WO2011036189A2 - The catalyst and method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols - Google Patents
The catalyst and method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols Download PDFInfo
- Publication number
- WO2011036189A2 WO2011036189A2 PCT/EP2010/064001 EP2010064001W WO2011036189A2 WO 2011036189 A2 WO2011036189 A2 WO 2011036189A2 EP 2010064001 W EP2010064001 W EP 2010064001W WO 2011036189 A2 WO2011036189 A2 WO 2011036189A2
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- WIPO (PCT)
- Prior art keywords
- catalyst
- copper
- glycols
- esters
- hydroxysilicate
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 31
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 150000002334 glycols Chemical class 0.000 title claims abstract description 18
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 61
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052802 copper Inorganic materials 0.000 claims abstract description 46
- 150000002148 esters Chemical class 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000002829 reductive effect Effects 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 15
- 230000031700 light absorption Effects 0.000 claims description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 32
- 238000005984 hydrogenation reaction Methods 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 235000013772 propylene glycol Nutrition 0.000 description 14
- 229960004063 propylene glycol Drugs 0.000 description 12
- 229910052681 coesite Inorganic materials 0.000 description 10
- 229910052906 cristobalite Inorganic materials 0.000 description 10
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 10
- 229910052682 stishovite Inorganic materials 0.000 description 10
- 229910052905 tridymite Inorganic materials 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 238000005034 decoration Methods 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229940116333 ethyl lactate Drugs 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 3
- -1 alkyl oxalates Chemical class 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229940057867 methyl lactate Drugs 0.000 description 3
- 150000002895 organic esters Chemical class 0.000 description 3
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 150000000180 1,2-diols Chemical class 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- IUOVJOAPNLRTRK-UHFFFAOYSA-N [Si].OOO Chemical class [Si].OOO IUOVJOAPNLRTRK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- 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
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to processes for the production of diols with high yield and selectivity by hydrogenation of hydroxycarboxylic acid esters in gas phase over copper containing catalysts.
- the present invention relates to a process for the production of ethylene and propylene glycols.
- the ethylene and propylene glycols are used in a wide variety of applications such as monomers in polyester resins; in antifreeze and de-icing fluids; in the manufacture of food, drugs and cosmetic products; and in liquid detergents.
- commercial production of glycols is petroleum-based and involves hydrolysis of alkylene oxides at high pressure and high temperature.
- the price of the resulting 1,2-diols depends on the price of oil and other hydrocarbon.
- the new method is required for production glycols from renewable resources such as plants.
- the present invention relates to processes for the low-cost production of glycols from esters of hydroxycarboxylic acids under relatively mild conditions with high conversion of esters, selectivity to glycols and glycol yield.
- the present invention provides a catalyst for conversion of hydroxycarboxylic acid esters to 1,2-propanediol, which contains the phase of hydroxysilicate of copper with chrysocolla structure or reduced copper hydroxysilicate.
- the present invention provides also a process for the production of glycols, which comprises a stage of contacting a mixture of esters of hydroxycarboxylic acid and hydrogen in gas phase with the catalyst, which contains the copper hydroxysilicate or reduced copper hydroxysilicate.
- the said copper hydroxysilicate (CuH) 4 Si 4 0io(OH)8 nH 2 0 can be prepared by deposition precipitation method using highly dispersed silica, aqueous soluble copper salt and urea as the raw materials.
- the said copper hydroxysilicate can also be got from natural deposits of chrysocolla mineral, however in this case mineral admixtures can worsen the catalyst selectivity and/or activity.
- the said copper hydrosilicate can be prepared also by hydrothermal treatment.
- the structure of chrysocolla is discriminated from other copper-containing oxides and oxyhydroxides by FTIR method, showing four bands at ca.
- Reduced copper hydroxysilicate can be prepared by treating of copper hydrosilicate with the gas, which contains hydrogen, CO or another reducing agent at elevated temperatures from 100 to 500°C.
- the reduced copper hydroxysilicate comprises metallic copper nanoparticles decorated with amorphous silicon oxyhydroxide clusters. This system differs a lot from the system "metallic copper particles supported by silica” by its physical, spectral, catalytic and adsorptive properties (including its catalytic activity and selectivity in hydroxycarboxylic acid esters hydro genation).
- the decoration of metallic copper particles can be unambigously monitored by UV-Vis spectroscopy, since decorated metallic copper particles have much lower energy of surface plasmon resonance (below 16500 cm “1 , while 17000-18000 cm “1 is observed for the supported Cu/Si0 2 having no decoration by the support [see e.g. E. Cattaruzza, G. Battaglin, P. Canton, T. Finotto and C. Sada, Mater.Sci. and Eng.: C, 26(5-7) (2006) 1092-1096]. Lowering in energy of surface plasmon resonance energy is caused by changes in the properties of the metallic copper nanoparticle surface due to decoration of the said particles by Si-oxyhydroxide shell, having high dielectric constant.
- the reduction of the hydroxysilicate of copper within the catalyst may be performed after loading the catalyst in the reactor by contacting the catalyst with hydrogen of the hydrogen- containing gas mixture at elevated temperatures, including contacting the catalyst with the mixture of hydrogen and hydro xycarboxylic acid esters.
- the catalyst may contain other constituents, which improve its rheological properties, pore structure or mechanical strength, like graphite, zinc oxide etc.
- the content of copper in the catalyst should be more than 10 % wt. It is also preferable that the catalyst doesn't contain other copper-containing oxyhydroxide or oxide compounds, except copper hydroxysilicate, since it may worsen the selectivity of the catalyst. However, minor impurities of such oxides may be present in the catalyst composition and don't affect the catalytic properties significantly.
- the catalytic properties of the said catalyst in hydrogenation of hydro xycarboxylic acid esters are significantly advantageous with respect to the known supported Cu/Si0 2 catalysts or with respect the catalysts obtained by the reduction of the copper-containing oxide mixtures (e.g. CuO and ZnO mixture) as it is illustrated by the Examples below.
- the copper-containing oxide mixtures e.g. CuO and ZnO mixture
- esters of aliphatic alcohols and lactic and glycolic acids were used as esters of hydroxycarboxylic acid resulting in formation of propylene and ethylene glycols correspondingly.
- the catalyst was prepared by reductive thermal treatment of a stoichiometric copper hyroxysilicate with Cu:Si ratio of 1 :2 at. with chrysocolla structure under flow of hydrogen and temperature 300°C during 1 hour.
- the chrysocolla structure of the catalyst before reduction is proved by the presence of bands at 480, 670, 1035 and 3624 cm “1
- catalyst doesn't contain phases of Cu nitrate, CuO, Cu 2 0 phases, as it is proved by XRD.
- the catalyst is characterized by the resonant absorption of light at 14600 cm "1 , which shows high extent of decoration of metallic copper particles.
- Liquid butyl lactate (a flow rate 0.5 ml/min) evaporated and mixed with a stream of hydrogen (a flow rate 300 ml/min).
- the gaseous mixture of hydrogen and butyl lactate fed into a tubular quartz reactor packed with 5 g of a catalyst (Table 1, Catalyst number 1). Temperature in the reactor was maintained at about 190 ⁇ 2°C. The pressure - 10 bar. Process was carried out within 24 hours. Mole ration of butyl lactate : hydrogen was 1 : 3.97.
- the vaporous mixture exiting the reactor was passed through a water cooled condenser and then through a second refrigerated condenser through which coolant at 0°C was passed.
- the resulting condensate was analyzed.
- the condensate has the following composition, %wt : butyl lactate - 28.5; propylene glycol - 33.9; butanol - 34.9; l-hydroxy-2-propanone - 1.9; unidentified by-products - 0.8.
- the conversion of butyl lactate was 71.5 %mol, selectivity to propylene glycol was 91.3 %mol.
- the propylene glycol yield (g glycol/g catalyst/hour) was 2.01.
- the catalyst was prepared similarly to Example 1 , but the Cu:Si atomic ratio in the catalyst was 1 :8.
- the catalyst before reduction contains hydro xysilicate with chrysocolla structure which is proved by the presence of bands at 470, 668, 1040 and 3620 cm “1 , catalyst doesn't contain phases of Cu nitrate, CuO, Cu 2 0 phases, as it is proved by XRD, some poorly- crystallized Si0 2 is present in the sample, as follows from XRD and FT-IR data.
- the catalyst is characterized by the resonant absorption of light at 14300 cm "1 , which shows high extent of decoration of metallic copper particles.
- the catalyst was prepared by the incipient wetness impregnation of highly dispersed silica (aerosil A- 180) with copper nitrate, as it is proposed by R.D. Cortright, M. Sanchez-Castillo, J. A. Dumesic in [Applied Catalysis B : Environmental 39 (2002) 353-359]. After the reductive treatment the catalyst contains 10 % wt. of metallic copper and Si0 2 . The surface plasmon resonance absorption by the reduced catalyst is registered at 17200 cm "1 , which shows the typical supported metallic copper over silica with low extent of copper decoration. Processes of hydrogenation were performed similarly to the examples 7 and 9.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to processes for the low-cost production of glycols from esters of hydroxycarboxylic acids. The esters of hydroxycarboxylic acids and hydrogen in gas phase are contacted with the catalyst which contains hydroxysilicate of copper or reduced hydroxysilicate of copper. The reduced hydrosilicate of copper contains metallic copper nanoparticles decorated by amorphous oxyhydroxide of silicon. Such decorated copper nanoparticles have advantageous activity and selectivity in catalytic hydrogenation of hydroxycarboxylic acid esters to glycols.
Description
The catalyst and method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols
BACKGROUND OF THE INVENTION Field of the Invention
The present invention relates to processes for the production of diols with high yield and selectivity by hydrogenation of hydroxycarboxylic acid esters in gas phase over copper containing catalysts. In particular, the present invention relates to a process for the production of ethylene and propylene glycols.
Description of Related Art
The ethylene and propylene glycols are used in a wide variety of applications such as monomers in polyester resins; in antifreeze and de-icing fluids; in the manufacture of food, drugs and cosmetic products; and in liquid detergents. At present, commercial production of glycols is petroleum-based and involves hydrolysis of alkylene oxides at high pressure and high temperature.
Since this process starts with ethylene and propylene, the price of the resulting 1,2-diols depends on the price of oil and other hydrocarbon. The new method is required for production glycols from renewable resources such as plants.
It is well known that plants produce carbohydrates from atmospheric carbon dioxide and sunlight in the process of photosynthesis. Furthermore, as carbon dioxide is a greenhouse gas, so any additional removal of the gas from the atmosphere helps to offset the increase in this gas by industrial emissions. The method based on hydroxycarboxylic acids obtained by fermentation of crude biomass is promising way for glycols production (WO 2000030744, US 6455742, US 6479713).
It is known that liquid-phase hydrogenation of carboxyl groups occurs under high hydrogen pressure. To perform the hydrogenation process under milder conditions carboxylic acids are usually converted into more readily reducible esters. Various patents and articles disclose the reduction of hydroxycarboxylic acid esters. For example, the hydrogenation of organic esters to alcohols and glycols in a liquid phase was reported by Adkins and co-workers who were able to achieve 80% yields of propylene glycol from methyl lactate over copper/chromium oxide and Raney nickel catalysts at temperature from 150 to 250 °C and extremely high hydrogen pressures from 20 to 30 MPa (Bowden and Adkins, J. Am. Chem. Soc. 56: 689 (1934); Adkins and Billica, J. Am. Chem. Soc. 70: 3118 (1948); Adkins and Billica, J. Am. Chem Soc. 70: 3121 (1948)).
In addition to high pressure high catalyst loading is necessary to achieve these relatively high yields. Broadbent et al. (J. Org. Chem. 24: 1847 (1959)) was able to obtain propylene glycol from ethyl lactate over rhenium black catalysts with yield as high as 80% at 150°C but at very high hydrogen pressure of about 25 MPa.
The hydrogenation of organic esters to glycols in a liquid phase was reported by Luo and coworkers who have achieved 83% yield of propylene glycol from ethyl lactate over Ru-Sn/γ- A1203 at 150D C and 5.5 MPa. (Luo, G., Yan, S., Qiao, M., Zhuang, J., Fan, K. Appl. Catal. A. 275: 95 (2004)).
The serious disadvantage of all mentioned above hydrogenation processes in liquid phase is necessity to use a high hydrogen pressure.
Carrying out the process of hydrogenation in a vapor phase allows lowering hydrogen pressure. For example, the hydrogenation of organic esters to alcohols and glycols in a vapor phase over the reduced mixture of copper and zinc oxides at 234°C, 1.6 MPa and LHSV=1.06 IT1 was reported by Bradley and co-workers (Pat. WO8203854, 1982 to Davy McKee Ltd.) who have achieved 97.7% selectivity to propylene glycol and 34.7 % conversion of ethyl lactate. The yield of propylene glycol is 0.038 g of propylene glycol /(ml of catalyst *h). Similar approach was claimed by the patent [GB2150860, 1983 to Davy McKee Ltd.] Reduced mixture of CuO and ZnO oxides was used for hydrogenation of carboxylic acid esters. Carbon dioxide is added to the gaseous mixture in the latter invention.
Copper containing catalysts attracted more efforts to find a process for production of 1,2- propanediol from biomass-derived stuff. R.D. Cortright, M. Sanchez-Castillo, J.A. Dumesic in [Applied Catalysis B: Environmental 39 (2002) 353-359] reported high selectivity and activity of Cu/Si02 impregnated catalyst, which comprises copper nitrate over silica surface. Authors achieved 88 % selectivity to 1,2-propanediol at 7 bar and 100 % conversion of lactic acid.
The invention [US Pat. 4628129; to Union Carbide Corporation, 1986] claims Cu/Si02 supported catalysts (prepared by impregnation method, as it follows from the text) to be useful for conversion of alkyl oxalates and alkyl glycolates to ethylene glycol.
Despite these efforts, a need for new methods of production of glycols remains that can be performed under relatively mild conditions and which results in high conversion of esters, selectivity to glycols and glycol yield.
Summary of the invention
The present invention relates to processes for the low-cost production of glycols from esters of hydroxycarboxylic acids under relatively mild conditions with high conversion of esters, selectivity to glycols and glycol yield. In particular, the present invention provides a catalyst for conversion of hydroxycarboxylic acid esters to 1,2-propanediol, which contains the phase of hydroxysilicate of copper with chrysocolla structure or reduced copper hydroxysilicate. The present invention provides also a process for the production of glycols, which comprises a stage of contacting a mixture of esters of hydroxycarboxylic acid and hydrogen in gas phase with the catalyst, which contains the copper hydroxysilicate or reduced copper hydroxysilicate.
The said copper hydroxysilicate (CuH)4Si40io(OH)8 nH20 can be prepared by deposition precipitation method using highly dispersed silica, aqueous soluble copper salt and urea as the raw materials. The said copper hydroxysilicate can also be got from natural deposits of chrysocolla mineral, however in this case mineral admixtures can worsen the catalyst selectivity and/or activity. The said copper hydrosilicate can be prepared also by hydrothermal treatment. The structure of chrysocolla is discriminated from other copper-containing oxides and oxyhydroxides by FTIR method, showing four bands at ca. 470, 670, 1040 and 3620 cm"1, which are only characteristic of this hydroxysilicate [T.M.Yurieva, G.N.Kustova, T.P. Minyukova, E.K. Poels, A. Bliek, M.P.Demeshkina, L.M.Plyasova, T.A.Kriger, V.I. Zaikovskii. Mater. Res. Innov., 5 (1) (2001) 3-11].
Reduced copper hydroxysilicate can be prepared by treating of copper hydrosilicate with the gas, which contains hydrogen, CO or another reducing agent at elevated temperatures from 100 to 500°C. The reduced copper hydroxysilicate comprises metallic copper nanoparticles decorated with amorphous silicon oxyhydroxide clusters. This system differs a lot from the system "metallic copper particles supported by silica" by its physical, spectral, catalytic and adsorptive properties (including its catalytic activity and selectivity in hydroxycarboxylic acid esters hydro genation). The decoration of metallic copper particles can be unambigously monitored by UV-Vis spectroscopy, since decorated metallic copper particles have much lower energy of surface plasmon resonance (below 16500 cm"1 , while 17000-18000 cm"1 is observed for the supported Cu/Si02 having no decoration by the support [see e.g. E. Cattaruzza, G. Battaglin, P. Canton, T. Finotto and C. Sada, Mater.Sci. and Eng.: C, 26(5-7) (2006) 1092-1096]. Lowering in energy of surface plasmon resonance energy is caused by changes in the properties of the metallic copper nanoparticle surface due to decoration of the said particles by Si-oxyhydroxide shell, having high dielectric constant. Examples of the
impact of Cu nanoparticles decoration by an oxide shell on their optical properties are reported in literature (see e.g. data for Cu-ZnO system [A.A. Khassin, S.F. Ruzankin, V.F. Anufrienko, A.A. Altynnikov, T.V. Larina, J.C. van den Heuvel, T.M. Yurieva and V.N. Parmon. Doklady Phys. Chem. 409 (1) (2006) 193-197.] and for Cu-Cu20 [T Ghodselahi, M A Vesaghi and A Shafiekhani, J. Phys. D: Appl. Phys. 42 (2009) 015308]).
The reduction of the hydroxysilicate of copper within the catalyst may be performed after loading the catalyst in the reactor by contacting the catalyst with hydrogen of the hydrogen- containing gas mixture at elevated temperatures, including contacting the catalyst with the mixture of hydrogen and hydro xycarboxylic acid esters.
The catalyst may contain other constituents, which improve its rheological properties, pore structure or mechanical strength, like graphite, zinc oxide etc. Preferably, the content of copper in the catalyst should be more than 10 % wt. It is also preferable that the catalyst doesn't contain other copper-containing oxyhydroxide or oxide compounds, except copper hydroxysilicate, since it may worsen the selectivity of the catalyst. However, minor impurities of such oxides may be present in the catalyst composition and don't affect the catalytic properties significantly.
The catalytic properties of the said catalyst in hydrogenation of hydro xycarboxylic acid esters are significantly advantageous with respect to the known supported Cu/Si02 catalysts or with respect the catalysts obtained by the reduction of the copper-containing oxide mixtures (e.g. CuO and ZnO mixture) as it is illustrated by the Examples below.
For the illustration of the method, the esters of aliphatic alcohols and lactic and glycolic acids were used as esters of hydroxycarboxylic acid resulting in formation of propylene and ethylene glycols correspondingly.
Examples
Three catalysts were prepared: two according to the present invention and one according to [R.D. Cortright, M. Sanchez-Castillo, J.A. Dumesic Applied Catalysis B: Environmental 39 (2002) 353-359] as a comparative. The data on these samples are summarized in Table 1.
Example 1
The catalyst was prepared by reductive thermal treatment of a stoichiometric copper hyroxysilicate with Cu:Si ratio of 1 :2 at. with chrysocolla structure under flow of hydrogen and temperature 300°C during 1 hour. The chrysocolla structure of the catalyst before reduction is proved by the presence of bands at 480, 670, 1035 and 3624 cm"1, catalyst doesn't contain phases of Cu nitrate, CuO, Cu20 phases, as it is proved by XRD. After the
reduction the catalyst is characterized by the resonant absorption of light at 14600 cm"1, which shows high extent of decoration of metallic copper particles.
Liquid butyl lactate (a flow rate 0.5 ml/min) evaporated and mixed with a stream of hydrogen (a flow rate 300 ml/min). The gaseous mixture of hydrogen and butyl lactate fed into a tubular quartz reactor packed with 5 g of a catalyst (Table 1, Catalyst number 1). Temperature in the reactor was maintained at about 190±2°C. The pressure - 10 bar. Process was carried out within 24 hours. Mole ration of butyl lactate : hydrogen was 1 : 3.97.
The vaporous mixture exiting the reactor was passed through a water cooled condenser and then through a second refrigerated condenser through which coolant at 0°C was passed. The resulting condensate was analyzed. The condensate has the following composition, %wt : butyl lactate - 28.5; propylene glycol - 33.9; butanol - 34.9; l-hydroxy-2-propanone - 1.9; unidentified by-products - 0.8. The conversion of butyl lactate was 71.5 %mol, selectivity to propylene glycol was 91.3 %mol. The propylene glycol yield (g glycol/g catalyst/hour) was 2.01.
Examples 2-12
Processes of hydrogenation were repeated similarly to an example 1, but under various conditions.
Conditions and results of hydrogenation butyl lactate are shown in Table 2. Examples 13-15 Processes of hydrogenation were performed similarly to an example 1, but methyl lactate was used as ester of hydro xycarboxylic acid.
Conditions and results of hydrogenation of methyl lactate under various conditions are shown in Table 2.
Examples 16-18 Processes of hydrogenation were performed similarly to an example 1, but ethyl lactate was used as ester of hydro xycarboxylic acid.
Conditions and results of hydrogenation ethyl lactate under various conditions are shown in Table 2.
Examples 19-20
Processes of hydro genation were performed similarly to an example 1, but methyl glycolate was used as ester of hydro xycarboxylic acid.
Conditions and results of hydrogenation methyl glycolate to ethylene glycol under various conditions are shown in Table 2.
Examples 21-22 (low copper content)
The catalyst was prepared similarly to Example 1 , but the Cu:Si atomic ratio in the catalyst was 1 :8. The catalyst before reduction contains hydro xysilicate with chrysocolla structure which is proved by the presence of bands at 470, 668, 1040 and 3620 cm"1, catalyst doesn't contain phases of Cu nitrate, CuO, Cu20 phases, as it is proved by XRD, some poorly- crystallized Si02 is present in the sample, as follows from XRD and FT-IR data. After the reduction the catalyst is characterized by the resonant absorption of light at 14300 cm"1, which shows high extent of decoration of metallic copper particles.
Processes of hydrogenation were performed similarly to the examples 7 and 9, but with lower content of copper in the catalyst as described above.
Examples 23-24 (comparative)
The catalyst was prepared by the incipient wetness impregnation of highly dispersed silica (aerosil A- 180) with copper nitrate, as it is proposed by R.D. Cortright, M. Sanchez-Castillo, J. A. Dumesic in [Applied Catalysis B : Environmental 39 (2002) 353-359]. After the reductive treatment the catalyst contains 10 % wt. of metallic copper and Si02. The surface plasmon resonance absorption by the reduced catalyst is registered at 17200 cm"1, which shows the typical supported metallic copper over silica with low extent of copper decoration. Processes of hydrogenation were performed similarly to the examples 7 and 9.
Conditions and results of hydrogenation methyl glycolate to ethylene glycol under various conditions are summarized in Table 2. It can be seen from the data that the proposed by this invention copper hydroxysilicate catalyst is advantageous with respect to the supported Cu/Si02 catalyst, having no decoration of the metallic copper.
Table 1. The characteristics of the catalysts
Surface Plasmon
Cu:Si
Phase composition of the resonance band Phase composition of at.
catalyst catalyst maximum for the the reduced catalyst ratio
reduced catalyst
Cuu decorated by
Copper hydrosilicate
1 1 14600 cm"1 amorphous
(CuH)4Si40io(OH)8 nH20
hydroxyoxide of
silicon
Cu° decorated by
Copper hydrosilicate l amorphous (CuH)4Si40io(OH)8 nH20 0.14 14300 cm" hydroxyoxide of and Si02 silicon and
amorphous silica
Cu(N03)2 and Si02 0.1 17200 cm"1 Cu° and Si02
Table 1. Conditions and results of hydro genation of esters of hydro xycarboxylic acids.
Claims
1. A catalyst for catalytic hydrogenation of esters of hydroxycarboxylic acids to glycols, wherein the catalyst contains hydroxysilicate of copper.
2. The catalyst according to claim 1, wherein the catalyst contains 10-55 % wt. of copper.
3. The catalyst for catalytic hydrogenation of esters of hydroxycarboxylic acids to glycols, wherein the catalyst contains the reduced hydroxysilicate of copper and its UV-Vis spectrum contains light absorption band having maximum in the range from 11000 to 16000 cm"1.
4. The catalyst according to claim 3, wherein the catalyst contains 10-55 % wt. of copper.
5. A method for preparation of catalyst according to claim 3, wherein the catalyst is prepared by treatment of the composition, which contains hydroxysilicate of copper, with the hydrogen-containing gas mixture.
6. The method of catalytic hydrogenation of esters of hydroxycarboxylic acids to glycols, which comprises contacting the mixture containing ester of hydroxycarboxylic acid and hydrogen in gas phase with the catalyst wherein the catalyst used is the catalyst according to claims 1-4.
7. The method according to claim 6, wherein the processes is carried out at pressure from 1 to 15 bar and temperature between 140 and 220 °C.
8. The method according to claim 6, wherein the processes is carried out at temperature between 180 and 200 °C.
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| EP10765981A EP2480329A2 (en) | 2009-09-22 | 2010-09-22 | The catalyst and method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols |
| EA201200528A EA021350B1 (en) | 2009-09-22 | 2010-09-22 | Method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols |
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| EEP200900073 | 2009-09-22 | ||
| EEP200900073A EE200900073A (en) | 2009-09-22 | 2009-09-22 | Catalyst and Method for the Catalytic Hydrogenation of Carboxylic Acid Esters to Gl Schools |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013010618A1 (en) | 2011-07-20 | 2013-01-24 | Thyssenkrupp Uhde Gmbh | Production of optically pure propane-1,2-diol |
| WO2018073581A1 (en) * | 2016-10-19 | 2018-04-26 | Johnson Matthey Davy Technologies Limited | Process |
| CN112517017A (en) * | 2020-11-30 | 2021-03-19 | 陕西延长石油（集团）有限责任公司 | Methyl acetate hydrogenation doped copper silicate nanotube catalyst, and preparation method and application thereof |
| CN116459846A (en) * | 2023-05-09 | 2023-07-21 | 中国科学院兰州化学物理研究所 | Hydroxy ester hydrogenation nano Cu-based catalyst and preparation method and application thereof |
Families Citing this family (1)
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| RU2734237C1 (en) * | 2020-01-27 | 2020-10-13 | Андрей Владиславович Курочкин | Apparatus for complex gas treatment by low-temperature condensation |
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- 2010-09-22 EA EA201200528A patent/EA021350B1/en not_active IP Right Cessation
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| WO2013010618A1 (en) | 2011-07-20 | 2013-01-24 | Thyssenkrupp Uhde Gmbh | Production of optically pure propane-1,2-diol |
| DE102011107959A1 (en) | 2011-07-20 | 2013-01-24 | Thyssenkrupp Uhde Gmbh | Preparation of optically pure propane-1,2-diol |
| WO2018073581A1 (en) * | 2016-10-19 | 2018-04-26 | Johnson Matthey Davy Technologies Limited | Process |
| GB2565378A (en) * | 2016-10-19 | 2019-02-13 | Johnson Matthey Davy Technologies Ltd | Process |
| KR20190072576A (en) * | 2016-10-19 | 2019-06-25 | 존슨 매티 데이비 테크놀로지스 리미티드 | Way |
| US10532967B2 (en) | 2016-10-19 | 2020-01-14 | Johnson Matthey Davy Technologies Limited | Process for the production of propylene glycol from lactate ester |
| KR102587537B1 (en) | 2016-10-19 | 2023-10-11 | 존슨 매티 데이비 테크놀로지스 리미티드 | Process for producing propylene glycol from lactate ester |
| CN112517017A (en) * | 2020-11-30 | 2021-03-19 | 陕西延长石油（集团）有限责任公司 | Methyl acetate hydrogenation doped copper silicate nanotube catalyst, and preparation method and application thereof |
| CN112517017B (en) * | 2020-11-30 | 2023-05-05 | 陕西延长石油（集团）有限责任公司 | Doped copper silicate nanotube catalyst for methyl acetate hydrogenation and preparation method and application thereof |
| CN116459846A (en) * | 2023-05-09 | 2023-07-21 | 中国科学院兰州化学物理研究所 | Hydroxy ester hydrogenation nano Cu-based catalyst and preparation method and application thereof |
| CN116459846B (en) * | 2023-05-09 | 2024-03-26 | 中国科学院兰州化学物理研究所 | Hydroxy ester hydrogenation nano Cu-based catalyst and preparation method and application thereof |
Also Published As
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| WO2011036189A3 (en) | 2012-02-23 |
| EP2480329A2 (en) | 2012-08-01 |
| EA021350B1 (en) | 2015-05-29 |
| EA201200528A1 (en) | 2012-09-28 |
| EE200900073A (en) | 2011-06-15 |
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