottoms may contain as much as of dinonyl phenol and as little as 25% of nonyl phenol.
  • a product obtained from another manufacturer contained approxi mately 65 dinonyl phenol and 35% nonyl phenol.
  • Various samples contain the two phenols in amounts equivalent to 100% of the product.
  • the commercially available product appears to contain little or no trinonyl phenol but may have some polymerized nonylene or the like.
  • a typical example of commercially available product is characterized by the following:
  • Boiling point 5% (760 mm.); over 325.
  • Part III is a description of conventional aromatic sol; vent soluble nonionic demulsifiers used as one of the two components in the mixture which exemplifies the present process.
  • Part IV is concerned with suitable mixtures of the materials described in Part II and Part III precedingto yield the demulsifiers as here employed.
  • 7 Part V is concerned with the use of said demulsifiers for the resolution of petroleum emulsions of the water- PART I In our co-pending application Serial No. 52
  • Sulfonated alkyl aromatic hydrocarbons have been widely used as wetting, washing, emulsifying and detergent agents.
  • the sulfonated alkyl aromatic hydrocarbons are either preferentially watersoluble or preferentially oil soluble.
  • alkyl benzene sulfonates in which the alkyl group contains from about to about carbon atoms are preferentially water-soluble and are useful as wetting and/or dtergent agents.
  • the higher alkyl benzene suifonates that is, alkyl benzene sulfonates containing more than 16 carbon atoms and usually from about 18 to about 30 carbon atoms in the alkyl groups, are preferentially oilsoluble.
  • These preferentially oil-soluble alkyl aromatic sulfonates in many respects resemble the preferentially oil-soluble sulfonates obtained in the treatment of petroleum oils With concentrated or fuming sulfuric acid.
  • These preferentially oil soluble petroleum sulfonates because of their characteristic color are generally referred to as mahogany soaps although certain preferentially oilsoluble petroleum sulfonates having a characteristic brownish color are called brown acid soaps.
  • oil soluble petroleum sulfonates obtained in the manner described in the aforementioned U. S. Patent 2,448,184 are obviously a substitute for mahogany soap for a variety of purposes for which mahogany soaps are ordinarily used.
  • the present invention can be applied to a wide variety of alkyl aromatic compounds in which the alkyl substituent has at least 18 carbon atoms in the chain.
  • the aromatic nucleus can be, for example, benzene, toluene, xylene, cumene, naphthalene, methyl naphthalenes, ethyl naphthalenes, isopropyl or alkyl naphthalenes, diphenyl, alkyl phenyls, anthracene, and alkyl anthracene.
  • Halogen, nitro, hydroxy or other derivatives of the aromatic hydrocarbons can also be sulfonated in accordance with the present invention.
  • the displacement, or de alkylation is accompanied by complex side reactions in- 4 volving oxidation, hydrogen-transfer, and tar formation, with accompanying sulfonation of both the tar and the dealkylated benzene nucleus, that are reactions which are all undesirable in the manufacture of high quality detergent sulfonic acids.
  • the invention is not concerned with the use of another oil soluble sulfonate as such but to its use in combination with the components of a demulsifying mixture described in Part III following.
  • a demulsifying mixture described in Part III following.
  • the effectiveness of the sulfonate is to be found largely in introducing an anti-sludging property in the sense that when demulsification does take place by means of a mixed demulsifier, a comparatively clean interface is obtained at the interface surface between the oil and water layer, or at least a bright transparent upper oil layer.
  • Typical detergent alkylate foots have the following properties:
  • Example I a A 100 lb. charge consisting of nonyl phenol foots and 20% detergent alkylate foots was placed in a conventional sulphonator. The phenol foots consisted of assess? approximately 75% dinonyl and 25% nonyl phenol. For a description of a typical sulphonator, see Unit Processes in Organic Synthesis, Groggins, 4th ed.,
  • Example 2a 7 i In this example the crude nonyl phenol foots contained .about 65% dinonyl phenol and 35% nonyl phenol. 80
  • Example 3a A mixture of crude phenol and keryl benzene residue wassulphonated exactly as in Example 2a, with identical amounts of reactants.
  • the crude phenol consisted of 68% dinonyl phenol, 25% nonyl phenol, and 7% of non phen'olic matter.
  • the non-phenols were assumed to i be aromatic hydrocarbons and perhaps some polymerized nonenes.
  • the detergent alkylate foots was the same as used in Example 2a.
  • the yield of sulphonic acid was 126 pounds.
  • the active material contained 15% combined S0 plus 2% free S0
  • the ammonium sulphonates were soluble'in Xylene, kerosene, alcohol, and simil'ar solvents. The sulphonate was adjustedto 75% of active material with an aromatic solvent.
  • Example 4a The crude phenol'detergent alkylate foots mixture'of Example la was sulphonatedwith anhydrous sulfur trioxide.
  • the reactor used was similar to the type described in British Patent 664,577 to Newby, January 9, 1952. 100 pounds of mixturewas held at 75 C. while 15.5 pounds of sulphur-trioxide gas was run in over a twohour period. The S0 gas was diluted with 9 volumes of dry air. A yield of 115 pounds ofsulphonic acids was obtained, containing 12.3% combined S0 and 0.7% free 80 Solvent was added in an amount such that a 75% active sulphonate remained after neutralization with 26.5 pounds of ammonium hydroxide. The product was slightly more viscous and darker than that of Example 1a, but otherwise substantially identical. p
  • Example 5a The crude mixture of Example 2a was usedin this case. 100 pounds was chargedto the sulphon-ator together with 30 pounds of mineral spirits. The solvent was" added merely to'reduce viscosity and took no part in the sulphonation. 16% pounds of gaseous 80 diluted with 9 volumes of dry air was admitted over'a two-hour period.- The yield was 11-6- pounds of sulphonic acids containing 13% combined S0 and 0.5% free S0 27.8 pounds of ammonium hydroxide was required for neutralization. Additional solvent was added to give a product containing 75 ammonium sulphonates.
  • Example 6a The procedure used in Example 1a was followed here. The batch consisted of two parts of this crude nonyl phenol and one part of the detergent alkylate foots. The sulphonates contained 14% combined and were somewhat less viscous than those in Example la.
  • Example 8a Example 2a was repeated. The batch used consisted of,
  • Example 9a Example 3a was repeated. The batch used consisted of two parts crude phenol to one part detergent alkylate foots. The sulphonates contained 15% combined S0 Example 10a
  • Example 4a Example 4a was repeated. The batch consisted of two parts crude phenol to one part detergent alkylate foots. An additional onepound of 80;, was used. The sulphonates contained 13% combined S0 and were somewhat less viscous than the sulphonates of Example 40.
  • Example 11a Example 5a was repeated. The batch consisted of two parts crude phenol to 1 part detergent alkylate foots. An additional 1.5 pounds of S0 was used. The sulphonates contained 13.5% combined S0 Example 12a Example 651 was repeated. The batch consisted of two,
  • the demulsifying agents employed in the present vprocessare obtained by mixing ammonium sulfonates of the kind described elsewhere in this specification with conventional nonionic aromatic soluble de-' mulsifiers.
  • Conventional noniom'c demulsifiers are obtained by a reaction with ethylene oxide, propylene oxide, butylene oxide, and glycide.
  • the initial reactant may be a water soluble product such as alcohol, alkylated phenol, an amide, acid, or the like.
  • Such react-ants may and usually do contain at least one radical having not less than 8 uninterrupted carbon atoms.
  • Some conventional nonioni-c demulsifiers may have free carboxyl radicals or maybe obtained by linear polymeriz-a- The product was soluble in xylene, kero Such products are characterized by the fact,
  • conventional demulsifying agents are made which are initially hydrophile in character comparable to ordinary household liquid detergent. They are insoluble in aromatic hydrocarbons which is understood to mean a non oxygenated hydrocarbon aromatic solvent such as benzene, toluene, xylene, high boiling solvent derived from coal tar, cracking of petroleum, hydrogenated coal, etc.
  • aromatic hydrocarbons which is understood to mean a non oxygenated hydrocarbon aromatic solvent such as benzene, toluene, xylene, high boiling solvent derived from coal tar, cracking of petroleum, hydrogenated coal, etc.
  • a large number of conventional nonionic demulsifying agents are soluble in the aromatic solvent of the kind described. For example one can readily prepare a solution of 10 parts of such conventional demulsifier by Weight and 100 parts of xylene by weight at ordinary or slightly elevated temperatures.
  • the present invention is limited to such aromatic solvent soluble nonionic demulsifiers.
  • Demulsifiers of the type referred to immediately preceding are described in a number of patents. See U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser. Still another type are the kind described in U. S. Patent No. 2,562,878, dated August 7, 1951, to Blair.
  • Patent N 0. 2,629,704.
  • 56 See demulsifying agent defined by claim 5 of aforementioned U. S. Patent No. 2,629,704.
  • 6b See demulsifying agent defined by claim 6 of aforementioned U. S. Patent No. 2,629,764.
  • 7b See demulsifying agent defined by claim 3 of aforementioned Reissue Patent U. S. 23,851. 8! See demulsifying agent defined by claim 4 of aforementioned Reissue Patent U. S. 23,851. 9!) See demulsifying agent defined by claim 5 of aforementioned Reissue Patent U. S. 23,851. 10! See demulsifying agent defined in claims 3, 4 and 5 of aforementioned U. S. Patent 2,629,706.
  • Norn.--Pluronics is the trademark of Wyandotte Chemicals Corp. to identify products of the kind described in aforementioned U. S. Patent 2,674,619.
  • PART IV Dernulsifiers are ordinarily used in concentrations of approximately to 80%.
  • the purpose is to supply the demulsifier in the form of a liquid which can be employed by means of a metering pump or other measuring device. Since solvent is usually present in the final mixed product We have found it more convenient to make a solution of the ammonium sulfonate and the nonionic demulsifierseparately in a high boiling aromatic solvent. Generally, a to solution is used. The two solutions are then mixed so as to give the desired ratio between the two components and have a suitable solvent present. Nore solvent can be added if desired.
  • Table II illustrates a variety of suitable mixtures.
  • demulsifiers are indeed primarily to use as such without further formulation.
  • the efiectiveness of the herein described demulsifier is its ability to break oil field emulsions under conventional conditions without sludge and at the same time yielding bright pipeline oil, i. e., pipe line oil that is free from the minute traces of foreign matter, whether suspended water or suspended emulsion droplets, that are due to non-resovable 10 made to explain the efiect obtained by the added anionic ammonium sulfonate.
  • the haze in the upper layer pipeline oil and the sludge of the interface is not a refractory emulsion. As has been stated previously in the resolution of petroleum emulsions one sometimes obtains a sludge in the interface.
  • This sludge may be of two different types or, for that matter, a mixture of two.
  • One type is non-resolvable sludge. It consists of exceedingly fine iron oxide or sulfide or other solids as described hereinafter.
  • l insolubles Furthermore, the insolubles may be organic Appearance N H4 Appearance Appearance Test Demuls. Demuls Mixed sul- Non- No. temp ratio demuls. ionate ionic F. a used 011 Interalone 011 phase Interface alone Oil phase Interface phase face la. 70 1:12, 500 1c Bright Sharp to No treatment... No treatment... Bright Heavy sludge. 2d 70 1:10, 000 7c do d0 5:: do do 80 do Do.
  • the added anionic ammonium sulfonate does not act as a demulsifier but merely acts as a dispersant or a deflocculating agent for non-emulsified insolubles as noted above.
  • the trace of impurity that would appear at the interface and the trace of haze that appeared in the upper layer when the nonionic demulsifier was used alone simply was dispersed in a much finer state by virtue of the presence of the anionic ammonium sulfonate and thus bright oil without a sludge layer was obtained and the upper layer still would meetpipeline requirements for the presence offoreign matter. 7
  • a pr oce ss for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifying agentysaid demulsifying agent being a mixture of at least by weight and not over 90% byweight of (A) an aromatic solvent-soluble nonionic demulsifier, containing a plurality of lower oxy-' alkylene groups and at least 10% by weight and not over 40% by weight of (B) ammonium salts obtained by mono sulfonation and neutralization of a sulphonatable mixture;
  • said sulphonatable mixture consisting of (a) nonyl phenol foots; said foots being characterized by a dinonyl phenol to nonyl phenol ratio within the range of'2zl to 3:1 andwith the proviso that said nonyl phenol foots contain not less than 90% of nonylated phenols and (b) dodecyl benzene bottoms consisting essentially of didodecyl benzene and otherlpolyalkylated benzenes; the ratio of (a) to (b) being within the range of 2:1 to 4:1.
  • the processor claim 1 with the p'rovisothat the nonionic demulsifyingagent be obtained by use of at least one olefin oxide selected from the class consisting of ethylene oxide, propylene oxide and butylene oxide.
  • a process for breaking petroleum emulsions of the '1! water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being obtained by a mixture of at least 60% by weight and not over 90% by weight of (A) an aromatic solvent-soluble nonionic demulsifier containing a plurality of lower oxyalkylene groups; said demulsifier being obtained by the use of propylene oxide and ethylene oxide exclusively with the proviso that not less than 25% by weight of the alkylene oxide reactant be propylene oxide, and at least by weight and not over 40% by weight of (B) ammonium salts obtained by mono sulfonation and neutralization of a sulphonatable mixture; said sulphonatable mixture consisting of (a) nonyl phenol foots; said foots being characterized by a dinonyl phenol to nonyl phenol ratio within the range of 2:1 to 3:1 and with the proviso that said nonyl foots contain not less
  • a process for breaking petroleum emulsions of the watcr-in-oil type characterized by subjecting the emulsion to the action of a demulsifying agent; said demulsifying agent being a mixture of at least 60% by weight and not over 90% by weight of (A) an aromatic solvent-soluble nonionic demulsifier, containing a plurality of lower oxyalkylene groups and at least 10% by weight and not over 40% by weight of (B) ammonium salts obtained by mono sulfonation and neutralization of a sulphonatable mixture; said sulphonatable mixture consisting of (a) nonyl phenol fcots; said foots being characterized by a dinonyl phenol to nonyl phenol ratio within the range of 2:1 to 3:1 and with the proviso that said nonyl phenol foots contain not less than 90% of nonylated phenols and (b) dodecyl benzene bottoms consisting essentially of didodecyl benzene and other
  • nonionic demulsifying agent be obtained by use of at least one olefin oxide selected from the class consisting of ethylene oxide, propylene oxide and butylene oxide. 1 12. The process of claim 10 with the proviso that the nonionic demulsifier be obtained by the use of ethylene oxide in combination with propylene oxide.
  • a process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being obtained' by a mixture of at least 60% 'by weight and not over 90% by weight of (A) an aromatic solvent-soluble nonionic demulsifier containing a plurality of lower oxyalkylene groups; said demulsifier being obtained by the use of propylene oxide and ethylene exclusively with the proviso that not less than 25% by weight of the alkylene oxide reactant be propylene oxide, and at least 10% by weight and not over 40% by weight of (B) ammonium salts obtained by monosulphonation and neutralization of a sulphonatable mixture; said sulphonatable mixture consisting of (a) nonyl phenol foots; said foots being characterized by a dinonyl phenol to nonyl phenol ratio within the range of 2:1 to 3:1 and with the proviso that said.
  • nonyl phenol toots contain not less than 90% of nonylated phenois and (b) dodecyl benzene bottoms consisting essentially of didodecyl benzene and other polyalkylated' benzenes; the ratio of (a) to (b) being within the range of 2:1 to 4:1; said emulsion resolution being characterized by a substantially bright upper phase and a sludgefree interface. 7
  • a process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifying agent; said demulsifying agent being a mixture of at least 60% by weight and not over by weight of (A) an aromatic solvent-soluble. nonionic demulsifier, containing a plurality of lower oxy alkylene groups and at least 10% by weight and not over 40% by weight of (B) ammonium salts obtained by mono sulphonation and neutralization of a sulphonatable mixture; said sulphonatable mixture consisting of (a) nonyl phenol foots; said foots being characterized by a dinonyl.
  • phenol to nonyl phenol ratio within the range of 2:1 to 3:1 and with the proviso that said nonyl phenol foots contain not less than 90% of nonylated phenols and (b) dodecyl benzene bottoms consisting essentially of didodecyl benzene and other polyalkylated benzenes; the ratio of (a) to (b) being within the range of 2:1 to 4:1; said emulsion resolution being characterized by a substantially bright upper phase and a sludge-free interface; and with the further proviso that the amount of demulsifier used is sufiicient that the aromatic solvent soluble nonionic de-' mulsifier in the absence of the ammonium sulfonate would cause the emulsion to break.
  • nonionic demulsifying agent be obtained by use of at least one olefin oxide selected from the class consisting of ethylene oxide, propylene oxide and butylene oxide.
  • a process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being ob: tained by a mixture of. at least 60% by weight and not over 90% by weight of (A) an aromatic solvent-soluble nonionic demulsifier containing a plurality of lower oxyalkylene groups; said demulsifier being obtained by the use of propylene oxide and ethylene oxide exclusively with 13 the proviso that not less than 25% by weight of the alkylene oxide reactant be propylene oxide, and at least by weight and not over 40% by weight of (B) ammonium salts obtained by mono sulphonation and neutralization of a sulphonatable mixture; said sulphonatable mixture consisting of (a) nonyl phenol foots; said foots being characterized by a dinonyl phenol to nonyl phenol ratio within the range of 2:1 to 3:1 and with the proviso that said nonyl phenol

Description

i for resolving-petroleum emulsions of the water-in-oil type foots. or alkylate detergent bottoms.
one dodecyl benzene radical'and another radical having PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, and Alvin Howard S mith, Glendale, Mo., assignors to Petrolite Corporatlon, Wilmington, Del. a corporation of Delaware No Drawing. Application August 3, 1955 9 Serial No. 526,330
27 Claims. (Cl. 252-332) The present invention relates to processes or procedures particularly adapted for preventing, breaking, or resolving petroleum emulsions of the water-in-oil type, and particularly petroleum emulsions.
Our invention provides an economical and rapid process that are commonly'referred to as cut oil, roily oil,
emulsified oil, etc., and which comprises fin'e droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.
, It also provides an economical 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 emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil. r e
- The present invention is concerned with a process for breaking petroleum emulsions of the water-'i'n-oil type characterized by subjecting theemulsion to the action of a demulsifying agent comprising a mixture of at least I 60% by weight and not over 90% by weight of (A) a conventional aromatic solvent-soluble non-ionic demulsifier, and at least 10% by weight and not over 40% by weight of-(B) ammonium salts obtained by monosulfonation and neutralization of a sulfonatable mixture consisting of (a) nonyl phenol foots characterized by a dinonyl phenol to nonly phenol ratio within the range of 2:1
to 3:1 and containing not less than 90% of nonylated phenols and (b) dodecyl benzene bottoms consisting essentially of didodecyl benzene and other polyalkylated benzenes. For convenience such bottoms will be referred to by customary trade name, to wit, alkyl'ate detergent i There is produced a large amount of aproduct Which is essentially monododecyl benzene. This product is frequently referred to as detergent alkylate The reason isthat the product is subjected to monosulfonation followed by neutralization to give one of the most important commercial synthetic detergents. In the alkylation of benzene there is produced some dialkylated, and possibly even trialkylated, benzene. For the most part the dodecyl benzene foots consist essentially of didodecyl benzene and other polyalkylated benzenes. It is possible that in some instances there is introduced into the aromatic nucleus a fewer number of carbon atoms, for instance, 6 or 8.
i As to a further description ofsuchdodecyl bottoms of facts see Industrial'and Engineering.Chemistry,' vol. 46, No. 11, page 248, 1954, and U. S. Patent No. 2,671,762, dated March 9, 1954, to Wisherd. Attention is directed to the fact that the aforementioned Patent U. S. 2,671,762 not only describes the sulfonation and neutralization of the bottoms produced in'det'ergentalkylate manufacture but also the use of such product for the resolution ofpetroleum emulsions of the water-in-oil type. Needless to in-oil type.
' 2,828,267 Patented Maru'ZS, 1958 I ce say detergent alkylate foots can be sulfonated by the use of oleum, sulfur trioxide, or the like, in the same manner as is employed in the sulfonation of dodecyl benzene or more highly alkylated benzenes including keryl benzene.
The nonionic demulsifiers of the kind described are well known and numerous examples will be included subsequently. Nonyl phenol foots consisting largely of dinonyl phenol and sometimes referred to as dinonyl phenol crude or as nonyl phenol bottoms has been available only recently as a commercial product. The reason is as follows: Nonyl phenol is finding substantial use in the form of its ethylene oxide addition product as a synthetic detergent. The nonyl phenol used for this purpose is preferably colorless and free from dinonyl phenol. In the alkylation of phenol to produce the nonyl phenol there is invariably produced some dinonyl phenol. The nonyl phenol is removed by distillation. The residual product referred to as nonyl phenol bottoms, nonyl phenol foots, or as crude dinonyl phenol, depending on its method of manufacture, may contain as much as of dinonyl phenol and as little as 25% of nonyl phenol. A product obtained from another manufacturer contained approxi mately 65 dinonyl phenol and 35% nonyl phenol. Various samples contain the two phenols in amounts equivalent to 100% of the product. The commercially available product appears to contain little or no trinonyl phenol but may have some polymerized nonylene or the like. A typical example of commercially available product is characterized by the following:
Physical form Viscous amber liquid;
Boiling point 5% (760 mm.); over 325. C. Hydroxyl number -165. Specific gravity At 25/25 (3.: -92.
For the above reason we are not aware whether sulfo nated nonyl phenol foots have been described in the patent literature or elsewhere and for this reason there will be included a'complete description of the mono sulfona-v 'tion followed by conversion into the ammonium salt. i For convenience what is said hereinafter is divided into five parts sidered as a single component as far as composition with the nonionic demulsifier is concerned.
Part III is a description of conventional aromatic sol; vent soluble nonionic demulsifiers used as one of the two components in the mixture which exemplifies the present process. Part IV is concerned with suitable mixtures of the materials described in Part II and Part III precedingto yield the demulsifiers as here employed. 7 Part V is concerned with the use of said demulsifiers for the resolution of petroleum emulsions of the water- PART I In our co-pending application Serial No. 52
6,329, filed August 3, 1955, the following text concerned with the use of sulphonates derived from nonyl phenol foots applies with equal force'to the present mixture wherein the sulphonate employed is in reality derived not only from nonyl phenol foots but by the use of detergent alkylate foots in combination. The-text of said co-pending appli;
cation statesr V The use of sulfonates for resolution of petroleum emulsions'is well known, See U. S. Patent 1,299,385, dated April 1, 1919, to Rogers. It is noted in said "patent that it was concerned primarily with the use'of sulfonates obtained from mineral oil. Over a period of years although a large number of petroleum sulfonates have been used in demulsification either as the sole component of the demulsifier or in admixture with other Well known demulsifiers it has happened that for many years the overwhelming percentage of such material, probably more than 90% consumed as demulsifiers, happened to be oil soluble type or mahogany acid soap type.
For a number of years it has been recognized that al-- though the composition of mahogany soaps might vary, and undoubtedly does vary, a better understanding of the oil solubility of hydrocarbon sulfonates is obtained by a study of alkylated aromatic sulfonates.
U. S. Patent 2,448,184, dated August 31, 1948, to Lemmon states:
Sulfonated alkyl aromatic hydrocarbons have been widely used as wetting, washing, emulsifying and detergent agents. Depending upon the length of the alkyl chain of the alkyl substituent, the sulfonated alkyl aromatic hydrocarbons are either preferentially watersoluble or preferentially oil soluble. For example, alkyl benzene sulfonates in which the alkyl group contains from about to about carbon atoms are preferentially water-soluble and are useful as wetting and/or dtergent agents. The higher alkyl benzene suifonates, that is, alkyl benzene sulfonates containing more than 16 carbon atoms and usually from about 18 to about 30 carbon atoms in the alkyl groups, are preferentially oilsoluble. These preferentially oil-soluble alkyl aromatic sulfonates in many respects resemble the preferentially oil-soluble sulfonates obtained in the treatment of petroleum oils With concentrated or fuming sulfuric acid. These preferentially oil soluble petroleum sulfonates, because of their characteristic color are generally referred to as mahogany soaps although certain preferentially oilsoluble petroleum sulfonates having a characteristic brownish color are called brown acid soaps.
Thus, oil soluble petroleum sulfonates obtained in the manner described in the aforementioned U. S. Patent 2,448,184 are obviously a substitute for mahogany soap for a variety of purposes for which mahogany soaps are ordinarily used.
In the aforementioned U. S. Patent 2,448,184 it was also pointed out that hydroxy compounds, i. e., phenols can be sulfonated in the manner described. The patent states:
The present invention can be applied to a wide variety of alkyl aromatic compounds in which the alkyl substituent has at least 18 carbon atoms in the chain. The aromatic nucleus can be, for example, benzene, toluene, xylene, cumene, naphthalene, methyl naphthalenes, ethyl naphthalenes, isopropyl or alkyl naphthalenes, diphenyl, alkyl phenyls, anthracene, and alkyl anthracene. Halogen, nitro, hydroxy or other derivatives of the aromatic hydrocarbons can also be sulfonated in accordance with the present invention.
The process described in said aforementioned U. S. Patent 2,448,184 involves the use of anhydrous sulfur trioxide. See claim 1. However, it is known that when sulfur trioxide is employed that changes may take place in the side chain or side chains. See British Patent 664,- 577 which in discussing sulfonation of an alkyl aromatic hydrocarbon states as follows:
The difficulties associated with the sulfonation of long chain alkylaromatic hydrocarbons are especially acute in the case of poly-substituted benzenes, for example the long chain alkyl toluenes such as dodecyltoluene. The introduction of a sulfonic group into the nucleus tends to displace the long chain alkyl group, particularly if it is tertiary and to lesser extent if it is secondary. This displacement, which is negligible with monoalkyl benzenes, is increased as the temperature increases, and may reach as high as 20 percent in the case of p-tertiary dodecyl toluene above 40f C. The displacement, or de alkylation is accompanied by complex side reactions in- 4 volving oxidation, hydrogen-transfer, and tar formation, with accompanying sulfonation of both the tar and the dealkylated benzene nucleus, that are reactions which are all undesirable in the manufacture of high quality detergent sulfonic acids.
in light of the lack of specificity in regard to the composition of mahogany soaps and in regard to oil soluble sulfonates obtained by the sulfonation of alkylated aromatics particularly alkylated benzene, then the introduction of 18 carbon atoms or more, a single side chain or more than one side chain generally yields oil soluble sulfonates. Needless to say, in the case of a phenol if one introduces three alkyl radicals it might be more difiicult to sulfonate than if the product were mono or disubstituted and thus tend towards the increased production of by-products.
For the above reason although as stated it is not known whether sulfonated nonyl phenol foots or bottoms have been described and also not withstanding the fact that the total number of carbon atoms in the side chain may be somewhat less than the normal borderline, i. e., about 15 carbon atoms instead of 18 and not withstanding the fact that the hydroxyl radical does contribute a hydrophile effect, even so no claim is made in regard to these herein described sulfonates alone as demulsifiers. Likewise no significance is attached to the above statement that the alkyl carbon atoms even where there are as many as 18 present are divided into two alkyl chains. Even so the invention is not concerned with the use of another oil soluble sulfonate as such but to its use in combination with the components of a demulsifying mixture described in Part III following. In such mixture as will be pointed out in Part IV following the effectiveness of the sulfonate is to be found largely in introducing an anti-sludging property in the sense that when demulsification does take place by means of a mixed demulsifier, a comparatively clean interface is obtained at the interface surface between the oil and water layer, or at least a bright transparent upper oil layer.
Typical detergent alkylate foots have the following properties:
ASTM D-158 Engler Distn.: Foots or bottoms R With l-inch immersion thermometer. See aforementioned refere2ne to Industrial Engineering Chemistry, volume 46, page PART II As previously pointed out, the sulphonation of the mixed phenol foots-detergent alkylate foots is conventional and one can use any one of a number of acceptable sulphonating agents such as sulphur trioxide, oleum, etc. The acidic mass is then neutralized with anhydrous ammonia or a commercial aqua ammonia. The following examples 1a through 12a illustrate the procedure:
Example I a A 100 lb. charge consisting of nonyl phenol foots and 20% detergent alkylate foots was placed in a conventional sulphonator. The phenol foots consisted of assess? approximately 75% dinonyl and 25% nonyl phenol. For a description of a typical sulphonator, see Unit Processes in Organic Synthesis, Groggins, 4th ed.,
McGraw-Hill, New York, 1952, page .266. The batch was agitated while 55 lbs. of 25% ol-eum were run in. The oleum addition was controlled so as not to produce a temperature higher than 80 C. After this, the batch was agitated for 1 hour and then cooled back to 40 C. 28 pounds of water were added and the batch allowed to settle overnight. When the spent acid had been withdrawn, a yield of 123 pounds of sulphonic acid remained.
Example 2a 7 i In this example the crude nonyl phenol foots contained .about 65% dinonyl phenol and 35% nonyl phenol. 80
pounds of the phenols were mixed with 20 pounds of detergent alkylate foots. The sulphonator used was the same as described in Example 1a, preceding. The batch was sulphonated at 80 C. as before with 65 pounds of 25% oleum. After being washed with 35 pounds of water and settled overnight, the sulphonic acids were recovered by drawing off the spent acid. The yield was 128 pounds. Solvents were added together with 30 pounds of ammonium'hydroxide. The active sulphonate contained 14.5% combined 80;, plus 1.5 free S The batch was adjusted to 75 active with solvent and appeared to have properties very similar to the sulphonate in Example 1a.
Example 3a A mixture of crude phenol and keryl benzene residue wassulphonated exactly as in Example 2a, with identical amounts of reactants. The crude phenol consisted of 68% dinonyl phenol, 25% nonyl phenol, and 7% of non phen'olic matter. The non-phenols were assumed to i be aromatic hydrocarbons and perhaps some polymerized nonenes. The detergent alkylate foots was the same as used in Example 2a. The yield of sulphonic acid was 126 pounds. The active material contained 15% combined S0 plus 2% free S0 The ammonium sulphonates were soluble'in Xylene, kerosene, alcohol, and simil'ar solvents. The sulphonate was adjustedto 75% of active material with an aromatic solvent.
7 Example 4a a The crude phenol'detergent alkylate foots mixture'of Example la was sulphonatedwith anhydrous sulfur trioxide. The reactor used was similar to the type described in British Patent 664,577 to Newby, January 9, 1952. 100 pounds of mixturewas held at 75 C. while 15.5 pounds of sulphur-trioxide gas was run in over a twohour period. The S0 gas was diluted with 9 volumes of dry air. A yield of 115 pounds ofsulphonic acids was obtained, containing 12.3% combined S0 and 0.7% free 80 Solvent was added in an amount such that a 75% active sulphonate remained after neutralization with 26.5 pounds of ammonium hydroxide. The product was slightly more viscous and darker than that of Example 1a, but otherwise substantially identical. p
Example 5a The crude mixture of Example 2a was usedin this case. 100 pounds was chargedto the sulphon-ator together with 30 pounds of mineral spirits. The solvent was" added merely to'reduce viscosity and took no part in the sulphonation. 16% pounds of gaseous 80 diluted with 9 volumes of dry air was admitted over'a two-hour period.- The yield was 11-6- pounds of sulphonic acids containing 13% combined S0 and 0.5% free S0 27.8 pounds of ammonium hydroxide was required for neutralization. Additional solvent was added to give a product containing 75 ammonium sulphonates.
Example 6a The procedure used in Example 1a was followed here. The batch consisted of two parts of this crude nonyl phenol and one part of the detergent alkylate foots. The sulphonates contained 14% combined and were somewhat less viscous than those in Example la.
Example 8a Example 2a was repeated. The batch used consisted of,
two parts crude phenol to one part detergent alkylate foots. The sulphonates contained 15% combined S0 Example 9a Example 3a was repeated. The batch used consisted of two parts crude phenol to one part detergent alkylate foots. The sulphonates contained 15% combined S0 Example 10a Example 4a was repeated. The batch consisted of two parts crude phenol to one part detergent alkylate foots. An additional onepound of 80;, was used. The sulphonates contained 13% combined S0 and were somewhat less viscous than the sulphonates of Example 40.
Example 11a Example 5a was repeated. The batch consisted of two parts crude phenol to 1 part detergent alkylate foots. An additional 1.5 pounds of S0 was used. The sulphonates contained 13.5% combined S0 Example 12a Example 651 was repeated. The batch consisted of two,
parts crude phenol to one part deter-gent alkyl-ate foot's. An additional pound of S0 was used. The sulphonates contained 14% combined S0 PART III As previously stated the demulsifying agents employed in the present vprocessare obtained by mixing ammonium sulfonates of the kind described elsewhere in this specification with conventional nonionic aromatic soluble de-' mulsifiers. Conventional noniom'c demulsifiers are obtained by a reaction with ethylene oxide, propylene oxide, butylene oxide, and glycide. The initial reactant may be a water soluble product such as alcohol, alkylated phenol, an amide, acid, or the like. Such react-ants may and usually do contain at least one radical having not less than 8 uninterrupted carbon atoms.
In some instances, however, one may start withwater' soluble substances for instance low molal glycols such In such instances the manufacture of the conventional nonionic demulsifying agent invariably involves the use.
of either propylene oxide or butylene oxide or both along with either ethylene oxide or glycide or both. Some conventional nonioni-c demulsifiers may have free carboxyl radicals or maybe obtained by linear polymeriz-a- The product was soluble in xylene, kero Such products are characterized by the fact,
"7 tion between a low molal dicarboxy acid and an alkylene oxide derivative. The unneutralized carboxyl group does not introduce any measurable anionic surf-ace active properties.
In some instances effective conventional demulsifying agents are made which are initially hydrophile in character comparable to ordinary household liquid detergent. They are insoluble in aromatic hydrocarbons which is understood to mean a non oxygenated hydrocarbon aromatic solvent such as benzene, toluene, xylene, high boiling solvent derived from coal tar, cracking of petroleum, hydrogenated coal, etc. A large number of conventional nonionic demulsifying agents are soluble in the aromatic solvent of the kind described. For example one can readily prepare a solution of 10 parts of such conventional demulsifier by Weight and 100 parts of xylene by weight at ordinary or slightly elevated temperatures.
The present invention is limited to such aromatic solvent soluble nonionic demulsifiers.
Demulsifiers of the type referred to immediately preceding are described in a number of patents. See U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser. Still another type are the kind described in U. S. Patent No. 2,562,878, dated August 7, 1951, to Blair.
Other types are obtained by the oxyethylation of polypropylene-glycols. See U. S. Patent No. 2,674,619, dated April 6, 1954, to Lundsted.
See also U. S. Patent No. 626,942, dated January 27,
1953, to De Groote; U. S. Patent No. 2,629,704, dated February 24, 1953, to De Groote et al.; U. S. Reissue Patent No. 23,851, dated July 13, 1954, to De Groote et al.; U. S. Patent No. 2,629,706, dated February 24, 1953, to De Groote et al.; U. S. 2,549,434, dated April 17, 1951, to De Groote et al.; U. S. 2,552,528, dated May 15, 1951, to De Groote; and U. S. 2,552,529, dated May 15, 1951, to De Groote.
Typical conventional nonionic aromatic solvent soluble demulsifiers are indicated in the following table:
TABLE I Example Description of aromatic solvent soluble nonionic N 0. demulsifiers 1b See EXBEDIG 18C in aforementioned U. S. Patent No. 2, 26,9 2b SeQefifiExgfaple 26C in aforementioned U. S. Patent No.
, e, 2. 3b See gxginple 43C in aforementioned U. S. Patent No.
2. 4b See demulsifier defined by claim 3 of aforementioned U. S.
Patent N 0. 2,629,704. 56 See demulsifying agent defined by claim 5 of aforementioned U. S. Patent No. 2,629,704. 6b See demulsifying agent defined by claim 6 of aforementioned U. S. Patent No. 2,629,764. 7b See demulsifying agent defined by claim 3 of aforementioned Reissue Patent U. S. 23,851. 8!) See demulsifying agent defined by claim 4 of aforementioned Reissue Patent U. S. 23,851. 9!) See demulsifying agent defined by claim 5 of aforementioned Reissue Patent U. S. 23,851. 10!) See demulsifying agent defined in claims 3, 4 and 5 of aforementioned U. S. Patent 2,629,706. 111) See demulsifying agent defined in claim 9 of aforementioned patent U. S. 2,562,878 and derived from polypropyleneglycol molecular weight, 2,000. 120 See demulsifying agent defined in claim 9 of aforementioned patent U. S. 2,562,878 and derived from polypropylene glycol molecular weight 2,250. 136 See demulsifying agent defined in claim 9 of aforementioned patent U. S. 2,562,878 and derived from polypropylene glycol molecular weight 2500.
See demulsifying agent defined in claim 9 of aforementioned patent U. S. 2,562,878 and derived from polypropylene glycol molecular weight 2,750.
See industrial pamphlet Pluronics of Wyandotte Chemical Corporation, Wyandotte, Michigan. Pluronic L72. See also aforementioned U. S. Patent 2,674,619.-
See industrial pamphlet Pluronics of WyandotteChen-iical Corporation, Wyandotte, Michigan. Pluronic See also aforementioned U. S. Patent 2,674,619.
See industrial pamphlet Pluronics of Wyandottc Chemical Corporation, Wyandotte, Michigan. Pluronic L64. See also aforementioned U. S. Patent 2,674,619.
See industrial pamphlet Pluronies of Wyandotte Chen:-
ical Corporation, Wyandotte, Michigan. Pluronic L3l. See also aforementioned U. S. Patent 2,674,619.
See industrial pamphlet Pluronies of Wyandotte Chemical Corporation, Wyandotte, Michigan. Pluronic L-61. See also aforementioned U. 5. Patent 2,674,619.
TABLE I--Continued Example Description of aromatic solvent soluble nonionic No. demulsifiers 20!) See industrial pamphlet Pluronics of Wyandotte Cl1cmcal Corporation, Wyandotte, Michigan. Pluronic L81. See also aforementioned U. S. Patent 2,674,619.
211) See industrial pamphlet Plur'onics of Wyandotte Chemical Corporation, Wyandotte, Michigan. Pluronie L42. See also aforementioned U. S. Patent 2.674,6l9.
22b See industrial pamphlet Pluronics of Wyandotte Chemical Corporation, Wyandotte, Michigan. Pluronie L33. See also aforementioned U. S. Patent 2,674,619.
23') See Example B in aforementioned U. S. Patent 2,549,434.
Propylene oxide added first, then ethylene oxide.
240 See Example E in aforementioned U. S. Patent 2,549,434.
Propylene oxide added first, then ethylene oxide.
25!) See Example C in aforementioned U. S. Patent 2,549,434.
Propylene oxide added first, then ethylene oxide.
26') See Example M of aforementioned U. S. Patent 2,552,529.
Propylene added first, then ethylene oxide.
27!) See Example 25 of aforementioned U. S. Patent 2,552,528.
Norn.--Pluronics is the trademark of Wyandotte Chemicals Corp. to identify products of the kind described in aforementioned U. S. Patent 2,674,619.
PART IV Dernulsifiers are ordinarily used in concentrations of approximately to 80%. The purpose is to supply the demulsifier in the form of a liquid which can be employed by means of a metering pump or other measuring device. Since solvent is usually present in the final mixed product We have found it more convenient to make a solution of the ammonium sulfonate and the nonionic demulsifierseparately in a high boiling aromatic solvent. Generally, a to solution is used. The two solutions are then mixed so as to give the desired ratio between the two components and have a suitable solvent present. Nore solvent can be added if desired. Hereto attached Table II illustrates a variety of suitable mixtures.
TABLE II.MIXED DEMULSIFIER [Ammonium sulfonates used is indicated by designation 1a, 2a, ete. in parentheses. The nonionic demulsifier used is indicated by the designation 1b, 212, etc. outside the parentheses. "lhe percentage by weight of ammonium sulfonates used is indicated at the head of the column and the remainder is nonionic demulsifier. Percentage by weight is on solvent free basis] 1b (1 1) M M N 1H (7 5 (4a) 11 M g M 0M) 11b( (4 M 11) 13!? 141) (1 1 (4 M 1 200 (111) 21b( M (5c) M (l M (3 22b( PART V admixture with other conventional demulsifiers. The
herein described demulsifiers are indeed primarily to use as such without further formulation.
It has been previously pointed out that the efiectiveness of the herein described demulsifier is its ability to break oil field emulsions under conventional conditions without sludge and at the same time yielding bright pipeline oil, i. e., pipe line oil that is free from the minute traces of foreign matter, whether suspended water or suspended emulsion droplets, that are due to non-resovable 10 made to explain the efiect obtained by the added anionic ammonium sulfonate. In some instances the haze in the upper layer pipeline oil and the sludge of the interface is not a refractory emulsion. As has been stated previously in the resolution of petroleum emulsions one sometimes obtains a sludge in the interface. This sludge may be of two different types or, for that matter, a mixture of two. One type is non-resolvable sludge. It consists of exceedingly fine iron oxide or sulfide or other solids as described hereinafter. l insolubles. Furthermore, the insolubles may be organic Appearance N H4 Appearance Appearance Test Demuls. Demuls Mixed sul- Non- No. temp ratio demuls. ionate ionic F. a used 011 Interalone 011 phase Interface alone Oil phase Interface phase face la. 70 1:12, 500 1c Bright Sharp to No treatment... No treatment... Bright Heavy sludge. 2d 70 1:10, 000 7c do d0 5:: do do 80 do Do.
70 1:8, 000 11c do do.. 411 do 11b Slight haze Light sludge.
in 150 1:8, 000 18c do do Go do 19b Bright Heavy sludge. 5a 160 1:10,000 24c d0.. ..d0 .do. 266 do Do.
NOTE 1.--The following oils were used in the above tests: 1d, oil from Greta, Texas: 2d, oil trom Andrews, Texas; 3d, oil from Thompson, Texas;
4d, oil from Br'ookhaven, Miss; 5d, oil from Village Mills, Texas.
N OIE 2.-Ihe phrase N 0 Treatment as applied to the action of the N114 sulfonate alone should be qualified. In some cases the sulfonate may cause some of the emulsified water to drop out of the oil; but the amount is usually so small as to leave the oil still unfit for use. Addition of larger amounts of sulfonate does not further improve the situation, and may even cause'gelation of some of the emulsion.
NOTE 3.The above tests were conducted in the manner described in a treatise entitled Treating Oil Field Emulsions issued by the American Petroleum Institute in cooperation with the University of Texas (1949).
In examining the results in the above table there are two things which are particularly striking. One is the and the second (b) that the amount of sludge formed is slight and requires being drawn oif once or twice a month from a second gun barrel, stock tank or the like. The amount of oil so discarded is insignificant either from the standpoint of the value of the oil or stream contamination.
However, whether justified or not it is frequently the practice to use a demulsifier that produces absolutely bright haze-free oil in the top layer and yields no interface layer at any time and not even over a period of time in the stock tank.
In such cases merely increasing the amount of nonionic demulsifier from 1 part to 15,000 emulsion to 1 part to 12,000 for example frequently causes no change in respect to either the haze or interface sludge or both.
However, if an admixture is made as previously described, and the mixture used so that one obtains hazefree oil without an interface layer, in such instances frequently it win be found that the amount of such demulsifier is substantially thesame as would be requiredin absence of the ammonium sulfonate, to give a conventionally acceptable resolutionl Stated another'way, the
1 ammonium sulfonate in the admixture appears to contribute little or nothing as far as any demulsifying action in the usual sense of the word, but does either by itselfor by synergistic combination result in the haze-free, sludge-free emulsion resolution. I
I What has been said immediately preceding may appear inconsistent in light of what was said in regard to U. S. Patent.1,-299,385, dated April 1, 1919, to Rogers.
At the time of the issuance of theRogers patent a ratio of- 1 to 1,000 to 1 to'2,000 was considered excellent. Total foreign matter acceptable in pipeline oil at that time ran from 1 to 3% and as a matter of fact a sludge layer or interface layer was taken forgrantedin many instances.
, A slight sludge layer or interface layer is illustrated for,
example in a drawing ,whichispart of theU. S. Patent 1,223,659, dated April 24, "19l7','to Barnickel. v
In light of what has been said previously no attempt is resistant or refractory sludge which apparently has beenimmune to demulsification in the usualoperation. Sometimes either type of sludge or both separate out in tanks and become tank bottoms.
We have satisfied ourselves, that in some instances and, perhaps in the majority of instances, the added anionic ammonium sulfonate does not act as a demulsifier but merely acts as a dispersant or a deflocculating agent for non-emulsified insolubles as noted above. In other words the trace of impurity that would appear at the interface and the trace of haze that appeared in the upper layer when the nonionic demulsifier was used alone simply was dispersed in a much finer state by virtue of the presence of the anionic ammonium sulfonate and thus bright oil without a sludge layer was obtained and the upper layer still would meetpipeline requirements for the presence offoreign matter. 7
Having thus described our invention what we claim as new and desire tosecure by Letters Patent isz.
l. A pr oce ss for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifying agentysaid demulsifying agent being a mixture of at least by weight and not over 90% byweight of (A) an aromatic solvent-soluble nonionic demulsifier, containing a plurality of lower oxy-' alkylene groups and at least 10% by weight and not over 40% by weight of (B) ammonium salts obtained by mono sulfonation and neutralization of a sulphonatable mixture;
said sulphonatable mixture consisting of (a) nonyl phenol foots; said foots being characterized by a dinonyl phenol to nonyl phenol ratio within the range of'2zl to 3:1 andwith the proviso that said nonyl phenol foots contain not less than 90% of nonylated phenols and (b) dodecyl benzene bottoms consisting essentially of didodecyl benzene and otherlpolyalkylated benzenes; the ratio of (a) to (b) being within the range of 2:1 to 4:1.
2. The processor claim 1 with the p'rovisothat the nonionic demulsifyingagent be obtained by use of at least one olefin oxide selected from the class consisting of ethylene oxide, propylene oxide and butylene oxide.
3. The process ofclairn 1 with the proviso that the 1 nonionic demulsifier, be obtained by the use of ethylene oxidein combination with propylene oxide. t
4. A process for breaking petroleum emulsions of the '1! water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being obtained by a mixture of at least 60% by weight and not over 90% by weight of (A) an aromatic solvent-soluble nonionic demulsifier containing a plurality of lower oxyalkylene groups; said demulsifier being obtained by the use of propylene oxide and ethylene oxide exclusively with the proviso that not less than 25% by weight of the alkylene oxide reactant be propylene oxide, and at least by weight and not over 40% by weight of (B) ammonium salts obtained by mono sulfonation and neutralization of a sulphonatable mixture; said sulphonatable mixture consisting of (a) nonyl phenol foots; said foots being characterized by a dinonyl phenol to nonyl phenol ratio within the range of 2:1 to 3:1 and with the proviso that said nonyl foots contain not less than 90% of nonylated phenols and (b) dodecyl benzene bottoms consisting essentially of didodecyl benzene and other polyalkylated benzenes; the ratio of (a) to (b) being within the range of 2:1 to 4:1.
5. The process of claim 4 with the proviso that the ratios of the two components, (A) and (B), be roughly 90 parts by Weight and 10 parts by weight; the latter being the ammonium sulfonate.
6. The process of claim 4 with the proviso that the ratios of the two components, (A) and (B), be roughly 80 parts by weight and parts by weight; the latter being the ammonium sulfonate.
7. The process of claim 4 with the proviso that the ratios of the two components, (A) and (B), be roughly 75 parts by weight and parts by weight; the latter being the ammonium sulfonate.
66.7 parts by weight and 33.3 parts by weight; the latter being the ammonium sulfonate.
9. The process of claim 4 with the proviso that the ratios of the two components, (A) and (B), be roughly 60 parts by weight and 40 parts by weight; the latter being the ammonium sulfonate.
10. A process for breaking petroleum emulsions of the watcr-in-oil type characterized by subjecting the emulsion to the action of a demulsifying agent; said demulsifying agent being a mixture of at least 60% by weight and not over 90% by weight of (A) an aromatic solvent-soluble nonionic demulsifier, containing a plurality of lower oxyalkylene groups and at least 10% by weight and not over 40% by weight of (B) ammonium salts obtained by mono sulfonation and neutralization of a sulphonatable mixture; said sulphonatable mixture consisting of (a) nonyl phenol fcots; said foots being characterized by a dinonyl phenol to nonyl phenol ratio within the range of 2:1 to 3:1 and with the proviso that said nonyl phenol foots contain not less than 90% of nonylated phenols and (b) dodecyl benzene bottoms consisting essentially of didodecyl benzene and other polyalkylated benzenes; the ratio of (a) to (b) being within the range of 2:1 to 4:1; said emulsion resolution being characterized by a substantially bright upper phase and a sludge-free interface.
11. The process of claim 10 with the proviso that the nonionic demulsifying agent be obtained by use of at least one olefin oxide selected from the class consisting of ethylene oxide, propylene oxide and butylene oxide. 1 12. The process of claim 10 with the proviso that the nonionic demulsifier be obtained by the use of ethylene oxide in combination with propylene oxide.
' 13. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being obtained' by a mixture of at least 60% 'by weight and not over 90% by weight of (A) an aromatic solvent-soluble nonionic demulsifier containing a plurality of lower oxyalkylene groups; said demulsifier being obtained by the use of propylene oxide and ethylene exclusively with the proviso that not less than 25% by weight of the alkylene oxide reactant be propylene oxide, and at least 10% by weight and not over 40% by weight of (B) ammonium salts obtained by monosulphonation and neutralization of a sulphonatable mixture; said sulphonatable mixture consisting of (a) nonyl phenol foots; said foots being characterized by a dinonyl phenol to nonyl phenol ratio within the range of 2:1 to 3:1 and with the proviso that said. nonyl phenol toots contain not less than 90% of nonylated phenois and (b) dodecyl benzene bottoms consisting essentially of didodecyl benzene and other polyalkylated' benzenes; the ratio of (a) to (b) being within the range of 2:1 to 4:1; said emulsion resolution being characterized by a substantially bright upper phase and a sludgefree interface. 7
14. The process of claim 13 with the proviso that thei ratios of the two components, (A) and (B), be roughly 90 parts by weight and 10 parts by weight; the latter being the ammonium sulfonate.
15. The process of claim 13 with the proviso that the ratios of the two components, (A) and (B), be roughly parts by weight and 20 parts by weight; the latter beingthe ammonium sulfonate.
16. The process of claim 13 with the proviso that the ratios of the two components, (A) and (B), be roughly 75 parts by weight and 25 parts by weight; the latter being the ammonium sulfonate.
17. The process of claim 13 with the proviso that the ratios of the two components, (A) and (B), be roughly 66.7 parts by weight and 33.3 parts by weight; the latter being the ammonium sulfonate.
18. The process of claim 13 with the proviso that the ratios of the two components, (A) and (B), be roughly 60 parts by weight and 40 parts by weight; the latter being the ammonium sulfonate.
19. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifying agent; said demulsifying agent being a mixture of at least 60% by weight and not over by weight of (A) an aromatic solvent-soluble. nonionic demulsifier, containing a plurality of lower oxy alkylene groups and at least 10% by weight and not over 40% by weight of (B) ammonium salts obtained by mono sulphonation and neutralization of a sulphonatable mixture; said sulphonatable mixture consisting of (a) nonyl phenol foots; said foots being characterized by a dinonyl. phenol to nonyl phenol ratio within the range of 2:1 to 3:1 and with the proviso that said nonyl phenol foots contain not less than 90% of nonylated phenols and (b) dodecyl benzene bottoms consisting essentially of didodecyl benzene and other polyalkylated benzenes; the ratio of (a) to (b) being within the range of 2:1 to 4:1; said emulsion resolution being characterized by a substantially bright upper phase and a sludge-free interface; and with the further proviso that the amount of demulsifier used is sufiicient that the aromatic solvent soluble nonionic de-' mulsifier in the absence of the ammonium sulfonate would cause the emulsion to break.
20. The process of claim 19 with the proviso that the nonionic demulsifying agent be obtained by use of at least one olefin oxide selected from the class consisting of ethylene oxide, propylene oxide and butylene oxide.
21. The process of claim 19 with the proviso that the nonionic demulsifier be obtained by the use of ethylene oxide in combination with propylene oxide.
22. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being ob: tained by a mixture of. at least 60% by weight and not over 90% by weight of (A) an aromatic solvent-soluble nonionic demulsifier containing a plurality of lower oxyalkylene groups; said demulsifier being obtained by the use of propylene oxide and ethylene oxide exclusively with 13 the proviso that not less than 25% by weight of the alkylene oxide reactant be propylene oxide, and at least by weight and not over 40% by weight of (B) ammonium salts obtained by mono sulphonation and neutralization of a sulphonatable mixture; said sulphonatable mixture consisting of (a) nonyl phenol foots; said foots being characterized by a dinonyl phenol to nonyl phenol ratio within the range of 2:1 to 3:1 and with the proviso that said nonyl phenol foots contain not less than 90% of nonylated phenols and (b) dodecyl benzene bottoms consisting essentially of didodecyl benzene and other polyalkylated benzenes; the ratio of (a) to (b) being Within the range of 2:1 to 4:1; said emulsion resolution being characterized by a substantially bright upper phase and a sludge-free interface; and with the further proviso that the amount of demulsifier used is sufiicient that the aromatic solvent soluble nonionic demulsifier in the absence of the ammonium sulfonate would cause the emulsion to break.
23. The process of claim 22 with the proviso that the ratios of the two components, (A) and (B), be roughly 90 parts by weight and 10 parts by weight; the latter being the ammonium sulfonate.
24. The process of claim 22 with the proviso that the ratios of the two components, (A) and (B), be roughly 80 parts by weight and parts by weight; thelatter being the ammonium sulfonate.
25. The process of claim 22 with the proviso that the ratios of the two components, (A) and (B), be roughly 75 parts by weight and 25 parts by weight; the latter being the ammonium sulfonate.
26. The process of claim 22 with the proviso that the ratios of the two components, (A) and (B), be roughly 66.7 parts by weight and 33.3 parts by weight; the latter being the ammonium sulfonate.
27. The process of claim 22 with the proviso that the ratios of the two components, (A) and (B), be roughly 60 parts by weight and parts by weight; the latter being the ammonium sulfonate.
References Cited in the file of this patent UNITED STATES PATENTS

Claims (1)

1. A PROCESS OF BREAKING PERTOLUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTEWRIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFYING AGENT; SAID DEMULSIFYING AGENT BEING A MIXTURE OF AT LEAST 60% BY WEIGHT AND NOT OVER 90% BY WEIGHT OF (A) AN AROMATIC SOLVENT-SOLUBLE MONIOMIC DEMULSIFIER, CONTAINING A PLURALITY OF LOWER OXYALKYLENE GROUPS AND AT LEAST 10% BY WEIGHT AND NOT OVER 40% BY WEIGHT OF (B) AMMONIUM SALTS OBTAINED BY MONO SULFONATION AND NEUTRALIZATION OF A SULPHONATABLE MIXTURE; SAID SULPHONATION MIXTURE CONSISTING OF (A) DINONYL PHENOL FOOTS; SAID FOOTS BEING CHARACTERIZED BY A DINONYL PHENOL TO NONYL PHENOL RATIO WITHIN THE RANGE OF 2:1 TO 3:1 AND WITH THE PRIVISO THAT SAID NONYL PHENOL CONTAINS NOT LESS THAN 90% OF NONYLATED PHENO/LS AND (B) DODECYL BENZENE BOTTOMS CONSISTING ESSENTIALLY OF DIDODECYL BENZENE AND OTHER POLYALKYLATED BENZENES; AND THE RATIO OF (A) TO (B) BEING WITHIN THE RANGE OF 2:1 TO 4:1.
US526330A 1955-08-03 1955-08-03 Process for breaking petroleum emulsions Expired - Lifetime US2828267A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US526330A US2828267A (en) 1955-08-03 1955-08-03 Process for breaking petroleum emulsions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US526330A US2828267A (en) 1955-08-03 1955-08-03 Process for breaking petroleum emulsions

Publications (1)

Publication Number Publication Date
US2828267A true US2828267A (en) 1958-03-25

Family

ID=24096893

Family Applications (1)

Application Number Title Priority Date Filing Date
US526330A Expired - Lifetime US2828267A (en) 1955-08-03 1955-08-03 Process for breaking petroleum emulsions

Country Status (1)

Country Link
US (1) US2828267A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3513005A (en) * 1966-10-05 1970-05-19 Ibe Ltd Coating with emulsions
US4439345A (en) * 1981-06-11 1984-03-27 Marathon Oil Company Demulsification of a crude oil middle phase emulsion
US20100025300A1 (en) * 2008-07-30 2010-02-04 Bp Corporation North America Inc. Controlling emulsion stability during fuel stock processing

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2249757A (en) * 1933-09-26 1941-07-22 Nat Aniline & Chem Co Inc Alkyl hydroxy aromatic sulphonate
US2568116A (en) * 1950-01-06 1951-09-18 Petrolite Corp Processes for breaking petroleum emulsions
US2602052A (en) * 1950-08-03 1952-07-01 Petrolite Corp Processes for breaking petroleum emulsions
US2671762A (en) * 1951-03-24 1954-03-09 Sinclair Refining Co Process for resolving emulsions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2249757A (en) * 1933-09-26 1941-07-22 Nat Aniline & Chem Co Inc Alkyl hydroxy aromatic sulphonate
US2568116A (en) * 1950-01-06 1951-09-18 Petrolite Corp Processes for breaking petroleum emulsions
US2602052A (en) * 1950-08-03 1952-07-01 Petrolite Corp Processes for breaking petroleum emulsions
US2671762A (en) * 1951-03-24 1954-03-09 Sinclair Refining Co Process for resolving emulsions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3513005A (en) * 1966-10-05 1970-05-19 Ibe Ltd Coating with emulsions
US4439345A (en) * 1981-06-11 1984-03-27 Marathon Oil Company Demulsification of a crude oil middle phase emulsion
US20100025300A1 (en) * 2008-07-30 2010-02-04 Bp Corporation North America Inc. Controlling emulsion stability during fuel stock processing

Similar Documents

Publication Publication Date Title
US2076624A (en) Process for breaking petroleum emulsions
US2050924A (en) Process for breaking petroleum emulsions
US2828267A (en) Process for breaking petroleum emulsions
US2828266A (en) Process for breaking petroleum emulsions
US2353694A (en) Process for breaking petroleum emulsions
US2828269A (en) Process for breaking petroleum emulsions
US2839477A (en) Table ii
US2076623A (en) Process for breaking petroleum emulsions
US2226118A (en) Process for resolving petroleum emulsions
US1940394A (en) Process for breaking petroleum emulsions
US2278170A (en) Process for breaking petroleum emulsions
US2344978A (en) Process for breaking petroleum emulsions
US2671762A (en) Process for resolving emulsions
US2083225A (en) Process for breaking petroleum emulsions
US2344979A (en) Process for breaking petroleum emulsions
US2278164A (en) Process for breaking petroleum emulsions
US1988832A (en) Process for breaking petroleum emulsions
US2083224A (en) Process for breaking petroleum emulsions
US2050925A (en) Process for breaking petroleum emulsions
US2278167A (en) Process for breaking petroleum emulsions
US2372258A (en) Process for breaking petroleum emulsions
US2602057A (en) Process for breaking petroleum emulsions
US2108960A (en) Process for breaking petroleum emulsions
US2086215A (en) Processes for breaking petroleum emulsions
US1943815A (en) Process for breaking petroleum emulsions