US2417236A - Heating oil - Google Patents

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US2417236A
US2417236A US571100A US57110045A US2417236A US 2417236 A US2417236 A US 2417236A US 571100 A US571100 A US 571100A US 57110045 A US57110045 A US 57110045A US 2417236 A US2417236 A US 2417236A
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heating oil
heating
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oil
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Artie Q Cato
Wash George
Albert J Shmidl
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Standard Oil Development Co
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Standard Oil Development Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/04Liquid carbonaceous fuels essentially based on blends of hydrocarbons

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  • the present invention is directed to a liquid composition particularly adapted for use as a fuel oil in home heating installations. More particularly, it relates to a composition of good color stability and product quality which is produced by blending petroleum heating oil fractions.
  • Heating oils as mentioned herein will be taken to include petroleum oil fractions boiling up to about 660 F. and having a gravity of at least 30 API.
  • the oil should be of at least 10 color as measured by the Tag-Robinson color machine ⁇ and should have a ash point between about 130 and 190 F.
  • the oil should not corrode or plug the burning equipment and this tendency is usually reflected by an oil passing the suspended sediment and copper strip corrosion tests.
  • the conventional treating methods for heating oil fractions in the petroleum refinery usually include distillation, acid treating, caustic washing and doctor sweetening operations.
  • distillation acid treating, caustic washing and doctor sweetening operations.
  • streams for filtration which filtration operation is usually required to remove from the heating oils suspended matter which, if left to remain in the heating oil, would be objectionable in operation of the heating equipment.
  • Heating oil fractions boiling up to about 660 F. may be obtained by distilling either cracked or crude petroleum products. These materials usually require nishing treatment before they are suitable for use as fuel for heating systems.
  • heating oil fractions were obtained from thermally cracked products and from crude petroleum. These fractions as mentioned before are amenable to finishing operations which may include acid treatment, caustic washing, doctor sweetening, and finally filtration.
  • finishing operations may include acid treatment, caustic washing, doctor sweetening, and finally filtration.
  • the main object of the present invention to provide a treating and blending procedure for obtaining a heating oil of good quality which includes heating oi1 components from crude petroleum, thermally cracked naphtha and catalytically cracked naphtha.
  • heating oil fractions i. e., fractions boiling between about 350 and 700 F. are segregated from crude petroleum, and mixed with the heating oil fraction from a thermal cracking operation after the heating oil fraction from the thermal cracking operation has undergone acid treatment, caustic neutralization and rerunning to segregate from the acid treated product a fraction similar in boiling range to that obtained from the distillation of the crude petroleum.
  • the combined streams are then treated withan alkaline solution, and after removal of the alkaline solution from the treated oil, the oil is then doctor sweetened as in conventional practice. Following the doctor sweetening operation the resulting alkali treated and sweetened oil is combined with a heating oil fraction from a catalytic cracking operation. It is preferred to pass the mixture through a filter containing an adsorbent material, such as fullers earth and the like, as a nal finishing step to insure the removal of foreign bodies, which lmay be carried by the oil from the previous treating steps.
  • an adsorbent material such as fullers earth and the like
  • the final ltering step is essential for the oils which have undergone treatment with an alkaline reagent, and is desirable in some instances for the oil from the catalytic cracking operation, it is possible to omit the filtering step for the oil from the catalytic cracking operation and combine this fraction with the filtered oils and obtain a stable heating oil of commercial grade.
  • catalytic cracking causes the formation of certain types of hydrocarbons in appreciably larger quantities than heretofore have been obtained in thermal cracking operations.
  • These types of hydrocarbon compounds include, among others, the cyclo-olenic hydrocarbons which are quite reactive; furthermore, the catalytically cracked materials contain appreciable quantities of hydrocarbons of branch structure which are known to be more reactive than those consisting essentially of straight chains. It is believed that these large quantities of cyclo-olenic compounds and hydrocarbons of branch structure enter into reaction with other types of compounds quite readily and even more readily in the presence of an alkaline material such as used in conventional treating operations in the modern renery. It is to be understood that the foregoing hypothesis is given only by way of explanation for the unusual result of the present invention, and not as a restriction or limitation on the scope of the invention.
  • catalytic cracking unit I2 designates a feed line through which a hydrocarbon in the gas oil boiling range is introduced into catalytic cracking unit I2.
  • Catalytic cracking unit I2 may be aV cracking operation such as the so-calledfThermofor. cracking operation, or a fixed bed catalytic cracking operation, r a huid catalyst cracking operation.
  • Fractionation zone I4 is provided with line I5 for removing an overhead fraction boiling below 420 F., with line I6 for removal of a heavy gas oil fraction boiling above 600 F. and with line I7 for the discharge of oil containing small amounts of catalyst when the catalytic cracking operation is of the iiuid catalyst type.
  • Treating system IQ may include acid treating, caustic washing, o-r doctor Asweetening operations, or all of them.
  • treating system I9 includes an acid treating step, it must also include a rerunning step for removal of polymers resulting from the acidl treating operation. In a preferred operation, however, treating system I9 is'by-passed by closing off valve 2li in line I8 and opening valve 2I in branch line 22, thereby by-passing treating system i9 completely.
  • valve 23 in line 24 Will also be closed oi.
  • the heating oil 4 fraction from the catalytic cracking ⁇ unit routed through line 22 is then further handled, as wil be described hereinafter.
  • thermal cracking unit 25 Operating in parallel with catalytic cracking unit I2 is a thermal cracking unit 25 into which a gas oil fraction is introduced by way of line 26. rI'he conditions for the satisfactory operation of a thermal cracking unit have been disclosed in detail in the patent literature and will not be repeated here.
  • the thermally cracked product issuing from thermal cracking unit 25 discharges by way of line 21 into fractionation zone 28, which is provided with a line 29 for removal of material boiling below about 400 E'. and line 30 for discharge of material boiling above about '706 F.
  • Fractionation Zone 28 is also provided with line 3i through which a heating oil fraction discharges into treating system 32.
  • Treating system 32 in this particular instance includes an acid treating system for removal of unstable hydrocarbons from the thermally cracked heating oil fraction.
  • Line 8 serves as a means for injecting sulfuric acid into treating system 32, and line 9 as a means for withdrawing acid sludge therefrom.
  • the acid treated oil issuing from treating systemv 32 discharges by way of line 33 into fractionation zone 34 which is provided with line 35 for removal of constituents boiling below about 400 to 420 F., line 36 for removal of a heavy gas oil fraction and line 3l for discharge of polymerized material resulting from the acid treating operation.
  • the heating oil fraction dis- K charges from fractionation zone 34 by way ofline vsolution at an optimum 38 and is admixed with a heating oil fraction introduced into line 38 by way of line 39 and obtained in a manner to be described.
  • rI'he heating oil fraction in line v3! is obtained by charging a crude petroleum fromr crude oil storage tank t0 by Way of line 4I and pump 42 into fractionation zone t3. From fractionation zone fl-3, a light fraction boiling below about 400 to 420 F. is removed by line Mi, .and a fraction boiling above the heating oil boiling range is removed by line t5 while the heating oil fraction is withdrawn by line 39. y
  • the mixture of thermally cracked Vand natural heating oils is conducted by line 38 and is admixed with an alkaline solution, introduced by way 'of line d6, in incorporator di' and passed thence by way of line 48v int-o settler '29.
  • Alkaline solution is withdrawn from settler 49 by way of line 5G. This solution may be recycled 4by lines 5I and t5 to line 38. From time to time it will become necessary to discard a po-rtionof the alkaline reagent discharged from settler d@ bylway of line 53. This is accomplished by opening valve 52. In a similar manner fresh alkaline reagent is .introduced by line i5 by opening valve 53 therein. Y n
  • rIhe alkalineV treated mixture of thermally cracked and natural heating oils discharges from settler 49 by way of line 51%,has doctor reagent added thereto by line 55 and passes throughinccrporator 55 and line 5l into settler T5S-which allows gravittl separation between the hydrocarbon phase and the doctor reagent phase.
  • the doctor reagent phase may be withdrawn by line 59 and recycled to line 54 by way of line 55.
  • fresh doctorreagent may be introduced into the system, by"
  • Spent doctor reagent may be discarded intermittently to maintain'the @I in line 62.
  • This rerun material was then blended', plished by contacting the doctor treated hydrowith a heating oil fraction from a crude petrocarbons with a spent caustic solution which usleum, and similar to the rSt run, was treated ually contains sodium p-olysuliide compounds and with 40 B. caustic followed by dOCOr SWBEtGYliIlg, is usually followed by washing with water. sodium polysulfide and water washing, and filtra- The hydrocarbons issuing from settler 58 by l0 tion. This material was also tested to deter- Way of line 63 admix with the catalytically mine its characteristics.
  • filter 65 is was admixed with a heating oil ffnet/i011 frOm packed with an adsorbent material such as fulcrude petroleum and SUbJ'GCed t0 Similar treat'. lers earth, kieselguhr, bauxite, or other similar ment with caustic, doctor Sweetening, sodium adsorbents well known to the art.
  • a fourth run tems. was made in which an acid treated and rerun The final filtering step is desirable for the heating oil from a thermal cracking Operation. production of a nigh grade heating oil but for was admiXed with a heating 011 from a crude operability of the process it is not essential that petroleum and the admixture then caustic the catalytically cracked heating oil fraction washed, doctor sweetened, sodium polysulde from line 22 be passed through the filter B5. If it 25 washed and water washed.
  • oils such as sodium salts of naphthenic acids produced in prior treatment with an alkaline reagent and when a component of the heating oil of the present invention is not treated with an alkalinel reagent the filtration step, so far as that particular oil is concerned, may be omitted.
  • heating oil fractions from the three sources mentioned before in the specification, were subjected to various treating procedures.
  • an acid treated and rerun heating oil fraction from a thermal cracking operation a heating oil fraction from crude petroleum, and a heating oil fraction from a catalytic cracking operation were blended together and then contacted with 40 B. caustic. After the caustic wash the heating oil was doctor sweetened, given a sodium polysulde and water wash and then filtered. Tests were obtained on the filtered material.
  • a heating oil .fraction from the same thermal It will be readily seen that the product obtained in accordance with the practice of the present invention in run 4 is superior in quality to those obtained by the other handling methods.
  • the superiority in quality of the product of the present invention is further indicated by tests under storage conditions of samples of the composition of the present invention and samples of heating oil finished in accordance with a conventional procedure.
  • the results of these tests are set out in Table II below.
  • the samples employed in runs 1 and 3 were finished in the same manner as the samples employed in run 1 of Table I in that an acid treated and rerun heating oil fraction from a thermal cracking operation, a heating oil fraction from crude petroleum and a heating oil fraction from a catalytic ⁇ cracking operation were blended together, contacted with 40 B. caustic, doctor sweetened, Washed with sodium polysulde, washed with Water and subsequently filtered.
  • samples used for runs 2 and 4 represented the preferred embodiment of the present inventio-n. It may be pointed out that although the same treatment was given samples 1 and 3, that of sample 1 was carried out in the laboratory and that of sample 3 was carried out in plant operation and similarly sample 2 was treated in the laboratory while sample 4 was obtained from a stock treated in plant operation.
  • a composition prepared for use as a distillatetype heating oil comprising chemically unrefined catalytically cracked naphtha distillate and chemically reiined crude petroleum and thermally cracked naphtha distillates, said :composition boiling within the range of about 350 F. and '700 F. and having a Tag-Robinson color no less than of the order of 15 after being subjected to storage under atmospheric temperature for approximately siX weeks.

Description

Tf? Il, EM?. l A. Q. CATOYETAL 294179236 HEATING on.
Filed Jan. 2,
34"" rfi-f ATTORNEY Patented Mar. 11, 194i HEATING OIL Artie Q. Cato, Houston, George Wash, Galveston, and Albert J. Shmidl, Houston, Tex., assignors to Standard Oil Development Company, a corporation of Delaware Application January 2, 1945, Serial No. 571,100
1 Claim. 1
This application is a continuation-impart of application Serial No. 522,124, led February 12, 1944, now Patent No. 2,380,294, issued July 10, 1945.
The present invention is directed to a liquid composition particularly adapted for use as a fuel oil in home heating installations. More particularly, it relates to a composition of good color stability and product quality which is produced by blending petroleum heating oil fractions.
Heating oils as mentioned herein will be taken to include petroleum oil fractions boiling up to about 660 F. and having a gravity of at least 30 API. The oil should be of at least 10 color as measured by the Tag-Robinson color machine` and should have a ash point between about 130 and 190 F. Of course, it must be realized that the oil should not corrode or plug the burning equipment and this tendency is usually reflected by an oil passing the suspended sediment and copper strip corrosion tests.
The conventional treating methods for heating oil fractions in the petroleum refinery usually include distillation, acid treating, caustic washing and doctor sweetening operations. For economy of equipment it is always good practice to combine the treating operations such that oils from Various sources are handled in one system of equipment. It would be uneconomical, for example, to segregate each fraction and handle it in its own tankage, distillation, acid treating, caustic Washing and doctor sweetening equipment. In a similar manner it is economical to combine streams for filtration, which filtration operation is usually required to remove from the heating oils suspended matter which, if left to remain in the heating oil, would be objectionable in operation of the heating equipment.
Heating oil fractions boiling up to about 660 F. may be obtained by distilling either cracked or crude petroleum products. These materials usually require nishing treatment before they are suitable for use as fuel for heating systems. Heretofore heating oil fractions were obtained from thermally cracked products and from crude petroleum. These fractions as mentioned before are amenable to finishing operations which may include acid treatment, caustic washing, doctor sweetening, and finally filtration. However, with the advent of catalytic cracking entirely new handling procedures become necessary since applicants have found that the conventional methods are not applicable to heating oil fractions from catalytically cracked hydrocarbons. For example, when a catalytically cracked heating oil fraction is admixed with heating oil fractions from thermally cracked products and crude petroleum, the admixture of the oils is seriously impaired in color when subjected to the conventional finishing operation which includes treatment with a strong alkaline reagent.
It is, therefore, the main object of the present invention to provide a treating and blending procedure for obtaining a heating oil of good quality which includes heating oi1 components from crude petroleum, thermally cracked naphtha and catalytically cracked naphtha.
In one specific embodiment of the present invention heating oil fractions, i. e., fractions boiling between about 350 and 700 F. are segregated from crude petroleum, and mixed with the heating oil fraction from a thermal cracking operation after the heating oil fraction from the thermal cracking operation has undergone acid treatment, caustic neutralization and rerunning to segregate from the acid treated product a fraction similar in boiling range to that obtained from the distillation of the crude petroleum.
The combined streams are then treated withan alkaline solution, and after removal of the alkaline solution from the treated oil, the oil is then doctor sweetened as in conventional practice. Following the doctor sweetening operation the resulting alkali treated and sweetened oil is combined with a heating oil fraction from a catalytic cracking operation. It is preferred to pass the mixture through a filter containing an adsorbent material, such as fullers earth and the like, as a nal finishing step to insure the removal of foreign bodies, which lmay be carried by the oil from the previous treating steps. While the final ltering step is essential for the oils which have undergone treatment with an alkaline reagent, and is desirable in some instances for the oil from the catalytic cracking operation, it is possible to omit the filtering step for the oil from the catalytic cracking operation and combine this fraction with the filtered oils and obtain a stable heating oil of commercial grade.
If the fuel oil fraction from the catalytic cracking step had been admixed with the other two streams and the blend contacted with the alkaline solution, a product of greatly Vinferior quality would have been obtained. The reason for the unexpected result of the present invention is not completely understood, but it is believed that in the heating oil fractions obtained from Vcrude petroleum there are present certain4 naphthenic type compounds, which in the presence of alkaline reagents react with the oleinic and aromatic constituents in the heating oil fraction from the catalytically cracked product. These reaction products are dark colored materials which evidently undergo polymerization reactions on storage and cause the oil to darken to a tarry appearance and to precipitate sedimentary bodies which plug and foul straining equipment and the burner tips of heating systems. In the handling procedure of the present invention these deleterious effects are not obtained.
By way of explanation, it might be mentioned that catalytic cracking causes the formation of certain types of hydrocarbons in appreciably larger quantities than heretofore have been obtained in thermal cracking operations. These types of hydrocarbon compounds include, among others, the cyclo-olenic hydrocarbons which are quite reactive; furthermore, the catalytically cracked materials contain appreciable quantities of hydrocarbons of branch structure which are known to be more reactive than those consisting essentially of straight chains. It is believed that these large quantities of cyclo-olenic compounds and hydrocarbons of branch structure enter into reaction with other types of compounds quite readily and even more readily in the presence of an alkaline material such as used in conventional treating operations in the modern renery. It is to be understood that the foregoing hypothesis is given only by way of explanation for the unusual result of the present invention, and not as a restriction or limitation on the scope of the invention.
The present invention will be further illustrated by reference to the drawing in which the single figure is a low diagram of a preferred 'method of conducting the invention. Y Referring now to the drawing, numeral I I designates a feed line through which a hydrocarbon in the gas oil boiling range is introduced into catalytic cracking unit I2. Catalytic cracking unit I2 may be aV cracking operation such as the so-calledfThermofor. cracking operation, or a fixed bed catalytic cracking operation, r a huid catalyst cracking operation. These several catalytic cracking operations have been described elsewhere in the patent literature and further reference thereto need not be made here. The product issuing from catalytic cracking unit I2 is conducted therefrom by way of line I3 and discharges into a fractionation zone Ill. Fractionation zone I4 is provided with line I5 for removing an overhead fraction boiling below 420 F., with line I6 for removal of a heavy gas oil fraction boiling above 600 F. and with line I7 for the discharge of oil containing small amounts of catalyst when the catalytic cracking operation is of the iiuid catalyst type.
A fraction having heating oil characteristics discharges from fractionation zone I4 by way of line I8 and may be introduced thereby into a treating system I9. Treating system IQ may include acid treating, caustic washing, o-r doctor Asweetening operations, or all of them. When treating system I9 includes an acid treating step, it must also include a rerunning step for removal of polymers resulting from the acidl treating operation. In a preferred operation, however, treating system I9 is'by-passed by closing off valve 2li in line I8 and opening valve 2I in branch line 22, thereby by-passing treating system i9 completely. In the cases where treating system I9 is luy-passed,v it will be understood that valve 23 in line 24 Will also be closed oi. The heating oil 4 fraction from the catalytic cracking `unit routed through line 22 is then further handled, as wil be described hereinafter.
Operating in parallel with catalytic cracking unit I2 is a thermal cracking unit 25 into which a gas oil fraction is introduced by way of line 26. rI'he conditions for the satisfactory operation of a thermal cracking unit have been disclosed in detail in the patent literature and will not be repeated here. The thermally cracked product issuing from thermal cracking unit 25 discharges by way of line 21 into fractionation zone 28, which is provided with a line 29 for removal of material boiling below about 400 E'. and line 30 for discharge of material boiling above about '706 F. Fractionation Zone 28 is also provided with line 3i through which a heating oil fraction discharges into treating system 32. Treating system 32 in this particular instance includes an acid treating system for removal of unstable hydrocarbons from the thermally cracked heating oil fraction. Line 8 serves as a means for injecting sulfuric acid into treating system 32, and line 9 as a means for withdrawing acid sludge therefrom. The acid treated oil issuing from treating systemv 32 discharges by way of line 33 into fractionation zone 34 which is provided with line 35 for removal of constituents boiling below about 400 to 420 F., line 36 for removal of a heavy gas oil fraction and line 3l for discharge of polymerized material resulting from the acid treating operation. The heating oil fraction dis- K charges from fractionation zone 34 by way ofline vsolution at an optimum 38 and is admixed with a heating oil fraction introduced into line 38 by way of line 39 and obtained in a manner to be described.
rI'he heating oil fraction in line v3! is obtained by charging a crude petroleum fromr crude oil storage tank t0 by Way of line 4I and pump 42 into fractionation zone t3. From fractionation zone fl-3, a light fraction boiling below about 400 to 420 F. is removed by line Mi, .and a fraction boiling above the heating oil boiling range is removed by line t5 while the heating oil fraction is withdrawn by line 39. y
The mixture of thermally cracked Vand natural heating oils is conducted by line 38 and is admixed with an alkaline solution, introduced by way 'of line d6, in incorporator di' and passed thence by way of line 48v int-o settler '29. Alkaline solution is withdrawn from settler 49 by way of line 5G. This solution may be recycled 4by lines 5I and t5 to line 38. From time to time it will become necessary to discard a po-rtionof the alkaline reagent discharged from settler d@ bylway of line 53. This is accomplished by opening valve 52. In a similar manner fresh alkaline reagent is .introduced by line i5 by opening valve 53 therein. Y n
rIhe alkalineV treated mixture of thermally cracked and natural heating oils discharges from settler 49 by way of line 51%,has doctor reagent added thereto by line 55 and passes throughinccrporator 55 and line 5l into settler T5S-which allows gravittl separation between the hydrocarbon phase and the doctor reagent phase. The doctor reagent phase may be withdrawn by line 59 and recycled to line 54 by way of line 55. As required, from time to time, fresh doctorreagent may be introduced into the system, by"
opening valve t@ in line 5.5. Spent doctor reagent may be discarded intermittently to maintain'the @I in line 62.
strength by opening valve eration described in connection with incorporator 56 and settler 58 it is usual practice to include alkaline sulde and water washes to remove occluded or suspended lead compounds from the cracking operation and a heating' oil 'fractionl from a catalytic cracking operation were blended together and subjected to treatment with sul-f furic acid and rerun to proper distillation charf doctor 'sweetened oil. This is usually accom- 5 acteristics. This rerun material was then blended', plished by contacting the doctor treated hydrowith a heating oil fraction from a crude petrocarbons with a spent caustic solution which usleum, and similar to the rSt run, was treated ually contains sodium p-olysuliide compounds and with 40 B. caustic followed by dOCOr SWBEtGYliIlg, is usually followed by washing with water. sodium polysulfide and water washing, and filtra- The hydrocarbons issuing from settler 58 by l0 tion. This material was also tested to deter- Way of line 63 admix with the catalytically mine its characteristics. In a third operationan' cracked heating oil fraction from line 2| and acid treated and rerun heating oil from the same oommingle in line te and are introduced thereby thermally cracked operation as runs one and twov into filter 65. As mentioned before, filter 65 is was admixed with a heating oil ffnet/i011 frOm packed with an adsorbent material such as fulcrude petroleum and SUbJ'GCed t0 Similar treat'. lers earth, kieselguhr, bauxite, or other similar ment with caustic, doctor Sweetening, sodium adsorbents well known to the art. The filtered DOIYSuldE and Water Washing as outlined in the oil discharges from lter 65 by way of line 66 preceding two runs and likewise submitted to tests and is then suitable for use in heating oil systo determine its characteristics. A fourth run tems. was made in which an acid treated and rerun The final filtering step is desirable for the heating oil from a thermal cracking Operation. production of a nigh grade heating oil but for was admiXed with a heating 011 from a crude operability of the process it is not essential that petroleum and the admixture then caustic the catalytically cracked heating oil fraction washed, doctor sweetened, sodium polysulde from line 22 be passed through the filter B5. If it 25 washed and water washed. To this treated adis desired to omit the filtration of the catalytmixture was added a heating oil fraction from` ically cracked fraction, valve 2| in line 22 is a catalytic cracking operation and the resultant closed and valve 6'! in line 68 opened allowing composition was then filtered. This fourth run this fraction to by-pass filter 65 and the filtered is the preferred embodiment of the present inmixture of the thermally cracked fraction and the vention. crude fraction commingle in line 66 with the The comparison of the tests obtained on the catalytically cracked fraction introduced thereto materials resulting from the four runs is preby line 68. The filtering step removes foreign sented in the following table:
Table I Run l 2 3 4 Calci?, 'Iag-Robinson, at various stages of nishing:
ee After treatment With 40 B. sodium hydroxide After 40 B. sodium hydroxide treatment, doctor sweetening, sodium polysulfide washing, water washing and filtering. Other tests on finished product:
Colorho1d,1 16 hours at 212 F Corrosion, 1 hour at 212 F Scum test 9% 2% Barely passes. Does not pass.
1 75 m1. of the oil to be tested is measured into a dry 4 ounce sample bottle and the unstoppered bottle is maintained in an oven for 16 hours at 212 F. The sample bottle is then removed from the oven, allowed to cool to approximately room temperature and the TagRobinson color oi the sample then determined and reported as the colorhold.
bodies from the oils such as sodium salts of naphthenic acids produced in prior treatment with an alkaline reagent and when a component of the heating oil of the present invention is not treated with an alkalinel reagent the filtration step, so far as that particular oil is concerned, may be omitted.
In order to illustrate further the beneficial effects obtained by processing heating oil fractions in accordance with the present invention,
several runs were made in which heating oil fractions, from the three sources mentioned before in the specification, were subjected to various treating procedures. In the rst run an acid treated and rerun heating oil fraction from a thermal cracking operation, a heating oil fraction from crude petroleum, and a heating oil fraction from a catalytic cracking operation were blended together and then contacted with 40 B. caustic. After the caustic wash the heating oil was doctor sweetened, given a sodium polysulde and water wash and then filtered. Tests were obtained on the filtered material. In a second run a heating oil .fraction from the same thermal It will be readily seen that the product obtained in accordance with the practice of the present invention in run 4 is superior in quality to those obtained by the other handling methods. Special attention is directed to the vastly improved color of the products of run 4 as compared to the products of runs 1 and 2. Run 3 did not contain any catalytically cracked material; therefore, it is not strictly comparable with run 4. It will be noted, however, that the color stability, as reflected by the colorhold test of run 3, similar to runs 1 and 2, is vastly inferior to that of run 4. The other tests likewise reflect the superior product obtained by the practice of the present invention.
The superiority in quality of the product of the present invention is further indicated by tests under storage conditions of samples of the composition of the present invention and samples of heating oil finished in accordance with a conventional procedure. The results of these tests are set out in Table II below. In this table the samples employed in runs 1 and 3 were finished in the same manner as the samples employed in run 1 of Table I in that an acid treated and rerun heating oil fraction from a thermal cracking operation, a heating oil fraction from crude petroleum and a heating oil fraction from a catalytic `cracking operation were blended together, contacted with 40 B. caustic, doctor sweetened, Washed with sodium polysulde, washed with Water and subsequently filtered. The samples employed for runs 2 and 4 were prepared in the same Way as was the sample for run 4 of Table I in that an acid treated and rerun heating oil from a, thermal cracking operation was aclmiXed with a heating oil from a. crude petroleum,
the admixture caustic washed, doctor sweetened,r
polysulde washed and water washed and to this treated mixture was added a heating oil fraction from a catalytic cracking operation and the resulting composition ltered. In other words, the samples used for runs 2 and 4 represented the preferred embodiment of the present inventio-n. It may be pointed out that although the same treatment was given samples 1 and 3, that of sample 1 was carried out in the laboratory and that of sample 3 was carried out in plant operation and similarly sample 2 was treated in the laboratory while sample 4 was obtained from a stock treated in plant operation.
Table II Runs l 2 3 4 Inspections on finished heating Color, Tag-Robinson 10% 18 10 18% Colorhold, 16 hrs. at 212 F 9% 17% 7 14% Storage temperature Atms. Atms. Atms. Atms.
or, Tag-Robinson, alte Weeks storage. 10% 18 10 18% 2 Weeks storage- 91/2 18 l0 17% 4 weeks storage.. 9% 16% 10 16% 6 Weeks storage 9V 16 9% 15% necessary to obtain the several fractions processed as described. Likewise, the amount and strength of the treating reagents are not given in describing the present invention. These amounts can be determined by experimentation and may vary with the type of stock undergoing treatment.
The nature and objects of the present invention having been described and illustrated, what We wish to claim as new and useful and to secure by Letters Patent is:
A composition prepared for use as a distillatetype heating oil comprising chemically unrefined catalytically cracked naphtha distillate and chemically reiined crude petroleum and thermally cracked naphtha distillates, said :composition boiling within the range of about 350 F. and '700 F. and having a Tag-Robinson color no less than of the order of 15 after being subjected to storage under atmospheric temperature for approximately siX weeks.
ARTIE'Q. CATO. GEORGE WASH. ALBERT J. SHMIDL.
REFERENCES CllTED The following references are of record in the le of this patent:
UNITED STATES PATENTS Number Name Date 2,360,272 Plummer Oct. 10, 1944 2,246,760 Ryan et al. June 24, 1941 2,315,935 Child Apr. 6, 1943 2,104,919 Whitney Jan. 11, 1938 2,252,082 Lloyd et al Api'. 12, 1941 2,048,371 Calderwood July 21, 1936 OTHER REFERENCES North Dakota Report 1941, issued Aug. 1942, Bulletin #68, pages 58to 61.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2687991A (en) * 1952-02-04 1954-08-31 Standard Oil Dev Co Heating oil
US2719105A (en) * 1952-02-27 1955-09-27 Exxon Research Engineering Co Process for the production of high quality heating oil blends
US2755229A (en) * 1953-07-02 1956-07-17 Gulf Research Development Co Stabilization of fuel oil
US2892769A (en) * 1953-09-02 1959-06-30 Tidewater Oil Company Automatic burner fuels and process of making them

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US2048371A (en) * 1932-11-07 1936-07-21 Shell Dev Blending of mineral oils and residues
US2104919A (en) * 1936-06-05 1938-01-11 Shell Dev Stabilized fuel oil
US2246760A (en) * 1939-03-22 1941-06-24 Texas Co Stable fuel oil
US2252082A (en) * 1939-03-07 1941-08-12 Standard Oil Dev Co Production of heating oils
US2315935A (en) * 1940-08-10 1943-04-06 Standard Oil Dev Co Stabilizing heavy fuel oil
US2360272A (en) * 1941-06-11 1944-10-10 Standard Oil Co Residual fuel oils

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Publication number Priority date Publication date Assignee Title
US2048371A (en) * 1932-11-07 1936-07-21 Shell Dev Blending of mineral oils and residues
US2104919A (en) * 1936-06-05 1938-01-11 Shell Dev Stabilized fuel oil
US2252082A (en) * 1939-03-07 1941-08-12 Standard Oil Dev Co Production of heating oils
US2246760A (en) * 1939-03-22 1941-06-24 Texas Co Stable fuel oil
US2315935A (en) * 1940-08-10 1943-04-06 Standard Oil Dev Co Stabilizing heavy fuel oil
US2360272A (en) * 1941-06-11 1944-10-10 Standard Oil Co Residual fuel oils

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2687991A (en) * 1952-02-04 1954-08-31 Standard Oil Dev Co Heating oil
US2719105A (en) * 1952-02-27 1955-09-27 Exxon Research Engineering Co Process for the production of high quality heating oil blends
US2755229A (en) * 1953-07-02 1956-07-17 Gulf Research Development Co Stabilization of fuel oil
US2892769A (en) * 1953-09-02 1959-06-30 Tidewater Oil Company Automatic burner fuels and process of making them

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