WO1999043430A9 - Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions - Google Patents
Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactionsInfo
- Publication number
- WO1999043430A9 WO1999043430A9 PCT/US1999/003402 US9903402W WO9943430A9 WO 1999043430 A9 WO1999043430 A9 WO 1999043430A9 US 9903402 W US9903402 W US 9903402W WO 9943430 A9 WO9943430 A9 WO 9943430A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- noble metal
- oxidation catalyst
- catalyst
- promoter
- atoms
- Prior art date
Links
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- 239000007791 liquid phase Substances 0.000 title abstract description 21
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- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- 229910021637 Rhenium(VI) chloride Inorganic materials 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical class ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 229940120503 dihydroxyacetone Drugs 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Chemical class 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- Other by-products also may form, such as formic acid, which is formed by the oxidation of the formaldehyde byproduct; and aminomethylphosphonic acid (“AMPA”), which is formed by the oxidation of N- (phosphonomethyl) glycine .
- AMPA aminomethylphosphonic acid
- the Franz method produces an acceptable yield and purity of N- (phosphonomethyl) glycine, high losses of the costly noble metal into the reaction solution (i.e. , "leaching") result because under the oxidation conditions of the reaction, some of the noble metal is oxidized into a more soluble form and both PMIDA and N- (phosphonomethyl) glycine act as ligands which solubilize the noble metal .
- Felthouse U.S. Patent No. 4,582,650 teaches using two catalysts: (i) an activated carbon to effect the oxidation of PMIDA into N- (phosphonomethyl) glycine, and (ii) a co-catalyst to concurrently effect the oxidation of formaldehyde into carbon dioxide and water.
- the co-catalyst consists of an aluminosilicate support having a noble metal located within its pores. The pores are sized to exclude N- (phosphonomethyl) glycine and thereby prevent the noble metal of the co-catalyst from being poisoned by N-
- the present invention is directed to a novel oxidation catalyst comprising a carbon support having a noble metal at its surface.
- the catalyst is characterized as yielding no more than about 0.7 mmole of carbon monoxide per gram of catalyst when a dry sample of the catalyst in a helium atmosphere is heated from about 20 to about 900°C at a rate of about 10°C per minute, and then at about 900°C for about 30 minutes.
- an oxidation catalyst comprising a carbon support having a noble metal at its surface
- the support also has carbon and oxygen at the surface.
- the ratio of carbon atoms to oxygen atoms at the surface is at least about 30:1 as measured by x- ray photoelectron spectroscopy.
- an oxidation catalyst comprising a carbon support having a noble metal at its surface
- the support also has a promoter, carbon, and oxygen at the surface.
- the catalyst is characterized as having a ratio of carbon atoms to oxygen atoms of at least about 30:1 at the surface as measured by x-ray photoelectron spectroscopy after the catalyst is heated at a temperature of about 500°C for about 1 hour in a hydrogen atmosphere and before the catalyst is exposed to an oxidant following the heating in the hydrogen atmosphere .
- an oxidation catalyst comprising a carbon support having a noble metal at its surface
- the support also has a surface layer which has a thickness of about 50 A as measured inwardly from the surface.
- This surface layer comprises oxygen and carbon, with the ratio of carbon atoms to oxygen atoms in the surface layer being at least about 30:1.
- the catalyst is prepared by a process comprising depositing a noble metal at the surface, and then heating the surface at a temperature greater than about 500 °C.
- an oxidation catalyst comprising a carbon support having a noble metal at its surface
- the catalyst is prepared by a process comprising depositing a noble metal at the surface, and then heating the surface at a temperature of at least about 400°C.
- the carbon support before the noble metal deposition, has carbon and oxygen at its surface in amounts such that the ratio of carbon atoms to oxygen atoms at the surface is at least about 20:1 as measured by x-ray photoelectron spectroscopy.
- an oxidation catalyst comprising a carbon support having a noble metal at its surface
- the catalyst is prepared by a process comprising depositing a noble metal at the surface, and then exposing the surface to a reducing environment.
- the carbon support has carbon and oxygen at its surface in amounts such that the ratio of carbon atoms to oxygen atoms at the surface is at least about 20:1 as measured by x-ray photoelectron spectroscopy.
- This invention is also directed to a process for the preparation of an oxidation catalyst.
- the process comprises depositing a noble metal at a surface of a carbon support, and then heating the surface at a temperature greater than about 500°C.
- the catalyst is prepared from a carbon support having carbon and oxygen at a surface of the carbon support .
- the process comprises depositing a noble metal at the surface of the carbon support, and then heating the surface at a temperature of at least about 400°C.
- the ratio of carbon atoms to oxygen atoms at the surface of the carbon support is at least about 20:1 as measured by x-ray photoelectron spectroscopy.
- the process comprises depositing a noble metal at the surface, and then exposing the surface to a reducing environment to reduce the surface so that the ratio of carbon atoms to oxygen atoms at the surface is at least about 30:1 as measured by x-ray photoelectron spectroscopy.
- This invention is also directed to a process for oxidizing a reagent in a mixture (typically a solution or a slurry, and most typically a solution) , wherein the mixture has the ability to solubilize a noble metal.
- This process comprises contacting the mixture with an oxidation catalyst in the presence of oxygen.
- the catalyst comprises a carbon support having a noble metal at its surface.
- the catalyst is characterized as yielding no more than about 1.2 mmole of carbon monoxide per gram of catalyst when a dry sample of the catalyst in a helium atmosphere is heated from about 20 to about 900°C at a rate of about 10°C per minute, and then at about 900°C for about 30 minutes.
- the catalyst comprises a carbon support having a noble metal and a promoter at a surface of the carbon support.
- the catalyst is characterized as yielding no more than about 1.2 mmole of carbon monoxide per gram of catalyst when a dry sample of the catalyst, after being heated at a temperature of about 500 °C for about 1 hour in a hydrogen atmosphere and before being exposed to an oxidant following the heating in the hydrogen atmosphere, is heated in a helium atmosphere from about 20 to about 900°C at a rate of about 10°C per minute, and then at about 900°C for about 30 minutes.
- the catalyst comprises a carbon support having a noble metal, carbon, and oxygen at a surface of the carbon support.
- the ratio of carbon atoms to oxygen atoms at the surface is at least about 20:1 as measured by x-ray photoelectron spectroscopy.
- the catalyst comprises a carbon support having a noble metal, a promoter, carbon, and oxygen at a surface of the carbon support.
- the catalyst is characterized as having a ratio of carbon atoms to oxygen atoms at the surface which is at least about 20:1 as measured by x-ray photoelectron spectroscopy after the catalyst is heated at a temperature of about 500 °C for about 1 hour in a hydrogen atmosphere and before the catalyst is exposed to an oxidant following the heating in the hydrogen atmosphere .
- the catalyst comprises a carbon support having a noble metal at a surface of the carbon support.
- the support comprises a surface layer having a thickness of about 50 A as measured inwardly from the surface and comprising oxygen and carbon.
- the ratio of carbon atoms to oxygen atoms in the surface layer is at least about 20:1 as measured by x-ray photoelectron spectroscopy.
- the catalyst is prepared by a process comprising depositing a noble metal at a surface of a carbon support, and then exposing the surface to a reducing environment.
- the carbon support before the noble metal deposition, has carbon and oxygen at the surface of the carbon support in amounts such that the ratio of carbon atoms to oxygen atoms at the surface is at least 20:1 as measured by x-ray photoelectron spectroscopy.
- the catalyst comprises a carbon support having a noble metal at a surface of the carbon support .
- the carbon support also comprises a surface layer having a thickness of about 50 A as measured inwardly from the surface and comprising carbon and oxygen.
- the ratio of carbon atoms to oxygen atoms in the surface layer is at least about 20:1 as measured by x-ray photoelectron spectroscopy.
- the catalyst is prepared by a process comprising depositing a noble metal at a surface of a carbon support, and then heating the surface at a temperature of at least about 400°C.
- the catalyst comprises a carbon support having a noble metal, a promoter, carbon, and oxygen at a surface of the carbon support .
- the catalyst comprises a carbon support having a noble metal and a promoter at a surface of the carbon support.
- the catalyst also comprises a surface layer having a thickness of about 50 A as measured inwardly from the surface.
- This surface layer comprises carbon and oxygen.
- the catalyst is characterized as having a ratio of carbon atoms to oxygen atoms in the surface layer which is at least about 20:1 as measured by x-ray photoelectron spectroscopy after the catalyst is heated at a temperature of about 500 °C for about 1 hour a hydrogen atmosphere and before the catalyst is exposed to an oxidant following the heating in the hydrogen atmosphere .
- the oxidation catalyst of the present invention may be used to catalyze liquid phase (i.e. , in an aqueous solution or an organic solvent) oxidation reactions, especially in acidic oxidative environments and in the presence of solvents, reactants, intermediates, or products which solubilize noble metals.
- the catalyst exhibits significantly improved resistance to noble metal leaching under these conditions.
- the catalyst additionally exhibits an improved oxidation (i.e. , destruction) of the formaldehyde and formic acid by-products during the oxidation of PMIDA to N- (phosphonomethyl) glycine .
- the catalyst of this invention advantageously exhibits significantly longer life as long as the noble metal is not lost by leaching, or sintered (i.e. , in the form of undesirably thick layers or clumps) by processes such as dissolution and re-deposition or noble metal agglomeration.
- a noble metal may be more effective than carbon at effecting the oxidation.
- the carbon component of the catalyst primarily effects the oxidation of PMIDA to N- (phosphonomethyl) glycine
- oxygen-containing functional groups e.g.
- an oxygen-containing functional group is "at the surface of the carbon support” if it is bound to an atom of the carbon support and is able to chemically or physically interact with compositions within the reaction mixture or with the metal atoms deposited on the carbon support.
- a catalyst is considered "dry" when the catalyst has a moisture content of less than about 1% by weight.
- a catalyst may be dried by placing it into a N 2 purged vacuum of about 25 inches of Hg and a temperature of about 120°C for about 16 hours.
- the ratio is at least about 30:1, more preferably at least about 40:1, even more preferably at least about 50:1, and most preferably at least about 60:1.
- the ratio of oxygen atoms to metal atoms at the surface preferably is less than about 8:1 (oxygen atoms :metal atoms) . More preferably, the ratio is less than 7:1, even more preferably less than about 6:1, and most preferably less than about 5:1.
- the carbon supports used in the present invention are well known in the art. Activated, non-graphitized carbon supports are preferred. These supports are characterized by high adsorptive capacity for gases, vapors, and colloidal solids and relatively high specific surface areas.
- the support suitably may be a carbon, char, or charcoal produced by means known in the art, for example, by destructive distillation of wood, peat, lignite, coal, nut shells, bones, vegetable, or other natural or synthetic carbonaceous matter, but preferably is "activated" to develop adsorptive power. Activation usually is achieved by heating to high temperatures (800 - 900°C) with steam or with carbon dioxide which brings about a porous particle structure and increased specific surface area.
- hygroscopic substances such as zinc chloride and/or phosphoric acid or sodium sulfate, are added before the destructive distillation or activation, to increase adsorptive capacity.
- the carbon content of the carbon support ranges from about 10% for bone charcoal to about 98% for some wood chars and nearly 100% for activated carbons derived from organic polymers.
- the non-carbonaceous matter in commercially available activated carbon materials normally will vary depending on such factors as precursor origin, processing, and activation method. Many commercially available carbon supports contain small amounts of metals. Carbon supports having the fewest oxygen-containing functional groups at their surfaces are most preferred.
- the support is a monolithic support. Suitable monolithic supports may have a wide variety of shapes. Such a support may be, for example, in the form of a screen or honeycomb. Such a support may also, for example, be in the form of a reactor impeller. In a particularly preferred embodiment, the support are in the form of particulates . Because particulate supports are especially preferred, most of the following discussion focuses on embodiments which use a particulate support. It should be recognized, however, that this invention is not limited to the use of particulate supports.
- Suitable particulate supports may have a wide variety of shapes.
- such supports may be in the form of granules. Even more preferably, the support is in the form of a powder.
- These particulate supports may be used in a reactor system as free particles, or, alternatively, may be bound to a structure in the reactor system, such as a screen or an impeller.
- a support which is in particulate form comprises a broad size distribution of particles.
- At least about 95% of the particles are from about 2 to about 300 ⁇ m in their largest dimension, more preferably at least about 98% of the particles are from about 2 to about 200 ⁇ m in their largest dimension, and most preferably about 99% of the particles are from about 2 to about 150 ⁇ m in their largest dimension with about 95% of the particles being from about 3 to about 100 ⁇ m in their largest dimension.
- Particles being greater than about 200 ⁇ m in their largest dimension tend to fracture into super- fine particles (i.e. , less than 2 ⁇ m in their largest dimension) , which are difficult to recover.
- the specific surface area of the carbon support is preferably from about 10 to about 3,000 m 2 /g (surface area of carbon support per gram of carbon support) , more preferably from about 500 to about 2,100 m 2 /g, and still more preferably from about 750 to about 2,100 m 2 /g. In some embodiments, the most preferred specific area is from about 750 to about 1,750 m 2 /g.
- Carbon supports for use in the present invention are commercially available from a number of sources. The following is a listing of some of the activated carbons which may be used with this invention: Darco G-60 Spec and Darco X (ICI -America, Wilmington, DE) ; Norit SG Extra, Norit EN4 , Norit EXW, Norit A, Norit Ultra-C, Norit ACX, and Norit 4 X 14 mesh (Amer. Norit Co., Inc., Jacksonville, FL) ; Gl-9615, VG-8408, VG-8590, NB-9377, XZ , NW, and JV (Barnebey-Cheney, Columbus, OH); BL Pulv.
- Darco G-60 Spec and Darco X ICI -America, Wilmington, DE
- Norit SG Extra Norit EN4 , Norit EXW, Norit A, Norit Ultra-C, Norit ACX, and Norit 4 X 14 mesh
- the catalyst of this invention preferably has one or more noble metal (s) at its surface.
- the noble metal (s) is selected from the group consisting of platinum (Pt) , palladium (Pd) , ruthenium (Ru) , rhodium (Rh) , iridium (Ir) , silver (Ag) , osmium (Os) , and gold
- the dispersion of the noble metal at the surface of the carbon support preferably is such that the concentration of surface noble metal atoms is from about 10 to about 400 ⁇ mole/g ( ⁇ mole of surface noble metal atoms per gram of catalyst) , more preferably, from about 10 to about 150 ⁇ mole/g, and most preferably from about 15 to about 100 ⁇ mole/g. This may be determined, for example, by measuring chemisorption of H 2 or CO using a Micromeritics ASAP 2010C (Micromeritics, Norcross, GA) or an Altamira AMI100 (Zeton Altamira, Pittsburgh, PA) .
- noble metal particles are too small, there tends to be an increased amount of leaching when the catalyst is used in an environment that tends to solubilize noble metals, as is the case when oxidizing PMIDA to form N- (phosphonomethyl) glycine.
- the particle size increases, there tends to be fewer noble metal surface atoms per total amount of noble metal used. As discussed above, this tends to reduce the activity of the catalyst and is also an uneconomical use of the costly noble metal.
- the promoter (s) alternatively may be, for example, a metal selected from the group consisting of tin (Sn) , cadmium (Cd) , magnesium (Mg) , manganese (Mn) , nickel (Ni) , aluminum (Al) , cobalt (Co) , bismuth (Bi) , lead (Pb) , titanium (Ti) , antimony (Sb) , selenium (Se) , iron (Fe) , rhenium (Re) , zinc (Zn) , cerium (Ce) , and zirconium (Zr) .
- the promoter is selected from the group consisting of bismuth, iron, tin, and titanium.
- the promoter is tin. In another particularly preferred embodiment, the promoter is iron. In an additional preferred embodiment, the promoter is titanium. In a further particularly preferred embodiment, the catalyst comprises both iron and tin. Use of iron, tin, or both generally (1) reduces noble metal leaching for a catalyst used over several cycles, and (2) tends to increase and/or maintain the activity of the catalyst when the catalyst is used to effect the oxidation of PMIDA. Catalysts comprising iron generally are most preferred because they tend to have the greatest activity and stability with respect to formaldehyde and formic acid oxidation. In one preferred embodiment, the promoter is more easily oxidized than the noble metal. A promoter is "more easily oxidized" if it has a lower first ionization potential than the noble metal. First ionization potentials for the elements are widely known in the art and may be found, for example, in the CRC Handbook of
- alloy encompasses any metal particle comprising a noble metal and at least one promoter, irrespective of the precise manner in which the noble metal and promoter atoms are disposed within the particle (although it is generally preferable to have a portion of the noble metal atoms at the surface of the alloyed metal particle) .
- the alloy may be, for example, any of the following:
- a substitutional alloy has a single, continuous phase, irrespective of the concentrations of the noble metal and promoter atoms. Typically, a substitutional alloy contains noble metal and promoter atoms which are similar in size (e.g. , platinum and silver; or platinum and palladium) . Substitutional alloys are also referred to as "monophasic alloys.”
- a multiphasic alloy is an alloy that contains at least two discrete phases. Such an alloy may contain, for example Pt 3 Sn in one phase, and tin dissolved in platinum in a separate phase.
- a segregated alloy is a metal particle wherein the particle stoichiometry varies with distance from the surface of the metal particle.
- An interstitial alloy is a metal particle wherein the noble metal and promoter atoms are combined with non-metal atoms, such as boron, carbon, silicon, nitrogen, phosphorus, etc.
- the alloyed metal particles need not have a uniform composition; the compositions may vary from particle to particle, or even within the particles themselves.
- the catalyst may further comprise particles consisting of the noble metal alone or the promoter alone. Nevertheless, it is preferred that the composition of metal particles be substantially uniform from particle to particle and within each particle, and that the number of noble metal atoms in intimate contact with promoter atoms be maximized. It is also preferred, although not essential, that the majority of noble metal atoms be alloyed with a promoter, and more preferred that substantially all of the noble metal atoms be alloyed with a promoter. It is further preferred, although not essential, that the alloyed metal particles be uniformly distributed at the surface of the carbon support .
- the promoter tends to become oxidized if the catalyst is exposed to an oxidant over a period of time.
- an elemental tin promoter tends to oxidize to form Sn(II)0
- Sn(II)0 tends to oxidize to form Sn(IV)0 2 .
- This oxidation may occur, for example, if the catalyst is exposed to air for more than about 1 hour.
- promoter oxidation has not been observed to have a significant detrimental effect on noble metal leaching, noble metal sintering, catalyst activity, or catalyst stability, it does make analyzing the concentration of detrimental oxygen-containing functional groups at the surface of the carbon support more difficult.
- the concentration of detrimental oxygen-containing functional groups may be determined by measuring (using, for example, TGA-MS) the amount of CO that desorbs from the catalyst under high temperatures in an inert atmosphere.
- TGA-MS the amount of CO that desorbs from the catalyst under high temperatures in an inert atmosphere.
- Such oxygen atoms of an oxidized promoter also can interfere with obtaining a reliable prediction of noble metal leaching, noble metal sintering, and catalyst activity from the simple measurement (via, for example, x-ray photoelectron spectroscopy) of oxygen atoms at the catalyst surface.
- the catalyst comprises at least one promoter which has been exposed to an oxidant and thereby has been oxidized (e.g. , when the catalyst has been exposed to air for more than about 1 hour)
- This reduction preferably is achieved by heating the catalyst to a temperature of about 500°C for about 1 hour in an atmosphere consisting essentially of H 2 .
- the measurement of detrimental oxygen-containing functional groups at the surface preferably is performed (a) after this reduction, and (b) before the surface is exposed to an oxidant following the reduction. Most preferably, the measurement is taken immediately after the reduction.
- the preferred concentration of metal particles at the surface of the carbon support depends, for example, on the size of the metal particles, the specific surface area of the carbon support, and the concentration of noble metal on the catalyst. It is presently believed that, in general, the preferred concentration of metal particles is roughly from about 3 to about 1,500 particles/ ⁇ m 2 (i.e. , number of metal particles per ⁇ m 2 of surface of carbon support), particularly where: (a) at least about 80% (number density) of the metal particles are from about 1.5 to about 7 nm in their largest dimension, (b) the carbon support has a specific surface area of from about 750 to about 2100 m 2 /g (i.e.
- the concentration of noble metal at the carbon support surface is from about 1 to about 10 wt.% ([mass of noble metal ⁇ total mass of catalyst] x 100%) .
- narrower ranges of metal particle concentrations and noble metal concentrations are desired.
- the concentration of metal particles is from about 15 to about 800 particles/ ⁇ m 2
- the concentration of noble metal at the carbon support surface is from about 2 to about 10 wt.%.
- the concentration of metal particles is from about 15 to about 600 particles/ ⁇ m 2
- the concentration of noble metal at the carbon support surface is from about 2 to about 7.5 wt.%.
- the concentration of the metal particles is from about 15 to about 400 particles/ ⁇ m 2 , and the concentration of noble metal at the carbon support surface is about 5 wt.%.
- concentration of metal particles at the surface of the carbon support may be measured using methods known in the art.
- the surface of the carbon support preferably is deoxygenated before the noble metal is deposited onto it.
- the surface is deoxygenated using a high- temperature deoxygenation treatment.
- a treatment may be a single-step or a multi-step scheme which, in either case, results in an overall chemical reduction of oxygen-containing functional groups at the surface of the carbon support .
- the carbon support preferably is first treated with a gaseous or liquid phase oxidizing agent to convert oxygen-containing functionalities in relatively lower oxidation states (e.g. , ketones, aldehydes, and alcohols) into functionalities in relatively higher oxidation states (e.g. , carboxylic acids) , which are easier to cleave from the surface of the catalyst at high temperatures.
- oxidation states e.g. , ketones, aldehydes, and alcohols
- relatively higher oxidation states e.g. , carboxylic acids
- Representative liquid phase oxidizing agents include nitric acid, H 2 0 2 , chromic acid, and hypochlorite, with concentrated nitric acid comprising from about 10 to about 80 grams of HN0 3 per 100 grams of aqueous solution being preferred.
- gaseous oxidants include molecular oxygen, ozone, nitrogen dioxide, and nitric acid vapors. Nitric acid vapors are the preferred oxidizing agent. With a liquid oxidant, temperatures of from about 60 to about 90°C are appropriate, but with gaseous oxidants, it is often advantageous to use temperatures from about 50 to about 500°C or even greater.
- the time during which the carbon is treated with the oxidant can vary widely from about 5 minutes to about 10 hours. Preferably, the reaction time is from about 30 minutes to about 6 hours. Experimental results indicate that carbon load, temperature, oxidant concentration, etc. in the first treatment step are not narrowly critical to achieving the desired oxidation of the carbon material and thus may be governed by convenience over a wide range.
- the oxidized carbon support is pyrolyzed (i.e. , heated) at a temperature preferably in the range of from about 500 to about 1500°C, and more preferably from about 600 to about 1,200°C, in a nitrogen, argon, helium, or other non-oxidizing environment (i.e. , an environment consisting essentially of no oxygen) to drive off the oxygen-containing functional groups from the carbon surface.
- a nitrogen, argon, helium, or other non-oxidizing environment i.e. , an environment consisting essentially of no oxygen
- an environment may be used which comprises a small amount of ammonia (or any other chemical entity which will generate NH 3 during pyrolysis) , steam, or carbon dioxide which aid in the pyrolysis.
- the pyrolysis is preferably conducted in a non-oxidizing atmosphere (e.g. , nitrogen, argon, or helium) .
- a non-oxidizing atmosphere e.g. , nitrogen, argon, or helium
- the non-oxidizing atmosphere comprises ammonia, which tends to produce a more active catalyst in a shorter time as compared to pyrolysis in the other atmospheres.
- the pyrolysis may be achieved, for example, using a rotary kiln, a fluidized bed reactor, or a conventional furnace.
- the carbon support generally is pyrolyzed for a period of from about 5 minutes to about 60 hours, preferably from about 10 minutes to about 6 hours. Shorter times are preferred because prolonged exposure of the carbon at elevated temperatures tends to reduce the activity of the catalyst. Without being bound to any particular theory, it is presently believed that prolonged heating at pyrolytic temperatures favors the formation of graphite, which is a less preferred form of a carbon support because it normally has less surface area. As discussed above, a more active catalyst typically may be produced in a shorter time by using an atmosphere which comprises ammonia.
- high-temperature deoxygenation is carried out in one step.
- This one-step treatment may consist of merely performing the pyrolysis step of the two-step high- temperature deoxygenation treatment discussed above. More preferably, however, the single-step treatment consists of pyrolyzing the carbon support as described above while simultaneously passing a gas stream comprising N 2 , NH 3 (or any other chemical entity which will generate NH 3 during pyrolysis) , and steam over the carbon.
- the flow rate of the gas stream preferably is fast enough to achieve adequate contact between the fresh gas reactants and the carbon surface, yet slow enough to prevent excess carbon weight loss and material waste.
- a non-reactive gas may be used as a diluent to prevent severe weight loss of the carbon.
- Methods used to deposit the noble metal onto the surface of the carbon support are generally known in the art, and include liquid phase methods such as reaction deposition techniques (e.g. , deposition via reduction of noble metal compounds, and deposition via hydrolysis of noble metal compounds) , ion exchange techniques, excess solution impregnation, and incipient wetness impregnation; vapor phase methods such as physical deposition and chemical deposition; precipitation; electrochemical deposition; and electroless deposition. See generally, Cameron, D.S., Cooper, S.J., Dodgson, I.L., Harrison, B., and Jenkins, J.W. "Carbons as Supports for Precious Metal Catalysts, " Catalysis Today, 7, 113-137 (1990) .
- reaction deposition techniques e.g. , deposition via reduction of noble metal compounds, and deposition via hydrolysis of noble metal compounds
- ion exchange techniques excess solution impregnation, and incipient wetness impregnation
- Catalysts comprising noble metals at the surface of a carbon support also are commercially available, e.g. , Aldrich Catalog No. 20,593- 1, 5% platinum on activated carbon (Aldrich Chemical Co., Inc., Milwaukee, Wl) ; Aldrich Catalog No. 20,568-0, 5% palladium on activated carbon.
- the noble metal is deposited via a reactive deposition technique comprising contacting the carbon support with a solution comprising a salt of the noble metal, and then hydrolyzing the salt.
- a suitable platinum salt which is relatively inexpensive is hexachloroplatinic acid (H 2 PtCl 6 ) .
- H 2 PtCl 6 hexachloroplatinic acid
- the noble metal is deposited onto the surface of the carbon support using a solution comprising a salt of a noble metal in one of its more reduced oxidation states.
- a salt of Pt(IV) e.g. , H 2 PtCl 6
- Pt(II) a salt of Pt(II)
- platinum in its elemental state e.g. , colloidal platinum
- Using these more reduced metal precursors leads to less oxidation of the carbon support and, therefore, less oxygen-containing functional groups being formed at the surface of the support while the noble metal is being deposited onto the surface.
- a Pt(II) salt is K 2 PtCl 4 .
- Pt(II) salt is diamminedinitrito platinum(II) .
- Example 11 shows that using this salt to deposit the noble metal produces a catalyst which is more resistant to leaching than a catalyst prepared using H 2 PtCl 6 as the metal precursor. Without being bound by any particular theory, it is believed that this is due to the fact that diamminedinitrito platinum(II) generates ammonia in-situ during reduction which further promotes removal of the oxygen-containing functional groups at the surface of the carbon support. This benefit, however, should be weighed against a possible explosion danger associated with the use of diamminedinitrito platinum (II) .
- a promoter (s) may be deposited onto the surface of the carbon support before, simultaneously with, or after deposition of the noble metal onto the surface.
- a salt solution comprising the promoter is used to deposit the promoter.
- a suitable salt that may be used to deposit bismuth is Bi (N0 3 ) 3 -5H 2 0, a suitable salt that may be used to deposit iron is FeCl 3 -6H 2 0, and a suitable salt that may be used to deposit tin is SnCl 2 -2H 2 0. It should be recognized that more than one promoter may be deposited onto the surface of the carbon support. Examples 13, 14, 15, and 17 demonstrate depositing a promoter onto a carbon surface with a salt solution comprising a promoter.
- Example 18 demonstrates depositing more than one promoter (i.e. , iron and Sn) onto a carbon surface using salt solutions comprising the promoters.
- reactive deposition is used to form metal particles containing a noble metal alloyed with a promoter.
- Reactive deposition may comprise, for example, reductive deposition wherein a surface of a carbon support is contacted with a solution comprising: (a) a reducing agent; and (b) (i) a compound comprising the noble metal and a compound comprising the promoter, or (ii) a compound comprising both the noble metal and the promoter.
- reducing agents such as sodium borohydride, formaldehyde, formic acid, sodium formate, hydrazine hydrochloride, hydroxy1amine, and hypophosphorous acid.
- Amine com 1 exes . These include, for example,
- Phosphine complexes include, for example, Pt (P (CH 3 ) 3 ) 2 C1 2 ; IrClCO (P (C 6 H 5 ) 3 ) 2 ; PtClH(PR 3 ) 2 , wherein each R is independently a hydrocarbyl , such as methyl , ethyl , propyl , phenyl, etc
- Organometallic complexes include , for example , Pt 2 (C 3 H 6 ) 2 C1 4 ; Pd 2 (C 2 H 4 ) 2 C1 4 ; Pt (CH 3 COO) 2 / Pd (CH 3 COO) 2 ; K [Sn (HCOO) 3 ] ; Fe (CO) 5 ; Fe 3 ( CO) 12 ; Fe 4 (CO) 16 ; Sn 3 (CH 3 ) 4 ; and T ⁇ (OR) 4 , wherein each R is independently a hydrocarbyl, such as methyl, ethyl, propyl, phenyl, etc.
- Noble metal/promoter complexes include, for example, Pt 3 (SnCl 3 ) 2 (C 8 H 12 ) 3 and [Pt (SnCl 3 ) 5 ] 3 .
- hydrolysis reactions are used to deposit a noble metal alloyed with a promoter.
- ligands containing the noble metal and promoter are formed, and then hydrolyzed to form well-mixed, metal oxide and metal hydroxide clusters at the surface of the carbon support .
- the ligands may be formed, for example, by contacting the surface of the support with a solution comprising (a) a compound comprising the noble metal and a compound comprising the promoter, or (b) a compound comprising both the noble metal and the promoter.
- a solution comprising (a) a compound comprising the noble metal and a compound comprising the promoter, or (b) a compound comprising both the noble metal and the promoter.
- Suitable compounds comprising a noble metal and/or a promoter are listed above with respect to reductive deposition.
- Hydrolysis of the ligands may be achieved, for example, by heating (e.g. , at a temperature of at least about 60 °C) the mixture.
- Example 17 further demonstrates the use of hydrolysis reactions to deposit a noble metal (i.e. , platinum) alloyed with a promoter (i.e. , iron) .
- a noble metal i.e. , platinum
- a promoter i.e. , iron
- the alloy in addition to the above-described reactive deposition techniques, there are many other techniques which may be used to form the alloy. These include, for example : 1. Forming the alloy by introducing metal compounds (which may be simple or complex, and may be covalent or ionic) to the surface of the support via impregnation, adsorption from a solution, and/or ion exchange. 2. Forming the alloy by vacuum co-deposition of metal vapors containing the noble metal and promoter onto the surface .
- metal compounds which may be simple or complex, and may be covalent or ionic
- Elements i.e. , Fe, Co, Ni , Ru, Rh, Pd, Os, Ir, and Pt
- Elements i.e. , Fe, Co, Ni , Ru, Rh, Pd, Os, Ir, and Pt
- Forming the alloy by: (a) depositing metal complexes containing metals in the zero valence state (e.g. , carbonyl, pi-allyl, or cyclopentadienyl complexes of the noble metal and of the promoter) at the surface of the carbon support; and (b) removing the ligands by, for example, heating or reduction to form the alloy particles at the surface.
- metal complexes containing metals in the zero valence state e.g. , carbonyl, pi-allyl, or cyclopentadienyl complexes of the noble metal and of the promoter
- the support is often preferable to dry the support using, for example, a sub-atmospheric, non-oxidizing environment (preferably, N 2 , a noble gas, or both) .
- a drying step is particularly preferred where the surface of the support is to be subsequently reduced by heating the surface (and even more preferred where the heating is to be conducted in a non-oxidizing environment) .
- the support is dried to reduce the moisture content of the support to less than about 5% by weight .
- the surface of the catalyst preferably is reduced.
- the surface of the catalyst suitably may be reduced, for example, by heating the surface at a temperature of at least about 400°C. It is especially preferable to conduct this heating in a non-oxidizing environment (e.g. , nitrogen, argon, or helium) . It is also more preferred for the temperature to be greater than about 500°C. Still more preferably, the temperature is from about 550 to about 1,200°C, and most preferably from about 550 to about 900°C.
- the heating is conducted in the presence of a gas-phase reducing agent (the method of heating the catalyst in the presence of a gas-phase reducing agent will sometimes be referred to as "high- temperature gas-phase reduction").
- gas-phase reducing agents may be used during the heating, including but not limited to H 2 , ammonia, and carbon monoxide.
- Hydrogen gas is most preferred because the small molecular size of hydrogen allows better penetration into the deepest pores of the carbon support.
- the remainder of the gas consists essentially of a non- oxidizing gas, such as nitrogen, argon, or helium.
- the preferred amount of time that the catalyst surface is heated depends on the mass transfer of the reducing agent to the catalyst surface.
- the reducing agent is a non-oxidizing gas comprising from about 10 to about 20 volume% H 2
- the surface preferably is heated for from about 15 minutes to about 24 hours at from about 550 to about 900°C with a space velocity of from about 1 to about 5,000 hour -1 . More preferably, the space velocity is from about 10 to about 2,500 hour -1 , and even more preferably from about 50 to about 750 hour "1 .
- the heat-treatment is conducted at the above preferred temperatures and space velocities for from about 1 to about 10 hours.
- Heating the surface at space velocities of less than 1 hour -1 is disadvantageous because the oxygen-containing functional groups at the surface of the carbon support may not be sufficiently destroyed. On the other hand, heating the surface at space velocities greater than 5,000 hour -1 is uneconomical .
- this heating step enhances the platinum-carbon interaction on the catalyst by removing oxygen-containing functional groups at the surface of the carbon support , including those formed by depositing the noble metal onto the surface. It is believed that these oxygen-containing functional groups are unstable anchor sites for the noble metal because they tend to interfere with the potentially stronger ⁇ interactions between the noble metal and the carbon support. Heating alone will decompose and thereby remove many of the oxygen-containing functional groups at the surface of the carbon support. However, by heating the surface in the presence of a reducing agent (e.g. , H 2 ) , more oxygen-containing functional groups are able to be eliminated.
- a reducing agent e.g. , H 2
- the surface of the carbon support is less than about 20:1 before the noble metal is deposited onto the surface of the support, the surface preferably is reduced using the above-described high-temperature gas-phase reduction treatment at a temperature greater than 500°C, although the surface may optionally be treated with other reduction environments in addition to high-temperature gas-phase reduction.
- various alternative reduction environments may be used instead of high- temperature gas-phase reduction.
- the surface of the catalyst may be reduced, at least in part, by treating it with an amine, such as urea, a solution comprising ammonium ions (e.g. , ammonium formate or ammonium oxalate) , or ammonia gas, with ammonia gas or a solution comprising ammonium ions being most preferred.
- an amine such as urea
- a solution comprising ammonium ions e.g. , ammonium formate or ammonium oxalate
- ammonia gas e.g. , ammonium formate or ammonium oxalate
- the support may be washed with a solution comprising ammonium ions or placed into contact with a gas comprising ammonia.
- the catalyst surface is washed with diluted aqueous ammonia after depositing the noble metal .
- the catalyst is added to pure water and stirred for a few hours to wet the surface of the catalyst .
- a solution comprising ammonium ions is added to the catalyst slurry in an amount sufficient to produce a pH of greater than 7 , more preferably from about 8 to about 12, and most preferably from about 9.5 to about 11.0. Because the temperature and pressure are not critical, this step preferably is performed at room temperature and atmospheric pressure. Example 10 further demonstrates this reduction treatment.
- Sodium borohydride also may be used to reduce the surface of the catalyst.
- this treatment preferably is used in addition to other reduction treatments, and most preferably is used before high-temperature gas-phase reduction.
- the support is washed with a solution of NaBH 4 in the presence of NaOH at a pH of from about 8 to about 14 for about 15 to about 180 minutes.
- the amount of NaBH 4 used preferably is sufficient to reduce all the noble metal. Because the temperature and pressure are not critical, this step preferably is performed at room temperature and atmospheric pressure.
- Example 12 further demonstrates this reduction treatment . It should be recognized that any of the above treatments which may be used to reduce the surface of the catalyst also may be used to deoxygenate the surface of the carbon support before the noble metal is deposited onto the surface.
- the above-described catalyst is especially useful in liquid phase oxidation reactions at pH levels less than 7, and in particular, at pH levels less than 3. It also is especially useful in the presence of solvents, reactants, intermediates, or products which solubilize noble metals.
- One such reaction is the oxidation of PMIDA or a salt thereof to form N- (phosphonomethyl) glycine or a salt thereof in an environment having pH levels in the range of from about 1 to about 2.
- the description below will disclose with particularity the use of the above-described catalyst to effect the oxidative cleavage of PMIDA or a salt thereof to form N- (phosphonomethyl) glycine or a salt thereof.
- the catalyst concentration preferably is from about 0.2 to about 5 wt.%, and most preferably from about 0.3 to about 1.5 wt.%. Concentrations greater than about 10 wt.% are difficult to filter. On the other hand, concentrations less than about 0.1 wt.% tend to produce unacceptably low reaction rates.
- oxygen is fed into the reactor as described above until the bulk of PMIDA reagent has been oxidized, and then a reduced oxygen feed rate is used.
- This reduced feed rate preferably is used after about 75% of the PMIDA reagent has been consumed. More preferably, the reduced feed rate is used after about 80% of the PMIDA reagent has been consumed.
- the reduced feed rate may be achieved by purging the reactor with air, preferably at a volumetric feed rate which is no greater than the volumetric rate at which the pure molecular oxygen was fed before the air purge.
- the reduced oxygen feed rate preferably is maintained for from about 2 to about 40 min. , more preferably from about 5 to about 20 min. , and most preferably from about 5 to about 15 min.
- Concentrations of formaldehyde in the product mixture are typically less than about 0.5% by weight, more preferably less than about 0.3%, and still more preferably less than about 0.15%.
- Example 1 Measuring pore volume of carbon support
- Total surface area determination involves exposing a known weight of a solid to some definite pressure of a non-specific adsorbate gas at a constant temperature, e.g. , at the temperature of liquid nitrogen, -196°C.
- a constant temperature e.g. , at the temperature of liquid nitrogen, -196°C.
- gas molecules leave the bulk gas to adsorb onto the surface which causes the average number of molecules in the bulk gas to decrease which, in turn, decreases the pressure.
- the relative pressure at equilibrium, p as a fraction of the saturation vapor pressure, p 0 , of the gas is recorded. By combining this decrease in pressure with the volumes of the vessel and of the sample, the amount (i.e.
- Kelvin equation and methods developed by Barrett, Joyner and Halenda BJH
- the reduced catalysts were used to catalyze the oxidation of PMIDA to N- (phosphonomethyl) glycine (i.e., "glyphosate") using the reaction conditions set forth in Example 5.
- Table 1 shows the results.
- Use of the deoxygenated carbon support resulted in smaller CO desorption values, less noble metal leaching, higher formaldehyde activity, and shorter reaction times.
- Table 1 Effect of Deoxygenating the Carbon Support before Dispersing Noble Metal onto Its Surface
- Example 3 Depositing platinum onto the surface of a carbon support
- NUCHAR activated carbon SA-30 Westvaco Corp. Carbon, Department Covington, VA
- H 2 PtCl 6 dissolved in about 900 ml of water was added dropwise over a period of 3 to 4 hours .
- the slurry was stirred for 90 more minutes.
- the pH of the slurry then was readjusted to 10.5 using NaOH, and stirred for 10 to 14 more hours.
- the resulting slurry was filtered and washed with water until the filtrate reached a constant conductivity.
- the wet cake was dried at 125°C under vacuum for 10 to 24 hours. This material produced 5% platinum on carbon upon reduction.
- Aldrich catalyst consisting of 5% platinum on an activated carbon support (catalog No. 20,593-1, Aldrich Chemical Co., Inc., Milwaukee, Wl) was heated at 640°C for 4-6 hours in the presence of 20% H 2 and 80% argon. Subsequently, it was used to catalyze the oxidation of PMIDA to Glyphosate. Its performance was compared to the performance of a sample of the Aldrich catalyst which was used as received from Aldrich.
- the performances of six catalysts in catalyzing the PMIDA oxidation were compared. These catalysts were: (a) a catalyst consisting of 5% platinum on an activated carbon support (Catalog No. 33,015-9, Aldrich Chemical Co., Inc., Milwaukee, Wl) ; (b) the catalyst after being washed with ammonia (ammonia washing was conducted using the same technique described in Example 10 except that the pH of the catalyst slurry was adjusted to and maintained at 11.0 rather than 9.5); (c) the catalyst after being heated at 75°C in 20% H 2 and 80% argon for 4-6 hours (GPR@75°C) ; (d) the catalyst after being heated at 640°C for 4-6 hours in the presence of 20% H 2 and 80% argon (GPR@640°C) ; and (e) two catalysts after being washed with ammonia and then heated at 640°C for 4-6 hours in the presence of 20% H 2 and 80% argon.
- the PMIDA oxidation reaction conditions were
- Table 3 shows the results.
- the untreated catalyst showed relatively high leaching and poor formaldehyde activity.
- High-temperature gas-phase reduction at 640°C in the presence of H 2 leads to the greatest decrease in leaching and increase in formaldehyde activity.
- Heating the catalyst at 75°C in 20% H 2 at 75°C decreased leaching to a lesser extent, but did not enhance the formaldehyde activity.
- Table 3 PMIDA Oxidation Results for 5% Pt on Activated Carbon (Aldrich Cat. No. 33.015-9)
- ND means none detec ted .
- catalysts were analyzed while catalyzing the PMIDA oxidation. These catalysts were: (a) a catalyst consisting of 5% platinum on NUCHAR SA-30 (Westvaco Corp., Carbon Department, Covington, VA) ; (b) the catalyst after being treated with NaBH 4 (see Example 12 for protocol) ; (c) the catalyst after being heated at 75°C in 20% H 2 and 80% argon for 4-6 hours (GPR@75°C) ; (d) the catalyst after being heated at 640°C in 20% H 2 and 80% argon for 4-6 hours (GPR@640°C) ; (e) the catalyst after being washed with ammonia (using the same technique described in Example 10) and then heated at 640°C in 20% H 2 and 80% argon for 4-6 hours.
- the reaction conditions were the same as those in Example 5.
- Table 4 shows the results.
- the untreated catalyst showed relatively high platinum leaching and low formaldehyde activity.
- the catalyst also showed high leaching and low formaldehyde activity after being treated with NaBH 4 , as did GPR@75°C.
- GPR@640°C showed a greater formaldehyde activity and less leaching.
- the carbon atom to oxygen atom ratio and the oxygen atom to platinum atom ratio at the surfaces of various fresh catalysts were analyzed using a PHI Quantum 2000 ESCA Microprobe Spectrometer (Physical Electronics, Eden Prairie, MN) .
- the surface analysis was performed by electron spectroscopy for chemical analysis ("ESCA") with the instrument in a retardation mode with the analyzer at fixed band pass energy (constant resolution) .
- the analysis entails irradiation of the sample with soft X- rays, e.g., Al K-, (1486.6 eV) , whose energy is sufficient to ionize core and valence electrons.
- the ejected electrons leave the sample with a kinetic energy that equals the difference between the exciting radiation and the "binding energy" of the electron (ignoring work function effects) .
- ESCA is inherently a surface sensitive technique.
- the kinetic energy of the electrons is measured using an electrostatic analyzer and the number of electrons are determined using an electron multiplier. The data are presented as the number of electrons detected versus the binding energy of the electrons.
- ESCA survey spectra were taken using monochromatic Al K ⁇ - x-rays for excitation of the photoelectrons with the analyzer set for a 117 eV band pass energy.
- the X-ray source was operated at 40 watts power and data were collected from the 200 ⁇ m spot on the sample being irradiated. These conditions give high sensitivity but low energy resolution.
- the spectra were accumulated taking a 1.0 eV step size across the region from 1100 eV to 0 eV and co-adding repetitive scans to achieve acceptable signal/noise in the data.
- the elements present were identified and quantified using the standard data processing and analysis procedures provided with the instrumentation by the vendor. From the relative intensities of the photoelectron peaks, the relative atomic concentrations of the elements Pt/C/O are obtained.
- ESCA analysis is generally cited as having a precision of ⁇ 20% using tabulated response factors for a particular instrument configuration.
- Table 5 shows the C/O and O/Pt ratios at the surface of each fresh catalyst, and the amount of leaching for each of the catalysts during a single-cycle PMIDA oxidation reaction.
- the carbon support was deoxygenated using the singe- step high-temperature deoxygenation technique #2 described in Example 2.
- Example 8 Analysis of catalyst surface using thermogravimetric analysis with in-line mass spectroscopy (TGA-MS)
- the concentration of oxygen-containing functional groups at the surfaces of various fresh catalysts was determined by thermogravimetric analysis with in-line mass spectroscopy (TGA-MS) under helium.
- TGA-MS thermogravimetric analysis with in-line mass spectroscopy
- a dried sample (100 mg) of fresh catalyst is placed into a ceramic cup on a Mettler balance.
- the atmosphere surrounding the sample then is purged with helium using a flow rate 150 ml/min. at room temperature for 10 minutes.
- the temperature subsequently is raised at 10°C per minute from 20 to 900°C, and then held at 900°C for 30 minutes.
- the desorptions of carbon monoxide and carbon dioxide are measured by an in-line mass spectrometer.
- the mass spectrometer is calibrated in a separate experiment using a sample of calcium oxalate monohydrate under the same conditions.
- Table 6 shows the amount of carbon monoxide desorbed per gram of each catalyst using TGA-MS, and the amount of leaching for each of the catalysts during a single-cycle PMIDA oxidation reaction using the same reaction conditions as in Example 5. As Table 6 shows, leaching tends to decrease as the amount of CO desorption decreases, and is particularly low when the desorption is no greater than 1.2 mmole/g (mmole CO desorbed per gram of catalyst) .
- An unreduced catalyst having 5% platinum on an activated carbon support (which was deoxygenated using the single-step high-temperature deoxygenation technique #2 described in Example 2 before the platinum is deposited) was heated at various temperatures in 10% H 2 and 90% argon for about 2 hours. The catalyst then was used to catalyze the PMIDA oxidation reaction. The reaction was conducted in a 250 ml glass reactor using 5 g PMIDA, 0.157% catalyst (dry basis), 200 g total reaction mass, a temperature of 80°C, a pressure of 0 psig, and an oxygen flow rate of 150 ml/min.
- a normalized value of 1.00 corresponds to the highest amount of Pt observed in solution during this experiment .
- An unreduced catalyst (6.22 g) consisting of 5% platinum on an activated carbon support (which was deoxygenated using the single-step high-temperature deoxygenation technique #2 described in Example 2 before the platinum was deposited onto the support) was slurried in 500 ml of water for 30 minutes. Afterward, the pH of the slurry was adjusted to 9.5 with diluted aqueous ammonia, and the slurry was stirred for one hour, with aqueous ammonia being periodically added to maintain the pH at 9.5. The resulting slurry was filtered and washed once with about 300 ml of water. The wet cake then was dried at 125°C under vacuum for about 12 hours.
- This catalyst was heated at 640°C for 11 hours in 10% H 2 and 90% argon, and then compared with two other catalysts consisting of 5% platinum on NUCHAR activated carbon: (a) one reduced at room temperature with NaBH 4 (see Example 12 for protocol) , and (b) one heated at 640°C in 10% H 2 and 90% argon for 11 hours.
- the reactions were the same as those in Example 5.
- Example 11 Use of a less oxidizing noble metal precursor
- Platinum was deposited on an activated carbon support using diamminedinitrito platinum (II) .
- an activated carbon support was deoxygenated using the single-step high-temperature deoxygenation technique #2 described in Example 2. Next, it was slurried in 2 L of water for 2 hours. Approximately 51.3 g of a 3.4% solution of diamminedinitrito platinum (II) , diluted to 400 g with water, then was added dropwise over a period of 3-4 hours. After addition was complete, stirring was continued for 90 more minutes. The pH was re-adjusted to 10.5 by adding diluted aqueous NaOH, and stirring was conducted for 10-14 more hours. The slurry then was filtered and washed with a plentiful amount of water until the filtrate reached constant conductivity. The wet cake was dried at 125°C under vacuum for 10-24 hours. The resulting catalyst was heated at 640°C for 4-6 hours in 10% H 2 and 90% argon.
- II diamminedinitrito platinum
- a control was prepared using H 2 PtCl 6 to deposit platinum onto the same carbon.
- the control was heated under the same conditions as the catalyst prepared using diamminedinitrito platinum (II) .
- the purpose of this example is to demonstrate the effects of reducing the catalyst using NaBH 4 .
- an activated carbon support (which was deoxygenated using the single-step high-temperature deoxygenation technique #2 described in Example 2 before the platinum was deposited onto the support) was slurried with 85 ml of distilled water in a 250 ml round bottom flask. The slurry was stirred in a vacuum for about 1 hour. Next, 0.706 g of H 2 PtCl 6 in 28 ml of distilled water was added to the slurry at a rate of about 1 ml per 100 seconds with the vacuum still being applied. After stirring overnight in the vacuum, the reactor was brought to atmospheric pressure by admitting a flow of N 2 .
Abstract
Description
Claims
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AU27707/99A AU761345B2 (en) | 1998-02-25 | 1999-02-17 | Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions |
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IL13808199A IL138081A0 (en) | 1998-02-25 | 1999-02-17 | Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions |
SK1256-2000A SK12562000A3 (en) | 1998-02-25 | 1999-02-17 | Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions |
KR1020007009463A KR20010041349A (en) | 1998-02-25 | 1999-02-17 | Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions |
JP2000533219A JP2002504427A (en) | 1998-02-25 | 1999-02-17 | Deeply reduced oxidation catalyst and its use to catalyze liquid phase oxidation reactions |
HU0101891A HUP0101891A3 (en) | 1998-02-25 | 1999-02-17 | Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions |
CA002321923A CA2321923C (en) | 1998-02-25 | 1999-02-17 | Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions |
BRPI9908252-7A BRPI9908252B1 (en) | 1998-02-25 | 1999-02-17 | process for the preparation of n- (phosphonomethyl) glycine or an n- (phosphonomethyl) glycine salt |
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1999
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