US2227811A - Process for removing naphthenic acids from hydrocarbon oils - Google Patents
Process for removing naphthenic acids from hydrocarbon oils Download PDFInfo
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- US2227811A US2227811A US273575A US27357539A US2227811A US 2227811 A US2227811 A US 2227811A US 273575 A US273575 A US 273575A US 27357539 A US27357539 A US 27357539A US 2227811 A US2227811 A US 2227811A
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- Prior art keywords
- naphthenic acids
- catalyst
- temperatures
- oil
- hydrocarbon oils
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- 125000005608 naphthenic acid group Chemical group 0.000 title description 25
- 239000003921 oil Substances 0.000 title description 22
- 229930195733 hydrocarbon Natural products 0.000 title description 9
- 150000002430 hydrocarbons Chemical class 0.000 title description 9
- 238000000034 method Methods 0.000 title description 8
- 239000004215 Carbon black (E152) Substances 0.000 title description 6
- 239000003054 catalyst Substances 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 11
- 238000005336 cracking Methods 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 125000005609 naphthenate group Chemical group 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000001339 alkali metal compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000006187 pill Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 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
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- -1 fatty acid salts Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
- C10G17/095—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with "solid acids", e.g. phosphoric acid 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
Definitions
- Hydrocarbon oils often contain considerable amounts of acidic components, which during the processing of the oils, particularly at elevated temperatures, may cause severe corrosion of the treating equipment.
- corrosion difliculties have been experienced, for instance, when distilling, with or without steam, relatively high boiling oils such as gas oil, Diesel fuel oils, lubricating oils, etc., containing free naphthenic acids, particularly if their acid numbers are above about .2.
- various means have been employed, all of which, however, have certain disadvantages. For instance it has been attempted to subject the oils to selective cracking at temperatures between about 315 C. to 400 C. whereby it was hoped the naphthenic acids would be decomposed to neutral compounds and C02, while the hydrocarbon oils remain substantially uncracked. It was found that under these conditions some decomposition of naphthenic acids takes place, but it is slow and incomplete. Moreover the corrosion during this treatment may be severe and may persist in subsequent treatments.
- Another method consisted of passing vapors of mineral oil containing naphthenic acids over alkaline earth metal oxide at temperatures of about 200 C. to produce alkaline earth naphthenates, and heating the naphthenates so produced to about 400 C. to remove therefrom ketones and CO2, thereby restoring the alkali earth oxide.
- This intermittent process has the disadvantage that it requires frequent changes of temperatures of the reacting masses, which reduce the available operating time, make operating of the process on a large scale difiicult, and raise operating expenses.
- naphthenic acids can be eliminated quickly and substantially completely in a single step operation from mineral oils containing them by conducting the oil, preferably in the vapor phase, at an elevated temperature, if desired in the presence of steam and under conditions substantially to avoid cracking of the hydrocarbons over a mixed catalyst mass containing both inorganic alkali metal compounds and alkaline earth compounds, whereby the harmful carboxyl groups of the naphthenic acids are catalytically destroyed or converted into nonacidic groups.
- the reaction by which the naphthenic acids are eliminated is one of decomposition, free CO2 and neutral compounds, presumably ketones and/or hydrocarbons being formed.
- the metal compounds in the catalyst are preferably in the form of their oxides or carbonates, or of compounds capable of forming such oxides or carbonates under the reaction conditions.
- the compounds should be solid at the reaction temperatures.
- an active catalyst may comprise an oxide or carbonate of lithium, sodium and/or potassium together with an oxide or carbonate of magnesium, calcium, strontium and/or barium.
- Such a catalyst contains side by side, substances having a strongly alkaline reaction, 1. e. the alkali metal compounds, and substances having a less strongly alkaline reaction, i. e. the alkaline earth metal compounds.
- both the alkali metal compound and the alkali earth compounds be present in substantial proportions.
- the ratio of the two types of compounds be between not less than 1:20 not more than 20:1 and preferably be between the limits of 1:10 and 10:1.
- An apparent exception is found in the case of lithium, which in concentrations of 1% and lower is capable of activating alkali earth compounds as disclosed in the copending application, Serial No. 181,702.
- the catalysts are preferably prepared in such a manner as to ensure a large active surface and high porosity.
- This object may be obtained by grinding the oxides and/or carbonates to a very fine particle size.
- suitable carbonates of the alkali metals and alkaline earth metals may be obtained from solutions of soluble salts by precipitation if necessary in the presence of a precipitant such as lower alcohols, or by calcining or igniting their bicarbonates, or carboxylic acid salts which upon heating will decompose to form carbonates, in particular acetates and higher fatty acid salts and naphthenate's.
- Carbonates obtained by heat treatment are usually more efficient than the precipitated forms.
- One may also start from a compound yielding the desired catalyst after decomposition.
- a very active catalyst is produced by heating the double compound of magnesium carbonate and potassium carbonate (the Engel salt) at about 400 C.
- the active catalysts may be deposited on carriers such as coal, coke, concrete, pumice, metals, (for example copper gauze and steel wool) etc. and if desired may be mixed with activators.
- carriers such as coal, coke, concrete, pumice, metals, (for example copper gauze and steel wool) etc. and if desired may be mixed with activators.
- activators for example, oxides of copper, silver, zinc, cadmium and manganese, may serve as activators.
- Suitable contact temperatures range from about 300 C. to temperatures of incipient cracking or slightly above, i. e. about 475 C.
- Incipient cracking temperatures and rates of cracking at a given cracking temperature vary somewhat with the boiling range and the nature of the oil as shown by Geniesse and Reuter in Industrial and Engineering Chemistry 24 (1932) pages 219 etc. Exposure of the oil to temperatures above incipient cracking temperatures should be so limited to avoid substantial cracking. In general treating temperatures should not exceed about 475 C. and are preferably below about 450 C.
- the limited time of contact available when treating without substantial cracking at temperatures above incipient cracking is, however, more than sufficient to eliminate the largest portion of naphthenic acids contained in hydrocarbon oils. For instance, whereas at 450 C. it requires between 3 to 4 seconds to crack a gas oil to the extent of 1%, a contact time of ,4 second is usually sufficient at temperatures from 400 C. to 450 C. to remove the naphthenic acids practically quantitatively with an active mixed alkali and alkaline earth carbonate catalyst. Since in some cases a longer time of contact may result in a more complete removal of the naph thenic acids, I may extend this time to several seconds, where this can be done without the danger of cracking or otherwise adversely affecting the oil.
- the following examples further illustrate my process.
- a catalyst suitable for the process of my invention was prepared by thoroughly mixing 80 parts by weight of anhydrous soda and 20 parts by weight of voluminous magnesium oxide in a ball mill, compressing the mixture to pills and subsequently breaking the said pills and reducing them to a grain size A. S. T. M. sieve /20.
- the treated oil vapors were condensed and small amounts of gaseous CO2 were separated from the liquid.
- the naphthenic acids were found to be removed practically quantitatively even after 100 hours of catalyst life.
- magnesium oxide free from sodium carbonate was used as a catalyst in an experiment similar to the above, the de-acidification was at the outset markedly less intensive that in the case of a sodium carbonate catalyst or a catalyst composed of sodium carbonate and magnesium oxide. In addition to being less effective than the above catalysts, the activity of the magnesium oxide catalyst decreased very rapidly.
- the steps comprising contacting said oil in a heated vaporous condition at a temperature between 300 C. and 475 C. with a catalyst comprising calcium carbonate containing about 1% lithium carbonate, fora time suificient to decompose a major portion of the naphthenic acids, thereby liberating gaseous CO2, but insufiicient to substantially crack the oil.
Description
Patented Jan. 7, 1941 rnoonss FOR REMOVING NAPHTHENIG ACIDS FROM HYDROGARBON OILS Franz Rudolf Moser, Amsterdam, Netherlands, assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application May 13, 1939, Serial No. 273,575. In Great Britain May 23, 1938 1 Claim.
This invention is a continuation in part of my copending application, Serial No. 181,702, filed December 24, 1937, now Patent 2,186,425 and relates to the removal of naphthenic acids from 5 hydrocarbon oils by catalytic destruction of the latter at elevated temperatures, and in particular deals with the removal of naphthenic acids from mineral lubricating oil distillates.
Hydrocarbon oils often contain considerable amounts of acidic components, which during the processing of the oils, particularly at elevated temperatures, may cause severe corrosion of the treating equipment. Thus corrosion difliculties have been experienced, for instance, when distilling, with or without steam, relatively high boiling oils such as gas oil, Diesel fuel oils, lubricating oils, etc., containing free naphthenic acids, particularly if their acid numbers are above about .2. In order to overcome this difiiculty various means have been employed, all of which, however, have certain disadvantages. For instance it has been attempted to subject the oils to selective cracking at temperatures between about 315 C. to 400 C. whereby it was hoped the naphthenic acids would be decomposed to neutral compounds and C02, while the hydrocarbon oils remain substantially uncracked. It was found that under these conditions some decomposition of naphthenic acids takes place, but it is slow and incomplete. Moreover the corrosion during this treatment may be severe and may persist in subsequent treatments.
Another method consisted of passing vapors of mineral oil containing naphthenic acids over alkaline earth metal oxide at temperatures of about 200 C. to produce alkaline earth naphthenates, and heating the naphthenates so produced to about 400 C. to remove therefrom ketones and CO2, thereby restoring the alkali earth oxide. This intermittent process has the disadvantage that it requires frequent changes of temperatures of the reacting masses, which reduce the available operating time, make operating of the process on a large scale difiicult, and raise operating expenses.
Other methods of removing naphthenic acids comprise distilling oils containing naphthenic acids, for instance, over caustic soda under conditions to retain the naphthenic acids in the alkaline-reacting residue in the form of a socalled soda asphalt, which, however, is a troublesome material of little use.
It is a purpose of this invention to provide a continuous method whereby naphthenic acids contained in mineral oil can be eliminated quickly and substantially completely, without produc ing an undesirable residue and without materially decomposing or otherwise damaging the hydrocarbons with which the acids are associated.
I have discovered that naphthenic acids can be eliminated quickly and substantially completely in a single step operation from mineral oils containing them by conducting the oil, preferably in the vapor phase, at an elevated temperature, if desired in the presence of steam and under conditions substantially to avoid cracking of the hydrocarbons over a mixed catalyst mass containing both inorganic alkali metal compounds and alkaline earth compounds, whereby the harmful carboxyl groups of the naphthenic acids are catalytically destroyed or converted into nonacidic groups.
The reaction by which the naphthenic acids are eliminated is one of decomposition, free CO2 and neutral compounds, presumably ketones and/or hydrocarbons being formed.
The metal compounds in the catalyst are preferably in the form of their oxides or carbonates, or of compounds capable of forming such oxides or carbonates under the reaction conditions. To be suitable the compounds should be solid at the reaction temperatures. Thus an active catalyst may comprise an oxide or carbonate of lithium, sodium and/or potassium together with an oxide or carbonate of magnesium, calcium, strontium and/or barium. Such a catalyst contains side by side, substances having a strongly alkaline reaction, 1. e. the alkali metal compounds, and substances having a less strongly alkaline reaction, i. e. the alkaline earth metal compounds.
In accordance with my invention I have found such mixtures to have a better catalytic effect than each of the substances individually. A possible explanation may be as follows: The action of the catalyst is conceivably split up into two successive stages, e. g. (1) The binding of the naphthenic acids and, (2) The decomposition of the bound naphthenic acids. For binding the naphthenic acids the alkali metal compounds, being the more strongly basic substances, are most desirable. However, the naphthenates of the alkaline earths decompose at lower temperatures and melt at higher temperatures then the naphthenates of the alkali metals, and hence the presence of the alkaline earth compounds materially accelerates the decomposition of naphthenic acids and simultaneously stabilizes the catalyst. Consequently to aid in the decomposition of the naphthenates and to give the catalyst a higher melting point to prolong the activity of its surface, alkaline earth metals are desirable. It is, therefore, of advantage to use mixtures of the said substances as catalysts.
In order that both reaction stages may proceed properly, it is desirable that both the alkali metal compound and the alkali earth compounds be present in substantial proportions. Thus it is desirable that the ratio of the two types of compounds be between not less than 1:20 not more than 20:1 and preferably be between the limits of 1:10 and 10:1. An apparent exception is found in the case of lithium, which in concentrations of 1% and lower is capable of activating alkali earth compounds as disclosed in the copending application, Serial No. 181,702.
The catalysts are preferably prepared in such a manner as to ensure a large active surface and high porosity. This object may be obtained by grinding the oxides and/or carbonates to a very fine particle size. Or else suitable carbonates of the alkali metals and alkaline earth metals may be obtained from solutions of soluble salts by precipitation if necessary in the presence of a precipitant such as lower alcohols, or by calcining or igniting their bicarbonates, or carboxylic acid salts which upon heating will decompose to form carbonates, in particular acetates and higher fatty acid salts and naphthenate's. Carbonates obtained by heat treatment are usually more efficient than the precipitated forms. One may also start from a compound yielding the desired catalyst after decomposition. Thus a very active catalyst is produced by heating the double compound of magnesium carbonate and potassium carbonate (the Engel salt) at about 400 C.
The active catalysts may be deposited on carriers such as coal, coke, concrete, pumice, metals, (for example copper gauze and steel wool) etc. and if desired may be mixed with activators. Thus the addition of small amounts of certain substances, for example, oxides of copper, silver, zinc, cadmium and manganese, may serve as activators.
Suitable contact temperatures range from about 300 C. to temperatures of incipient cracking or slightly above, i. e. about 475 C. Incipient cracking temperatures and rates of cracking at a given cracking temperature, vary somewhat with the boiling range and the nature of the oil as shown by Geniesse and Reuter in Industrial and Engineering Chemistry 24 (1932) pages 219 etc. Exposure of the oil to temperatures above incipient cracking temperatures should be so limited to avoid substantial cracking. In general treating temperatures should not exceed about 475 C. and are preferably below about 450 C.
The limited time of contact available when treating without substantial cracking at temperatures above incipient cracking, is, however, more than sufficient to eliminate the largest portion of naphthenic acids contained in hydrocarbon oils. For instance, whereas at 450 C. it requires between 3 to 4 seconds to crack a gas oil to the extent of 1%, a contact time of ,4 second is usually sufficient at temperatures from 400 C. to 450 C. to remove the naphthenic acids practically quantitatively with an active mixed alkali and alkaline earth carbonate catalyst. Since in some cases a longer time of contact may result in a more complete removal of the naph thenic acids, I may extend this time to several seconds, where this can be done without the danger of cracking or otherwise adversely affecting the oil. The following examples further illustrate my process.
A catalyst suitable for the process of my invention was prepared by thoroughly mixing 80 parts by weight of anhydrous soda and 20 parts by weight of voluminous magnesium oxide in a ball mill, compressing the mixture to pills and subsequently breaking the said pills and reducing them to a grain size A. S. T. M. sieve /20. A lubricating oil distillate containing naphthenic acids and having an acid number of 2 mg. KO'H per gram of oil, produced by distillation of a Venezuelan crude oil, was passed in the vapor phase at a pressure of 100 millimeters Hg. and temperature of 400 C. and in the presence of 2.5% by weight of steam over 10 cm. of this catalyst at a rate of 100 cm. per hour. The calculated time of contact was second.
The treated oil vapors were condensed and small amounts of gaseous CO2 were separated from the liquid. The naphthenic acids were found to be removed practically quantitatively even after 100 hours of catalyst life.
When substituting a sodium carbonate catalyst free from magnesium oxide in the above experiment which had been prepared in a similar manner, the de-acidifying effect at first was the same as that of the catalyst described above, but after only a few hours the activity decreased considerably.
When magnesium oxide free from sodium carbonate was used as a catalyst in an experiment similar to the above, the de-acidification was at the outset markedly less intensive that in the case of a sodium carbonate catalyst or a catalyst composed of sodium carbonate and magnesium oxide. In addition to being less effective than the above catalysts, the activity of the magnesium oxide catalyst decreased very rapidly.
I I claim as my invention:
In the process of removing naphthenic acids from hydrocarbon oils containing same, the steps comprising contacting said oil in a heated vaporous condition at a temperature between 300 C. and 475 C. with a catalyst comprising calcium carbonate containing about 1% lithium carbonate, fora time suificient to decompose a major portion of the naphthenic acids, thereby liberating gaseous CO2, but insufiicient to substantially crack the oil.
FRANK RUDOLF MOSER.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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GB2227811X | 1938-05-23 |
Publications (1)
Publication Number | Publication Date |
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US2227811A true US2227811A (en) | 1941-01-07 |
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Application Number | Title | Priority Date | Filing Date |
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US273575A Expired - Lifetime US2227811A (en) | 1938-05-23 | 1939-05-13 | Process for removing naphthenic acids from hydrocarbon oils |
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Country | Link |
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US (1) | US2227811A (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2478897A (en) * | 1946-04-30 | 1949-08-16 | Koppers Co Inc | Prevention of corrosion in catalytic reactions involving the use of phosphorus acid catalysts |
US2478900A (en) * | 1946-04-17 | 1949-08-16 | Koppers Co Inc | Process of rendering noncorrosive the products resulting from catalytic alkylation |
US2795532A (en) * | 1954-10-04 | 1957-06-11 | Sun Oil Co | Refining heavy mineral oil fractions with an anhydrous mixture of sodium hydroxide and potassium hydroxide |
US2938862A (en) * | 1958-01-07 | 1960-05-31 | Pure Oil Co | Method of refining aromatic extract oils with barium compounds |
US3761534A (en) * | 1971-12-29 | 1973-09-25 | Dow Chemical Co | Removal of acidic contaminants from process streams |
EP0809683A1 (en) * | 1995-02-17 | 1997-12-03 | Exxon Research And Engineering Company | Thermal decomposition of naphthenic acids |
US5820750A (en) * | 1995-02-17 | 1998-10-13 | Exxon Research And Engineering Company | Thermal decomposition of naphthenic acids |
US5914030A (en) * | 1997-08-29 | 1999-06-22 | Exxon Research And Engineering. Co. | Process for reducing total acid number of crude oil |
US5976360A (en) * | 1995-10-20 | 1999-11-02 | Exxon Research And Engineering Company | Viscosity reduction by heat soak-induced naphthenic acid decomposition in hydrocarbon oils |
US6086751A (en) * | 1997-08-29 | 2000-07-11 | Exxon Research And Engineering Co | Thermal process for reducing total acid number of crude oil |
KR100451614B1 (en) * | 1995-10-20 | 2004-11-20 | 엑손 리써치 앤드 엔지니어링 컴파니 | Pyrolysis method of naphthenic acid |
US20100292349A1 (en) * | 2007-11-16 | 2010-11-18 | Statoil Asa | Process |
US20120190907A1 (en) * | 2009-06-22 | 2012-07-26 | Statoil Petroleum As | Method for isolation and quantification of naphthenate forming acids ("arn acids") |
-
1939
- 1939-05-13 US US273575A patent/US2227811A/en not_active Expired - Lifetime
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2478900A (en) * | 1946-04-17 | 1949-08-16 | Koppers Co Inc | Process of rendering noncorrosive the products resulting from catalytic alkylation |
US2478897A (en) * | 1946-04-30 | 1949-08-16 | Koppers Co Inc | Prevention of corrosion in catalytic reactions involving the use of phosphorus acid catalysts |
US2795532A (en) * | 1954-10-04 | 1957-06-11 | Sun Oil Co | Refining heavy mineral oil fractions with an anhydrous mixture of sodium hydroxide and potassium hydroxide |
US2938862A (en) * | 1958-01-07 | 1960-05-31 | Pure Oil Co | Method of refining aromatic extract oils with barium compounds |
US3761534A (en) * | 1971-12-29 | 1973-09-25 | Dow Chemical Co | Removal of acidic contaminants from process streams |
EP0809683A1 (en) * | 1995-02-17 | 1997-12-03 | Exxon Research And Engineering Company | Thermal decomposition of naphthenic acids |
US5820750A (en) * | 1995-02-17 | 1998-10-13 | Exxon Research And Engineering Company | Thermal decomposition of naphthenic acids |
EP0809683B1 (en) * | 1995-02-17 | 2001-11-14 | ExxonMobil Research and Engineering Company | Thermal decomposition of naphthenic acids |
US5976360A (en) * | 1995-10-20 | 1999-11-02 | Exxon Research And Engineering Company | Viscosity reduction by heat soak-induced naphthenic acid decomposition in hydrocarbon oils |
KR100451614B1 (en) * | 1995-10-20 | 2004-11-20 | 엑손 리써치 앤드 엔지니어링 컴파니 | Pyrolysis method of naphthenic acid |
US6086751A (en) * | 1997-08-29 | 2000-07-11 | Exxon Research And Engineering Co | Thermal process for reducing total acid number of crude oil |
US5914030A (en) * | 1997-08-29 | 1999-06-22 | Exxon Research And Engineering. Co. | Process for reducing total acid number of crude oil |
US20100292349A1 (en) * | 2007-11-16 | 2010-11-18 | Statoil Asa | Process |
US9222035B2 (en) | 2007-11-16 | 2015-12-29 | Statoil Petroleum As | Process for stabilizing an oil-in-water or water-in-oil emulsion |
US10202550B2 (en) | 2007-11-16 | 2019-02-12 | Equinor Energy As | Process for stabilizing an oil-in-water or water-in-oil emulsion |
US20120190907A1 (en) * | 2009-06-22 | 2012-07-26 | Statoil Petroleum As | Method for isolation and quantification of naphthenate forming acids ("arn acids") |
US8674161B2 (en) * | 2009-06-22 | 2014-03-18 | Statoil Petroleum As | Method for isolation and quantification of naphthenate forming acids (“ARN-acids”) |
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