US2735218A - Amino nitriles as metal complexing - Google Patents
Amino nitriles as metal complexing Download PDFInfo
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- US2735218A US2735218A US2735218DA US2735218A US 2735218 A US2735218 A US 2735218A US 2735218D A US2735218D A US 2735218DA US 2735218 A US2735218 A US 2735218A
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- 125000005219 aminonitrile group Chemical group 0.000 title description 24
- 229910052751 metal Inorganic materials 0.000 title description 4
- 239000002184 metal Substances 0.000 title description 4
- 230000000536 complexating Effects 0.000 title 2
- -1 AMINO NITRILE Chemical class 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 description 36
- 239000010949 copper Substances 0.000 description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 34
- 239000003963 antioxidant agent Substances 0.000 description 18
- 239000003209 petroleum derivative Substances 0.000 description 18
- LRDFRRGEGBBSRN-UHFFFAOYSA-N 2-methylpropanenitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 14
- 150000002430 hydrocarbons Chemical class 0.000 description 14
- 230000001939 inductive effect Effects 0.000 description 14
- 239000003208 petroleum Substances 0.000 description 14
- 230000003078 antioxidant Effects 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 229910001385 heavy metal Inorganic materials 0.000 description 10
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 8
- 230000000111 anti-oxidant Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- HOSVESHQDSFAST-UHFFFAOYSA-N 2-[2-(2-cyanopropan-2-yl)hydrazinyl]-2-methylpropanenitrile Chemical compound N#CC(C)(C)NNC(C)(C)C#N HOSVESHQDSFAST-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000003464 sulfur compounds Chemical class 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- VAMBUGIXOVLJEA-UHFFFAOYSA-N 4-(butylamino)phenol Chemical compound CCCCNC1=CC=C(O)C=C1 VAMBUGIXOVLJEA-UHFFFAOYSA-N 0.000 description 4
- SUSQOBVLVYHIEX-UHFFFAOYSA-N Benzyl cyanide Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 4
- DTUQWGWMVIHBKE-UHFFFAOYSA-N Phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(Z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative Effects 0.000 description 4
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- HWXOHKGATNULJP-UHFFFAOYSA-N 3-(3-methoxyphenyl)-3-oxopropanenitrile Chemical compound COC1=CC=CC(C(=O)CC#N)=C1 HWXOHKGATNULJP-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-Aminophenol Chemical class NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 229940043253 Butylated Hydroxyanisole Drugs 0.000 description 2
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N Butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N DETA Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- UDGSVBYJWHOHNN-UHFFFAOYSA-N N',N'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 2
- KVKFRMCSXWQSNT-UHFFFAOYSA-N N,N'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N P-Phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N Propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 101710036362 Ten-m Proteins 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N Triethylenetetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 2
- 125000004432 carbon atoms Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 150000002730 mercury Chemical class 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 229940100595 phenylacetaldehyde Drugs 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS 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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/226—Organic compounds containing nitrogen containing at least one nitrogen-to-nitrogen bond, e.g. azo compounds, azides, hydrazines
Definitions
- This invention relates to a method of improving the quality of petroleum hydrocarbons, and more particularly, to improving the quality of petroleum hydrocarbons which have been treated with heavy metal salts, such as mercury salts, copper-containing reagents, etc., for the removal or conversion of sulfur compounds.
- heavy metal salts such as mercury salts, copper-containing reagents, etc.
- an object of our invention to provide an improved method of rendering harmless heavy metal salts, such as those of copper, in petroleum hydrocarbons. Another object is to render petroleum hydrocarbons, such as cracked gasoline, more stable to oxidative deterioriation catalyzed by metals and to permit more effective use of gasoline antioxidants.
- Still another object is to provide a new class of effective treating agents for petroleum hydrocarbons, such as cracked gasoline.
- Other objects will become apparent from a consideration of the following description and examples.
- R, R1, R2, R3, R4, R5, R7, R8 and R9 each represents a hydrogen atom, an alkyl group (e. g. methyl, ethyl, etc.), or an aryl group (e. g. phenyl, o-, 111-, and p-tolyl, etc.)
- Rs represents a hydrocarbon aryl group (e. g. phenyl, 0-, m-, and p-tolyl, etc.)
- X represents an alkylene group or an arylene group
- d represents a positive integer of from 1 to 3
- n represents a positive integer of from 1 to 2.
- N N 2.
- the exact concentration of amino nitrile will, of course, depend somewhat on the concentration of heavy metal salt which remains after the sweetening operation.
- the amino nitrile deactivator can be added to the petroleum hydrocarbon in its natural state, or it can be added in the form of a concentrated solution in some organic solvent, such 'as methanol, benzene, 1,4- dioxane, etc.
- the petroleum hydrocarbon containing the deactivator can be further stabilized by the addition of conventional antioxidants, such as p-aminophenols, hydroquinone, butylated hydroquinone, butylated hydroxyanisole, pphenylenediamines, etc.
- conventional antioxidants such as p-aminophenols, hydroquinone, butylated hydroquinone, butylated hydroxyanisole, pphenylenediamines, etc.
- the efliciency of the amino nitrile deactivators of our invention was determined by means of oxygen bomb stability tests on treated and untreated samples of coppercontaining cracked gasoline.
- the gasoline contained one of the conventional antioxidants, which was conveniently added just prior to testing. Simultaneously, control tests were made on gasoline containing various combinations of copper and antioxidant, no deactivator being added.
- the copper was added in the form of a benzene solution of copper oleate and the antioxidant used wa N-n-butylp-aminophenol.
- the oxygen bomb stability test described above paralleled that described in Industrial and Engineering Chemistry, volume 24 (1932), page 1375. The induction period was measured as the times in minutes before rapid oxidation of the gasoline began, as evidenced by a sharp drop in oxygen pressure.
- the following examples will serve to illustrate more fully the manner whereby we practice our invention.
- Example 1 Pennsylvania cracked gasoline having a blank induction period of 45 minutes, which was raised to 445 minutes upon addition of 0.0048 weight percent of the gasoline antioxidant, N-n-butyl-p-aminophenol, was treated with a benzene solution of copper oleate sufiicient to introduce 1.0 mg. of copper per liter. This treatment reduced the induction period to 165' minutes, thus showing the harmful effect of copper upon gasoline stability even in the presence of an eflicient antioxidant. However, the addition of 0.0010 weight percent of a-anilinobutyronitrile to this inhibited copper-containing gasoline gave an induction period of 362 minutes, thus indicating considerable restoration of the induction period lost because of the presence of the copper.
- the gasoline antioxidant N-n-butyl-p-aminophenol
- Example 2 The same inhibited (i. e. containing N-nbutyl-p-aminophenol), copper-containing gasoline described in Example 1 was treated with 0.0010 weight percent of a,a'-triethylenetetramino-bis (isobutyronitrile) raising the induction period to 330 minutes.
- a,a'-triethylenetetramino-bis isobutyronitrile
- Example 3 The same inhibited, copper-containin g gasoline described in Example 1 above was treated with 0.0010 weight percent of hydrazodiisobutyronitrile raising the induction period to 300 minutes.
- 0010 345 (lsobutyronitrile) 1. 0 a,zx'-Ethylenedlamino-bis 0. 0010 335 (phenylacetonltrile). 1.0 a,a-Trlethylenetetra- 0.0010 330 mino-b1s(is0butyronitrile). 9 0.0048 1.0 a,a-Triethylenctetra- 0.0010 265 miI10-biS(a-I)h enylpropionltrlle) 10 0. 0048 1. 0 a-Anilinolsobutyronitrilc. 0.
- 0010 302 11 0.0048 1.0 a,a-p-Phenylencdin- 0.0010 375 rhino-bis (lsobutyronitrlle)
- the amino n1tr1les represented by Formulas I, II and III above can be prepared by condensing a monoamine or polyamine with an aldehyde or ketone in the presence of hydrocyanic acid according to the process described in Ulrich et al. U. S. Patent 2,205,995, issued June 25, 1940. Typical amines which can be used in the process of Ulrich et a1.
- Typical aldehydes or ketones which can be used comprise formaldehyde, acetaldehyde, propionaldehyde, isobutryoaldehyde, phenylacetaldehyde, acetone, methylethyl ketone, etc.
- the hydrocyanic acid used in the condensation is generally formed in situ as described in Ulrich U. S. Patent 2,205,995.
- a cracked gasoline which has been treated with a copper-containing reagent, containing from 0.0001 to 0.1 weight percent, based on the cracked gasoline, of an amino nitrile selected from the group consisting of those represented by the following general formulas:
- R, R1, R2, R3, R4, R5, R7, Ra, and R9 each represents a member selected from the group consisting of. a hydrogen atom, a lower alkyl group, and a monocyclic aryl group
- R6 represents a monocyclic hydrocarbon aryl group
- X represents a member selected from the group consisting of an alkylene group and a phenylene group
- d represents a positive integer of from 1 to 3
- n represents a positive integer of from 1 to 2.
- a cracked gasoline which has been sweetened with a copper-containing reagent, containing from 0.0001 to 0.1 weight percent, based on the weight of the petroleum hydrocarbon, of a,a'-p-phenylenediamino-bis(isobutyronitrile).
- a cracked gasoline which has been sweetened with a--copper-containing.reagent, containing from 0.0001 to 0.1 weight percent, based on the weight of the petroleum hydrocarbon, of a,a'-ethylenediamino-bis (isobutyronitrile).
- a cracked gasoline which has been sweetened with a copper-containing reagent, containing from 0.0001 to 0.1 weight percent, based on the weight of the petroleum hydrocarbon, of a,u'-ethylenediamino-bis (phenylacetonitrile).
- a cracked gasoline which has been sweetened with a copper-containing reagent, containing from 0.0001 to 0.1 weight percent, based on the weight of the petroleum hydrocarbon, of a,a-triethylenetetramino-bis (isobutyronitrile).
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- 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
AMINO NITRILES AS METAL COMPLEXING AGENTS IN CRACKED GASOLINE Donald J. Shields, John W. Thompson, and M B Knowles,
Kingsport, Tenm, assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application March 28, 1952, Serial No. 279,215
6 Claims. (Cl. 44-72) This invention relates to a method of improving the quality of petroleum hydrocarbons, and more particularly, to improving the quality of petroleum hydrocarbons which have been treated with heavy metal salts, such as mercury salts, copper-containing reagents, etc., for the removal or conversion of sulfur compounds.
It is well known to remove sulfur compounds, such as mercaptans, from petroleum hydrocarbons, such as gasoline motor fuels, or to convert such mercaptans into less objectionable compounds by appropriate chemical treatment, generally referred to as a sweetening operation. One quite common method of sweetening involves the use of a doctor solution made from sodium hydroxide and lead oxide. Treatment of the sour gasoline with this solution and added sulfur converts the mercaptans to alkyl disulfides. The amount of sulfur used must be very carefully controlled since excess sulfur in the gasoline is harmful with respect to corrosiveness, lead susceptibility, and inhibitor susceptibility. On the other hand, the use of insuificient sulfur causes lead mercaptides to be left in the fuel.
Instead of using the doctor solution method, it has been previously proposed to substitute other sweetening operations employing copper salts for the purpose of removing the sulfur compounds or converting them into less objectionable substances. This operation is widely used for the treatment of petroleum motor fuels, such as gasoline. Frequently, in the copper sweetening process, various copper compounds may be carried over into the treated gasoline where they are very objectionable, since even in trace concentrations they catalyze oxidative deterioration of the treated hydrocarbon. This dif- Qiculty is somewhat alleviated through the use of the known antioxidants, although the amount of improvement is not great enough to completely overcome the objections noted above. It is, therefore, desirable to provide some method which would substantially completely remove, or render harmless, all heavy metal compounds from the petroleum hydrocarbon, thus allowing the antioxidant to function at its fullest efficiency.
It is, therefore, an object of our invention to provide an improved method of rendering harmless heavy metal salts, such as those of copper, in petroleum hydrocarbons. Another object is to render petroleum hydrocarbons, such as cracked gasoline, more stable to oxidative deterioriation catalyzed by metals and to permit more effective use of gasoline antioxidants.
Still another object is to provide a new class of effective treating agents for petroleum hydrocarbons, such as cracked gasoline. Other objects will become apparent from a consideration of the following description and examples.
According to our invention, we provide the novel efnited States Patent fects mentioned above by treating a petroleum hydrocarbon containing heavy metal salts, such as those of copper, with an amino nitrile. The amino nitriles useful in practicing our invention comprise those represented by the following general formulas:
wherein R, R1, R2, R3, R4, R5, R7, R8 and R9 each represents a hydrogen atom, an alkyl group (e. g. methyl, ethyl, etc.), or an aryl group (e. g. phenyl, o-, 111-, and p-tolyl, etc.), Rs represents a hydrocarbon aryl group (e. g. phenyl, 0-, m-, and p-tolyl, etc.), X represents an alkylene group or an arylene group, d represents a positive integer of from 1 to 3, and n represents a positive integer of from 1 to 2. Amino nitriles containing only carbon, hydrogen and nitrogen atoms have been found to be especially useful in practicing our invention. Typical amino nitriles included within the scope of Formulas I, II and III above comprise the following:
1. Hydrazodiisobutyronitrile CH: (3H3 C Ila-4 -NH-NH-C C H;
N N 2. a,af-Ethylenediamino-bis (propionitrile) CH;CHNH-CH:CHNHGH-CH3 ON N . a,u'-Ethylenediamino-bis (isobutyronitrile) $113 CH3 CHz-C-NH-CHzCHq-NH- OH3 N ON 4. a,a-Ethylenediamino-bis (phenylacetonitrile) H OsH NHCHzCHz-NHCeH N ON 5. a,a'-Triethylenetetramino-bis (isobutyronitrile) CH on, o m-d NH-C Hie Hz-NH-O 112C Hz-NH-O H20 nrNH-b-o H,
6. a,m'-Triethylenetetramino-bis a-phenylpropionitrile CH3 CH3 0 fins-( 3 -NHO HQC H NH-C Hi0 Hz-NH-C 11,0 Hz-NH-(l-C 0151 N nn 7. a-Anilinoisobutyronitrile 8. a,a-p-Phenylenediamino-bis (isobutyronitrile) The amount of amino nitrile used according to our invention can be varied depending upon the particular petroleum hydrocarbon which is being stabilized. Generally, on the order of from 0.0001 to 0.1 weight percent of the amino nitrile is adequate for the purposes of our invention. The exact concentration of amino nitrile will, of course, depend somewhat on the concentration of heavy metal salt which remains after the sweetening operation. The amino nitrile deactivator can be added to the petroleum hydrocarbon in its natural state, or it can be added in the form of a concentrated solution in some organic solvent, such 'as methanol, benzene, 1,4- dioxane, etc.
The petroleum hydrocarbon containing the deactivator can be further stabilized by the addition of conventional antioxidants, such as p-aminophenols, hydroquinone, butylated hydroquinone, butylated hydroxyanisole, pphenylenediamines, etc.
The efliciency of the amino nitrile deactivators of our invention was determined by means of oxygen bomb stability tests on treated and untreated samples of coppercontaining cracked gasoline. In some instances, the gasoline contained one of the conventional antioxidants, which was conveniently added just prior to testing. Simultaneously, control tests were made on gasoline containing various combinations of copper and antioxidant, no deactivator being added. In the examples described below, the copper was added in the form of a benzene solution of copper oleate and the antioxidant used wa N-n-butylp-aminophenol. The oxygen bomb stability test described above paralleled that described in Industrial and Engineering Chemistry, volume 24 (1932), page 1375. The induction period was measured as the times in minutes before rapid oxidation of the gasoline began, as evidenced by a sharp drop in oxygen pressure. The following examples will serve to illustrate more fully the manner whereby we practice our invention.
Example 1.--A Pennsylvania cracked gasoline having a blank induction period of 45 minutes, which was raised to 445 minutes upon addition of 0.0048 weight percent of the gasoline antioxidant, N-n-butyl-p-aminophenol, was treated with a benzene solution of copper oleate sufiicient to introduce 1.0 mg. of copper per liter. This treatment reduced the induction period to 165' minutes, thus showing the harmful effect of copper upon gasoline stability even in the presence of an eflicient antioxidant. However, the addition of 0.0010 weight percent of a-anilinobutyronitrile to this inhibited copper-containing gasoline gave an induction period of 362 minutes, thus indicating considerable restoration of the induction period lost because of the presence of the copper.
Example 2.-The same inhibited (i. e. containing N-nbutyl-p-aminophenol), copper-containing gasoline described in Example 1 was treated with 0.0010 weight percent of a,a'-triethylenetetramino-bis (isobutyronitrile) raising the induction period to 330 minutes.
Example 3.The same inhibited, copper-containin g gasoline described in Example 1 above was treated with 0.0010 weight percent of hydrazodiisobutyronitrile raising the induction period to 300 minutes.
In a like manner, a number of other compounds falling within Formulas I, II and III above were tested as copper I deactivators, and the results obtained, along with those TABLE Eflectiveness of aminonitriles as copper deactivators for gasoline BA Deactivator g wt" p, as: Percent Y Wt. Period ame Percent 0 None 0 45 0 ..do.. 0 445 1.0 do 0 l. 0 Hydrazodiisobutyronitrile. 0. 0010 300 1. 0 a,a'-Ethylenediamino-bis 0. 0010 255 (propioru'trile) -1. 0 u,a-Ethylenediamino-bis 0. 0010 345 (lsobutyronitrile) 1. 0 a,zx'-Ethylenedlamino-bis 0. 0010 335 (phenylacetonltrile). 1.0 a,a-Trlethylenetetra- 0.0010 330 mino-b1s(is0butyronitrile). 9 0.0048 1.0 a,a-Triethylenctetra- 0.0010 265 miI10-biS(a-I)h enylpropionltrlle) 10 0. 0048 1. 0 a-Anilinolsobutyronitrilc. 0. 0010 302 11 0.0048 1.0 a,a-p-Phenylencdin- 0.0010 375 rhino-bis (lsobutyronitrlle) The amino n1tr1les represented by Formulas I, II and III above can be prepared by condensing a monoamine or polyamine with an aldehyde or ketone in the presence of hydrocyanic acid according to the process described in Ulrich et al. U. S. Patent 2,205,995, issued June 25, 1940. Typical amines which can be used in the process of Ulrich et a1. comprise hydrazine, ethylene diamine, diethylenetriamine, triethylenetetramine, N,N'-dimethylethylenediamine, N,N-diethylethylenediamine, p-phenylenediamine, aniline, etc. Typical aldehydes or ketones which can be used comprise formaldehyde, acetaldehyde, propionaldehyde, isobutryoaldehyde, phenylacetaldehyde, acetone, methylethyl ketone, etc. The hydrocyanic acid used in the condensation is generally formed in situ as described in Ulrich U. S. Patent 2,205,995.
What we claim and desire secured by Letters Patent of the United States is:
1. A cracked gasoline, which has been treated with a copper-containing reagent, containing from 0.0001 to 0.1 weight percent, based on the cracked gasoline, of an amino nitrile selected from the group consisting of those represented by the following general formulas:
11 wherein R, R1, R2, R3, R4, R5, R7, Ra, and R9 each represents a member selected from the group consisting of. a hydrogen atom, a lower alkyl group, and a monocyclic aryl group, R6 represents a monocyclic hydrocarbon aryl group, X represents a member selected from the group consisting of an alkylene group and a phenylene group, d represents a positive integer of from 1 to 3, and n represents a positive integer of from 1 to 2.
2. A cracked gasoline, which has been sweetened with a copper-containing reagent, containing from 0.0001 to 0.1 weight percent, based on the weight of the petroleum hydrocarbon, of a,a'-p-phenylenediamino-bis(isobutyronitrile).
3. A cracked gasoline, which has been sweetened with a--copper-containing.reagent, containing from 0.0001 to 0.1 weight percent, based on the weight of the petroleum hydrocarbon, of a,a'-ethylenediamino-bis (isobutyronitrile).
4. A cracked gasoline, which has been sweetened with a copper-containing reagent, containing from 0.0001 to 0.1 weight percent, based on the weight of the petroleum hydrocarbon, of a,u'-ethylenediamino-bis (phenylacetonitrile).
5. A cracked gasoline, which has been sweetened with a copper-containing reagent, containing from 0.0001 to 0.1 weight percent, based on the weight of the petroleum hydrocarbon, of a,a-triethylenetetramino-bis (isobutyronitrile).
References Cited in the file of this patent UNITED STATES PATENTS Guillaudeu Feb. 16, 1932 Lewis Dec. 6, 1938
Claims (1)
1. A CRACKED GASOLINE, WHICH HAS BEEN TREATED WITH A COPPER-CONTAINING REAGENT, CONTAINING FROM 0.0001 TO 0.1 WEIGHT PERCENT, BASED ON THE CRACKED GASOLINE, OF AN AMINO NITRILE SELECTED FROM THE GROUP CONSISTING OF THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULAS:
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US2735218A true US2735218A (en) | 1956-02-21 |
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US2735218D Expired - Lifetime US2735218A (en) | Amino nitriles as metal complexing |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4031015A (en) * | 1973-03-26 | 1977-06-21 | The Lubrizol Corporation | Nitrile-amine reaction products |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1845708A (en) * | 1930-10-24 | 1932-02-16 | Swift & Co | Fatty compositions |
US2139088A (en) * | 1937-04-02 | 1938-12-06 | Tide Water Associated Oil Comp | Lubricating oil and lubrication therewith |
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0
- US US2735218D patent/US2735218A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1845708A (en) * | 1930-10-24 | 1932-02-16 | Swift & Co | Fatty compositions |
US2139088A (en) * | 1937-04-02 | 1938-12-06 | Tide Water Associated Oil Comp | Lubricating oil and lubrication therewith |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4031015A (en) * | 1973-03-26 | 1977-06-21 | The Lubrizol Corporation | Nitrile-amine reaction products |
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