US3436339A - Removal of iron contaminants from hydrocarbon oils - Google Patents
Removal of iron contaminants from hydrocarbon oils Download PDFInfo
- Publication number
- US3436339A US3436339A US649451A US3436339DA US3436339A US 3436339 A US3436339 A US 3436339A US 649451 A US649451 A US 649451A US 3436339D A US3436339D A US 3436339DA US 3436339 A US3436339 A US 3436339A
- Authority
- US
- United States
- Prior art keywords
- oil
- iron
- removal
- acid
- metals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title description 50
- 239000003921 oil Substances 0.000 title description 43
- 229910052742 iron Inorganic materials 0.000 title description 25
- 239000004215 Carbon black (E152) Substances 0.000 title description 10
- 229930195733 hydrocarbon Natural products 0.000 title description 10
- 150000002430 hydrocarbons Chemical class 0.000 title description 10
- 239000000356 contaminant Substances 0.000 title description 8
- 238000000034 method Methods 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 11
- 239000003085 diluting agent Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- 239000011260 aqueous acid Substances 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 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
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CMTOAZYCDKAFHL-UHFFFAOYSA-N CC1=CC=CC=C1.CC1=CC=CC=C1.CC1=CC=CC=C1 Chemical compound CC1=CC=CC=C1.CC1=CC=CC=C1.CC1=CC=CC=C1 CMTOAZYCDKAFHL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 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
- C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
- C10G17/02—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acids or acid-containing liquids, e.g. acid sludge
- C10G17/04—Liquid-liquid treatment forming two immiscible phases
- C10G17/06—Liquid-liquid treatment forming two immiscible phases using acids derived from sulfur or acid sludge thereof
Definitions
- This invention relates to the removal of metallic contaminants from hydrocarbon oils and, in particular, to the removal of iron contaminants therefrom.
- This iron is brought into a catalytic unit, along with the other unfilterable metallic impurities, such as nickel and vanadium, with the feedstock in the form of metalloorganic compounds. It is the removal of these iron contaminants with which the present invention is concerned.
- the process of this invention is a process for removing iron from metals-containing hydrocarbon oils while leaving the content of the oil of metals other than iron substantially unchanged.
- the process involves contacting the oil with aqueous sulfuric acid in a concentration of 0.l-5 Weight percent H followed by separating the iron-free oil from the aqueous acid phase to which the iron has been transferred.
- the process of this invention comprises contacting the iron-contaminated oil with dilute, aqueous sulfuric acid having a concentration of 0.1-5 weight percent H 50 followed by separation of the ironfree oil from the aqueous phase to which the iron has been transferred.
- the temperature at which the contacting takes place is in a range of -50'O F.
- the temperature at which the contacting takes place is in the range of 225 F.
- the acid concentration is between 0.1 and 1.0 weight percent H 80 Contacting time may be between one minute and two hours.
- the hydrocarbon oil/aqueous acid weight ratio may range from 0.05 :1 to 5:1, depending upon the iron content of the hydrocarbon oil and the acid content of the aqueous phase.
- a light hydrocarbon diluent may be added to the oil to reduce its viscosity and facilitate contacting of the acid and oil.
- the amount of diluent used may be any amount necessary to reduce the viscosity of the oil to the desired viscosity for contacting. In general, this amount will be approximately one volume of diluent per volume of oil, although in the case of highly viscous oils, several volumes of diluent per volume of oil may be used.
- Table I illustrates the significant amount of iron removal which is obtainable by this process. It will be noted from the data that, at lower temperatures, the iron removal is decreased.
- Table II illustrates the fact that this process is essentially specific to iron removal.
- the data show that, while It has now been discovered, however, that sulfuric acid 65 most of the iron was removed from a typical feed, very concentrations which are one or two orders of magnitude less concentrated than those heretofore known to the little of the nickel, vanadium, or sodium also present in metals contaminated oil was removed.
- a process for the removal of iron contaminants from an iron-contaminated hydrocarbon oil which comprises contacting the oil with aqueous sulfuric acid in a concentration of 0.1-5 weight percent H 80 separating the resulting oil having a reduced iron content from the iron-containing aqueous acid phase and recovering said resulting oil.
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
United States Patent US. Cl. 208-252 9 Claims ABSTRACT OF THE DISCLOSURE A process for the selective removal of iron from ironcontaminated oils by contacting the oils with dilute sulfuric acid, containing 0.1- weight percent H 80 Other metals in the oils are essentially unaffected by the acid.
Background of the invention This invention relates to the removal of metallic contaminants from hydrocarbon oils and, in particular, to the removal of iron contaminants therefrom.
In catalytic cracking, it has been known for some time that certain metals, particularly iron, nickel and vanadium, are very harmful to cracking catalysts. When deposited on cracking catalysts in concentrations of about 0.1% or less, such metals cause the production of excessive amounts of coke and gas at the expense of valuable gasoline and heating oil fractions. This leads to an overloading of the regeneration and gas handling equipment and reduces the allowable feed rate to the catalytic cracking units. Iron has been found to be a particularly detrimental contaminant, not only in catalytic cracking, but also in other catalytic processes such as hydrocracking.
This iron is brought into a catalytic unit, along with the other unfilterable metallic impurities, such as nickel and vanadium, with the feedstock in the form of metalloorganic compounds. It is the removal of these iron contaminants with which the present invention is concerned.
It has previously been known that iron, nickel, vanadium and other metals could be removed from oils by using concentrated sulfuric acid. More recently, it was disclosed in US. Patent No. 2,778,777 that sulfuric acid concentrations as low as weight percent H 80 would also effect removal of these metals. However, in the past it has been believed that acid concentrations below 10% would be ineffective for promoting substantial metals Patented Apr. 1, 1969 prior art, will effect substantial iron removal from ironcontaminated oils. This process appears to be specific to iron removal, for other metals in metals-contaminated oils are substantially unaffected by acids of these extremely low concentrations.
Summary The process of this invention is a process for removing iron from metals-containing hydrocarbon oils while leaving the content of the oil of metals other than iron substantially unchanged. Basically, the process involves contacting the oil with aqueous sulfuric acid in a concentration of 0.l-5 Weight percent H followed by separating the iron-free oil from the aqueous acid phase to which the iron has been transferred.
Detailed description of the invention In its broadest form, the process of this invention comprises contacting the iron-contaminated oil with dilute, aqueous sulfuric acid having a concentration of 0.1-5 weight percent H 50 followed by separation of the ironfree oil from the aqueous phase to which the iron has been transferred.
In a preferred embodiment, the temperature at which the contacting takes place is in a range of -50'O F.
In a more preferred embodiment, the temperature at which the contacting takes place is in the range of 225 F.
In another preferred embodiment, the acid concentration is between 0.1 and 1.0 weight percent H 80 Contacting time may be between one minute and two hours.
The hydrocarbon oil/aqueous acid weight ratio may range from 0.05 :1 to 5:1, depending upon the iron content of the hydrocarbon oil and the acid content of the aqueous phase. If desired, a light hydrocarbon diluent may be added to the oil to reduce its viscosity and facilitate contacting of the acid and oil. The amount of diluent used may be any amount necessary to reduce the viscosity of the oil to the desired viscosity for contacting. In general, this amount will be approximately one volume of diluent per volume of oil, although in the case of highly viscous oils, several volumes of diluent per volume of oil may be used.
Table I illustrates the significant amount of iron removal which is obtainable by this process. It will be noted from the data that, at lower temperatures, the iron removal is decreased.
TABLE I Run No.
Type of Oil Crude Gas 011 Gas oil Deasphalted Deasphalted Deasphalted White oil oil oil oil Acid cgncentration, wt. percent 5 5 1 5 5 5 0. 0
4 Temperature, F 195-205 210 -210 160490 74 -195 210-215 Contacting time, min 60 60 10 15 15 15 15 Oil/acid, wtJwt 2. 5:1 2. 5:1 2. 5:1 0.511 0. 5:1 0. 5:1 1:1 Diluent None None None Toluene Toluene Toluene None Oil/diluent, vol./vol 1:1 1: 1 1: 1 Deduction of iron content,
percent. 99 82. 5 91 76 54 74 97 removal. This has been, in fact, shown to be true in the case of nickel and vanadium.
Table II illustrates the fact that this process is essentially specific to iron removal. The data show that, while It has now been discovered, however, that sulfuric acid 65 most of the iron was removed from a typical feed, very concentrations which are one or two orders of magnitude less concentrated than those heretofore known to the little of the nickel, vanadium, or sodium also present in metals contaminated oil was removed.
3 TABLE II Feed: Deasphalted oil Acid concentration, weight percent H 50 5 Metals reduction, weight percent:
Iron "a- 76 Nickel 12 Vanadium 15 Sodium 12 The above examples are given for illustrative purposes only. It is apparent that many widely difierent embodiments of this invention may be made without departing from the scope and spirit thereof, and, therefore, it is not intended to be limited except as indicated in the appended claims.
I claim:
1. A process for the removal of iron contaminants from an iron-contaminated hydrocarbon oil which comprises contacting the oil with aqueous sulfuric acid in a concentration of 0.1-5 weight percent H 80 separating the resulting oil having a reduced iron content from the iron-containing aqueous acid phase and recovering said resulting oil.
2. The process of claim 1 wherein the contacting temperature is in the range of 100500 F.
3. The process of claim 2 wherein the temperature is in the range of 150-225 F.
4. The process of claim 1 wherein the oil and the acid are contacted for between one minute and two hours.
5. The process of claim 1 wherein the aqueous sulfuric acid concentration is 0.1-1.0 weight percent H 6. The process of claim 5 wherein the contacting temperature is in the range of 500 F.
7. The process of claim 6 wherein the temperature is in the range of l50225 F.
8. The process of claim 5 wherein the oil and the acid are contacted for between one minute and two hours.
9. The process of claim 1 wherein the hydrocarbon oil contains other metallic contaminants in addition to iron, and the steps of contacting said hydrocarbon oil with said acid and separating said acid from said resulting oil, results in a selective removal of iron from said hydrocarbon oil with removal of only minor amounts of said other metallic contaminants.
References Cited UNITED STATES PATENTS 2,778,777 1/1957 Powell 196-440 DELBERT E. GANTZ, Primary Examiner.
J. D. MYERS, Assistant Examiner.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64945167A | 1967-06-28 | 1967-06-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3436339A true US3436339A (en) | 1969-04-01 |
Family
ID=24604845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US649451A Expired - Lifetime US3436339A (en) | 1967-06-28 | 1967-06-28 | Removal of iron contaminants from hydrocarbon oils |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3436339A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5075044A (en) * | 1986-07-07 | 1991-12-24 | Electricite De France Service International | Process for the radioactive decontamination of an oil |
| US10435632B2 (en) | 2014-09-16 | 2019-10-08 | Temple University—Of the Commonwealth System of Higher Education | Removal of iron contaminants from hydrocarbon oils and aqueous by-products of oil and gas recovery/production |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2778777A (en) * | 1954-02-16 | 1957-01-22 | Texas Co | Removal of metal components from petroleum oils |
-
1967
- 1967-06-28 US US649451A patent/US3436339A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2778777A (en) * | 1954-02-16 | 1957-01-22 | Texas Co | Removal of metal components from petroleum oils |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5075044A (en) * | 1986-07-07 | 1991-12-24 | Electricite De France Service International | Process for the radioactive decontamination of an oil |
| US10435632B2 (en) | 2014-09-16 | 2019-10-08 | Temple University—Of the Commonwealth System of Higher Education | Removal of iron contaminants from hydrocarbon oils and aqueous by-products of oil and gas recovery/production |
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