GB1571210A - Cerium compounds method of obtaining said compounds and applications thereof - Google Patents
Cerium compounds method of obtaining said compounds and applications thereof Download PDFInfo
- Publication number
- GB1571210A GB1571210A GB2643577A GB2643577A GB1571210A GB 1571210 A GB1571210 A GB 1571210A GB 2643577 A GB2643577 A GB 2643577A GB 2643577 A GB2643577 A GB 2643577A GB 1571210 A GB1571210 A GB 1571210A
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- GB
- United Kingdom
- Prior art keywords
- cerium
- salt
- mixture
- organic acid
- salts
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 20
- 150000001785 cerium compounds Chemical class 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 title description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 48
- 150000003839 salts Chemical class 0.000 claims description 46
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 34
- -1 alkyl hydrogen sulphate Chemical compound 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000000446 fuel Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 239000003973 paint Substances 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 11
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000002966 varnish Substances 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 9
- 239000011833 salt mixture Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 5
- 244000060011 Cocos nucifera Species 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- DPUCLPLBKVSJIB-UHFFFAOYSA-N cerium;tetrahydrate Chemical compound O.O.O.O.[Ce] DPUCLPLBKVSJIB-UHFFFAOYSA-N 0.000 claims description 2
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000002910 rare earth metals Chemical group 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 150000000703 Cerium Chemical class 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000002816 fuel additive Substances 0.000 description 2
- 125000005609 naphthenate group Chemical group 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/12—Straight chain carboxylic acids containing eighteen carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F9/00—Compounds to be used as driers, i.e. siccatives
-
- 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
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
-
- 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
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
-
- 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
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
- C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only
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)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
Description
(54) 1MPRvEMENS IN OR RELATING TO CERIUM
COMPOUNDS, METHOD OF OBTAINING SAID COMPOUNDS
AND APPLICATIONS THEREOF
(71) We, GAMLEN EUROPE SA a,
Body Corporate organized under the laws of
France of 2, rue Huntziger-92112 Clichy, France, do hereby declare the invention forl which we pray that a patent may be grantedl to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to novel cerium compounds, a method of preparing the said compounds as well as their applicatiot in the field of paints and varnishes and alsot in the field of liquid fuels.
There are known organosoluble cerium compounds that find application as dryers for paints and varnishes and as fuel additives.
The cerium compounds thus known and used are cerium soaps prepared by submits ting cerium hydroxide or a cerium salt to the action of a long-chain carboxylic acid (with more than 8 carbon atoms) or of one of its alkaline salts. The reactions involved are stoichiometric and the derivatives obtained have a composition according to which a trivalent cerium atom is linked substantially to three fatty acid molecules.
Thus, the aforementioned favourable action of cerium, in the form of its salt, upon paints, varnishes and fuels is obtained with compounds comprising a relatively large number of fatty acid molecules compared with the necessary number of metal atoms.
However with the present invention, the organic cerium salts soluble in organic solvents, used according to the present invention, are characterized by a ratio r of the number of acid equivalents to the number of cerium atoms of between 0.2 and 1; by "number of acid equivalents" is meant the number of acid molecules when the acid used is monofunctional, and this number has to be doubled or trebled in the case of diacids or triacids and more generally multiplied by the number of acid functions in the case of a polyadd.
Thus, the cerium compounds employable in the present invention require only a much smaller amount of acid than the amount used previously with the same effectiveness.
Another advantage of the invention is that it allows solutions d high metal concentration, reaching 500 g/litre to be obtained, the said solutions remaining fluid and capable of being handled without difficulty while at the same time remaining completely soluble in hydrocarbon media.
According to one aspect of the invention there is provided a cerium organic acid salt which is soluble in oils and/or organic solvents or a mixture of such salts, wherein the salt or each component salt of the mixture has a ratio r between 0.2 and 1, the ratio r being the number of acid equivalents to the number of cerium atoms, and the or each organic acid from which the salt or each component salt is derived has a hydrocarbon radical containing at least 7 carbon atoms. Preferably the said or each said organic acid is any one od the following: RCOOH, RSO3H, ROSO3H, ROPO,H2 or (RO)2PO2H, wherein
R is a hydrocarbon radical containing at least 7 carbon atoms. The or each organic acid radical contains at least 7 carbon atoms and may be a linear or branched aliphatic radical or a cycloaliphatic radical which is optionally alkylated or an aromatic radical which is optionally alkylated. Desirably the or each organic acid is selected from oleic acid, dodecylbenzenesulphonic add, octadecylphosphoric acid, sulphonated paraffin containing at least 7 carbon atoms, alkyl hydrogen sulphate derived from copra and in which the alkyl radical contains at least 7 carbon atoms, and dicresyl phosphate. The cerium organic acid salt or a mixture of such salts may contain at least one other rare earth element in addition to cerium in an amount or total amount of up to 25 S of the total rare earth element content including cerium.
According to another aspect of the invention there is provided a composition, suitable as
a drying composition or as fuel additive, comprising the cerium organic acid salt or mixture of such salts as defined by the first aspect
of the invention dissolved in an organic sol
vent therefor. Such composition may com
prise more than 200 grams, preferably 250 to
350 grams, per litre of the composition. The
said composition may be included in a paint
or varnish or liquid fuel and the amount of the said salt or salt mixture may correspond to 10 to 200 p.p.m., preferably 30 to 100 p.p.m., of cerium.
According to a further aspect of the invention there is provided a method of obtaining a cerium organic acid salt or a mixture of such salts as defined by the first aspect of the invention, the method comprising reacting in an organic or an aqueous organic medium the said organic acid(s) and freshly prepared ceric hydroxide under such conditions that the resultant cerium organic acid salt(s) has/have a ratio r as hereinbefore defined of between 0.2 and 1. The reaction is preferably effected with heating and preferably the said organic medium is a hydrocarbon. It is found that after several hours part of the water (formed by the reaction) separates spontaneously. The preparation can be performed without difficulty from usual-grade cerium salts, in which there may also be found, up to 25% of rare earth elements other than cerium.
It is possible, after the reaction, to assist the separation of the water from the reaction medium by adding a further solvent such as a glycol, an alcohol or an alkyl glycol.
The solution thus obtained after the separation may be added as such, after adjusting the concentration with a suitable hydrocarbon, to paints, varnishes or liquid fuels, to serve as drying compositions or as combustion additive compositions, as the case may be.
The said compositions may be added according to their concentration in adequate proportions to paints, varnishes or liquid fuels
so that the latter contain from 10 to 200 p.p.m. of metal cerium in the form of its salt or salts, and preferably from 30 to 150 p.p.m., more preferably 30 to 100 p.p.m., of metal; this is the optimum concentration for ensuring the drying effects or combustion modifying effects of the compounds according to the invention.
The following examples illustrate the pre
sent invention.
EXAMPLE 1.
350 g of cerium hydroxide Ce (OH), obtained by precipitating cerium nitrate with aqueous ammonia, washed with water until the N03- ion has disappeared, and filtered until it contains only 15% of water, is reacted with 130 g of usual-grade oleic acid in 800 ml of white spirit at 800. After stirring for 4 hours, 30 ml of glycol is added, the separated water is eliminated and 90 ml of butyl-glycol is added. White spirit is thereafter added to complete to 1 litre.
The solution obtained contains 250 g/litre of cerium, the ratio r being 0.26. It is sufficiently fluid to be transferred and handled at normal or room temperature.
The drying capacity of this cerium solution is compared with that of a conventional naphthenate on a glycerophthalic paint containing 0.2% of metal cerium and 0.025% of cobalt.
The "tack-free" and hardening time of the paint thus treated as well as the aspect of the films after drying are equivalent (by "tack-free time" is meant the time after which the spread paint film no longer sticks to the fingers).
It is thus observed that with the compound of the invention the amount of acid used is much smaller than with the conventional naphthenate known up to the present. In other words, if use were made, in the paint considered, of the conventional cerium compounds corresponding to the same amount of acid as that used according to the present invention, a much less satisfactory result would be obtained.
EXAMPLE 2.
350 g of cerium hydroxide freshly precipitated with aqueous ammonia from cerium chloride is reacted under the same conditions as in Example 1 with 170 g of dodecylbenzenesulphonic acid and 500 ml of benzene.
After 3 hours heating at 700 with stirring, the water that has separated is eliminated and benzene is added to complete to 800 ml.
The solution contains 310 g per litre of metal cerium, the ratio r being 0.3. It is added at the rate of 1 litre per 10,000 litre to heavy fuel supplied to a boiler. The fuel then contains 31 p.p.m. of metal.
The particles emission rate passes from 2.32 g per kg of fuel in the case of the nontreated fuel to 0.45 g per kg of fuel in the case of the treated fuel without there having been any modification of burner adjustment
EXAMPLE 3.
The method used in Example 1 is applied, but the 130 g of oleic acid is replaced by 175 g of sulphonated paraffin containing at least 7 carbon atoms and having an acid value of 130.
The heating time necessary to complete the reaction is less than 1 hour.
The product contains 253 g per litre of metal cerium. The ratio r is 0.22. The technical results obtained with this product are
identical with those of the product described in Example 1 (effect on paint).
EXAMPLE 4.
The same method as in Example 1 is applied, but the 130 g of oleic acid is replaced with 525 g of alkyl hydrogen sulphate derived from copra and containing no free sulphuric acid and wherein the alkyl radical contains at least 7 carbons atoms. The ratio r is equal to 0.21.
The technical results of this product are identical with those of the product described in Example 1.
EXAMPLE 5.
The same method is applied as in Example 2, but the 170 g of dodecylbenzenesulphonic acid is replaced with 170 g of usual-grade octadecylphosphoric acid with an acid value of 329.
The product contains 30.5 % of metal cerium; the ratio r is equal to 0.57.
The results obtained with this product are identical with those of the product described in Example 2.
EXAMPLE 6.
350 g of cerium hydroxide obtained by reacting aqueous ammonia with cerium nitrate is washed until the NO,- ion disappears and then dried.
The said hydroxide is reacted in 800 ml of gas oil with 140 g of dicresyl phosphate.
After 3 hours heating at 900 the water that has separated is eliminated, 80 ml of butylglycol is added and then gas oil is added complete to 1 litre.
The solution contains 252 g per litre of metal cerium. The ratio r is 0.27.
1 litre of this solution is added to 10,000 litre of gas oil supplied to a Diesel engine, which then contains 25 p.p.m. of metal, and the opacity and specific consumption obtained with this fuel are compared with the same elements obtained with the same fuel in the non-treated state.
It is found that at any speed and any power there takes place a 15 to 30% reduction of the opacity of the exhaust gases according to the scale of the Hartridge apparatus.
Specific consumption of the engine is reduced by 2 to 3% depending on the speed and the power.
EXAMPLE 7.
The same method of preparation is applied as in Example 6, using a usual-grade cerium nitrate containing 85% of cerium and 15% of other metals of the rare-earth group. The ratio r is the same as for Example 6, namely 0.27. The product used under the same conditions as the product of Example 6 gives equivalent or barely inferior results.
WHAT WE CLAIM IS:- 1. A cerium organic acid salt which is soluble in oils and/or organic solvents or a mixture of such salts, wherein the salt or each component salt of the mixture has a ratio r between 0.2 and 1, the ratio r being the number of acid equivalents to the number ob cerium atoms, and the or each organic acid from which the salt or each component salt is derived has a hydrocarbon radical containing at least 7 carbon atoms.
2. A cerium organic acid salt or a mixture of such salts according to Claim 1, wherein the said or each said organic acid is any one of the following: RCOOH, RSO3H,
ROSO,H, ROPO3H2 or (RO)2PO2H, wherein
R is a hydrocarbon radical containing at least 7 carbon atoms.
3. A cerium organic acid salt or a mixture of such salts according to Claim 1 or Claim 2, wherein the or each organic acid radical is a linear or branched aliphatic radical containing at least 7 carbon atoms.
4. A cerium organic acid salt or a mixture of such salts according to Claim 1 or Claim 2, wherein the or each said hydrocarbon radical contains at least 7 carbon atoms and is a cycloaliphatic radical which is optionally alkylated or an aromatic radical which is optionally alkylated.
5. A cerium organic acid salt or a mixture of such salts according to any preceding claim, in which the or each organic acid is selected from oleic acid, dodecylbenzene suiphonic acid, octadecylphosphoric acid, sulphonated paraffin containing at least 7 carbon atoms, alkyl hydrogen sulphate derived from copra and in which the alkyl radical contains at least 7 carbon atoms, and dicresyl phosphate.
6. A cerium organic acid salt or a mixture of such salts, which contains at least one other rare earth element in addition to cerium in an amount or total amount ob up to 25% of the total rare earth element content m- cluding cerium.
7. A cerium organic acid salt or a mixture of such salts according to Claim 1 substantially as herein described and exemplified.
8. A composition comprising the cerium organic acid salt or mixture of such salts as defined in any preceding claim dissolved in an organic solvent therefor.
9. A composition according to Claim 8, which contains an amount of the said salt or salt mixture corresponding to more than 200 grams of cerium per litre of the composition.
10. A composition according to Claim 8 or Claim 9, which contains an amount of the
said salt or salt mixture corresponding to 250 to 350 grams of metal cerium per litre
of the composition.
11. A composition according to Claim 8
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (25)
1 litre of this solution is added to 10,000 litre of gas oil supplied to a Diesel engine, which then contains 25 p.p.m. of metal, and the opacity and specific consumption obtained with this fuel are compared with the same elements obtained with the same fuel in the non-treated state.
It is found that at any speed and any power there takes place a 15 to 30% reduction of the opacity of the exhaust gases according to the scale of the Hartridge apparatus.
Specific consumption of the engine is reduced by 2 to 3% depending on the speed and the power.
EXAMPLE 7.
The same method of preparation is applied as in Example 6, using a usual-grade cerium nitrate containing 85% of cerium and 15% of other metals of the rare-earth group. The ratio r is the same as for Example 6, namely 0.27. The product used under the same conditions as the product of Example 6 gives equivalent or barely inferior results.
WHAT WE CLAIM IS:- 1. A cerium organic acid salt which is soluble in oils and/or organic solvents or a mixture of such salts, wherein the salt or each component salt of the mixture has a ratio r between 0.2 and 1, the ratio r being the number of acid equivalents to the number ob cerium atoms, and the or each organic acid from which the salt or each component salt is derived has a hydrocarbon radical containing at least 7 carbon atoms.
2. A cerium organic acid salt or a mixture of such salts according to Claim 1, wherein the said or each said organic acid is any one of the following: RCOOH, RSO3H,
ROSO,H, ROPO3H2 or (RO)2PO2H, wherein
R is a hydrocarbon radical containing at least 7 carbon atoms.
3. A cerium organic acid salt or a mixture of such salts according to Claim 1 or Claim 2, wherein the or each organic acid radical is a linear or branched aliphatic radical containing at least 7 carbon atoms.
4. A cerium organic acid salt or a mixture of such salts according to Claim 1 or Claim 2, wherein the or each said hydrocarbon radical contains at least 7 carbon atoms and is a cycloaliphatic radical which is optionally alkylated or an aromatic radical which is optionally alkylated.
5. A cerium organic acid salt or a mixture of such salts according to any preceding claim, in which the or each organic acid is selected from oleic acid, dodecylbenzene suiphonic acid, octadecylphosphoric acid, sulphonated paraffin containing at least 7 carbon atoms, alkyl hydrogen sulphate derived from copra and in which the alkyl radical contains at least 7 carbon atoms, and dicresyl phosphate.
6. A cerium organic acid salt or a mixture of such salts, which contains at least one other rare earth element in addition to cerium in an amount or total amount ob up to 25% of the total rare earth element content m- cluding cerium.
7. A cerium organic acid salt or a mixture of such salts according to Claim 1 substantially as herein described and exemplified.
8. A composition comprising the cerium organic acid salt or mixture of such salts as defined in any preceding claim dissolved in an organic solvent therefor.
9. A composition according to Claim 8, which contains an amount of the said salt or salt mixture corresponding to more than 200 grams of cerium per litre of the composition.
10. A composition according to Claim 8 or Claim 9, which contains an amount of the
said salt or salt mixture corresponding to 250 to 350 grams of metal cerium per litre
of the composition.
11. A composition according to Claim 8
substantially as herein described and exemplified.
12. A method of obtaining a cerium organic acid salt or a mixture of such salts as defined in Claim 1, the method comprising reacting in an organic or an aqueous organic medium the said organic acid(s) and freshly prepared ceric hydroxide under such conditions that the resultant cerium organic acid salt(s) has/have a ratio r as defined in Claim 1 of between 0.2 and 1.
13. A method according to Claim 12, wherein the reaction is effected with heating.
14. A method according to Claim 12 or
Claim 13, wherein the said organic medium is a hydrocarbon.
15. A method according to any one of
Claims 12 to 14, wherein after the reaction a glycol, an alcohol or an alkyl glycol is added to the reaction medium.
16. A method according to Claim 12 substantially as herein described and exemplified.
17. A cerium organic acid salt or a mixture of such salts which has been obtained by the method claimed in any one of Claims 12 to 16.
18. A paint or varnish which includes a composition as defined in Claim 8.
19. A paint or varnish according to Claim 18, which contains an amount of the said salt or salt mixture corresponding to 10 to 200 p:p.m. of cerium.
20. A paint or varnish according to Claim 19, wherein the amount of the said salt or salt mixture corresponds to 30 to 150 p.p.m.
of cerium.
21. A paint or varnish according to Claim 18 substantially as herein described and exemplified.
22. A liquid fuel which includes a composition as defined in Claim 8.
23. A liquid fuel according to Claim 22, which contains an amount of the said salt or salt mixture corresponding to 10 to 200 p.p.m. of cerium.
24. A liquid fuel according to Claim 23, wherein the amount of the said salt or salt mixture corresponds to 30 to 100 p.p.m. of cerium.
25. A liquid fuel according to Claim 22 substantially as herein described and exemplified.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7622426A FR2359192A1 (en) | 1976-07-22 | 1976-07-22 | OLEOSOLUBLE COMPOUNDS OF CERIUM, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS SICCATING AGENTS OR COMBUSTION ADDITIVES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1571210A true GB1571210A (en) | 1980-07-09 |
Family
ID=9176026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB2643577A Expired GB1571210A (en) | 1976-07-22 | 1977-06-23 | Cerium compounds method of obtaining said compounds and applications thereof |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5312907A (en) |
| AU (1) | AU518590B2 (en) |
| BE (1) | BE856974A (en) |
| DE (1) | DE2729365A1 (en) |
| FR (1) | FR2359192A1 (en) |
| GB (1) | GB1571210A (en) |
| IT (1) | IT1202371B (en) |
| NL (1) | NL7707497A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2160527A (en) * | 1984-05-25 | 1985-12-24 | Kao Corp | Metal salts of phoshate monoesters |
| US4836830A (en) * | 1986-09-19 | 1989-06-06 | Rhone-Poulenc Inc. | Rare earth compositions for diesel fuel stabilization |
| FR2911607A1 (en) * | 2007-01-23 | 2008-07-25 | Rhodia Recherches & Tech | PROCESS FOR PREPARING A SOLUTION OF A RARE EARTH ORGANOPHOSPHATE |
| US9669375B2 (en) | 2012-01-30 | 2017-06-06 | Cerion, Llc | Method for production of stable cerium oxide organic colloids |
| US10544376B2 (en) | 2012-01-30 | 2020-01-28 | Cerion, Llc | Rapid method for production of cerium-containing oxide organic colloids |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2486083B1 (en) * | 1980-07-01 | 1986-03-07 | Gamlen Europ Sa | ORGANOSOLUBLE MANGANESE SALTS, PROCESS FOR PREPARING THE SAME, ORGANIC COMPOSITIONS, LIQUID FUELS, PAINTS AND VARNISHES CONTAINING THE SAME |
| DE3360378D1 (en) * | 1982-04-12 | 1985-08-14 | Rhone Poulenc Spec Chim | Process for the preparation of cerium carboxylates |
| US4545923A (en) * | 1982-06-11 | 1985-10-08 | Rhone-Poulenc Inc. | Process for preparing colloidal ceric oxide and complexes thereof with free organic acids |
| US4464227A (en) * | 1982-09-16 | 1984-08-07 | At&T Technologies, Inc. | Methods and apparatus for distilling a contaminated solvent |
| FR2537593B1 (en) * | 1982-12-10 | 1986-04-11 | Raffinage Cie Francaise | COMBINED ORGANOMETALLIC COMPOSITIONS COMPRISING ELEMENTS OF THE IRON AND LANTHANIDE GROUPS, PROCESS FOR THE PREPARATION AND APPLICATION OF THE SAME COMPOSITIONS AS ADDITIVES FOR FUELS OR FUELS |
| DE3245882A1 (en) * | 1982-12-11 | 1984-06-14 | Ruhrchemie Ag, 4200 Oberhausen | Process for improving the combustion of liquid fuels |
| US4462810A (en) * | 1983-08-17 | 1984-07-31 | Exxon Research & Engineering Co. | Zirconium-cerium additives for residual fuel oil |
| US4522631A (en) * | 1983-11-18 | 1985-06-11 | Texaco Inc. | Diesel fuel containing rare earth metal and oxygenated compounds |
| US4670020A (en) * | 1984-12-24 | 1987-06-02 | Ford Motor Company | Carbon ignition temperature depressing agent and method of regenerating an automotive particulate trap utilizing said agent |
| FR2583761B1 (en) * | 1985-06-20 | 1987-08-14 | Rhone Poulenc Spec Chim | PROCESS FOR THE PREPARATION OF A COLLOIDAL DISPERSION OF A METAL CATION COMPOUND IN ORGANIC MEDIA AND THE SOILS OBTAINED |
| JPH02182783A (en) * | 1989-01-09 | 1990-07-17 | Nippon Mining Co Ltd | Combustion of fuel with high residual carbon content |
| WO2024003254A1 (en) * | 2022-06-30 | 2024-01-04 | Umicore Specialty Materials Brugge | Fuel borne catalyst composition for oxidative soot removal |
-
1976
- 1976-07-22 FR FR7622426A patent/FR2359192A1/en active Granted
-
1977
- 1977-06-23 GB GB2643577A patent/GB1571210A/en not_active Expired
- 1977-06-29 DE DE19772729365 patent/DE2729365A1/en not_active Ceased
- 1977-06-30 IT IT2522577A patent/IT1202371B/en active
- 1977-07-06 NL NL7707497A patent/NL7707497A/en not_active Application Discontinuation
- 1977-07-12 AU AU26951/77A patent/AU518590B2/en not_active Expired
- 1977-07-20 BE BE179482A patent/BE856974A/en not_active IP Right Cessation
- 1977-07-20 JP JP8615377A patent/JPS5312907A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2160527A (en) * | 1984-05-25 | 1985-12-24 | Kao Corp | Metal salts of phoshate monoesters |
| US4836830A (en) * | 1986-09-19 | 1989-06-06 | Rhone-Poulenc Inc. | Rare earth compositions for diesel fuel stabilization |
| FR2911607A1 (en) * | 2007-01-23 | 2008-07-25 | Rhodia Recherches & Tech | PROCESS FOR PREPARING A SOLUTION OF A RARE EARTH ORGANOPHOSPHATE |
| WO2008090141A1 (en) * | 2007-01-23 | 2008-07-31 | Rhodia Operations | Method for preparing a solution of a rare earth organophosphate |
| US9669375B2 (en) | 2012-01-30 | 2017-06-06 | Cerion, Llc | Method for production of stable cerium oxide organic colloids |
| US10544376B2 (en) | 2012-01-30 | 2020-01-28 | Cerion, Llc | Rapid method for production of cerium-containing oxide organic colloids |
Also Published As
| Publication number | Publication date |
|---|---|
| NL7707497A (en) | 1978-01-24 |
| IT1202371B (en) | 1989-02-09 |
| FR2359192B1 (en) | 1981-10-30 |
| AU518590B2 (en) | 1981-10-08 |
| BE856974A (en) | 1977-11-14 |
| FR2359192A1 (en) | 1978-02-17 |
| JPS5312907A (en) | 1978-02-06 |
| AU2695177A (en) | 1979-01-18 |
| DE2729365A1 (en) | 1978-03-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19960623 |