[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

US2905540A - Difficultly hydrolysable additives for diesel fuels - Google Patents

Difficultly hydrolysable additives for diesel fuels Download PDF

Info

Publication number
US2905540A
US2905540A US638754A US63875457A US2905540A US 2905540 A US2905540 A US 2905540A US 638754 A US638754 A US 638754A US 63875457 A US63875457 A US 63875457A US 2905540 A US2905540 A US 2905540A
Authority
US
United States
Prior art keywords
nitrate
diesel
nitric acid
additives
cyclohexanol
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
Application number
US638754A
Inventor
Schickh Otto Von
Nottes Guenther
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Application granted granted Critical
Publication of US2905540A publication Critical patent/US2905540A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/23Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C203/00Esters of nitric or nitrous acid
    • C07C203/02Esters of nitric acid
    • C07C203/08Esters of nitric acid having nitrate groups bound to carbon atoms of rings other than six-membered aromatic rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00Systems containing only non-condensed rings
    • C07C2601/12Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14The ring being saturated

Definitions

  • the known nitrate-containing ignition improvers have the disadvantage that in general they are relatively readily saponifiable.
  • diesel oils which contain amyl nitrate as the ignition improver most usually employed comeinto contact with water, a hydrolysis of the amyl nitrate takes place and the nitric acid thereby split off causes a corrosion of the storage container. This corrosion is practically unavoidable especially when using diesel oils in shipping traffic, because the diesel oil comes into contact with seat water by filling up the tanks.
  • nitric acid esters of hydroaromatic or cycloaliphatic alcohols are especially well suited as additives to diesel fuels. They not only increase the ignition quality of the diesel fuels but are also products which are hydrolysable only with difficulty.
  • nitric acid esters of hydroaromatic or cycloaliphatic alcohols there come into question especially: cyclopentanol nitrate, cyclohexanol nitrate, the different isomers of methylcyclohexanol nitrate, the different isomers of dimethylcyclohexanol nitrate, ethylcyclohexanol nitrate, diethylcyclohexanol nitrate, c-yclooctanol nitrate and decahydronaphthol nitrate.
  • nitric acid esters of the foregoing saturated cycloaliphatic alcohols are difficulty saponifiable may be seen from the following table in which the saponification numbers of amyl nitrate and cyclohexanol nitrate in an excess of half-normal methanolic caustic potash solution are given. Whereas after boiling for 6 hours at the boiling point of the methanolic caustic potash solution about by volume of the amyl nitrate has been saponified, scarcely any saponification has taken place in the case of the cyclohexanol nitrate.
  • the diesel fuel should contain between about 0.1% and 3 or more percent by weight of the nitric acid esters of hydroaromatic or cycloaliphatic alcohols.
  • Example 1 The increase in the saponification number in a diesel oil to which 2% by volume of amyl nitrate have been added as compared with the same diesel oil to which 2% by volume of cyclohexanol nitrate have been added may be seen from the next table.
  • the diesel oil is boiled for 3 hours under reflux with an excess of half-normal methanolic caustic potash solution.
  • the cyclohexanol nitrate in the diesel oil is practically unattacked, while the amyl nitrate in the diesel oil has reacted substantially after a few hours.
  • Example 4 The good eifect of the ignition improvers according to this invention may be seen from the following table, the additions having been made in each case to a diesel fuel having a cetane value (C.Z.) of 50:
  • Example 5 0.5% by Weight of cyclo-octanol nitrate is added to a diesel oil having a fundamental cetane number of 50. The cetane number is increased to 60 by'this addition.
  • a diesel fuel containing the nitric acid ester of a cycloalkyl alcohol in an amount suflicient to increase the cetane number of said fuel.
  • a diesel fuel containing the nitric acid ester of cyclopentanol in an amount sufiicient to increase the cetane number of said fuel.
  • a diesel fuel containing the nitric acid ester of cyclohexanol in an amount sulficient to increase the cetane number of said fuel.
  • a diesel fuel containing the nitric acid ester of a methylcyclohexanol in an amount sufiicient to increase the cetane number of said fuel.
  • a diesel fuel containing the nitric acid ester of a dimethylcyclohexanol in an amount suflicient to increase the cetane number of said fuel.
  • a diesel fuel containing the nitric acid ester of cyclooctanol in an amount sufiicient to increase the cetane number of said fuel.
  • a diesel fuel containing the nitric acid ester of an ethylcyclohexanol in an amount suflicient to increase the cetane number of said fuel.
  • a diesel fuel containing about 0.1% to 3% by weight of the nitric acid ester of a cycloalkyl alcohol.
  • a diesel fuel containing about 0.1% to 3% by weight of the nitric acid ester of an alkylcyclohexanol.
  • a diesel fuel containing about 0.1% to 3% by weight of the nitric acid ester of cyclohexanol.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Description

Sept. 22, 1959 0. VON SCHICKH .ETAL 2,905,540
DIFFICULTLY HYDROLYSABLE ADDITIVES FOR DIESEL FUELS Filed Feb. 7, 1957 INVENTORS. OTTO VON SCHICKH GUENTHER NOTTES mgmj iv ATT"YS United States Patent iS'IFiiiCULILY HYDROLYSABLE ADDITIVES FOR DIESEL FUELS Otto Yon Schickh and Guenther Nottes, Ludwigshafen (Rhine), Germany, assignors to Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen am Rhine, state of Rhineland-Pfalz, Germany Application February 7, 1957, Serial No. 638,754
Claims priority, application Germany, February 14,, 1956 11 Claims. (Cl. 44-57) This invention relates to the improvement of diesel fuels.
The increase in the consumption of diesel fuels has led in many countries to a scarcity of hydrogen-rich products so that it is often necessary to use diesel oils poor in hydrogen, such as are obtained for example by cracking, which have relatively low cetane numbers, and to raise the cetane number of these oils by the addition of ignition improvers. As additives for improving cetane numbers there have hitherto been proposed a large number of chemical compounds, including nitrates (see for example Marder: Motorenkraftstoife, page 347 et seq.)
The known nitrate-containing ignition improvers, however, have the disadvantage that in general they are relatively readily saponifiable. For example when diesel oils which contain amyl nitrate as the ignition improver most usually employed, comeinto contact with water, a hydrolysis of the amyl nitrate takes place and the nitric acid thereby split off causes a corrosion of the storage container. This corrosion is practically unavoidable especially when using diesel oils in shipping traffic, because the diesel oil comes into contact with seat water by filling up the tanks.
We have now found that nitric acid esters of hydroaromatic or cycloaliphatic alcohols are especially well suited as additives to diesel fuels. They not only increase the ignition quality of the diesel fuels but are also products which are hydrolysable only with difficulty.
As nitric acid esters of hydroaromatic or cycloaliphatic alcohols there come into question especially: cyclopentanol nitrate, cyclohexanol nitrate, the different isomers of methylcyclohexanol nitrate, the different isomers of dimethylcyclohexanol nitrate, ethylcyclohexanol nitrate, diethylcyclohexanol nitrate, c-yclooctanol nitrate and decahydronaphthol nitrate.
The fact that the nitric acid esters of the foregoing saturated cycloaliphatic alcohols are difficulty saponifiable may be seen from the following table in which the saponification numbers of amyl nitrate and cyclohexanol nitrate in an excess of half-normal methanolic caustic potash solution are given. Whereas after boiling for 6 hours at the boiling point of the methanolic caustic potash solution about by volume of the amyl nitrate has been saponified, scarcely any saponification has taken place in the case of the cyclohexanol nitrate.
As a rule the diesel fuel should contain between about 0.1% and 3 or more percent by weight of the nitric acid esters of hydroaromatic or cycloaliphatic alcohols.
i atented Sept. 22, 1959 The following examples will further illustrate this invention but the invention is not restricted to these examples.
Example 1 The increase in the saponification number in a diesel oil to which 2% by volume of amyl nitrate have been added as compared with the same diesel oil to which 2% by volume of cyclohexanol nitrate have been added may be seen from the next table.
The diesel oil is boiled for 3 hours under reflux with an excess of half-normal methanolic caustic potash solution. The cyclohexanol nitrate in the diesel oil is practically unattacked, while the amyl nitrate in the diesel oil has reacted substantially after a few hours.
TABLE GIVING SAPONIFIOATION NUMBERS OF DIESEL OIL CONTAINING 2% BY VOLUME OF AN AGENT FOR IMPROVING THE CE'IANE NUMBER Saponification Material treated number after boiling for 3 hours Diesel oil without addition 0 Diesel oi1+amy1 nitrate 16. 7 Diesel oil-l-cyclohexanol nitrate 0 Example 3 Samples of gas oil which contain 1% by volume of cyclohexanol nitrate are rolled at room temperature for an hour with seat water in rolling flasks. Strips of clean sheet iron of the same size and the same weight are pre viously laid in the flasks,
Further samples which contain 1% by volume of amyl nitrate and samples which contain no additives for increasing cetane number (blank value) are treated under the same conditions.
In the flasks containing gas oil to which amyl nitrate has been added, there is surface attack clearly visible on the sheet iron even after one hour, whereas the sheet iron in the gas oil to which 1% by volume of cyclohexanol nitrate has been added, and in the blank sample, is practically unattacked.
Example 4 The good eifect of the ignition improvers according to this invention may be seen from the following table, the additions having been made in each case to a diesel fuel having a cetane value (C.Z.) of 50:
Addition O.Z Increase in C.Z.
0.2% of eyclopentanol nitrate 57. 0 7. 0 0.5% of cyclopentanol nitrate. 64. 5 14. 5 1.0% of cyciopentano1nitrate 72.0 22.0
0.2% of cyclohexanol nitrate 56. 5 6. 5 0.5% of cyclohexanol nitrate. 64. 0 14. 0 1.0% of cyclohexanol nitrate 70.0 20. 0 2.0% of cyclohexanol nitrate 81.0 31.0
0.2% of methylcyclohexanol nitrate 56.0 6.0 0.5% of methylcyclohexanol nitrate.-. 60. 0 10. 0 1.0% of methylcyclohexanol nitrate 68.0 18. 0
0.2% of dimethylcyclohexanol nitrate 56.0 6.0 0.5% of dimethylcyclohexa-nol nitrare 61.0 11.0 1.0% of dimethylcyclohexanol nitrate 67. 0 17.0
3 Example 5 Example 6 0.5% by Weight of cyclo-octanol nitrate is added to a diesel oil having a fundamental cetane number of 50. The cetane number is increased to 60 by'this addition.
What We claim is:
1. As a new composition of matter, a diesel fuel containing the nitric acid ester of a cycloalkyl alcohol in an amount suflicient to increase the cetane number of said fuel.
2. As a new composition of matter, a diesel fuel containing the nitric acid ester of cyclopentanol in an amount sufiicient to increase the cetane number of said fuel.
3. As a new composition of matter, a diesel fuel containing the nitric acid ester of cyclohexanol in an amount sulficient to increase the cetane number of said fuel.
4. As a new composition of matter, a diesel fuel containing the nitric acid ester of a methylcyclohexanol in an amount sufiicient to increase the cetane number of said fuel.
5. As a new composition of matter, a diesel fuel containing the nitric acid ester of a dimethylcyclohexanol in an amount suflicient to increase the cetane number of said fuel.
6. As a new composition of matter, a diesel fuel containing the nitric acid ester of cyclooctanol in an amount sufiicient to increase the cetane number of said fuel.
7. Asa new composition of matter, a diesel fuel containing'the nitric acid ester of decahydronaphthol in an amount sufiicient to increase the cetane number of said fuel.
8. As a new composition of matter, a diesel fuel containing the nitric acid ester of an ethylcyclohexanol in an amount suflicient to increase the cetane number of said fuel.
, 9. As a new composition of matter, a diesel fuel containing about 0.1% to 3% by weight of the nitric acid ester of a cycloalkyl alcohol.
10. As a new composition of matter, a diesel fuel containing about 0.1% to 3% by weight of the nitric acid ester of an alkylcyclohexanol.
11. As a new composition of matter, a diesel fuel containing about 0.1% to 3% by weight of the nitric acid ester of cyclohexanol.
References Cited in the file of this patent UNITED STATES PATENTS 2,031,497 Marvel Feb. 18, 1936 2,280,217 Cloud Apr. 21, 1942 2,560,904 Sugimoto July 17, 1951 2,645,079 Doumani et al July 14, 1953

Claims (1)

1. AS A NEW COMPOSITION OF MATTER, A DIESEL FUEL CONTAINING THE NITRIC ACID ESTER OF A CYCLOAKYL ALCOHOL IN AN AMOUNT SUFFICIENT TO INCREASE THE CETANE NUMBER OF SAID FUEL.
US638754A 1956-02-14 1957-02-07 Difficultly hydrolysable additives for diesel fuels Expired - Lifetime US2905540A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2905540X 1956-02-14

Publications (1)

Publication Number Publication Date
US2905540A true US2905540A (en) 1959-09-22

Family

ID=8000909

Family Applications (1)

Application Number Title Priority Date Filing Date
US638754A Expired - Lifetime US2905540A (en) 1956-02-14 1957-02-07 Difficultly hydrolysable additives for diesel fuels

Country Status (1)

Country Link
US (1) US2905540A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4417903A (en) * 1982-10-15 1983-11-29 Ethyl Corporation Diesel fuel composition
US4420311A (en) * 1982-11-09 1983-12-13 Ethyl Corporation Diesel fuel composition
US4421522A (en) * 1982-10-06 1983-12-20 Ethyl Corporation Diesel fuel composition
US5258049A (en) * 1993-02-17 1993-11-02 Arco Chemical Technology, L.P. Diesel fuel composition
US5405417A (en) * 1990-07-16 1995-04-11 Ethyl Corporation Fuel compositions with enhanced combustion characteristics
WO2013093100A1 (en) * 2011-12-22 2013-06-27 Shell Internationale Research Maatschappij B.V. Organic nitrates as ignition enhancers

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2031497A (en) * 1933-01-21 1936-02-18 Du Pont Fuel
US2280217A (en) * 1938-11-30 1942-04-21 Standard Oil Dev Co Super-diesel fuel
US2560904A (en) * 1950-07-28 1951-07-17 Ethyl Corp Diesel fuel
US2645079A (en) * 1944-06-06 1953-07-14 Union Oil Co Method of operating jet propulsion motors

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2031497A (en) * 1933-01-21 1936-02-18 Du Pont Fuel
US2280217A (en) * 1938-11-30 1942-04-21 Standard Oil Dev Co Super-diesel fuel
US2645079A (en) * 1944-06-06 1953-07-14 Union Oil Co Method of operating jet propulsion motors
US2560904A (en) * 1950-07-28 1951-07-17 Ethyl Corp Diesel fuel

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4421522A (en) * 1982-10-06 1983-12-20 Ethyl Corporation Diesel fuel composition
US4417903A (en) * 1982-10-15 1983-11-29 Ethyl Corporation Diesel fuel composition
US4420311A (en) * 1982-11-09 1983-12-13 Ethyl Corporation Diesel fuel composition
US5405417A (en) * 1990-07-16 1995-04-11 Ethyl Corporation Fuel compositions with enhanced combustion characteristics
US5258049A (en) * 1993-02-17 1993-11-02 Arco Chemical Technology, L.P. Diesel fuel composition
WO2013093100A1 (en) * 2011-12-22 2013-06-27 Shell Internationale Research Maatschappij B.V. Organic nitrates as ignition enhancers

Similar Documents

Publication Publication Date Title
US2905540A (en) Difficultly hydrolysable additives for diesel fuels
DE735276C (en) Process for the production of knock-proof petrol
US2021088A (en) Motor fuel
US1989528A (en) Distillate petroleum product and method of treating the same
USRE23239E (en) Inhibitor for gasoline
US3015547A (en) Motor fuel containing octane improver
US3033664A (en) Hydrocarbon distillate fuels
DE654470C (en) Motor fuel
US2227823A (en) Butyl 12-ketostearate
US3074787A (en) Motor fuels containing keto carboxylic acids
US2076581A (en) Method of refining gasoline
GB802181A (en) Motor fuel composition
US2918360A (en) Fuel compositions for spark ignition engines
US2287898A (en) Stabilization of gasoline and the like
DE1008959B (en) Additives to diesel fuels
DE913680C (en) Process for the catalytic cracking of hydrocarbon oils
AT216654B (en) Light petrol
DE713208C (en) Process for the production of non-sticking motor fuels
US2063516A (en) Process for stabilizing gasoline and the like
GB820773A (en) Process for the production of polyolefins
DE845502C (en) Process for the production of hydrocarbons
US2894828A (en) Hydrocarbon compositions containing the water-insoluble nitric acid oxidation product of naphthenic acids
DE871852C (en) Gasoline mixed with organometallic compounds
US3021203A (en) Motor fuel containing an octane appreciator
US2062463A (en) Fuels