US20070169406A1 - Cerium organic colloidal dispersion and element selected from rhodium and palladium and use thereof as additive to diesel fuel for internal combustion engines - Google Patents
Cerium organic colloidal dispersion and element selected from rhodium and palladium and use thereof as additive to diesel fuel for internal combustion engines Download PDFInfo
- Publication number
- US20070169406A1 US20070169406A1 US10/574,626 US57462604A US2007169406A1 US 20070169406 A1 US20070169406 A1 US 20070169406A1 US 57462604 A US57462604 A US 57462604A US 2007169406 A1 US2007169406 A1 US 2007169406A1
- Authority
- US
- United States
- Prior art keywords
- dispersion
- cerium
- particles
- acid
- rare earth
- 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.)
- Abandoned
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 35
- 239000010948 rhodium Substances 0.000 title claims abstract description 29
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 25
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000001246 colloidal dispersion Methods 0.000 title claims abstract description 23
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 20
- 238000002485 combustion reaction Methods 0.000 title claims description 9
- 239000000654 additive Substances 0.000 title abstract description 7
- 230000000996 additive effect Effects 0.000 title abstract description 5
- 239000002283 diesel fuel Substances 0.000 title abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title description 28
- 239000002245 particle Substances 0.000 claims abstract description 46
- 239000006185 dispersion Substances 0.000 claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 29
- 239000012074 organic phase Substances 0.000 claims abstract description 29
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 26
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 150000001785 cerium compounds Chemical class 0.000 claims abstract description 6
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims abstract 7
- 239000000203 mixture Substances 0.000 claims description 27
- 239000002244 precipitate Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- 239000000446 fuel Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 150000000703 Cerium Chemical class 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 239000002816 fuel additive Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- -1 rare earth compounds Chemical class 0.000 description 21
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 239000004071 soot Substances 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000000604 cryogenic transmission electron microscopy Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
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- 238000012546 transfer Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
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- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical group 0.000 description 3
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- 238000011068 loading method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 0 [1*]OCCCC=O Chemical compound [1*]OCCCC=O 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000006280 diesel fuel additive Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
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- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
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- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
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- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- SSILHZFTFWOUJR-UHFFFAOYSA-N hexadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCS(O)(=O)=O SSILHZFTFWOUJR-UHFFFAOYSA-N 0.000 description 1
- JDPSFRXPDJVJMV-UHFFFAOYSA-N hexadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCP(O)(O)=O JDPSFRXPDJVJMV-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- MAJZZCVHPGUSPM-UHFFFAOYSA-N nitric acid nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.O[N+]([O-])=O MAJZZCVHPGUSPM-UHFFFAOYSA-N 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002942 palmitic acid derivatives Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 150000004717 pyruvic acids Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0008—Sols of inorganic materials in water
- B01J13/0013—Sols of inorganic materials in water from a precipitate
-
- 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
- C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0026—Preparation of sols containing a liquid organic phase
-
- 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
-
- 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
- C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
Definitions
- the present invention relates to an organic colloidal dispersion of cerium and of an element selected from rhodium and palladium, and the use thereof as a diesel fuel additive for internal combustion engines.
- the colloidal dispersion of the invention is of the type comprising particles of a cerium compound, an acid and an organic phase, and is characterized in that it further comprises a compound of at least one element selected from rhodium and palladium.
- the colloidal dispersion is characterized in that it comprises particles of a compound of cerium and of another rare earth.
- the colloidal dispersion of the invention is characterized in that it comprises particles based on a compound of cerium, optionally of another rare earth, and of iron.
- rare earth means elements of the group consisting of yttrium and the elements of the Periodic Table with atomic numbers from 57 to 71 inclusive.
- colloidal dispersion designates any system consisting of fine solid particles of colloidal size based on a cerium compound and, according to the abovementioned variants, of a rare earth other than cerium and/or iron, in suspension in a liquid phase, said particles further optionally containing residual quantities of bound or adsorbed ions such as, for example, nitrates, acetates, citrates and ammoniums.
- Colloidal size means size between about 1 nm and about 500 nm.
- the particles may more particularly have an average size of not more than about 250 nm, particularly of not more than 100 nm, preferably of not more than 20 nm, and even more preferably of not more than 15 nm.
- the cerium, the other rare earth and/or the iron may be present either, preferably, completely in colloidal form, or in colloidal form and partially in ionic form.
- the particles of the dispersion of the invention are based on a compound of a plurality of elements, that is, cerium, another rare earth and/or iron, these elements are mixed within each particle, and generally have the form of mixed oxides and/or hydrated mixed oxides (oxyhydroxides).
- the cerium is mainly in the form of cerium IV.
- the cerium III content with respect to cerium IV (content expressed by the atomic ratio Ce III/Ce total) is generally not more than 40%. It may vary according to the embodiments of the dispersions used and may thus be not more than 20%, more particularly not more than 10%, and even more particularly not more than 1%.
- the rare earth other than cerium may be more particularly lanthanum or praseodymium.
- the present variant covers the case in which the particle is a compound of cerium and of a plurality of other rare earths in combination.
- the proportion of rare earth other than cerium is preferably at least 10%, more particularly at least 20% and even more particularly not more than 50%, in moles with respect to the total number of moles of cerium and of rare earth expressed as oxide.
- the proportion of cerium is preferably not more than 50%, more particularly not more than 20% and even more particularly not more than 10%, this proportion being expressed as moles of cerium oxide CeO 2 with respect to the total number of moles of cerium oxide and of iron oxide Fe 2 O 3 .
- the two variants may be combined, that is, the particles may be compounds of cerium, of at least one other rare earth, and of iron.
- the colloidal dispersion further contains a compound of at least one element selected from rhodium and palladium.
- the invention applies in particular to the case in which rhodium and palladium are present in combination.
- Palladium has the additional effect of favoring the oxidation of CO and unburnt hydrocarbons in exhaust gases.
- the rhodium and/or palladium content is not more than 5%, more particularly not more than 1% and even more particularly not more than 0.5% with respect to the combination of the elements cerium, other rare earth and iron in the particles. This content is expressed as a % by weight of rhodium and/or palladium metal with respect to the sum of the weights of the elements cerium, rare earth and iron.
- the upper limit for the rhodium and/or palladium content is not critical, but simply of an economic order, because an excessive quantity of these elements incurs a higher cost of the dispersion without providing technical advantages.
- the lower limit is that below which the rhodium and/or palladium have no observable effect for reducing the nitrogen oxide releases. This lower limit is generally about 100 ppm.
- the rhodium and/or palladium are also mainly present in the form of oxides or hydrated oxides.
- the rhodium and/or palladium are moreover present in the dispersion essentially as being bound to the particles of the cerium compound. This bond between the element rhodium and/or palladium and the particles may be of a chemical type and it may be produced by the adsorption of said element on the particle surface.
- the colloidal dispersion according to the invention comprises at least one acid, advantageously amphiphilic.
- the acid is more particularly selected from organic acids having at least 6 carbon atoms, even more particularly 10 to 60 carbon atoms, preferably 15 to 25 carbon atoms.
- These acids may be linear or branched. They may be aryl, aliphatic or arylaliphatic acids, optionally containing other functional groups provided that these functional groups are stable in the media in which the dispersions according to the present invention are to be used.
- aliphatic carboxylic acids aliphatic sulfonic acids, aliphatic phosphonic acids, alkylarylsulfonic acids and alkylarylphosphonic acids having about 10 to about 40 carbon atoms, whether natural or synthetic. It is obviously possible to use acid mixtures.
- carboxylic acids of which the carbon chain bears ketone functional groups such as pyruvic acids substituted with the ketone functional group in the alpha position. They may also be alpha-halocarboxylic acids or alphahydroxycarboxylic acids.
- the chain attached to the carboxylic group may carry unsaturated groups. In general, however, it is better to avoid too many double bonds because cerium catalyzes the crosslinking of double bonds.
- the chain may be interrupted by ether or ester functional groups provided that this does not excessively alter the lipophilicity of the chain bearing the carboxylic group.
- fatty acids of tallol, soybean oil, soot, linseed oil, oleic acid, linoleic acid, stearic acid and isomers thereof pelargonic acid, capric acid, lauric acid, myristic acid, dodecylbenzenesulfonic acid, 2-ethylhexanoic acid, naphthenic acid, hexoic acid, toluenesulfonic acid, toluenephosphonic acid, laurylsulfonic acid, laurylphosphonic acid, palmitylsulfonic acid, and palmitylphosphonic acid.
- amphiphilic acid may also designate other amphiphilic agents such as, for example, polyoxyethylene alkyl ether phosphates.
- phosphates here are phosphates of the formula:
- the radical R 1 may be in particular a hexyl, octyl, decyl, dodecyl, oleyl or nonylphenyl radical.
- the dispersions of the invention further comprise a liquid phase that is an organic phase and in which the particles are in suspension.
- an organic phase By way of example of an organic phase, mention can be made of aliphatic hydrocarbons such as hexane, heptane, octane, nonane, inert cycloaliphatic hydrocarbons such as cyclohexane, cyclopentane, cycloheptane, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylenes, liquid naphthenes.
- aliphatic hydrocarbons such as hexane, heptane, octane, nonane
- inert cycloaliphatic hydrocarbons such as cyclohexane, cyclopentane, cycloheptane
- aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylenes, liquid naphthenes.
- Solvesso type (trademarks of Exxon), particularly Solvesso 100 which essentially contains a mixture of methyl ethylbenzene and trimethylbenzene, Solvesso 150 which contains a mixture of alkylbenzenes, particularly dimethylbenzene and tetramethylbenzene and Isopar which essentially contains C-11 and C-12 isoparaffinic and cycloparaffinic hydrocarbons.
- Solvesso 100 which essentially contains a mixture of methyl ethylbenzene and trimethylbenzene
- Solvesso 150 which contains a mixture of alkylbenzenes, particularly dimethylbenzene and tetramethylbenzene
- Isopar which essentially contains C-11 and C-12 isoparaffinic and cycloparaffinic hydrocarbons.
- Petrolink® type marketed by Petrolink
- Isane® type marketed by Total.
- Chlorinated hydrocarbons can also be used for the organic phase, such as chlorobenzene or dichlorobenzene, and chlorotoluene.
- Ethers as well as aliphatic and cycloalophatic ketones such as, for example, diisopropyl ether, dibutyl ether, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, mesityl oxide, can be considered.
- Esters may also be considered, but their drawback is the risk of hydrolysis.
- ethers suitable for use mention can be made of those produced by the reaction of acids with C1 to C8 alcohols, and particularly palmitates of secondary alcohols such as isopropanol.
- the organic phase may be based on a mixture of two or more hydrocarbons or compounds of the type described above.
- the dispersions according to the invention have a concentration of cerium compounds, of the element rhodium and/or palladium and, optionally of the other rare earth and of iron, that generally may range up to 40% by weight of oxides of these elements with respect to the total weight of the dispersion. Above 40%, the viscosity of the dispersion is liable to be too high, particularly at low temperature. It is, however, preferable for this concentration to be at least 5%. Lower concentrations are economically less advantageous because of the volume of liquid phase which becomes too large.
- the proportion between the organic phase and the acid or acids is not critical.
- the weight ratio between the organic phase and the acid or acids is selected preferably between 0.3 and 2.0.
- the dispersion of the invention may be in a specific embodiment.
- the dispersion is such that at least 90% of the particles are single-crystal particles.
- Single-crystal particles means particles which, when the dispersion is examined under a TEM (high-resolution transmission electron microscope), appear to be individualized and consisting of a single crystallite.
- the cryo-TEM technique can also be used to determine the state of aggregation of the elementary particles.
- the transmission electron microscope TEM is used to observe samples that are kept frozen in their natural medium, which is either water or organic diluents such as aromatic or aliphatic solvents like, for example, Solvesso and Isopar, or certain alcohols such as ethanol.
- the frozen specimens are thin films about 50 to 100 nm thick frozen either in liquid ethane for aqueous samples or in liquid nitrogen for others.
- cryo-TEM With cryo-TEM, the state of dispersion of the particles is well preserved and representative of the state present in the real medium.
- the particles have a fine and narrow particle size distribution.
- they have a d 50 of between 1 and 5 nm, preferably between 2 and 4 nm.
- the particle size distribution properties refer to notations d, where n is a number from 1 to 99.
- This notation represents the particle size such that n % by number of said particles have a size smaller than or equal to said size.
- a d 50 of 3 nanometers means that 50% by number of the particles have a size of 3 nanometers or smaller.
- the particle size distribution is determined by conventional transmission electron microscopy (TEM), on a sample previously dried on a carbon membrane supported on a copper grid.
- TEM transmission electron microscopy
- the zones selected for the measurements are those that have a state of dispersion similar to that observed by cryo-TEM.
- an aqueous mixture comprising at least one cerium salt, optionally a salt of a rare earth other than cerium and an iron salt, and a salt of at least one element selected from rhodium and palladium;
- step (a) the aqueous mixture of step (a) is contacted with a basic medium to form a reaction mixture of which the pH is maintained at a basic pH. thereby producing a precipitate;
- the first step of the method (step a) consists in preparing an aqueous mixture, in the usual form of a solution or dispersion, of element(s) present in the composition of the particles to be obtained.
- This mixture comprises salts, preferably soluble, more particularly an acetate and/or a nitrate, of cerium and rhodium and/or palladium.
- this mixture may further comprise salts of other necessary elements, that is, salts of a rare earth other than cerium and/or an iron salt.
- step b) consists in contacting the abovementioned aqueous mixture with a basic medium.
- Basic medium means any medium with a pH above 7.
- the basic medium is normally an aqueous solution containing a base.
- Products of the hydroxide type can be used as a base in particular.
- Mention may be made of alkali metal or alkaline-earth metal hydroxides. Use may also be made of secondary, tertiary or quaternary amines. However, amines and ammonia may be preferred insofar as they decrease the risk of pollution by the alkali or alkaline-earth metal cations. Mention may also be made of urea.
- the above mixture is contacted with the basic medium under conditions such that the pH of the reaction mixture formed remains basic.
- the pH of the reaction mixture is maintained at a value of at least 7, more particularly of at least 7.5 and even more particularly of between 7.5 and 11.
- the aqueous mixture can be contacted with the basic medium by introducing the above mixture into the basic medium.
- Contact can be continuous, provided that the pH is controlled by adjusting the respective flow rates of the mixture and the basic medium.
- Constant pH means a pH variation of not more than ⁇ 0.2 pH units from the set value.
- Such conditions can be obtained by introducing an additional quantity of base into the reaction mixture formed, during the introduction of the mixture into the basic medium.
- the contacting is normally carried out at ambient temperature. This contacting can advantageously be obtained under an atmosphere of air or nitrogen or a nitrogen-air mixture.
- This precipitate can optionally be separated from its mother liquor by filtration, centrifugation or any other means known to a person skilled in the art for such a separation.
- the separated product can be washed.
- the precipitate is left in wet form, that is, it is not subjected to a drying or a freeze-drying step or any operation of this type.
- the precipitate can be used as such, or optionally after being placed again in aqueous suspension.
- the precipitate is then contacted with at least one acid and one organic phase, as defined above (step c).
- the precipitate is used in its wet form, and the proportion of oxides of cerium, of the other element rhodium and/or palladium and optionally of another rare earth and/or iron, of said precipitate may vary between 10 and 50% by weight of the weight of the wet precipitate.
- the percentages of total oxides can be determined by loss on ignition, for example, by calcination at 1000° C.
- the optionally redispersed precipitate is contacted with at least one acid and one organic phase like those described above.
- the quantity of acid to be incorporated may be defined by the molar ratio r: number of moles of acid/number of moles of cerium and/or optionally of the other rare earth and/or of iron.
- This molar ratio may be between 0.2 and 0.8, preferably between 0.3 and 0.6.
- the quantity of organic phase to be incorporated is adjusted in order to obtain a total oxide concentration such as that mentioned above.
- a promoter to the organic phase, its function being to accelerate the transfer of the particles of compound(s) from the aqueous phase to the organic phase and to improve the stability of the organic colloidal dispersions obtained.
- Promoters that are suitable include compounds with an alcohol function and particularly linear or branched aliphatic alcohols with 6 to 12 carbon atoms.
- an alcohol function particularly linear or branched aliphatic alcohols with 6 to 12 carbon atoms.
- the proportion of said agent is not critical and may vary within wide limits. However, a proportion of between 2 and 15% by weight is generally suitable.
- the order of introduction of the various reagents is immaterial.
- the precipitate or its aqueous suspension, the acid, the organic phase, and optionally the promoter, can be mixed simultaneously.
- the acid, the organic phase and optionally the promoter can also be premixed.
- the aqueous colloidal dispersion can be contacted with the organic phase in a reactor that is under an atmosphere of air, nitrogen or an air-nitrogen mixture.
- the aqueous colloidal dispersion can be contacted with the organic phase at ambient temperature, about 20° C., it is preferable to operate at a temperature selected in an interval ranging from 60° C. to 150° C., advantageously between 80° C. and 140° C.
- the resulting reaction mixture (mixture of aqueous colloidal dispersion, acid, organic phase and optionally promoter) is maintained with stirring throughout the duration of the heating, which may vary.
- the organic phase and the aqueous phase are then separated by conventional separation techniques: settling, centrifugation.
- the method described applies to the preparation of a dispersion according to the abovementioned specific embodiment. It is also possible to implement a method different from the one given above by the fact that it comprises, between steps (b) and (c), a drying of the precipitate particularly. by spray drying or freeze drying. This method leads to a dispersion according to the invention but the particles of the specific embodiment do not have the characteristic of being single crystals.
- organic colloidal dispersions described above can be employed as additives for motor fuels, particularly diesel, for internal combustion engines, more particularly as a diesel fuel additive for a diesel engine.
- the invention relates to a fuel for internal combustion engines that contains a colloidal dispersion of the type described above.
- This fuel is obtained by mixing a standard fuel, particularly of the diesel type, with the dispersion of the invention, generally in a proportion such that the ratio of element Ce+element Rh and/or Pd metal+optionally the rare earth element and iron, to the mass of fuel, is between 5 and 200 ppm.
- the presence of the dispersions of the invention in fuels has the effect of lowering the autoignition temperature of the soot and reducing the emission of nitrogen oxides in the engine exhaust gases, and it can also contribute to the oxidation of the carbon monoxide and unburnt hydrocarbons.
- This example relates to the preparation of a dispersion according to the invention, based on cerium, iron and rhodium. This preparation is made in two steps: the first leads to the formation of a solid precipitate in the aqueous phase, and the second relates to the transfer of this precipitate to the organic phase.
- ferric (III) nitrate nonahydrate Fe(NO 3 ) 3 .9H 2 O of 98% purity from Prolabo
- 1 l of purified water 206.1 g of ferric (III) nitrate nonahydrate (Fe(NO 3 ) 3 .9H 2 O of 98% purity from Prolabo) is dissolved in 1 l of purified water in order to prepare a solution containing 0.5 mol/l of Fe.
- 270 ml of a 10% by volume ammonia solution is added to the ferric nitrate solution thus prepared and stirred, using a peristaltic pump, at the rate of 10 ml/min.
- the neutral pH suspension obtained is centrifuged at 4500 rpm for 12 minutes.
- the precipitate recovered is replaced in suspension of the initial volume with purified water.
- the suspension is stirred for 15 minutes, the precipitate is separated again under the same conditions, and again replaced in suspension with an equivalent final volume.
- a dispersion with pH 6.5 is thereby obtained, to which 100 ml of acetic acid (CH 3 COOH 100% from Prolabo) is added, to yield an iron acetate solution with pH 2.7 and oxide concentration of 2.8% of Fe 2 O 3 (determined by loss on ignition).
- acetic acid CH 3 COOH 100% from Prolabo
- the precipitation is carried out in a continuous assembly comprising:
- the precipitate is recovered by centrifugation at 3000 rpm for 12 minutes and then replaced in suspension in purified water in a concentration of 50 g/l of total oxide.
- the two-phase mixture is then heated to 95° C. in 1 h 30 min, with the stirrer speed set at 220 rpm.
- the mixture is kept at 95° C. for 4 hours, and then left to cool at ambient temperature.
- the coalescence obtained when stirring is stopped reveals the formation of a black organic phase, above a clear aqueous phase.
- the oxide concentration of the aqueous phase, determined by loss on ignition, is negligible, attesting to a quantitative transfer.
- the concentration of the organic colloidal phase determined after evaporation of the Isopar L and calcination at 1000° C., is equal to 9.9% of total oxide.
- the composition of the oxide dispersed in the organic phase determined by potentiometric methods (Ce) and polarographic methods (Fe), is equimolar in Ce/Fe and contains 0.26% of rhodium (mass of rhodium metal/mass of elemental cerium and iron), the rhodium being determined by ICP/OES.
- Analysis by cryo-transmission electron microscopy of the organic colloidal phase reveals perfectly individualized particles with a diameter of 3 to 5 nm.
- This example relates to the evaluation on an engine test bench of the product obtained in the previous example.
- the evaluation is made using a Peugeot 2.2 l cubic capacity diesel engine, reference DW 12 TED4/L4, placed on a dynamometric test bench.
- the exhaust line is equipped with a silicon carbide particulate filter produced by Ibiden (5.66 ⁇ 6200 cpsi).
- the dispersion of the invention is added as an additive to a diesel containing 7 ppm of sulfur to obtain a proportion of 10 ppm (Ce+Fe+Rh metal) with respect to the diesel containing additive.
- the particulate filter is then loaded under the following conditions:
- the nitrogen oxide NO and NO 2 emissions are measured continuously using an Ecophysic CLD 700 analyzer.
- the results obtained are given below.
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0311614A FR2860443B1 (fr) | 2003-10-03 | 2003-10-03 | Dispersion colloidale organique de cerium et d'un element choisi parmi le rhodium et le palladium et son utilisation comme adjuvant de gazoles pour moteurs a combustion interne |
FR0311614 | 2003-10-03 | ||
PCT/FR2004/002491 WO2005032705A1 (fr) | 2003-10-03 | 2004-10-01 | Dispersion colloidale organique de cerium et d'un element choisi parmi le rhodium et le palladium et son utilisation comme adjuvant de gazoles pour moteurs a combustion interne |
Publications (1)
Publication Number | Publication Date |
---|---|
US20070169406A1 true US20070169406A1 (en) | 2007-07-26 |
Family
ID=34307400
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/574,626 Abandoned US20070169406A1 (en) | 2003-10-03 | 2004-10-01 | Cerium organic colloidal dispersion and element selected from rhodium and palladium and use thereof as additive to diesel fuel for internal combustion engines |
Country Status (10)
Country | Link |
---|---|
US (1) | US20070169406A1 (fr) |
EP (1) | EP1677905B1 (fr) |
JP (1) | JP4799410B2 (fr) |
KR (1) | KR100791147B1 (fr) |
CN (1) | CN100467111C (fr) |
AT (1) | ATE416028T1 (fr) |
CA (1) | CA2539480C (fr) |
DE (1) | DE602004018173D1 (fr) |
FR (1) | FR2860443B1 (fr) |
WO (1) | WO2005032705A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060196108A1 (en) * | 2003-04-04 | 2006-09-07 | Gilbert Blanchard | Colloidal dispersion of a rare earth compound comprising an anti-oxidant agent and use thereof as additive for diesel fuel for internal combustion engines |
US9914892B2 (en) | 2010-12-22 | 2018-03-13 | Rhodia Operations | Fuel additive composition containing a dispersion of iron particles and a detergent |
US10125333B2 (en) | 2010-12-22 | 2018-11-13 | Rhodia Operations | Organic dispersion of iron-based particles in crystallized form |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101326269B (zh) * | 2005-11-10 | 2014-09-24 | 卢布里佐尔公司 | 控制燃料燃烧的副产物或污染物的方法 |
GB0705920D0 (en) * | 2007-03-28 | 2007-05-09 | Infineum Int Ltd | Method of supplying iron to the particulate trap of a diesel engine exhaust |
JP2010121000A (ja) * | 2008-11-18 | 2010-06-03 | Yoshio Ichikawa | 燃料油改質添加剤および燃料油改質方法 |
FR2969652B1 (fr) * | 2010-12-22 | 2013-02-08 | Rhodia Operations | Utilisation de dispersions de particules de fer comme additif de carburant |
CN102688732A (zh) * | 2012-06-01 | 2012-09-26 | 同济大学 | 一种高比表面积稀土氧化物纳米多孔气凝胶的通用制备方法 |
WO2015091495A1 (fr) * | 2013-12-16 | 2015-06-25 | Rhodia Operations | Suspension liquide de particules d'oxyde de cérium |
CN105505490B (zh) * | 2015-12-08 | 2017-03-15 | 谢传林 | 氧化还原增压剂 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4680282A (en) * | 1984-07-30 | 1987-07-14 | Pro-Catalyse | Pollution control catalyst for internal combustion engine exhaust gases and process for producing it |
US5688439A (en) * | 1994-05-09 | 1997-11-18 | Rhone-Poulenc Chimie | Colloidal dispersions of cerium oxide core/titanium oxide sheath particulates and photocatalytic coatings provided thereby |
US6767526B1 (en) * | 1998-06-22 | 2004-07-27 | Rhodia Chimie | Method for treating by combustion carbon-containing particles in an internal combustion engine exhaust circuit |
US20050066571A1 (en) * | 2001-11-06 | 2005-03-31 | Gareth Wakefield | Cerium oxide nanoparticles |
US20060005465A1 (en) * | 1999-08-04 | 2006-01-12 | Gilbert Blanchard | Organic colloidal dispersion of essentially monocrystalline praticles of at least one compound based on at least one rare earth, a process for its preparation, and use thereof |
US7495033B1 (en) * | 1999-11-23 | 2009-02-24 | Rhodia Terres Rares | Aqueous colloidal dispersion based on at least a lanthanide compound and a complexing agent a process for its preparation and use thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1089985A (zh) * | 1993-01-12 | 1994-07-27 | 翟立国 | 一种柴油添加剂 |
FR2741281B1 (fr) * | 1995-11-22 | 1998-02-13 | Rhone Poulenc Chimie | Sol organique comportant au moins un compose oxygene de terre(s) rare(s), procede de synthese du dit sol et utilisation du dit sol pour la catalyse |
FR2789601B1 (fr) * | 1999-02-17 | 2001-05-11 | Rhodia Chimie Sa | Sol organique et compose solide a base d'oxyde de cerium et d'un compose amphiphile et procedes de preparation |
FR2833862B1 (fr) * | 2001-12-21 | 2004-10-15 | Rhodia Elect & Catalysis | Dispersion colloidale organique de particules de fer, son procede de preparation et son utilisation comme adjuvant de carburant pour moteurs a combustion interne |
FR2853261B1 (fr) * | 2003-04-04 | 2006-06-30 | Rhodia Elect & Catalysis | Dispersion colloidale d'un compose d'une terre rare comprenant un agent anti-oxydant et son utilisation comme adjuvant de gazole pour moteurs a combustion interne |
-
2003
- 2003-10-03 FR FR0311614A patent/FR2860443B1/fr not_active Expired - Fee Related
-
2004
- 2004-10-01 WO PCT/FR2004/002491 patent/WO2005032705A1/fr active Application Filing
- 2004-10-01 US US10/574,626 patent/US20070169406A1/en not_active Abandoned
- 2004-10-01 CN CNB2004800288085A patent/CN100467111C/zh not_active Expired - Fee Related
- 2004-10-01 KR KR1020067006383A patent/KR100791147B1/ko not_active IP Right Cessation
- 2004-10-01 DE DE602004018173T patent/DE602004018173D1/de active Active
- 2004-10-01 CA CA002539480A patent/CA2539480C/fr not_active Expired - Fee Related
- 2004-10-01 EP EP04791455A patent/EP1677905B1/fr not_active Not-in-force
- 2004-10-01 JP JP2006530413A patent/JP4799410B2/ja not_active Expired - Fee Related
- 2004-10-01 AT AT04791455T patent/ATE416028T1/de not_active IP Right Cessation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4680282A (en) * | 1984-07-30 | 1987-07-14 | Pro-Catalyse | Pollution control catalyst for internal combustion engine exhaust gases and process for producing it |
US5688439A (en) * | 1994-05-09 | 1997-11-18 | Rhone-Poulenc Chimie | Colloidal dispersions of cerium oxide core/titanium oxide sheath particulates and photocatalytic coatings provided thereby |
US6767526B1 (en) * | 1998-06-22 | 2004-07-27 | Rhodia Chimie | Method for treating by combustion carbon-containing particles in an internal combustion engine exhaust circuit |
US20060005465A1 (en) * | 1999-08-04 | 2006-01-12 | Gilbert Blanchard | Organic colloidal dispersion of essentially monocrystalline praticles of at least one compound based on at least one rare earth, a process for its preparation, and use thereof |
US7495033B1 (en) * | 1999-11-23 | 2009-02-24 | Rhodia Terres Rares | Aqueous colloidal dispersion based on at least a lanthanide compound and a complexing agent a process for its preparation and use thereof |
US20050066571A1 (en) * | 2001-11-06 | 2005-03-31 | Gareth Wakefield | Cerium oxide nanoparticles |
US7169196B2 (en) * | 2001-11-06 | 2007-01-30 | Oxonica Materials Limited | Fuel or fuel additive containing doped cerium oxide nanoparticles |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060196108A1 (en) * | 2003-04-04 | 2006-09-07 | Gilbert Blanchard | Colloidal dispersion of a rare earth compound comprising an anti-oxidant agent and use thereof as additive for diesel fuel for internal combustion engines |
US8506657B2 (en) | 2003-04-04 | 2013-08-13 | Rhodia Operations | Colloidal dispersion of a rare earth compound comprising an anti-oxidant agent and use thereof as additive for diesel fuel for internal combustion engines |
US9914892B2 (en) | 2010-12-22 | 2018-03-13 | Rhodia Operations | Fuel additive composition containing a dispersion of iron particles and a detergent |
US10125333B2 (en) | 2010-12-22 | 2018-11-13 | Rhodia Operations | Organic dispersion of iron-based particles in crystallized form |
Also Published As
Publication number | Publication date |
---|---|
KR100791147B1 (ko) | 2008-01-03 |
DE602004018173D1 (de) | 2009-01-15 |
WO2005032705A1 (fr) | 2005-04-14 |
CA2539480A1 (fr) | 2005-04-14 |
CN100467111C (zh) | 2009-03-11 |
ATE416028T1 (de) | 2008-12-15 |
FR2860443B1 (fr) | 2006-06-16 |
FR2860443A1 (fr) | 2005-04-08 |
EP1677905A1 (fr) | 2006-07-12 |
CA2539480C (fr) | 2009-09-29 |
JP4799410B2 (ja) | 2011-10-26 |
JP2007509193A (ja) | 2007-04-12 |
EP1677905B1 (fr) | 2008-12-03 |
CN1863589A (zh) | 2006-11-15 |
KR20060060050A (ko) | 2006-06-02 |
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