WO2010055341A2 - Améliorations de procédés catalytiques - Google Patents
Améliorations de procédés catalytiques Download PDFInfo
- Publication number
- WO2010055341A2 WO2010055341A2 PCT/GB2009/051522 GB2009051522W WO2010055341A2 WO 2010055341 A2 WO2010055341 A2 WO 2010055341A2 GB 2009051522 W GB2009051522 W GB 2009051522W WO 2010055341 A2 WO2010055341 A2 WO 2010055341A2
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- WIPO (PCT)
- Prior art keywords
- gold
- catalyst
- carbon
- gold particles
- deposited
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 31
- 230000008569 process Effects 0.000 title claims description 23
- 230000003197 catalytic effect Effects 0.000 title description 4
- 239000010931 gold Substances 0.000 claims abstract description 79
- 239000003054 catalyst Substances 0.000 claims abstract description 70
- 229910052737 gold Inorganic materials 0.000 claims abstract description 64
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- HSFWRNGVRCDJHI-UHFFFAOYSA-N Acetylene Chemical compound C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims description 27
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 12
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 230000009849 deactivation Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 8
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002071 nanotube Substances 0.000 description 6
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- -1 gold halide Chemical class 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- AHTSCRNWVSEMPI-UHFFFAOYSA-N gold;methane Chemical compound C.[Au] AHTSCRNWVSEMPI-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229960002523 mercuric chloride Drugs 0.000 description 2
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/04—Chloro-alkenes
- C07C21/06—Vinyl chloride
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
Definitions
- the present invention concerns improvements in catalytic processes, and improvements in catalysts for such processes. More particularly, it concerns processes and catalysts for manufacturing vinyl chloride monomer (“VCM”) from acetylene.
- VCM vinyl chloride monomer
- the mercury catalyst usually 8-10% mercuric chloride on activated charcoal, used in the original process is highly toxic. Such toxicity creates problems arising from handling during manufacture of the catalyst as well as during loading of catalyst and removing catalyst after a campaign.
- a campaign is generally of six month duration. Deactivation of the mercury catalyst and loss of HgCI 2 by sublimation or volatilisation from the reactor in use can be significant problems.
- the ethyne process using mercury-based catalyst requires a lower capital investment in plant than the ethylene process; if a non-volatile and less toxic catalyst could replace the mercury catalyst without requiring significant plant alterations in existing plant designs, this would be a significant advantage.
- the preparation of the catalyst is not described, and no commercial use of the process or the catalyst appears ever to have taken place.
- the present invention provides a process for reacting ethyne with HCI, comprising passing the reactants over a catalyst comprising metallic gold particles, suitably gold nanoparticles, carried on a carbon support.
- the invention also provides a gold-based catalyst for the process of the invention, comprising a carbon support and metallic gold particles, suitably gold nanoparticles.
- nanoparticles we mean metal particles having a diameter within the range 1 - 1000 nanometres.
- the catalysts of the invention may be considered to comprise gold particles having a core comprising metallic gold and a shell or surface layer comprising higher oxidation state gold species including Au 3+ .
- the shell need not be complete, but preferably all or substantially all the exposed surface of the particle has the surface higher oxidation state gold species; for example if the metallic gold is partially surrounded by carbon, the "shell" may extend only over the exposed particle surface.
- Au 3+ need not be the only higher oxidation state gold species present in the shell, and Au 1+ may also be present, for example.
- Such higher oxidation state species may be stabilised by halide.
- the core comprises metallic gold (Au 0 ) but other gold species may also be present in the core.
- the metallic gold in the core and the Au 3+ and/or other positive oxidation state species in the shell act as a redox couple, or the metallic gold core acts as an electron sink during the desired reaction(s).
- the gold particles are desirably dispersed over the surface of the carbon support, when the catalyst is fresh. After a period of use, the gold particles may especially be carried on carbon fibrils.
- the carbon fibrils may be carbon nanotubes.
- the catalysts of the invention have never previously been observed or described. In contrast to prior observations that coking of gold catalysts causes deactivation, we believe that rather than active gold catalyst particles being submerged under coke-type masses, in the present invention the carbon fibrils carry the catalytic gold particles in such a manner that they remain active and exposed to the reactants.
- the catalysts of the invention may be prepared starting from a high surface area activated carbon, preferably of surface area greater than 800 m 2 /g, such as a 1300 m 2 /g carbon extrudate.
- a high surface area activated carbon preferably of surface area greater than 800 m 2 /g, such as a 1300 m 2 /g carbon extrudate.
- Other carbon supports including powders or granulates or other forms of carbon may be used. Such materials are commercially available.
- washing for example an acid wash, may be applied, preferably using hydrochloric acid. It has been found that, if necessary, dispersing the carbon in 3% hydrochloric acid, bringing to the boil, draining, and washing with distilled or deionised water, is effective.
- Carbon extrudates are available as "high purity” or “ultra high purity” grades commercially and such grades are typically acid washed to remove impurities.
- Catalysts may be prepared using a variety of catalyst preparation techniques known generally in the art, for example impregnation, preferably using incipient wetness methods, deposition, precipitation and combinations of these.
- the gold may be applied to the carbon from gold precursors such as HAuCI 4 . xH 2 O salt or from an aqueous solution or by dissolving metallic gold or other precursor in a mixture of nitric acid and hydrochloric acid such as that commonly known as "aqua regia” then adding the solution to the carbon particles or extrudates or vice versa. It has been observed when using an aqua regia solution that the carbon turns a gold colour then within a few seconds, turns a dark brown/black, and an evolution of NOx fumes was noted.
- an aqua regia solution Whilst we do not wish to be bound by any theory, it is thought that the gold is initially deposited as a gold salt, and that the salt is reduced to metallic gold by the active carbon but either retains or forms a shell comprising the higher oxidation state species, including Au 3+ , where exposed to the aqua regia solution.
- the impregnated support may be washed following impregnation to remove excess aqua regia solution in order to reduce the amount of NOx fumes generated during drying. We have, however found that catalyst activity may be reduced in this manner and so it is not presently preferred to include this washing step after impregnation.
- the gold particles are preferred to comprise substantially 100% gold, but it is contemplated that alloys and/or composites may also be active catalysts for the reactions of interest. Possible alloys and/or composites may include Cu and/or Ag, which may also exhibit the effective higher oxidation state surface species.
- Fig 1 is an EPMA plot of a catalyst according to the invention.
- Fig 2 is a plot showing the conversion of acetylene using a catalyst of the invention and a prior art mercury catalyst.
- Fig 3 is a plot showing the conversion of acetylene using a catalysts 1a and 1 b of the invention.
- Fig 4 is a SEM micrograph showing the mass of nanotubes formed on sample after reaction for 25 days.
- Fig 5 is a SEM micrograph showing gold particle at end of nanotubes and open end of one nanotube.
- Fig 6 is an SEM micrograph of a sample of catalyst.
- Fig 7 is a plot showing the conversion of acetylene using comparative catalysts 1c and 1d.
- Fig 8 is an XPS plot of a catalyst according to the invention.
- An aqua regia solution was prepared by mixing 25ml HNO 3 (69%) with 50ml HCI (37%). This was added to a solution of HAuCI 4 containing 1.5Og Au in 83 ml water.
- the surface area (B. ET.) is 1225 m 2 /g, according to the manufacturer's data sheet, .
- the C extrudates were impregnated with the solution using an incipient wetness technique. After standing the material was washed twice with water and then dried at 105 0 C overnight.
- An aqua regia solution was prepared by mixing 25ml HNO 3 (69%) with 50ml HCI (37%). This was added to a solution of HAuCI 4 containing 1.5Og Au in 83 ml water. Carbon extrudate (15Og as in Example 1a) was impregnated with the solution using an incipient wetness technique. After standing the material was dried at 105 0 C overnight.
- Example 1a The method of Example 1a has also been used to form gold on 3mm diameter carbon extrudate catalyst.
- Fig 1 of the accompanying images and drawings shows an EPMA plot of three carbon extrudates of approximate thickness 5.5 mm having gold nanoparticles deposited according to the method of the invention.
- the machine used was a JEOL model JXA-8500F field emission electron probe microanalyser.
- the gold is shown clearly deposited in a thin surface layer of approximately 100 ⁇ m thickness. It is preferred that the majority of the gold is deposited on the carbon support in a layer of up to 200 ⁇ m, more preferably in a layer of up to 100 ⁇ m, thickness.
- Example 1c (comparative) 1 %Au/SiO 2 Spheres Preparation at 5Og scale:
- a stock solution of aqua regia solution was prepared by mixing 25ml HNO 3 (69%) with 75ml HCI (37%) and 25 ml water. An aliquot (22ml) was added to a solution of HAuCI 4 containing 0.5Og Au in 30 ml water. Silica spheres (5Og - 280 m 2 /g, 1.1 to 2.4 mm diameter) were impregnated with the solution using an incipient wetness technique. After standing, the material was dried, yielding a yellow product.
- Example 1d (comparative) 1 %Au/SiO 2 Spheres Preparation at 5Og scale: A solution of HAuCI 4 containing 0.5Og Au was diluted to 50 ml with water and used to impregnate silica spheres (5Og as in Example 1c) using an incipient wetness technique. After standing, the material was dried, yielding a yellow product.
- Example 1 b 5.05g of a catalyst prepared as described in Example 1 b above was loaded into a 2 cm diameter glass reactor, giving a bed depth of 4 cm.
- the glass reactor was surrounded by a jacket filled with flowing heated oil to initiate and maintain the reaction.
- Thermocouples were in place in the middle and top of the bed to monitor temperatures during the pre-treatment and reaction stages. Thus the temperatures noted below refer to the temperature in the middle of the catalyst bed.
- the catalyst was dried under a stream of flowing nitrogen (100 ml min 1 ) at 100 0 C for 30 minutes. At this point the nitrogen was replaced with a flow of hydrogen chloride gas (116 ml min-1 ) and an exothermic reaction was observed, lasting a few minutes. After the exotherm had subsided, the temperature was raised to 18O 0 C and the hydrogen chloride treatment was continued for one hour. At this point the reactor was flushed with nitrogen for 15 minutes, and the temperature dropped to 9O 0 C. The reactant gases (hydrogen chloride and acetylene) were then passed over the catalyst bed, in a nominal 1 :1 molar ratio.
- the gases Prior to entering the reactor, the gases were passed through a gas mixer and pre-heater unit, consisting of a heated column packed with glass beads. To avoid an excessive exotherm (> 18O 0 C), the gas flows and oil bath temperature were increased cautiously, until the maximum flow rates of 114 ml min '1 each of hydrogen chloride and acetylene were attained. Typically this took about 45 minutes, the temperature in the middle of the bed was then maintained at the desired temperature (typically 18O 0 C) by increasing the external oil temperature.
- a gas mixer and pre-heater unit consisting of a heated column packed with glass beads.
- the gas flows and oil bath temperature were increased cautiously, until the maximum flow rates of 114 ml min '1 each of hydrogen chloride and acetylene were attained. Typically this took about 45 minutes, the temperature in the middle of the bed was then maintained at the desired temperature (typically 18O 0 C) by increasing the external oil temperature.
- FIG 3 A plot of ethyne conversion for an Example 1a catalyst compared to an Example 1 b catalyst is shown in Fig 3.
- the Example 1 b catalyst which has not used the final water wash step, is more active and deactivates significantly less over the test period than the Example 1a catalyst.
- samples of the catalyst according to the invention from the upstream section of the reactor was studied by Scanning Electron Microscopy. The surface exhibited a mass of carbon fibrils. Two SEM micrographs at different magnifications are shown as Figures 4 and 5.
- Fig 4 is a SEM micrograph showing the mass of nanotubes formed on the sample after reaction for 25 days.
- Fig 5 shows that these are carbon nanotubes, which carry nanoparticles of metallic gold at their ends.
- Fig 5 shows the gold particle at end of nanotubes and the open end of one nanotube.
- a further image (Fig 6) is of a sample of used catalyst taken from the mid section of a tubular reactor, showing the beginning of formation of the carbon nanotubes, growing from the surface of the carbon support.
- Fig 8 shows the resulting plot containing peaks attributable to Au 0 and peaks at higher binding energy due to Au(III).
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Abstract
L’invention concerne un catalyseur qui comprend des nanoparticules d’or sur un support carboné. Le catalyseur selon l’invention est pratiquement non toxique et est actif pour la réaction d’éthyne avec du chlorure d’hydrogène pour former le monomère chlorure de vinyle.
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Cited By (6)
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CN102631947A (zh) * | 2012-04-01 | 2012-08-15 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | 一种用于乙炔氢氯化的金络合物催化剂 |
WO2013008004A2 (fr) | 2011-07-11 | 2013-01-17 | Johnson Matthey Public Limited Company | Catalyseur et son procédé de fabrication |
CN104707602A (zh) * | 2013-12-13 | 2015-06-17 | 索尔维公司 | 用于从乙炔和氯化氢制造氯乙烯的方法 |
WO2018109247A1 (fr) * | 2016-12-15 | 2018-06-21 | Consejo Superior De Investigaciones Científicas (Csic) | Chlorhydratation régiosélective, stéréosélective et catalytique d'alcynes |
US10239803B2 (en) | 2015-05-27 | 2019-03-26 | Johnson Matthey Public Limited Company | Process for the preparation of vinyl chloride |
EP4197635A1 (fr) | 2021-12-17 | 2023-06-21 | Johnson Matthey Public Limited Company | Catalyseur contenant de l'or, procédé de préparation et utilisation |
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CN106423287A (zh) * | 2016-09-10 | 2017-02-22 | 新疆大学 | 负载型无汞催化剂及其制备方法和在乙炔氢氯化制备氯乙烯中的应用 |
CN110841722B (zh) * | 2019-10-16 | 2022-09-06 | 鄂尔多斯市瀚博科技有限公司 | 一种用于氯乙烯合成的无汞催化剂钝化工艺 |
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CN101249451A (zh) * | 2008-04-10 | 2008-08-27 | 四川大学 | 可用于乙炔氢氯化反应的非汞催化剂及其制备方法 |
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MARCO CONTE ET AL: "Reactivation of a Carbon-supported Gold Catalyst for the Hydrochlorination of Acetylene" CATALYSIS LETTERS, KLUWER ACADEMIC PUBLISHERS-PLENUM PUBLISHERS, NE, vol. 124, no. 3-4, 22 July 2008 (2008-07-22), pages 165-167, XP019601430 ISSN: 1572-879X * |
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US10202320B2 (en) | 2011-07-11 | 2019-02-12 | Johnson Matthey Plc | Catalyst and method for its preparation |
WO2013008004A2 (fr) | 2011-07-11 | 2013-01-17 | Johnson Matthey Public Limited Company | Catalyseur et son procédé de fabrication |
WO2013008004A3 (fr) * | 2011-07-11 | 2013-05-16 | Johnson Matthey Public Limited Company | Catalyseur et son procédé de fabrication |
JP2014523810A (ja) * | 2011-07-11 | 2014-09-18 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニー | 金と含硫黄配位子を担体上に含む触媒とその調製方法 |
GB2492888B (en) * | 2011-07-11 | 2016-02-10 | Johnson Matthey Plc | Catalyst and method for its preparation |
US9409161B2 (en) | 2011-07-11 | 2016-08-09 | Johnson Matthey Plc | Catalyst and method for its preparation |
EA027629B1 (ru) * | 2011-07-11 | 2017-08-31 | Джонсон Мэтти Паблик Лимитед Компани | Катализатор и способ его получения |
EA032672B1 (ru) * | 2011-07-11 | 2019-06-28 | Джонсон Мэтти Паблик Лимитед Компани | Катализатор и способ его получения |
CN102631947A (zh) * | 2012-04-01 | 2012-08-15 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | 一种用于乙炔氢氯化的金络合物催化剂 |
CN104707602A (zh) * | 2013-12-13 | 2015-06-17 | 索尔维公司 | 用于从乙炔和氯化氢制造氯乙烯的方法 |
EA030122B1 (ru) * | 2013-12-13 | 2018-06-29 | Солвей Са | Способ получения винилхлорида из ацетилена и хлористого водорода |
US10239803B2 (en) | 2015-05-27 | 2019-03-26 | Johnson Matthey Public Limited Company | Process for the preparation of vinyl chloride |
US10800719B2 (en) | 2015-05-27 | 2020-10-13 | Johnson Matthey Public Limited Company | Process for the preparation of vinyl chloride |
WO2018109247A1 (fr) * | 2016-12-15 | 2018-06-21 | Consejo Superior De Investigaciones Científicas (Csic) | Chlorhydratation régiosélective, stéréosélective et catalytique d'alcynes |
EP4197635A1 (fr) | 2021-12-17 | 2023-06-21 | Johnson Matthey Public Limited Company | Catalyseur contenant de l'or, procédé de préparation et utilisation |
WO2023111537A1 (fr) | 2021-12-17 | 2023-06-22 | Johnson Matthey Public Limited Company | Catalyseur contenant de l'or, procédé de préparation et utilisation |
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CN101735005A (zh) | 2010-06-16 |
WO2010055341A3 (fr) | 2010-08-12 |
CN102282112A (zh) | 2011-12-14 |
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