US2766180A - Process for sweetening a hydrocarbon oil with an alkanol amine, sodium plumibte sulfur and air - Google Patents

Process for sweetening a hydrocarbon oil with an alkanol amine, sodium plumibte sulfur and air Download PDF

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US2766180A
US2766180A US361944A US36194453A US2766180A US 2766180 A US2766180 A US 2766180A US 361944 A US361944 A US 361944A US 36194453 A US36194453 A US 36194453A US 2766180 A US2766180 A US 2766180A
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oil
sweetening
sulfur
agent
pbs
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Mathew L Kalinowski
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Standard Oil Co
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Standard Oil Co
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Priority to BE528999D priority patent/BE528999A/xx
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Priority to FR1107139D priority patent/FR1107139A/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/02—Non-metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • C10G19/06—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions with plumbites or plumbates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/04—Metals, or metals deposited on a carrier

Definitions

  • This invention relates to the sweetening of sour hydrocarbon oils. More particularly the invention relates to an improvement in the sweetening of sour petroleum distillates by the doctor process.
  • doctor process The oldest and probably most common sweetening process now in use is the so-called doctor process wherein an aqueous caustic-sodium plumbite solution and free sulfur are used to convert the mercaptans to disulfides.
  • the doctor process has many disadvantages which arise primarily from the formation of insoluble lead sulfide. Frequently extremely prolonged settling times are required to remove the PbS from the hydrocarbon oil.
  • a blackstrap layer which is a fairly stable emulsion of doctor solution, PbS and oil can be separated only by long settling times or by filtration.
  • a further disability of the doctor process lies in the fact that kerosenes and heater oils that have been doctor sweetened generally show an increase in burner deposits as compared with the sour oil.
  • An object of the invention is to improve the sweetening of sour hydrocarbon oils by means of the doctor process. Another object is to improve the sweetening of sour. petroleum distillates which boil in the heavier-than-gasoline range, i. e., between about 325 and 650 F. Still ice another object is the sweetening of sour hydrocarbon oils by an improved doctor process wherein the spent doctor solution is regenerated at moderate temperatures in a reasonable time. A further object is the sweetening of sour hydrocarbon oils by an improved doctor process wherein the sweetening'reaction and the regeneration reaction are carried out substantially simultaneously.
  • a particular object isthe sweetening of a sour heater oil by an improved doctor process wherein substantially simultaneous regeneration of the doctor solution and the sweetening of the oil takesplace and the conventional separate spent doctor regeneration procedure is eliminated.
  • spent doctor solution from the treatment of sour hydrocarbon oils can be readily regenerated by free-oxygen contacting at moderate temperatures, i. e., below about F. by having present in said spent doctor solution an effective amount of an alkanolamine containing from 2 to 3 carbon atoms in each alkyl group.
  • the sweetening agent a doctor solution containing an effective amount of an alkanolamine containing from 2 to 3 carbon atoms in each alkyl group and contacting the free sulfur-sour oilagent mixture with free-oxygen for a time sufiicient not only to sweeten the sour oil but also to convert the PbS formed to water-soluble plumbite.
  • the aqueous sweetening agent phase is separated from the sweet oil phase and is recycled to the sweetening zone.
  • the hydrocarbon oil feed to the process of this invention may be any liquid hydrocarbon oil containing detectable amounts of mercaptans, i. e., the oil should be sour to the conventional doctor test or should have a mercaptan number or copper number above about 1.
  • the process is particularly suitable for the treatment of sour petroleum distillates boiling below about 750 F. Examples of these distillates are naphtha, kerosene, diesel oil, heater oil, gas oil, etc.
  • the process may be used on distillates obtained by the fractional distillation of crude petroleum or on distillates obtained from various conversion processes such as thermal cracking, catalytic cracking, reforming in the presence of hydrogen, etc. Sour petroleum distillates boiling in the heavier-than-gasoline range, i. e., between about 325 and 650 F., e. g., a heater oil boiling between about 330 and 575 F. are a preferred feed.
  • the sweetening agent of this invention consists of a conventional doctor solution and a water-soluble aliphatic amine.
  • the doctor solution is made up of an aqueous solution of an alkali metal hydroxide and the reaction product of litharge and the alkali metal hydroxide.
  • the amount of free-alkali metal hydroxide present in the doctor solution may be between about 5 and 30 weight percent, usually between about 10 and 15%.
  • the plumbite content is commonly given in terms of the percent of PbO theoretically present. This content for a fresh doctor solution is usually between about 1.5 and 2.5% based on aqueous caustic solution.
  • the process is operative with any range of doctor solution compositions that are operable in a conventional doctor process.
  • the preferred amines of this invention are the watersoluble alkanolamines.
  • the term water soluble is intended to include those alkanolamines which are sufliciently soluble to have a beneficial effect.
  • the alkanolamines should be soluble to the extent of at least about 2 volume percent based on doctor solution.
  • the most suitable alkanolamines are those wherein not more than 3 carbon atoms are present in each alkyl group or, conversely, wherein each alkyl group contains from 2 to 3 carbon atoms. Examples of these alkanolamines are mono, diand triethanolamine and the propanolamines.
  • amines which are suitable for the purposes of this invention are: (a) alkanol diamines containing from 3 to carbon atoms such as propanol diamines and butanol diamincs; (b) alliandiolamines containing from 3 to 5 carbon atoms such as the propandiolarnines and pentandiolamines; and (c) alkandiamines containing from 2 to 3 carbon atoms such as ethylene diamine and trimethylene diamine.
  • alkanolamines For purposes of brevity the invention is described hereinafter in terms of the alkanolamines.
  • the amount of alkanolamine present in the sweetening agent, i. e., the solution of doctor solution and alkanolamine must be at least enough to have an appreciable beneficial effect on the time of the PbS conversion.
  • beneficial effects are obtained when using amounts of alkanolamine as small as 0.5 volume percent. Larger amounts may be usei. e. g., as much as 50 volume percent; for reasons hereinatter explained, it is preferred to use between about 1 and 4%.
  • the optimum usage of alkanolamine will vary with the type of sour distillate being charged.
  • alkanolamine effects the sweetening reaction and the conversion reaction, i. e., PbS piumbite, differently. That is, the presence of alkanolamine increases the rate at which the PbS is converted and decreases the rate of sweetening.
  • high concentrations of alkanolarnine in the sweetening agent result in relatively short PbS conversion time and, on the other hand, the sweetening time is shortened by maintaining a low concentration of alkanolamine in the sweetening agent.
  • sweetening time in this process is somewhat longer than when using conventional doctor solution.
  • a practical balance between the sweetening reaction and the PbS conversion reaction is obtained when using be tween about 1 and 4% of alkanolamine such as triethanolamine.
  • the amount of sulfur present should be controlled to a level below that at which corrosive sulfur appears in the product oil, i. e., corrosive sulfur as determined by the copper strip test. Also, it has been found that the higher the concentration of alkanolamine, the greater the amount of excess sulfur that must be utilized in the process to obtain res'onable sweetening times, e. g., excess at 2% alkanolamine and 75% excess at 50% alkanolamine. In general the amount of sulfur added in excess of the theoretical amount (hereinafter referred to as a percentage of the theoretical quantity, e. g., 10% excess sulfur, is equal to 110% of the theoretical) may vary from 5% or less to as much as 100% or more. When operating on sour distillates boiling in the heavier-than-gasoline range it is preferred to use between about 10 and 30% excess free-sulfur.
  • a percentage of the theoretical quantity e. g. 10% excess sulfur
  • the free-oxygen may be introduced in the form of a readily reducible compound such as permanganate or hydrogen peroxide, or free-oxygen itself, or in the form of atmospheric air.
  • the temperature at which the sour oil-agent-oxygen-sulfur are contacted may be in general those temperatures used in conventional doctor treating, i. e., between about 50 and 175 F. It is to be understood that the treating temperature may be determined by the flash point of the particular sour oil charged to the process. Thus when operating with naphthas, temperatures on the order of 70 P. will be used; when operating with a kerosene, temperatures between about and F. may be used; and when operating with a high flash point material such as a high boiling furnace oil, temperatures as much as F. or higher may be used. Still another limitation on the contacting temperature may be color formation in the oil, e.
  • some herosenes rapidly develop color bodies when exposed for prolonged times at temperatures above about 100 F. It is preferred to operate at about the maximum temperature permitted by the type of stock used in order to decrease the PbS conversion time.
  • the PbS conversion time is very favorably iufluenced by increase in the temperature of the contacting zone.
  • the contact time needed in the contacting zone determined by the rate at which the simultaneous reactions take place.
  • the sweetening reaction and the PbS conversion reaction generally have different rates; it is possible by adjusting the alkanolamine concentration, the percent excess sulfur and the contacting temperature to obtain essentially identical reaction times.
  • the sweetening reaction is usually appreciably faster than the PbS con version reaction.
  • the concentration of alltanolaminc is increased the PbS conversion reaction rate increases while the sweetening reaction rate decreases.
  • the sweetening reaction is definitely slower than the PbS conversion reaction.
  • the amount of excess sulfur has a definite effect On the reaction rates.
  • the contacting must be maintained for a time at least long enough to both sweeten the oil and to convert substantially all the PbS to the plumbite. It has been found that the conversion of PbS continues after the separation of the agent phase from the oil phase. Thus it is not necessary to carry out the conversion reaction completely in the contacting zone. Usually a completely regenerated agent will be recycled to the contact-- ing zone when the PbS conversion reaction has proceeded to about 95% of completion prior to separation of the agent phase from the oil phase.
  • the contacting time is influenced by (a) the percent excess sulfur, (b) the alkanolamine concentration and (c) the temperature, contacting time will be discussed in terms of varying only one of these factors.
  • the contacting time for obtaining a sweet product and a regenerated agent may be as much as 4 to 6 hours at a temperature of about 60 F.; at a temperature of about 150 F. the contacting time may be as short as about 10 minutes. Thus higher temperatures correspond to shorter contacting times.
  • the necessary contacting time may be between about 1 and 2 hours at about 80 F. and 20% excess sulfur.
  • the contacting time may be between about 3 and 4 hours, i. e., the higher alkanolamine concentrations correspond to longer contacting times.
  • the sweetening time is essentially infinite.
  • the sweetening time at about 80 F. and 2% alkanolamine concentration is about 2 hours.
  • the corresponding contacting time is about onehalf hour, i. e., the higher free-sulfur usages correspond to the shorter contacting times.
  • the regeneration need not be carried out in the presence of the oil that is being sweetened.
  • the sweet oil may be separated from the spent sweetening agent prior to regeneration of the spent agent.
  • the regeneration may then be completed by contacting the spent sweetening agent with air for a time 'sufiicient to convert the PbS and thereby regenerate the agent.
  • This method of operation is of particular value in the sweetening of naphthas wherein the relatively low temperature of contacting requires a prolonged contacting time in order to regenerate the agent, i. e., when using low concentrations of alkanolamine and relatively small amounts of excess sulfur.
  • the sweetening agent, free-sulfur, free-oxygen and sour oil are contacted for a time sufiicient to complete the sweetening reaction. Some PbS conversion also takes place.
  • the sweet oil is then separated from the spent agent and the spent agent contacted with air either at the temperature of the sweetening zone or at some higher temperature in order to speed up the regeneration until the PbS has been converted.
  • the regenerated sweetening agent is then recycled to the sweetening zone.
  • sour oil from source 11 is passed by Way of line 12 into heat exchanger 13.
  • the sour oil is a heater oil boiling between about 330 and 570 F. and has a mercaptan number of 65. derived by distillation from a high sulfur Texas crude.
  • the sour oil is substantially HzS-free and no prewash with aqueous caustic solution is carried out.
  • the sour oil contains appreciable amounts of H28 it is desirable to avoid loss of the caustic in the agent by prewashing the sour oil with aqueous caustic solution.
  • the sour oil is raised in heat exchanger 13 to a temperature high enough to provide a contacting zone temperature of about 130 F.
  • the hot sour oil is passed from heat exchanger 13 into line 14.
  • a small amount of the hot sour oil is withdrawn from line 14 and is passed by way of valved line 16- into sulfur drum 17.
  • Sulfur drum 17 is a vessel filled with elemental sulfur such as flowers of sulfur. The hot sour oil dissolves some of this sulfur and the free-sulfur containing oil is passed from sulfur drum 17 by way of valved line 18 back into line 14 where it meets the remainder of the hot sour oil.
  • sufiicient free-sulfur is dissolved to have present in the sweetening zone about 30% more
  • This sour oil is the run proceeds the addition ofsweeteningagent will be limited to makeup quantities.
  • the amount of sweet-' ening agent is at least enough to form a separate sweetening agent phase and may be between about'l and 20 volume percent based on sour oil. In this illustration 4 volume percent of sweetening agent is used.
  • the sweet ening agent consists of (a) doctor solution composed of about 12% of free sodium hydroxide and about 2% of PbO and (b) 2.5 volume percent of triethanolamine.
  • Air from source 26 is passed by way of line 27' into line 23.
  • the amount of air present must be at least enough to oxidize the PbS formed in the reaction, i. e., 2 mols of free-oxygen per mol of PbS formed. More" than this amount is desirable.
  • the sweetening agent and the air in line 23 are introduced into line 14 at a point beyond the entry of the free-sulfur containing oil.
  • the sweetening agent, air, sour oil and free-sulfur are introduced into reactor 28.
  • Reactor 28 is a vertical cylindrical vessel provided with a vent 29 and a motor-driven stirrer 31.
  • the stirrer in this illustration is provided with three turbine blades.
  • In order to improve agitation reactor 28' is provided with horizontal baflles 32a and 32b.
  • a mechanically agitated reactor is shown herein, it is to be understood that other methods of ob taining intimate contacting may be used, e. g., the reactor may be agitated with air. Also, an orifice mixer which provides a sufiicient contacting, time may be used.
  • reactor 28 The contents of reactor 28 are maintained at a temperature of about F. for 30 minutes in order to insure sweetening and substantially complete conversion of the' PbS. Sweet oil. andagent are withdrawn at a trap-out point near the top of reactor 28 and are passed by way of line 34 into separator 36.
  • Separator 36 is a substantially horizontal cylindrical vessel providing suflicient settling time for the formation of a separate agent phase and an oil phase. Separator 36 is provided with a vent 37 for the withdrawal of excess air.
  • the lower agent phase is withdrawn from separator 36 by way of line 39. Normally the agent from line 39 is recycled to reactor 28 by way of lines 23 and 14. The conversion reaction results in the formation of water and sodium sulfate which dilute the agent. Periodically the agent is withdrawn from the system by way of line 39 and valved line 41.
  • the oil phase is withdrawn from separator 36 by way of line 44.
  • This oil phase contains a very slight amount of occluded agent.
  • the occluded agent may be removed from the sweet oil by either water Washing or by coalescing.
  • the oil phase is passed from line 44 into coalescer 46.
  • Coalescer 46 is a vertical cylindrical vessel provided with glass wool. Instead of glass wool, coalescer may be filled with crushed rock, sand or rock salt. Sweet hazefree product oil is withdrawn from the top of coalescer 46 and is passed to storage not shown by way of line 48.
  • the agent separated in coalescer 46 is withdrawn from the bottom thereof by way of line 51. This agent may be recycled to reactor 28 by way of valved line 52, line 39, etc.; or it may be withdrawn from the system by way of valved line 54-.
  • the agent withdrawn by way of lines 41 and 54 is preferably treated to recover the triethanolamine and the lead content.
  • the lead may be precipitated by treatment of the agent with hydrogen sulfide and oxidation of the PbS to PbO.
  • the triethanolamine may be recovered from aqueous solution by fractional distillation.
  • the contacting zone consisted of a 3- necked glass flask with a capacity of 2 liters.
  • the flask was provided with a motor-driven stirrer, a thermometer and an electrically heated jacket. The sides of the flask were creased to improve agitation.
  • One liter of HzS-free sour oil was charged in each run.
  • Twenty ml. of sweetening agent was used in each run. Except when indicated otherwise, the agent consisted of (a) doctor solution containing 11% NaOH and 1.8% Pb() and (b) the triethanolamine (hereinafter designated TEA). Unless otherwise indicated, all the experiments were carried out at 90 F.
  • the experiments were carried out by adding the sour oil and the agent to the flask in that order. Stirring was begun immediately after adding the sour oil. After the initial contact of sour oil and a ent, the desired amount of free-sulfur was added to the flask in the form of a 1% solution in xylene. Air was bubbled through the flask from the time of agent addition. The stirring was continued until both the sweetening reaction and the PbS conversion reaction were completed. The stirrer was then stopped and the contents of the flask settled for about 30 minutes, after which time the lower agent layer was separated. The product oil was dehazed by passage through a filter paper coalescer or by Water washing followed by dehazing through a filter paper coalescer.
  • the contacting temperature was 90 F. and 2 volume percent of agent was used.
  • Runs 1d, 2d and 30, which are examples of conventional doctor treating, show that no detectable amount of PbS conversion was obtained in the absence of TEA even though a sweet oil was obtained. These runs further show the conventional decrease in sweetening time as the percent excess sulfur is increased.
  • Runs 1, 2 and 3 clearly show the adverse effect of increasing TEA concentration on the sweetening time, at constant excess sulfur usage.
  • Runs 1, 2 and 3 clearly show the beneficial effect of increasing TEA concentration on the time needed to convert 9095% of the PbS formed. It is pointed out here that the times given are cumulative, i. e., the longer time represents the total time of contacting the oil and the agent.
  • Runs 10, 2c and 312 show the more normal situation wherein the sweetening time is shorter than the PbS conversion time.
  • the oil was found to be sweet to the doctor test in the times shown even though the contacting zone still contains'considerable amounts of PbS.
  • Run 10 shows that after 60 minutes the oil was sweet and that an'additional 60 minutes of agitation in the presence of air was needed to complete the PbS conversion reaction.
  • Sweet PbS Con- Oil version 10 5.0 240 75 0 l0 3. 5 240 0 10 2.0 60 120 1 10 None 50 C) 1+ 20 5.
  • Runs 1a, 2a and 3 illustrate situations where sweetening reaction was slower than the PbS conversion reaction.
  • the PbS precipitate was formed immediately after the addition of the agent to the sour oil and at the time indicated all the PbS had disappeared; however, the oil was still sour to the doctor test. Additional contacting was necessary after the PbS had disappeared in order to obtain a sweet oil.
  • Run 4 This run was carried out in the manner similar to Runs 1-3 except that the separated agent phase was used to contact a fresh portion of sour oil, i. e., conventional recycling procedure was simulated.
  • Run 4d shows that sweetening agent can be reused at least four times with no loss in etficiency and essentially no loss of plumbite. All the runs are at a 2% concentration of TEA in the agent. The results of these runs are presented below:
  • the eflFect on the corrosiveness of the product oil was measured by means of the copper strip test in Runs 1-3.
  • the copper strip corrosion is determined for an oil by immersing a copper strip in the oil for 3 hours at 212 F.
  • the corrosiveness of the oil in this specification has been determined by the Bolt copper strip number technique. This technique is described in the August 9, 1947 issue of the Oil and Gas Journal. In this method the number is assigned to a perfect strip, i. e., equal to a strip prior to being used in a test. The higher the number assigned to a strip after the test, the more corrosive the oil.
  • Run 6 In this run there was used a heater oil boiling between 332 and 560 F. having a mercaptan number of 64. These tests were carried out using 10 volume percent of doctor solution or 10 volume percent of agent based on oil. One hundred percent excess sulfur was used in each test and the contacting temperature was 120 F. The times needed for obtaining a sweet oil and for PbS conversion were noted at various TEA concentrations. In this run comparative information was obtained on the burning quality of the heater oil.
  • the Jungers burner is an example of an extremely sensitive sleeve-type burner. Because of this sensitivity the Jungers burner has been adopted by many refiners as a standard test burner for determining the burning quality of domestic heating oils.
  • a full scale test using the Jungers burner involves the burning of many gallons of oil and many days of operation.
  • a simple laboratory procedure has been developed which adequately predicts the results obtainable in the full size Jungers burner test. This laboratory method is known as the steel dish deposit test" or steel dish gum test.
  • the steel dish deposit test is carried out as follows: An 188 stainless steel dish is maintained at a temperature of 500 F. by means of a hot plate.
  • the dish is saucershaped and has the following dimensions: Outside diameter, 2 inches; thickness at the edge, f inch; thickness at the center of the dish, inch.
  • the depression in the dish corresponds :to a section of a sphere.
  • the dish is provided with a thermocouple which permits the temperature of the dish to be measured.
  • the dish i placed on a hot plate, the temperature of which is adjusted to maintain the dish at about 500 F.
  • the oil to be tested is dripped at a substantially constant rate onto the dish. The rate of evaporation of the oil from the dish should be substantially equal to the rate of addition of the oil to the dish, i.
  • the dish always contains a film of liquid oil.
  • a 400 ml. sample of oil is used in each test and the oil is added dropwise to the dish at a rate of about 1 ml. per minute.
  • the dish is removed from the hot plate and allowed to cool.
  • a doctor sweetening process which comprises contacting a hydrocarbon oil which contains an amount of mercaptans at least sufficient to render said oil positive to the doctor test, in the presence of free-sulfur, in an amount appreciably in excess of the theoretical amount needed to convert said mercaptans to disulfides, and freeoxygen, with doctor solution containing between about 0.5 and 50 volume percent of an alkanolamine containing not more than 3 carbon atoms in each alkyl group for a time at least suflicient to convert essentially all of said mercaptans to disulfides and separating a doctorsweet oil from said solution.
  • a process which comprises (A) contacting a sour petroleum distillate boiling in the heavier-than-gasoline range With between about 1 and 20 volume percent, based on distillate, of a sweetening agent comprising (a) from about 0.5 to 50 volume percent of an ethanolamine and (b) the remainder essentially conventional doctor solution, in the presence of (i) between about 5 and 100% in excess of the theoretical requirement of free-sulfur and (ii) at least a suflicient amount of free-oxygen to convert substantially all the PbS formed in the process, at a temperature between about 50 and 175 F. for a time at least suflicient to substantially sweeten said distillate and to convert substantially all of the PbS formed in the process, and (B) separating a substantially sweet distillate from a substantially regenerated sweetening agent phase.
  • a sweetening agent comprising (a) from about 0.5 to 50 volume percent of an ethanolamine and (b) the remainder essentially conventional doctor solution, in the presence of (i) between about 5 and
  • step (B) is recycled for reuse in step (A).

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US361944A 1953-06-16 1953-06-16 Process for sweetening a hydrocarbon oil with an alkanol amine, sodium plumibte sulfur and air Expired - Lifetime US2766180A (en)

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NL94791D NL94791C (sk) 1953-06-16
BE528999D BE528999A (sk) 1953-06-16
US361944A US2766180A (en) 1953-06-16 1953-06-16 Process for sweetening a hydrocarbon oil with an alkanol amine, sodium plumibte sulfur and air
FR1107139D FR1107139A (fr) 1953-06-16 1954-05-19 Perfectionnements relatifs au procédé <doctor> d'adoucissement des pétroles

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1767356A (en) * 1927-08-19 1930-06-24 Standard Oil Dev Co Process for purification of hydrocarbon oils
US2366545A (en) * 1943-12-08 1945-01-02 Petrolite Corp Processes for sweetening hydrocarbon oils

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1767356A (en) * 1927-08-19 1930-06-24 Standard Oil Dev Co Process for purification of hydrocarbon oils
US2366545A (en) * 1943-12-08 1945-01-02 Petrolite Corp Processes for sweetening hydrocarbon oils

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FR1107139A (fr) 1955-12-28

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