US2539808A - Treatment of hydrocarbon oils - Google Patents
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- US2539808A US2539808A US749062A US74906247A US2539808A US 2539808 A US2539808 A US 2539808A US 749062 A US749062 A US 749062A US 74906247 A US74906247 A US 74906247A US 2539808 A US2539808 A US 2539808A
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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
- C10G29/06—Metal salts, or metal salts deposited on a carrier
- C10G29/12—Halides
Definitions
- ⁇ This'invention relates .to the treatment of sour hydrocarbon :oils to sweetenthesame. :In one of its 'more ⁇ ,speciic aspects, ⁇ this invention relates to theremoval of @Water of .reaction ,from a sys- ⁇ :teni vutilized tin the syveeitening :of inatural gasofline, refinery :straight Krun and ucracked ggasolines, petroleurn Ysoli/ent naphthas, ⁇ liquefied petroleum gases, kerosenes, :and tne like, ato convert the lsulphur -compomds such as ,rnereaptans therein ⁇ which-are responsiblerforbad odors or v ⁇ sourness landfor corrosiveness .of thes,e:hydrocarbon materials.
- itsfmore speciiic aspects relates to theremoval of @Water of .reaction ,
- lthis invention ⁇ relates to improvement in the fsweetening .of mercaptan-'bearing lighthydrocai'-,
- azsolid treating "agent comprising ⁇ highly porous or adsorbent material uch'as fullers vearth,charcoal,l or the like, is impregnated with a concentrated solution of cupriochloride, or other -cupric ,halideJ or ⁇ of a water-soluble veupric salt, such -as cupric sulfate, and a halide, suoli as sodium-chloride.
- Astream comprising a mercaptanfsuch -asfa sour hydrocarbon material, -is contacted with said reagent by passing it in the ⁇ liquid state, together with ydissolved oxygen-containing gas, Vat ordinary temperatures through the reagent bed.
- An object of the invention is to provide an improvement for copper sweetening processes whereby the sweetening of a very sour light hydrocarbon material by means of a solid reagent comprising a solution of copper salt and a halide adsorbed on a solid adsorbent carrier material may be accomplished efficiently and economically for more extended periods of time.
- a further object of the invention is to substantially reduce the number of shutdowns required in a copper sweetening unit to dehydrate the reagent.
- a still further object of the invention is to provide an improved process for converting mercapans to disuldes.
- the improvement comprises recycling a portion of the product stream, cooling the recycled stream to precipitate water formed during the process of converting the mercaptans, passing it through a lter to separate out free water, and adding the thus partially-dried recycled stream to the feed stream. In this manner substantial amounts of water are removed from the recycled stream thus making the parts of Water per unit of material l treated substantially the same as that contained in the original feed stream, but with a greater hydrocarbon volume and therefore a capacity to remove or carry larger quantities of water in solution.
- Water may be removed from this recycle stream if desired, by cooling to a low temperature, and/or by contact with a suitable desiccant, such as bauxite, silica gel, calcium chloride, or the like.
- a suitable desiccant such as bauxite, silica gel, calcium chloride, or the like.
- This combined stream is then heated, to substantially increase the moisture absorbing potential of the stream, and is then passed through the copper reagent chamber. It will also be noted that by recycling a portion of the sweetened product a decrease in mercaptan content per unit of combined feed is obtained, although the same amount of mercaptan would be passed through the reactor and the same amount oit' water would be formed as if no recyclewere used.
- the recycle sweet hydrocarbon will dissolve as much water proportionally as the sour net charge with the advantage that it will not cause the formation of free water.
- the original temperature of the light or low boiling hydrocarbon oil which is introduced into the system through line 6 and pump 'i is generally substantially that of the atmosphere. As it passes through heater 8 it is raised to a temperature between about 110 F. and about 130 F., preferably about 120 F. In this manner the moisture absorbing potential of the oil is substantially increased. Air or an equivalent gas which is needed to furnish the essential oxygen for reactivation of the reagent is supplied to the system through line 9. Oxygen may be injected instead of air but air is generally used for purposes of economy. There is nothing critical about the point at which the air is to be injected. Equally as efficient results are obtained by introducing air to the feed stream before heating as after the heating step.
- the air is injected at a pressure of between about 25 and about pounds per square inch, but such pressure is limited only by the operating pressure limit of the plant equipment, usually from about 15 to about 100 pounds per square inch.
- the amount should be sufficient to effect complete regeneration, based on complete conversion of mercaptans to disuldes, in accordance with the previously discussed reactions.
- the heated feed is introduced through line I0 into reagent chamber I2 where the reaction, above described, takes place.
- Sweetened hydrocarbons are removed through line I3 and are directed to storage through line I4.
- a portion ofv the sweetened oil is drawn off through line I'I and is supplied to dehydration means, such as cooler I8 and wateriilter I9. In cooler I3 the temperature of the sweetened hydrocarbon stream is reduced to a 40 point between about F.
- a process for sweetening a sour low boiling hydrocarbon 4stream which comprises the steps of heating said fstream to a temperature between about 110 Fand about 130 F.,ffurnish ing oxygen to said stream, contacting said stream with a reagent comprising an adsorbent material impregnated with a copper salt and a halide in thepres'ence'pf asrna'll portionv o'f water, and 4withdrawing Ia 'sweetened ⁇ hydrocarbon 'from contact with said reagent; the improvement y which comprises the steps of'fcooling'aportion 'of said sweetened hydrocarbon toa temperaturebetween'about" Frand about90" F.
- a process for converting mercaptans to disuliides which comprises the steps of heating a hydrocarbon mercaptan-containing stream, furnishing oxygen to said stream, contacting said stream with a reagent comprising an adsorbent material impregnated with a cupric halide in the presence of a small portion of Water, withdrawing a disulfide-containing stream :from contact with said reagent; the improvement which comprises the steps of partially dehydrating a portion of said disulfide-containing stream, combining said partially dehydrated disulde-containing stream with said mercaptan-containing stream, contacting said combined streams with said reagent, and removing a portion of water which is formed in the conversion of the mercaptant to disulde by dissolving said water in said partially dehydrated disulfide-containing stream.
- a process for converting mercaptans to disuldes which comprises the steps of heating a hydrocarbon mercaptan-containing stream, fur-- nishing oxygen to said stream, contacting said stream with a reagent comprising an adsorbent material impregnated with a copper salt and a halide in the presence of a small portion of water, and withdrawing a hydrocarbon disulfide-containing stream from contact with said reagent; the improvement which comprises the steps ci' partially dehydrating a portion of said disulde stream, combining said partially dehydrated disulfide-containing stream with said mercaptancontaining stream, contacting said combined stream with said reagent, and removing a portion of water formed in the conversion of the mercaptans to disulfides by dissolving said water in said partially dehydrated disulfide-containing stream portion.
- the improvement which comprises the steps of cooling a portion of said sweetened hydrocarbon so as to precipitate in said hydrocarbon water formed in the sweetening of said hydrocarbon, separating said ⁇ precipitated water therefrom, combining said sweetened and dehydrated stream with said sour feed stream, contacting said combined feed stream with said re agent, and removing a portion of water formed during said sweetening step from said reagent by dissolving said water in said sweetened and dehydrated portion of said feed stream.
- a process for sweetening a sour low boiling hydrocarbon stream which comprises the steps of heating said stream to a temperature between about 110 F. and about 130 F., dissolving air in said stream, contacting said stream with a reagent comprising an adsorbent material impregnated with a cupric halide in the presenceof f tion of water formed during Vsaidsweetening step from Said reagent by dissolving said water in said sweetened and dehydrated portion of said feed stream.
- a process for sweetening a sour low boiling hydrocarbon stream which comprises the steps of heating said stream, furnishing oxygen to said stream, contacting said stream with a reagent comprising an adsorbent material imp-regnated with a copper salt and a halide in the presence of a small portion of water, and withdrawing a sweetened hydrocarbon from contact with said reagent; the improvement which comprises.. the steps of partially dehydrating said sweetened stream, combining said sweetened and partially dehydrated stream with said sour feed stream, contacting said combined feed stream with said reagent, and removing a portion of water formed during said sweetening step from said reagent by dissolving said water in said sweetened and partially dehydrated portion of said feed stream.
Description
Jan. 3o, 1951 G. M. BROONER 2,539,808
TREATMENT OF HYDROCARBON OILS l Filed May 19,1947
INVENTOR` o. M. BRooNER ATTORN EYSW.
Patented Jan. 30, 1951 UNIT-ED 1ST-Ares PATENT OFFICE "TREATMENT lOld" HYDRARBON OILS l George'li. Brooner, Bartlesville, Ghia., lassigner to `Phillips Petroleum Company, a corporation of Delaware Application .May 19, 1947, Serial No.1749j062 (Cl. l96-e29) 12 Claims.
`This'inventionrelates .to the treatment of sour hydrocarbon :oils to sweetenthesame. :In one of its 'more `,speciic aspects, `this invention relates to theremoval of @Water of .reaction ,from a sys- `:teni vutilized tin the syveeitening :of inatural gasofline, refinery :straight Krun and ucracked ggasolines, petroleurn Ysoli/ent naphthas, `liquefied petroleum gases, kerosenes, :and tne like, ato convert the lsulphur -compomds such as ,rnereaptans therein `which-are responsiblerforbad odors or v`sourness landfor corrosiveness .of thes,e:hydrocarbon materials. In another of ,itsfmore speciiic aspects,
lthis invention `relates to improvement in the fsweetening .of mercaptan-'bearing lighthydrocai'-,
bon Amaterials by means Joi` a moistzsolid reagenxu comprising` acopper salt and ahalide adsorbed on carriers.
:Such unrened petroleum products lcontain mercaptans commonly `icalled sour elements,
'which give :the product aan undesirable odor.
lThese compounds havesometimes been altered, bythe sri-called doctoi process, a laborious, V'cumbersome `and very `unecon'omical chemical `treatment with alkali plumbite and sulfur. In
some instances-e. `gnvvitha Vnatural gasoline, the
-sweetening "reaction has tbeen accomplished through the 'use of alkaline hypochlorite solutions, but-thismethod, too,hasnot proved satisfa'ctoryfin most cases. .Sometimes .the sour `elements seem jto be particularly diliicult to `sweeten,'thereby requiring-large'quantities of Vthe reagent, and in .othencases theftreatment seems .to result Vin the Iintroduction-into the oil :of undesirable yconstituents as badas those originally present. Still other --methods have .been suggested for removal -or'conversion vof the mercaptans but-almost'withoutexception these methods Ainvolve numerous treating lsteps which demand 4such .close control-of theoperation-that the operfatigng .costs-are increased rse-:much .as to render `such-methods uneeonomical.
Successful, economical Y methods 'of .sweetening :Whichhave 110W comeointo common use are yso- Lcalled copper,sweetenirlgcprocesses which are now y.wellknown"in Vthe petroleum industry. One such process is .described by Buell vin U. ;S,Patent 12,094,485. .Inthat'typefoi-process azsolid treating "agent comprising `highly porous or adsorbent material uch'as fullers vearth,charcoal,l or the like, is impregnated with a concentrated solution of cupriochloride, or other -cupric ,halideJ or `of a water-soluble veupric salt, such -as cupric sulfate, and a halide, suoli as sodium-chloride. Astream comprising a mercaptanfsuch -asfa sour hydrocarbon material, -is contacted with said reagent by passing it in the `liquid state, together with ydissolved oxygen-containing gas, Vat ordinary temperatures through the reagent bed.
When -mercaptanszare passed irl-such a process Aover such a copperjhalideecontaining reagent the (2) ecuciorfinoir-owecuonao2h20 Thus when free oxygen `is in solution withthe hydrocarbon `material. at the time of sweetening, `reactions l and 2 occur `simultaneously and the reagent is maintained in an active state,
Fromreaction 1(2) however, it is apparent that another undesirable situation 4arises in that considerable amounts of water are `formed in maintenance of the reagent in an active state. This Water, unless carried out by the prod-uct stream, r'tends to Asaturate the Vreagent and frequently causes Vshutdovvns so that thejreagent can be dehydrated. y In attempting to overcome this trouble, it has been common `practice to Vinstall in the feed stream, asalt filter, sand filter or other means to remove any free or entrained Water from the feed vand following this to preheat the feed stream `at some point ahead of the copper treating tower. The preheating increases the capacity of the leed stream to dissolve Water therein. Having a `greater capacity to ,dissolve Water, the feed stream will tend to dissolve more of .the water .ofreaction and. to carryv more of it out of the reagent tower than it would at lower temperatures. This practice however frequently fails to remove an amount of water sufcient to prevent the reagent from rapidly becoming saturated.
An object of the invention is to provide an improvement for copper sweetening processes whereby the sweetening of a very sour light hydrocarbon material by means of a solid reagent comprising a solution of copper salt and a halide adsorbed on a solid adsorbent carrier material may be accomplished efficiently and economically for more extended periods of time.
A further object of the invention is to substantially reduce the number of shutdowns required in a copper sweetening unit to dehydrate the reagent.
A still further object of the invention is to provide an improved process for converting mercapans to disuldes.
Still other objects and advantages will be apparent to those skilled in the art from a careful study of the accompanying detailed disclosure.
I have now discovered an important improvement in converting mercaptans to disuldes, such as in the sweetening of a light or low boiling hydrocarbon material according to the previously described process utilizing a solid copper-containing reagent when the mercaptan content of the sour hydrocarbon is so great that the resultant water produced tends to saturate the reagent in a relatively short period o time. This process of converting mercaptans to disuldes is generally used in the sweetening of a sour hydrocarbon stream wherein the mercaptan concentration is relatively small. It may, however, be used in a process for commercially converting mercaptans to disuldes wherein the mercaptan concentration in relation to its hydrocarbon or other diluent which is non-reactive with the reagent, is relatively large. The improvement comprises recycling a portion of the product stream, cooling the recycled stream to precipitate water formed during the process of converting the mercaptans, passing it through a lter to separate out free water, and adding the thus partially-dried recycled stream to the feed stream. In this manner substantial amounts of water are removed from the recycled stream thus making the parts of Water per unit of material l treated substantially the same as that contained in the original feed stream, but with a greater hydrocarbon volume and therefore a capacity to remove or carry larger quantities of water in solution. Water may be removed from this recycle stream if desired, by cooling to a low temperature, and/or by contact with a suitable desiccant, such as bauxite, silica gel, calcium chloride, or the like. This combined stream is then heated, to substantially increase the moisture absorbing potential of the stream, and is then passed through the copper reagent chamber. It will also be noted that by recycling a portion of the sweetened product a decrease in mercaptan content per unit of combined feed is obtained, although the same amount of mercaptan would be passed through the reactor and the same amount oit' water would be formed as if no recyclewere used. At the same time, however, the recycle sweet hydrocarbon will dissolve as much water proportionally as the sour net charge with the advantage that it will not cause the formation of free water. By operation in this manner it is possible for the copper reagent tank to be maintained on stream for Substantially much greater periods of time without shutdowns for the purpose of dehydrating the reagent.
Referring now to the accompanying diagrammatic drawing, the original temperature of the light or low boiling hydrocarbon oil which is introduced into the system through line 6 and pump 'i is generally substantially that of the atmosphere. As it passes through heater 8 it is raised to a temperature between about 110 F. and about 130 F., preferably about 120 F. In this manner the moisture absorbing potential of the oil is substantially increased. Air or an equivalent gas which is needed to furnish the essential oxygen for reactivation of the reagent is supplied to the system through line 9. Oxygen may be injected instead of air but air is generally used for purposes of economy. There is nothing critical about the point at which the air is to be injected. Equally as efficient results are obtained by introducing air to the feed stream before heating as after the heating step. Usually the air is injected at a pressure of between about 25 and about pounds per square inch, but such pressure is limited only by the operating pressure limit of the plant equipment, usually from about 15 to about 100 pounds per square inch. The amount should be sufficient to effect complete regeneration, based on complete conversion of mercaptans to disuldes, in accordance with the previously discussed reactions. The heated feed is introduced through line I0 into reagent chamber I2 where the reaction, above described, takes place. Sweetened hydrocarbons are removed through line I3 and are directed to storage through line I4. A portion ofv the sweetened oil is drawn off through line I'I and is supplied to dehydration means, such as cooler I8 and wateriilter I9. In cooler I3 the temperature of the sweetened hydrocarbon stream is reduced to a 40 point between about F. and about 90 F., but preferably to about F. In this manner the ability cf the hydrocarbon stream to carry dissolved water is reduced and substantial amounts of water which were formed in the sweetening reaction and carried in the hydrocarbon stream are precipitated. lIt is obvious that some additional water may be separated from the oil stream by cooling below 60 F., and a desiccant may be used in conjunction with or in place of such a cooler and lter, but in most instances it is unnecessary and uneconomical to do so. The hydrocarbon stream is then passed from cooler I8 to illter I 9 where the entrained water is removed. Any conventional material may be used in the filter to coalesce and remove the condensed water out of the hydrocarbon stream. I prefer to use either sand or salt. Water which has been removed from the recycle stream is drained off through line 2B while the stream is fed through line 2I to the feed stream in line 6. As the amount of mercaptan will remain constant and the volume of water of formation is the same, saturation of the reaction chamber will be substantially reduced by means of the recycle portion because the portion of the stream which is already sweetened will take up its portion of the water but will not cause water to be formed.
In the following table a material balance 'is shown for a copper sweetening operation with and without recycle when charging a sour gasoline weighing 260 pounds per barrel with a mer'- captan (RSH) content of 0.03 weight per cent and entering the unit at 80 F. and being heated to F. The recycle operation utilizes a recycle ratio of 1:1. ,j
nimma "The vfollowing*table\'disclosesf'd'ata*vvliicwslfrovv clearly the effect the invention has n1i"^"tlre'op\er atingtime l"forra copper-"sweetening unit These data based on `the preceding. material :balan'c'efare for "a unit utilizingl 2,000 "pounds *of reagent.
:.TabZ'eH f- .1 y WithoutRe- Operation With Recycle v .,cyde
Weten Pounds/Day:
In Charge Stream "6:2552 FormedinSweeteningrReacti .f 221.048
-`Total ,27..600 `27. 600 Water'Eliminatedz In sweetened?ProductrJ4 l' 14% V976 .ByBecycle y Total 141976 14;!976 Water Remain t AP.ounds/Day i -v` 4. 200 12. 624 Penniss'ible Accumulation @Rc-g, .agent ,i260 260 I.Days Operation Before Dehydratl ving Ye2 2o It is apparent that ia `great ideal ofv` eziibilityiis "possible "in thismethod of "controlling 'the water content of thereagent byvarying"theamounts of the'sweetened* hydrocarbon which are recycled to the sour feed.stream,-theiamount of water removed from the recycle 'strearn,ari"d methods for tp'artiall-y dehydrating-fsaid "recycle lstream. 'fThe Ting hydrocarbon stream vwhich fcompr'ises the vsteps of' heating said stream, .furnishing oxygen to said stream, contacting said stream with a reagent comprising an adsorbent material impregnated with a copper salt and a halide in the presence of a small portion of water, and withdrawing a sweetened hydrocarbon from contact with said reagent; the improvement which comprises the steps of cooling a portion of said sweetened hydrocarbon so as to precipitatein `said hydrocarbon Water formed in the sweetening of said hydrocarbon, separating said precipitated water therefrom, combining said sweetened and dehydrated stream with said sour feed stream, contacting said combined vfeed stream with said reagent, and removing a portion of water formed during lsaid sweeteningQstep from said reagent by dissolving said water in said sweetened and dehydrated portion f said feed stream.
2. In a process for sweetening a sour low boiling hydrocarbon 4stream which comprises the steps of heating said fstream to a temperature between about 110 Fand about 130 F.,ffurnish ing oxygen to said stream, contacting said stream with a reagent comprising an adsorbent material impregnated with a copper salt and a halide in thepres'ence'pf asrna'll portionv o'f water, and 4withdrawing Ia 'sweetened `hydrocarbon 'from contact with said reagent; the improvement y which comprises the steps of'fcooling'aportion 'of said sweetened hydrocarbon toa temperaturebetween'about" Frand about90" F. vso as 'to pre- 'cipitate in said hydrocarbon wateriormed in fthe lsweeten'ing 'otsaid hydrocarbon,separating said precipitated "water therefrom, -combining l'said sweetened and dehydrated stream withsaid sour feed stream, Wcontacting said combined feed "stream with'said Vreagrennand removing a portion'of water' formedduringsaidsweetening `step from said reagent by -dissolving saidwater insaid Asweetenedand dehydrated portion of saidieed stream.
3. 'In a process'ior sweetening a'sour low boilin'g hydrocarbon stream which comprises the "steps 'of 'heating'said streamv to `a temperature Vbetween about 11'0u F. and 'about 130 dissolving 'air in 'said stream, 'contacting"'saidstream with'a'reagent comprising an adsorbent material impregnated "with a copper 'salt and a halide lin the 'presence vof a Small portion 'of water, and withdrawing `a sweetened "hydrocarbon Vfrom contact with said reagent; the improvement lwhichcomprises thel stepsof cooling a portionof said sweetened hydrocarbon rto a temperature *betweenabout 60 .F.and about 90 F. so `as to precipitate insaid hydrocarbon water formed in tiie sweetening of said hydrocarbon, passing 'said `'sweetened `hydrocarbon"through 'a vlterto remove said .precipitated Vwater from said stream, -corx'ibi'ningsaid sweetenedand'dehydrated stream w'thvsaid sor 'feed stream, contacting said combinedfeed stream withzsaid reagent, and removing'a portionof wateriformed during said'sweetening step from said reagent by dissolving said water in said sweetened and dehydrated portion of said feed stream.
4. In a process for converting mercaptans to disuliides which comprises the steps of heating a hydrocarbon mercaptan-containing stream, furnishing oxygen to said stream, contacting said stream with a reagent comprising an adsorbent material impregnated with a cupric halide in the presence of a small portion of Water, withdrawing a disulfide-containing stream :from contact with said reagent; the improvement which comprises the steps of partially dehydrating a portion of said disulfide-containing stream, combining said partially dehydrated disulde-containing stream with said mercaptan-containing stream, contacting said combined streams with said reagent, and removing a portion of water which is formed in the conversion of the mercaptant to disulde by dissolving said water in said partially dehydrated disulfide-containing stream.
5. The process of claim 4, wherein oxygen is furnished by means of the introduction of air to said stream.
6. In a process for converting mercaptans to disuldes which comprises the steps of heating a hydrocarbon mercaptan-containing stream, fur-- nishing oxygen to said stream, contacting said stream with a reagent comprising an adsorbent material impregnated with a copper salt and a halide in the presence of a small portion of water, and withdrawing a hydrocarbon disulfide-containing stream from contact with said reagent; the improvement which comprises the steps ci' partially dehydrating a portion of said disulde stream, combining said partially dehydrated disulfide-containing stream with said mercaptancontaining stream, contacting said combined stream with said reagent, and removing a portion of water formed in the conversion of the mercaptans to disulfides by dissolving said water in said partially dehydrated disulfide-containing stream portion. l
7. The process of claim 4, `wherein oxygen is furnished by means of the introduction of air to said stream.
8. Ina process for sweetening a sour low boiling hydrocarbon stream which comprises the steps of heating said stream, furnishing oxygen to said stream, contacting said stream with a reagent comprising an adsorbent material impreg nated with a cupric halide in the presence of. a small portion of water, and withdrawing a sweetened hydrocarbon from contact with said reagent; the improvement which comprises the steps of cooling a portion of said sweetened hydrocarbon so as to precipitate in said hydrocarbon water formed in the sweetening of said hydrocarbon, separating said `precipitated water therefrom, combining said sweetened and dehydrated stream with said sour feed stream, contacting said combined feed stream with said re agent, and removing a portion of water formed during said sweetening step from said reagent by dissolving said water in said sweetened and dehydrated portion of said feed stream.
9. In a process for sweetening a sour low boiling hydrocarbon stream which comprises the steps of heating said stream to a temperature between about 110 F. and about 130 F., dissolving air in said stream, contacting said stream with a reagent comprising an adsorbent material impregnated with a cupric halide in the presenceof f tion of water formed during Vsaidsweetening step from Said reagent by dissolving said water in said sweetened and dehydrated portion of said feed stream.
10. The process of claim 9 wherein said filter is a sand lter.
11. rIhe process of claim 9 wherein said lter is a salt filter.
12. In a process for sweetening a sour low boiling hydrocarbon stream which comprises the steps of heating said stream, furnishing oxygen to said stream, contacting said stream with a reagent comprising an adsorbent material imp-regnated with a copper salt and a halide in the presence of a small portion of water, and withdrawing a sweetened hydrocarbon from contact with said reagent; the improvement which comprises.. the steps of partially dehydrating said sweetened stream, combining said sweetened and partially dehydrated stream with said sour feed stream, contacting said combined feed stream with said reagent, and removing a portion of water formed during said sweetening step from said reagent by dissolving said water in said sweetened and partially dehydrated portion of said feed stream.
' GEORGE'M. BROONER.
REFERENCES CITED The following references are of record in the file `of this patent:
Claims (1)
1. IN A PROCESS FOR SWEETENING A SOUR LOW BOILING HYDROCARBON STREAM WHICH COMPRISES THE STEPS OF HEATING SAID STREAM, FURNISHING OXYGEN TO SAID STREAM, CONTACTING SAID STREAM WITH A REAGENT COMPRISING AN ADSORBENT MATERIAL IMPREGNATED WITH A COPPER SALT AND A HALIDE IN THE PRESENCE OF A SMALL PORTION OF WATER, AND WITHDRAWING A SWEETENED HYDROCARBON FROM CONTACT WITH SAID REAGENT; THE IMPROVEMENT WHICH COMPRISES THE STEPS OF COOLING A PORTION OF SAID SWEETENED HYDROCARBON SO AS TO PRECIPITATE IN SAID HYDROCARBON WATER FORMED IN THE SWEETENING OF SAID HYDROCARBON, SEPARATING SAID PRECIPITATED WATER THEREFROM, COMBINING SAID SWEETENED AND DEHYDRATED STREAM WITH SAID SOUR FEED STREAM, CON-
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| US749062A US2539808A (en) | 1947-05-19 | 1947-05-19 | Treatment of hydrocarbon oils |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2653125A (en) * | 1950-12-27 | 1953-09-22 | Standard Oil Co | Process for sweetening hydrocarbon oils |
| US2859248A (en) * | 1956-07-11 | 1958-11-04 | Phillips Petroleum Co | Oxidation of organic sulfides |
| US3192152A (en) * | 1961-07-21 | 1965-06-29 | Shell Oil Co | Process for the removal of mercaptans from hydrocarbon oils |
| US4868336A (en) * | 1987-11-20 | 1989-09-19 | Phillips Petroleum Company | Manufacture of disulfides |
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| USRE20938E (en) * | 1938-12-06 | Process for purifying hydrocarbon | ||
| US2264220A (en) * | 1938-11-09 | 1941-11-25 | Phillips Petroleum Co | Treatment of hydrocarbon oils |
| US2297650A (en) * | 1939-10-19 | 1942-09-29 | Socony Vacuum Oil Co Inc | Method of treating oils |
| US2315820A (en) * | 1940-05-27 | 1943-04-06 | Phillips Petroleum Co | Process for sweetening sour hydrocarbon oil |
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1947
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE20938E (en) * | 1938-12-06 | Process for purifying hydrocarbon | ||
| US2264220A (en) * | 1938-11-09 | 1941-11-25 | Phillips Petroleum Co | Treatment of hydrocarbon oils |
| US2297650A (en) * | 1939-10-19 | 1942-09-29 | Socony Vacuum Oil Co Inc | Method of treating oils |
| US2315820A (en) * | 1940-05-27 | 1943-04-06 | Phillips Petroleum Co | Process for sweetening sour hydrocarbon oil |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2653125A (en) * | 1950-12-27 | 1953-09-22 | Standard Oil Co | Process for sweetening hydrocarbon oils |
| US2859248A (en) * | 1956-07-11 | 1958-11-04 | Phillips Petroleum Co | Oxidation of organic sulfides |
| US3192152A (en) * | 1961-07-21 | 1965-06-29 | Shell Oil Co | Process for the removal of mercaptans from hydrocarbon oils |
| US4868336A (en) * | 1987-11-20 | 1989-09-19 | Phillips Petroleum Company | Manufacture of disulfides |
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