WO2017035133A1 - Spray-dried butynediol catalysts - Google Patents
Spray-dried butynediol catalysts Download PDFInfo
- Publication number
- WO2017035133A1 WO2017035133A1 PCT/US2016/048183 US2016048183W WO2017035133A1 WO 2017035133 A1 WO2017035133 A1 WO 2017035133A1 US 2016048183 W US2016048183 W US 2016048183W WO 2017035133 A1 WO2017035133 A1 WO 2017035133A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- bismuth
- copper
- ethynylation catalyst
- slurry
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000002002 slurry Substances 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 13
- 238000001694 spray drying Methods 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 15
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 15
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 9
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000454 talc Substances 0.000 claims description 7
- 229910052623 talc Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 5
- 239000000378 calcium silicate Substances 0.000 claims description 5
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 5
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- 229960004643 cupric oxide Drugs 0.000 claims description 5
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 5
- NPKGQBIUYHHPOT-UHFFFAOYSA-N [Cu+2].[C-]#[C-] Chemical compound [Cu+2].[C-]#[C-] NPKGQBIUYHHPOT-UHFFFAOYSA-N 0.000 claims description 4
- 229940036348 bismuth carbonate Drugs 0.000 claims description 4
- 229940116318 copper carbonate Drugs 0.000 claims description 4
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 4
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 229940049676 bismuth hydroxide Drugs 0.000 claims description 2
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- FIMTUWGINXDGCK-UHFFFAOYSA-H dibismuth;oxalate Chemical compound [Bi+3].[Bi+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O FIMTUWGINXDGCK-UHFFFAOYSA-H 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003801 milling Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000005602 Reppe reaction Methods 0.000 description 1
- 150000000476 acetylides Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical class [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012956 testing procedure Methods 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/94—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/04—Acyclic alcohols with carbon-to-carbon triple bonds
- C07C33/042—Acyclic alcohols with carbon-to-carbon triple bonds with only one triple bond
- C07C33/044—Alkynediols
- C07C33/046—Butynediols
Definitions
- the present technology is generally related to catalysts for the production of butynediol. More specifically, the technology is related to methods of preparing such catalysts.
- the catalytic ethynylation of formaldehyde is known as the "Reppe Reaction,” or “Reppe Process.”
- Reppe Reaction The catalytic ethynylation of formaldehyde is known as the "Reppe Reaction,” or “Reppe Process.”
- Known processes of forming copper-containing catalysts used in the Reppe process include impregnation of silicate supports, co-precipitation, and deposition precipitation. However, uniform material preparation remains a challenge.
- a process of forming an ethynylation catalyst includes providing an aqueous slurry comprising water, a copper-containing material, a bismuth-containing material, a structural material, and a binder; spray-drying the slurry to form particles; and calcining the particles to form the ethynylation catalyst.
- aqueous slurry comprising water, a copper-containing material, a bismuth-containing material, a structural material, and a binder
- spray-drying the slurry to form particles and calcining the particles to form the ethynylation catalyst.
- Illustrative copper-containing materials may include, but are not limited to, copper carbonate, copper oxalate, copper hydroxide, cupric oxide, and cuprous oxide.
- Illustrative bismuth-containing materials may include, but are not limited to, bismuth carbonate, bismuth oxalate, bismuth hydroxide, bismuth oxide, and bismuth acetate.
- Illustrative structural materials may include, but are not limited to, a clay, talc, calcium silicate, kieselguhr, alumina, carbon, and silica.
- Illustrative binders may include, but are not limited to, a silica sol, an alumina sol, sodium silicate, and aluminum chlorohydrate.
- the particles may have an average particle diameter of about 5 ⁇ to about 100 ⁇ .
- the ethynylation catalyst formed according to any of the above embodiments is provided.
- a process of activating an ethynylation catalyst includes providing the ethynylation catalyst made by any of the above processes; exposing the ethynylation catalyst to formaldehyde to form a mixture; and maintaining the mixture at a sufficient temperature for a sufficient time to form an activated ethynylation catalyst.
- the sufficient temperature is about 80 °C.
- the sufficient time is from about 1 hour to about 10 hours.
- the activated ethynylation catalyst includes a copper acetylide species.
- the activated ethynylation catalyst formed according to the above processes is provided.
- a process of forming 1,4-butynediol includes, the exposing the activated ethynylation catalyst described above to acetylene in the presence of formaldehyde at a sufficient temperature for a sufficient time to produce 1,4- butynediol.
- a process of preparing a particulate catalyst via spray-drying is provided. After spray-drying the catalyst particles are calcined in air.
- the particulate catalyst contains copper oxide, bismuth oxide, a structural material, and a binder.
- the particulate catalyst is useful for the ethynylation of formaldehyde to form 1,4-butynediol, i.e. it is an ethynylation catalyst.
- a process for preparing a particulate catalyst via spray- drying.
- the process uses a metal-containing precursor of the copper or bismuth oxides of the particulate catalyst.
- metal-containing precursors may include carbonates, oxalates, citrates, sulfates, nitrates, and hydroxides.
- the precursor salt(s) are suspended, not dissolved, in a solvent such that a slurry is formed.
- the slurry may be milled until a desired particle size in the slurry is achieved.
- the precursor salts may be dry milled either individually, or together until a desired particle size is achieved, prior to formation of the slurry.
- the average particle size (APS) may be from less than about 0.5 ⁇ to about 10 ⁇ . In some embodiments, the APS may be from about 0.5 ⁇ to about 5 ⁇ . In some embodiments, the APS may be from about 0.5 ⁇ to about 3 ⁇ . In some embodiments, the APS may be from about 1 ⁇ to about 2 ⁇ . In some embodiments, the APS is less than about 2 ⁇ . Milling of the precursors may be continued for as long, or as short, as needed to achieve a desired particle size and particle size distribution. This may be from about 15 minutes to about 24, in some embodiments. In other embodiments, the time of milling may be from about 2 hours to about 20 hours.
- the time of milling is from about 10 hours to about 20 hours.
- Illustrative materials for structural material precursor include, but are not limited to, clay, talc, calcium silicate, kieselguhr, alumina, carbon, and silica.
- the structural component aids in the overall functionality of the catalyst.
- the structural component may be milled to provide a slurry of the material, or a material of appropriate particle size may be obtained and suspended to provide a slurry, or a pre-prepared slurry may be obtained.
- the milling and slurrying of the precursor salts and structural materials may be carried out in any appropriate solvent.
- the solvent may be water, an alcohol, a nitrile, a ketone, or an ether.
- water is the solvent.
- the slurry formed is an aqueous slurry.
- a binder may be added to the slurry.
- Illustrative binders may include, but are not limited to silica sols, alumina sols, sodium silicate, and aluminum chlorohydrate.
- the binder is Si0 2 .
- the amount of binder in the slurry is an amount necessary to bind the final catalyst. The amount may be from about 1 wt% to about 30 wt% based upon total solids. In some embodiments, the amount is from about 5 wt% to about 20 wt%. In other
- the amount is about 10 wt% binder based upon total solids.
- the slurry is adjusted in solids content such that when spray-drying is conducted the materials are readily flowable and sprayed.
- the solids content of the slurry may be adjusted to a value of about 1 wt% to about 50 wt%.
- the solids content of the slurry may be adjusted to a value of about 1 wt% to about 25 wt%.
- the solids content of the slurry may be adjusted to a value of about 2 wt% to about 20 wt%.
- the solids content of the slurry may be adjusted to a value of about 5 wt% to about 15 wt%.
- the solids content of the slurry may be adjusted to about 10 wt%. Additional solvent may be added, or solvent may be removed, to achieve the desired solids content of the slurry.
- the process of the spray-drying the slurry of the precursor salts, structural material, and binder may be carried out with a standard wheel spray-dryer, or a nozzle-type spray- dryer.
- the resulting powder has an average particle diameter of about 5 ⁇ to about 100 ⁇ . In some embodiments, the average particle diameter is about 5 ⁇ to about 60 ⁇ . In some embodiments, the average particle diameter is about 10 ⁇ to about 20 ⁇ . In some embodiments, the average particle diameter is about 15 ⁇ to about 40 ⁇ . In some embodiments, the average particle diameter is about 15 ⁇ .
- After obtaining the powder it is calcined at a temperature from about 250 °C to 600 °C to form a powdered, calcined catalyst material. In some embodiments, the calcination temperature is from 350 °C to 500 °C.
- the powdered, calcined catalyst material contains about 20 wt% to about 70 wt% copper oxide, and about 1 wt% to about 5 wt% bismuth oxide.
- Sodium levels (as Na 2 0) are typically less than about 3 wt%.
- the balance of the powdered, calcined catalyst material is mostly a variety of oxides that depend on the specific structural material used. For example, talc contains the both Mg and Si, clay contains Al and Si, calcium silicate contains Ca and Si, and binder may contain Si. Impurities in small amounts may be present.
- catalyst formation it may be activated for ethynylation reactions.
- the powdered, calcined catalyst is mixed with formaldehyde in water, and the pH is adjusted to a slightly basic value.
- the pH may be adjusted to a value from greater than about 7 to about 10.
- the pH is adjusted to about 8.
- the adjust of the pH is necessary to prevent or mitigate formic acid formation which would otherwise react with the copper-containing materials, thereby dissolving the copper into solution, rather than maintaining it as a slurry.
- the reaction of the catalyst with the formaldehyde produces an active Cu(I) acetylide species (Cu 2 C 2 ).
- the activated catalyst is then exposed to acetylene in a pressurized reactor in the presence of addition formaldehyde in water.
- the reaction with acetylene is carried out in an inert atmosphere where the acetylene is co-mixed with a gas such as nitrogen, argon, or helium.
- the reactor is gradually heated from room temperature to about 80 °C. After a period of time for reaction, evidenced by reduced acetylene uptake of the catalyst, the reactor is cooled under an acetylene flow.
- the reactor is purged with nitrogen and the product containing 1,4-butynediol and propargyl alcohol is recovered.
- Example 1 Copper carbonate and bismuth carbonate are mixed with water to about 30 wt% solids level and slurried. The slurry is then added to a batch-type ball mill (60% balls volume) and rotated on a roller stand for 16 hours, or until the average particle size (APS), or d 50 , is about 1 to 2 micrometers ( ⁇ ). Talc or other structural components may, if necessary, also undergo the same type of milling procedure, unless it is commercially available in the 2 or lower micron APS.
- APS average particle size
- d 50 average particle size
- Talc or other structural components may, if necessary, also undergo the same type of milling procedure, unless it is commercially available in the 2 or lower micron APS.
- the milled slurry (water, copper carbonate, bismuth carbonate, structural material) is then combined with the binder, Si0 2 (commercially available as Ludox® AS40 or Ludox® HS40), such that the overall binder level is about 10 wt%. Additional water may be added so that a predetermined overall solids content is obtained - about 10 wt% solids.
- the resulting slurry with about 10 wt% solids is then pumped to a spray-dryer, spray-dried, and the product is collected as a powder.
- the powder is then calcined at a temperature from about 250 °C to about 600 °C, more normally at 350 °C to 500 °C.
- the spray drier conditions are as set forth in Table 1, below.
- Table 1 General Spray -Drier Conditions.
- the catalyst contains about 20 wt% to about 60 wt% copper oxide, and about 1.0 wt% to about 4.5 wt% bismuth oxide.
- Sodium levels (as Na 2 0) are typically less than about 3 wt%.
- the balance of the catalyst is mostly a variety of oxides that depend on the specific structural material used. For example, talc contains the both Mg and Si, clay contains Al and Si, calcium silicate contains Ca and Si, and Ludox® contains the Si.
- Impurities in small amounts may be present.
- Various samples and their components for spray-drying, including weights, are provided in Table 2, and Table 3 provides data and conditions of formation for the components used in the various samples.
- Example 2 Catalyst Testing Procedure. Testing was generally carried out in two steps. First, the catalyst was activated to form an active copper acetylide. Second, the active copper acetylide was then transferred to the reaction vessel.
- catalyst activation was carried out in a 4-port quartz reactor flask containing 100 mL formalin (37 wt% formaldehyde in water).
- the pH of the formalin was adjusted to about 8 by adding 1.5 M NaOH.
- 15 g of powdered, calcined catalyst were added to the pH adjusted formalin.
- the reactor was purged with nitrogen, stirring was started, and acetylene was introduced at 50 mL/min to the catalyst - formalin slurry at room temperature.
- the flask was then lowered into a recirculating water bath and heated to 80 °C. This procedure forms the active Cu(I) acetylide species [Cu 2 C 2 ].
- the formic acid produced was continuously neutralized by adding 1.5 M NaOH to the slurry, thereby maintaining the pH at about 8. After 5 hours, the reactor was cooled to room temperature under flowing acetylene. Once at reached room temperature, the acetylene was purged from the flask with nitrogen, the reactor was disassembled, and the slurry removed. It was weighed, centrifuged, and decanted, leaving wet catalyst ready for activity testing.
- Example 3 Reaction Testing. Reaction studies were carried out using 0.5 g of the activated catalyst (dry basis) loaded into a stainless steel stirred autoclave containing 45 mL formalin. As with the activation procedure, the pH of the formalin was initially adjusted to about 8. The reactor was purged with nitrogen and acetylene before starting the reaction. The reactor was operated in a semi-batch fashion while stirring at 1450 RPM. At the start, acetylene from pressurized ballast cylinders was introduced to the reactor through a pressure regulator set at 15 psig (the reaction pressure), and the reactor was heated at approximately 2 °C per min to 80 °C.
- the reactor should not be heated in the absence of acetylene or the Cu acetylides will reduce to Cu°, deactivating the catalyst.
- acetylene uptake was monitored via pressure changes in the ballast cylinders. After 5 hours, the reactor was cooled in flowing acetylene and subsequently purged with nitrogen. The slurry was removed, centrifuged, and decanted. The product mixture was analyzed by gas chromatography. 1,4-butynediol (primary product) and propargyl alcohol (product intermediate) were quantified.
- Example 4 Activity Comparison. The activity of the catalysts measured as described above is provided in Table 4. The activities are compared to the commercial BASF catalyst Cu 5020P, as a control. The activity is reported as mols of butynediol plus propargyl alcohol formed per min per g of CuO. Note that the powder, calcined catalysts made via the above spray-drying methods are similar to, or superior to, the commercial catalyst.
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Abstract
Description
Claims
Priority Applications (5)
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JP2018510522A JP6808718B2 (en) | 2015-08-25 | 2016-08-23 | Spray-dried butynediol catalyst |
KR1020187007569A KR20180034668A (en) | 2015-08-25 | 2016-08-23 | The spray-dried butyne diol catalyst |
US15/754,261 US10537886B2 (en) | 2015-08-25 | 2016-08-23 | Spray-dried butynediol catalysts |
EP16839985.5A EP3341127A4 (en) | 2015-08-25 | 2016-08-23 | Spray-dried butynediol catalysts |
CN201680062287.8A CN108290146A (en) | 2015-08-25 | 2016-08-23 | It is spray-dried butynediols catalyst |
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US201562209485P | 2015-08-25 | 2015-08-25 | |
US62/209,485 | 2015-08-25 |
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WO2017035133A1 true WO2017035133A1 (en) | 2017-03-02 |
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PCT/US2016/048183 WO2017035133A1 (en) | 2015-08-25 | 2016-08-23 | Spray-dried butynediol catalysts |
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US (1) | US10537886B2 (en) |
EP (1) | EP3341127A4 (en) |
JP (1) | JP6808718B2 (en) |
KR (1) | KR20180034668A (en) |
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Cited By (4)
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CN106881097A (en) * | 2017-04-06 | 2017-06-23 | 上海迅凯新材料科技有限公司 | Bismuth catalyst of copper containing carrier for 1,4 butynediols of preparation and preparation method thereof |
CN111589836A (en) * | 2019-09-16 | 2020-08-28 | 徐光耀 | Method for treating waste containing acetylides |
CN116618059A (en) * | 2023-05-11 | 2023-08-22 | 高化学(江苏)化工新材料有限责任公司 | Novel catalyst for preparing 1, 4-butynediol and preparation method thereof |
WO2023227605A1 (en) * | 2022-05-24 | 2023-11-30 | Basf Se | Method for the preparation of a supported mixed metal oxide |
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WO2021222052A1 (en) * | 2020-04-28 | 2021-11-04 | Basf Corporation | Copper catalyst and method of making same |
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KR20180034668A (en) | 2018-04-04 |
US10537886B2 (en) | 2020-01-21 |
JP2018526205A (en) | 2018-09-13 |
CN108290146A (en) | 2018-07-17 |
EP3341127A1 (en) | 2018-07-04 |
US20180236439A1 (en) | 2018-08-23 |
EP3341127A4 (en) | 2019-04-17 |
JP6808718B2 (en) | 2021-01-06 |
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