US2102878A - Treatment of hydrocarbon oils - Google Patents
Treatment of hydrocarbon oils Download PDFInfo
- Publication number
- US2102878A US2102878A US81509A US8150936A US2102878A US 2102878 A US2102878 A US 2102878A US 81509 A US81509 A US 81509A US 8150936 A US8150936 A US 8150936A US 2102878 A US2102878 A US 2102878A
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- US
- United States
- Prior art keywords
- copper
- sweetened
- treatment
- sulfide
- hydrocarbon oils
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- Expired - Lifetime
Links
- 239000003921 oil Substances 0.000 title description 19
- 229930195733 hydrocarbon Natural products 0.000 title description 15
- 150000002430 hydrocarbons Chemical class 0.000 title description 15
- 238000011282 treatment Methods 0.000 title description 14
- 239000004215 Carbon black (E152) Substances 0.000 title description 12
- 238000000034 method Methods 0.000 description 15
- 239000005749 Copper compound Substances 0.000 description 13
- 150000001880 copper compounds Chemical class 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 150000004763 sulfides Chemical class 0.000 description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000005083 Zinc sulfide Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229910000286 fullers earth Inorganic materials 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000008262 pumice Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 238000005325 percolation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052952 pyrrhotite Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- HJEINPVZRDJRBY-UHFFFAOYSA-N Disul Chemical compound OS(=O)(=O)OCCOC1=CC=C(Cl)C=C1Cl HJEINPVZRDJRBY-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- -1 sulfur alcohols Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- 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
-
- 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
- C10G29/10—Sulfides
Definitions
- This invention relates particularly to the treatment of the lower boiling naphthas and gasolines produced in the straight run distillation and in the cracking of petroleum though it may also be applied to analogous low boiling distillates produced in the primary distillation of any naturally occurring hydrocarbonaceous materials or in the secondary distillation of their primary tars.
- the invention is concerned with improved methods for treating crude primary gasoline boiling range distillates to render them suificiently stable and pleasing in appearance and odor from a sales standpoint.
- a conventional sweetening treatment involves the use of sodium plumbite solutions followed by the addition of minimum amounts of sulfur to precipitate lead from the initially formed lead mercaptides and form the desired organic disul fldes.
- plumbite such as the tendency to emulsion formation and the danger of having to use too much sulfur to break the lead from solution
- numerous other sweetening treatments have been proposed and some have attained commercial importance.
- hypochlorites has been found applicable to certain distillates, principally those of. a straight run character and another developmeht has involved the use of copper compounds and it is with improvements in this last named type of sweetening process that the present invention is concerned.
- the present invention comprises the treatment of coppersweetened hydrocarbon oils for the removal of color and undesirable dissolved constituents by percolating said hydrocarbon oils through beds of granular solid contact materials comprising as their active constituent sulfides of heavy metals above hydrogen in the electrochemical series.
- the sulfides employed may be produced by precipitation or other methods or may be the naturally occurring minerals such as, for example, in the case of iron, the commonly known pyrites and pyrrhotite minerals and in the case of zinc the mineral sphalerite. These metal sulfides may be mixed with or distributed over the surface of relatively inert spacing materials or carriers such as fullers earth, bentonite clays, ground pumice,
- Sulfides may be deposited upon such inert carriers by allowing them first to absorb a soluble salt such as ferric chloride from aqueous solution, the absorbed salt being then converted into the hydroxide by ammonia treatment and further converted into a mixture of sulfides by treatment with hydrogen sulfide.
- the operation of the process is extremely simple and consists merely in passing the copper-sweetened gasoline through beds of granular material containing heavy metal sulfides at ordinary or slightly increased temperatures, using pressure it necessary to maintain substantially liquid phase conditions. It has been found that a small but 2,108,878 of heavy metal sulfides through which the sweetrather obscure character involving the conversion of dissolved reaction products, such as copper mercaptides into dialkyl disuifides on the one hand and copper compounds on the other. It is to be noted that copper is below hydrogen in the electrochemical series and there is a possibility that the initial reactions may involve the replacement of the copper in the reaction products by the metal in the sulfide used.
- Another possibility is that various compounds of copper containing sulfur, nitrogen or oxygen may react with the metal sulfides to form copper sulfide and metal oxides or hydroxides with the concurrent production of hydrocarbons.
- the color in the copper-sweetened distillates may be traceable to minute amounts of some of the copper salts originally used for sweetening and in this case the metal sulfides may again react to precipitate copper sulfide and form a compound of a heavy metal.
- Example I A sour Mid-Continent-West Texas cracked gasoline was sweetened by percolation at ordinary temperatures through a contact mass comprising cupric sulfate and ammonium chloride mixed with fullers earth. The sweetened product had a sulfide which brought the color back to that of the original sour stock and increased the induction period and inhibitor susceptibility. Similar results were obtained with pyrrhotite or with iron sulfide precipitated on pumice according to the method previously described. A yield of 30,000 barrels per ton of treated product was obtained and the following table shows the results of the treatment, along with the properties of the original sour stock.
- Nnna Nflnll 9 155 385 Copper Non Red...-. 40 120 Copper Ferrouuulfide 9 145 345 definite amount of moisture is essential to the Example II maintenanceof the activity of the solid materials.
- Another sour md continent west Texas treated may be due to some extent to removal of mechanically entrained finely divided particles but is evidently due principally to reactions of a cracked gasoline was sweetened during passage through a reagent consisting of 25 parts by weight of copper sulfate pentahydrate, 25 parts by weight of ammonium chloride and parts by weight of 16-30 mesh fullers earth.
- the eiiluent passed directly from the treating chamber into a tower containing a mixture of zinc sulfide and pumice.
- chloride of an alkali metal is meant the chlorides or sodium, potassium as well as the alkaline earth metals calcium and magnesium, and the hypothetical metal ammonium.
- a process for removing copper compounds from copper-sweetened'hydrocarbon oils which comprises treating the copper-sweetened oil with a solid sulfide of a heavy metal above hydrogen in the eiectro-chemical series.
- a process for removing copper compounds from copper-sweetened hydrocarbon oils which comprises percolating the copper-sweetened oil through a bed of granular solid material containing a substantially water-insoluble sulfide of a heavy metal above hydrogen in the electro-chemical series.
- a process for removing copper compounds from copper-sweetened hydrocarbon oils which comprises treating the copper-sweetened oil with zinc sulfide in solid Iorm.
- a process for removing copper compounds from copper-sweetened hydrocarbon oils which comprises treating the copper-sweetened oil with iron sulfide in solid form.
- a process for removing copper compounds from copper-sweetened hydrocarbon oils which comprises percolating the copper-sweetened oil through a bed of granular solid material containing zinc sulfide.
- a process for removing copper compounds from copper-sweetened hydrocarbon oils which comprises percolating the copper-sweetened oil through a bed of granular solid material containing iron sulfide.
- a process for removing copper compounds from copper-sweetened hydrocarbon oils which comprises treating the copper-sweetened oil in the presence of a relatively small amount or moisture with a solid sulfide of a heavy metal above hydrogen in the electro-chemlcal series.
Landscapes
- 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)
Description
Patented Dec. 21, 1937 PATENT OFFICE TREATMENT OF HYDROCARBON OILS Wayne L. Benedict, Chicago, 111., Universal Oil Products Company,
assignor to Chicago, IIL,
a corporation of Delaware No Drawing. Application May 23, 1938,
4 Serial No. 81,509
I Claims.
This invention relates particularly to the treatment of the lower boiling naphthas and gasolines produced in the straight run distillation and in the cracking of petroleum though it may also be applied to analogous low boiling distillates produced in the primary distillation of any naturally occurring hydrocarbonaceous materials or in the secondary distillation of their primary tars.
More specifically, the invention is concerned with improved methods for treating crude primary gasoline boiling range distillates to render them suificiently stable and pleasing in appearance and odor from a sales standpoint.
Primary naphthas and gasolines quite uniformly require some type of chemical treatment to eliminate objectionable constituents of a colored, odorous or' gummy character. Color has been variously attributed to suspended asphaltic and resinous materials, oxidized hydrocarbons, nitrogen compounds and even to some pure hydrocarbons. The objectionable odors are principally due to sulfur compounds of which the chief offenders are the sulfur alcohols or mercaptans. The gummy or potential gum-forming constituents are heavy hydrocarbon polymers or highly unsaturated hydrocarbons such as conjugated dioleflns respectively.
It is the object of chemical treatments to remove suflicient quantities of the groups of impurities mentioned above until they are reduced to a point corresponding to a finished gasoline. A conventional treatment consists in the primary use of sulfuric acid of graded strength to remove unsaturates and, to some extent sulfur and nitrogen compounds, followed by neutralizing and redistilling to leave high boiling polymers and sludge reaction products as a residue. The application of so-called sweetening agents may be practiced either before or after the distillation following acid treatment or may be applied to distillates which have not received any acid treatment. These sweetening reagents apparently transform the foul smelling mercaptans into the relatively odorless and stable dialkyl disulfldes by chemical reactions involving oxidations with the removal of the mercaptan hydrogen and the condensation of the residual radicals.
A conventional sweetening treatment involves the use of sodium plumbite solutions followed by the addition of minimum amounts of sulfur to precipitate lead from the initially formed lead mercaptides and form the desired organic disul fldes. Owing to the numerous operating difflculties attending the use of plumbite, such as the tendency to emulsion formation and the danger of having to use too much sulfur to break the lead from solution, numerous other sweetening treatments have been proposed and some have attained commercial importance. The use of hypochlorites has been found applicable to certain distillates, principally those of. a straight run character and another developmeht has involved the use of copper compounds and it is with improvements in this last named type of sweetening process that the present invention is concerned.
In one specific embodiment, the present invention comprises the treatment of coppersweetened hydrocarbon oils for the removal of color and undesirable dissolved constituents by percolating said hydrocarbon oils through beds of granular solid contact materials comprising as their active constituent sulfides of heavy metals above hydrogen in the electrochemical series.
Owing to the relatively small percentages of compounds involved in the sweetening reactions, the course of copper-sweetening from the chemical standpoint is not entirely certain. In such sweetening processes cupric chloride as such has given good results and also mixtures of copper salts, for example, copper sulfate, and chlorides of the alkali and alkaline earth metals and ammonium. When gasolines are sweetened by percolation through these salt mixtures advantages are gained in making composites containing in addition to the active salts earthy or clay-like materials such as fullers earth. In such sweetening processes a large number of copper compounds may be employed either in a dry state or in solution and while in some cases there may be some actual removal of sulfur by combination with copper, there may in other cases be merely the formation of copper mercaptides or a true oxidizing action depending upon the character of the copper salt employed. It is therefore not possible to state exactly what reaction products are present in a copper-sweetened gasoline such as, for example, a cracked gasoline, to cause an increase in color in the treated product, but it has been quite generally observed that this increase in color occurs. There are some indications that it may be due to copper mercaptides and that it may be due in part to oxidized compounds depending upon the copper compounds employed and the conditions of treatment, however, it has been found that the color of copper-sweetened gasolines is practically always materially reduced by the subsequent use chromium, iron, cadmium, cobalt, nickel, tin, lead,
etc., which have been given in diminishing order of their electro-positiveness. The reasons for the refining action of these sulfides and their efilciency in removing the objectionable by-products from copper-sweetened distillates are not entirely understood but have been uniformly observed. When dealing with different gasoline stocks which have been sweetened by different copper compounds and under different methods of operation some of the sulfides enumerated may act with greater emciency than others so that they cannot be placed on an .exactly equivalent basis even though they may be used alternatively. The sulfides of zinc and iron have been found applicable in the majority of instances.
The sulfides employed may be produced by precipitation or other methods or may be the naturally occurring minerals such as, for example, in the case of iron, the commonly known pyrites and pyrrhotite minerals and in the case of zinc the mineral sphalerite. These metal sulfides may be mixed with or distributed over the surface of relatively inert spacing materials or carriers such as fullers earth, bentonite clays, ground pumice,
etc. in order to give better distribution and a greater surface of contact. Sulfides may be deposited upon such inert carriers by allowing them first to absorb a soluble salt such as ferric chloride from aqueous solution, the absorbed salt being then converted into the hydroxide by ammonia treatment and further converted into a mixture of sulfides by treatment with hydrogen sulfide.
The operation of the process is extremely simple and consists merely in passing the copper-sweetened gasoline through beds of granular material containing heavy metal sulfides at ordinary or slightly increased temperatures, using pressure it necessary to maintain substantially liquid phase conditions. It has been found that a small but 2,108,878 of heavy metal sulfides through which the sweetrather obscure character involving the conversion of dissolved reaction products, such as copper mercaptides into dialkyl disuifides on the one hand and copper compounds on the other. It is to be noted that copper is below hydrogen in the electrochemical series and there is a possibility that the initial reactions may involve the replacement of the copper in the reaction products by the metal in the sulfide used. Another possibility is that various compounds of copper containing sulfur, nitrogen or oxygen may react with the metal sulfides to form copper sulfide and metal oxides or hydroxides with the concurrent production of hydrocarbons. There is a further possibility that the color in the copper-sweetened distillates may be traceable to minute amounts of some of the copper salts originally used for sweetening and in this case the metal sulfides may again react to precipitate copper sulfide and form a compound of a heavy metal.
The following examples are given to indicate the efilciency of the proposed supplementary treatment for copper sweetened gasolines though it is not intended to limit the scope of the invention in exact correspondence therewith.
. Example I A sour Mid-Continent-West Texas cracked gasoline was sweetened by percolation at ordinary temperatures through a contact mass comprising cupric sulfate and ammonium chloride mixed with fullers earth. The sweetened product had a sulfide which brought the color back to that of the original sour stock and increased the induction period and inhibitor susceptibility. Similar results were obtained with pyrrhotite or with iron sulfide precipitated on pumice according to the method previously described. A yield of 30,000 barrels per ton of treated product was obtained and the following table shows the results of the treatment, along with the properties of the original sour stock.
Induction period, min. Color 8 in txeatm t Sulfide tmatm at d g ssgb it Without was com.
inhibitor inhibitor Nnna Nflnll 9 155 385 Copper Non Red...-. 40 120 Copper Ferrouuulfide 9 145 345 definite amount of moisture is essential to the Example II maintenanceof the activity of the solid materials. Another sour md continent west Texas treated may be due to some extent to removal of mechanically entrained finely divided particles but is evidently due principally to reactions of a cracked gasoline was sweetened during passage through a reagent consisting of 25 parts by weight of copper sulfate pentahydrate, 25 parts by weight of ammonium chloride and parts by weight of 16-30 mesh fullers earth. The eiiluent passed directly from the treating chamber into a tower containing a mixture of zinc sulfide and pumice. Sampling indicated that the gasoline from the sweetening tower had a red color and that it contained dissolved copper compounds. The gasoline leaving the zinc sulfide tower gave no test for copper with ammonium sulfide and a mere tra'ce by a spectroscopic examination of the hydrochloric acid extract. The color of the final product was the same as the entering untreated sour gasoline and the following table indicates the changes in the induction period and inhibitor susceptibility, up to a yield of 3200 bbls. per'ton of sulfide.
By the term chloride of an alkali metal" is meant the chlorides or sodium, potassium as well as the alkaline earth metals calcium and magnesium, and the hypothetical metal ammonium.
I claim as my invention:
1. A process for removing copper compounds from copper-sweetened'hydrocarbon oils which comprises treating the copper-sweetened oil with a solid sulfide of a heavy metal above hydrogen in the eiectro-chemical series.
2. A process for removing copper compounds from copper-sweetened hydrocarbon oils which comprises percolating the copper-sweetened oil through a bed of granular solid material containing a substantially water-insoluble sulfide of a heavy metal above hydrogen in the electro-chemical series.
. 3. A process for removing copper compounds from copper-sweetened hydrocarbon oils which comprises treating the copper-sweetened oil with zinc sulfide in solid Iorm.
4. A process for removing copper compounds from copper-sweetened hydrocarbon oils which comprises treating the copper-sweetened oil with iron sulfide in solid form.
5. A process for removing copper compounds from copper-sweetened hydrocarbon oils which comprises percolating the copper-sweetened oil through a bed of granular solid material containing zinc sulfide.
6. A process for removing copper compounds from copper-sweetened hydrocarbon oils which comprises percolating the copper-sweetened oil through a bed of granular solid material containing iron sulfide.
7. A process for removing copper compounds from copper-sweetened hydrocarbon oils which comprises treating the copper-sweetened oil in the presence of a relatively small amount or moisture with a solid sulfide of a heavy metal above hydrogen in the electro-chemlcal series.
WAYNE L. BENEDICT.
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US81509A US2102878A (en) | 1936-05-23 | 1936-05-23 | Treatment of hydrocarbon oils |
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US81509A US2102878A (en) | 1936-05-23 | 1936-05-23 | Treatment of hydrocarbon oils |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2675344A (en) * | 1950-08-09 | 1954-04-13 | Socony Vacuum Oil Co Inc | Decolorization process |
DE954542C (en) * | 1951-07-05 | 1956-12-20 | British Petroleum Co | Process for sweetening petroleum distillates |
-
1936
- 1936-05-23 US US81509A patent/US2102878A/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2675344A (en) * | 1950-08-09 | 1954-04-13 | Socony Vacuum Oil Co Inc | Decolorization process |
DE954542C (en) * | 1951-07-05 | 1956-12-20 | British Petroleum Co | Process for sweetening petroleum distillates |
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