GB2360770A - Preparation of pentenoic acids - Google Patents
Preparation of pentenoic acids Download PDFInfo
- Publication number
- GB2360770A GB2360770A GB0007676A GB0007676A GB2360770A GB 2360770 A GB2360770 A GB 2360770A GB 0007676 A GB0007676 A GB 0007676A GB 0007676 A GB0007676 A GB 0007676A GB 2360770 A GB2360770 A GB 2360770A
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- GB
- United Kingdom
- Prior art keywords
- ester
- formylvaleric
- pentenoic
- catalyst
- noble metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- YIYBQIKDCADOSF-UHFFFAOYSA-N pentenoic acid group Chemical class C(C=CCC)(=O)O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 title description 6
- 150000002148 esters Chemical class 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 14
- -1 pentenoic ester Chemical class 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- KHJXZEQLODIMJX-UHFFFAOYSA-N methyl 3-formylpentanoate Chemical compound CCC(C=O)CC(=O)OC KHJXZEQLODIMJX-UHFFFAOYSA-N 0.000 claims description 2
- BNMZOZSVBKIOIW-UHFFFAOYSA-N methyl 4-methyl-5-oxopentanoate Chemical compound COC(=O)CCC(C)C=O BNMZOZSVBKIOIW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 229910052790 beryllium Inorganic materials 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011973 solid acid Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- KKQKUWIVJQYGCW-UHFFFAOYSA-N methyl 2-formylpentanoate Chemical compound CCCC(C=O)C(=O)OC KKQKUWIVJQYGCW-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- VEFDLKXOSOFUIN-UHFFFAOYSA-N 5-hydroxy-4-pentenoic acid d-lactone Chemical class O=C1CCC=CO1 VEFDLKXOSOFUIN-UHFFFAOYSA-N 0.000 description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 101100150182 Bacillus subtilis (strain 168) spsK gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000156303 Leek yellow stripe virus Species 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HBYOLNPZXLHVQA-UHFFFAOYSA-J dicalcium dicarbonate Chemical compound [Ca+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HBYOLNPZXLHVQA-UHFFFAOYSA-J 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005755 formation reaction 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
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
A process for preparing a pentenoic ester, heating a 3-, or 4-formylvaleric ester or mixtures thereof at 50{C to 400{C in the presence of a supported noble metal catalyst. The noble metal catalyst is supported on a mixed oxide (M<SP>1</SP>)<SB>a</SB>(M<SP>2</SP>)<SB>b</SB>(M<SP>3</SP>)<SB>c</SB>P<SB>d</SB>Al<SB>e</SB>SiO<SB>x</SB>, wherein M<SP>1</SP> is an alkali metal, M<SP>2</SP> is an alkaline earth metal, M<SP>3</SP> is a Group IVB metal, a=0.5 1.5, b=0.2 0.8, c=0.2 0.8, d=2 8, e=3 10, and x is the stoichiometric value. By means of the specific supported catalyst of the present invention, the selectivity of the 3- and 4-pentenoic esters can be increased and that of the 2-pentenoic ester can be greatly decreased.
Description
PROCESS FOR PREPARING PENTENOIC ESTERS BACKGROUND OF THE INVENTION 1. Field of the Invention: The present invention relates to a process for preparing a pentenoic ester, and more particularly to a process for preparing a pentenoic ester by using a 3- and 4-formylvaleric ester as the starting material in the presence of a specific mixed oxide-supported noble metal as the catalyst.
2. Description of the Prior Art: The conventional process for synthesizing caprolactam involves first reacting butadiene, carbon monoxide, and an alcohol to form a pentenoic acid, which is hydroformylated to form a formylvaleric ester. Then, the formylvaleric ester is reacted to form a 6- aminocaproate by amination, which is then cyclized to form caorolactam.
In the above process, when the pentenoic ester is hydroformylated, three kinds of isomers, including 3-, 4 , and 5-formylvaleric esters, are formed. However, only 5-formylvaleric esters can be reacted to form 6- aminocaproates., and thus 15-20% of the formations are undesirable byproducts, including 3- and 4-formylvaleric esters. Many attempts have been proposed to turn 3- and 4-formylvaleric esters back to pentenoic esters via dehydrocarbonylation, which can be used to prepare caprolactam, thus saving the cost of the raw material. 3- and 4-formylvaleric esters can be reacted to three kinds of isomers including 2-, 3-, and 4-pentenoic esters via dehydrocarbonylation. 3- and 4-pentenoic esters can be effectively reacted to 5-formylvaleric esters via hydroformylation, which can further be reacted to caprolactam. However, 2-pentenoic esters are very difficult to hydroformylate and are reacted to peroxides with oxygen. The result is that the hydroformylation catalyst loses its activity. Therefore, it is very important to decrease the selectivity of 2-pentenoic esters and increase the selectivity of 3- and 4-pentenoic esters.
Theoretically, when an aldehyde is reacted to an olefin, a Group VIII noble metal such as Pd (palladium), Pt (platinum), and Rh (rhodium) can be used as the catalyst.
J. Amer. Chem. Soc. 90 (1968), 94-98 discloses that n-decanal (an a.ldehyde) can be converted in the presence of palladium or platinum supported on active carbon to give olefins via dehydrocarbonylation. In addition, J. Amer. Chem. Soc. 90 (1968), 99-107 discloses that n- heptanal can be converted in the presence of rhodium complexes to give hexane by dehydrocarbonylation.
U.S. Patent No. 4,517,400 describes that when palladium, platinum, or rhodium is present, the straight- chain aldehydes can be cleaved to give olefins, while the branched aldehydes show virtually no reaction.
German Patent No. 1,917,244 describes a process for dehydrocarbonylating isobutyraldehyde using rhodium containing alumina as a catalyst at 280 C to 330 C_ European Patent Application No. 81,090 describes that formylvaleric esters, if heated to 150 C to 600 C, undergo cyclization to 3,4-dihydro-2-pyrones.
In U.S. Patent Nos. 4,879,405 and 4,879, 406, 3- and 4-formylvaleric esters can be converted in the presence of a Group VIII noble metal as a catalyst at 50 C to 400 C to give pentenoic esters via dehydrocarbonylation. However, the total selectivity of the 2-pentenoic ester and valeric ester is higher than 20%, and the total yield of the 3- and 4-pentenoic esters is lower than 80%.
SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the above-mentioned problems and to provide a process for preparing a pentenoic ester by converting' 3- and 4-formylvaleric esters. The yield of the pentenoic ester is higher than 85%, the selectivity of the 3- and 4-pentenoic esters is higher than 85%, and the selectivity of the 2-pantenoic ester can be greatly decreased.
To achieve the above-mentioned object, the process for preparing a pentenoic ester of the present invention includes heating a 3-, 4-formylvaleric ester or mixtures thereof at 50 C to 400 C in the presence of a supported noble metal catalyst.
One aspect of the present invention is that the noble metal catalyst is supported on a mixed oxide (M1) a (M2) b (M3) CP@Al@SiOx, wherein M1 is an alkali metal, M2 is an alkaline earth metal, M3 is a Group IV8 metal, a=0.5~1.5, b=0.2~0.8, c=0.2~0.8, d=2~8, e=3~10, and x is the stoichiometric value. In the above-mentioned mixed oxide, M1 can be Li, Na, or K, M2 can be Se, Mg, or Ca, M' can be Ti, Zr, or Hf. Preferably, a=0.7-1.3, b=0.4-0.7, c=0.4-0.7, d=4-7, and e=4-8.
Preferably, the noble metal catalyst used in the present invention contains a Group VIIIB metal, such as Pd (palladium), Pt (platinum), Rh (rhodium) or Ru (ruthenium).
DETAILED DESCRIPTION OF THE INVENTION According to the present invention, the specific supported noble metal catalyst includes the noble metal catalyst itself and the mixed oxide (M') a (M2)b (M3) cPdAleSiOx as the support, which has two functions of dehydrocarbonylation and isomierization. In the presence of such a supported catalyst, 3- and 4-formylvaleric esters can undergo dehydrocarbonylation on the noble metal to give 2-, 3-, and 4-pentenoic esters. Then, the 2-pentenoic ester can be converted via isomerization on the mixed oxide support into 3- and 4-pentenoic esters. In this manner, the selectivity of the 2-pentenoic ester can be decreased. In addition, cyclization to 3,4- dihydro-2-pyrones from formylvaleric esters can be inhibited by means of the mixed oxide. Therefore, the mixed oxide can serve as a catalyst and has the properties of acid and base, which belongs to a solid acid/base catalyst.
The noble metal catalyst can be supported on the (M1) a (M2) b (M3) cPdAleSiOx mixed oxide by ionic exchange, impregnation, or mechanical mixing. The noble metal catalyst to be supported can be in an amount of 0.01 to 10 wt%, preferably 0.1 to 5 wt%, based on the total weight of the noble metal catalyst and the mixed oxide support.
According to the present invention, the starting materials can be a 3-formylvaleric ester, 4-formylvaleric ester, or mixtures thereof. The starting materials are heated to a temperature of 50 C to 400 C, preferably to 100 C to 250 C, in the presence of the above -mentioned supported noble metal catalyst. In this way, the starting materials can be converted to a pentenoic ester via dehydrocarbonylation. The 3- and 4-formylvaleric esters can be independently an ester of alkyl, preferably an ester of alkyl having from 1 to 3 carbon atoms. Examples of alkyl are methyl, ethyl, propyl and isopropyl. Representative examples of the 3- and 4- formylvaleric esters include methyl 3-formylvalerate and methyl 4-formylvalerate.
The above-mentioned dehydrocarbonylation is preferably conducted in the presence of an oxygen- containing gas, such as air or oxygen. For example, 10 40% (in volume) of oxygen, which is diluted with an inert gas, can be introduced into the reactants. The inert gas can be nitrogen, carbon dioxide, helium, or argon.
Moreover, in order to minimize excess oxidation and byproduct generation, 0.01-10 wt% of water, based on the total weight of the formylvaleric esters, is preferably added to the starting materials. In addition, in order to avoid hydrolyzation of the formylvaleric esters 'and the pentenoic esters, alcohols, such as methanol, ethanol, butanol, or cyclohexanol, are preferably added to the starting materials. The alcohol is preferably in an amount of 30-90 wt% based on the total weight of the formylvaleric esters.
The liquid hour space velocity (LHSV) of the formylvaleric esters can be in a range of 0.1 to 10 hr-1, preferably 0.5 to 5 hr-1.
The conversion and selectivity mentioned in the present invention are calculated according to the following formulae, in which FV indicates formylvaleric ester and PTE indicates pentenoic ester:
conversion (mole%) = <U>FV weight in the feedstock - FV weight in the product</U> X100% FV weight in the feedstock selectivity (rnofe% ) = <U>PTE weight in the product -x molecular weight of F</U>V <U>I mo</U>l<U>ecular</U> w<U>eight of PTE</U> <U>- --</U> x100% mole of FV in the feedstock - mole of FV in the product yield (mole/ ) - -<U>PTE weight in the product x molecular weight o FV l molecular weight of PTE</U> <U>-- - - --</U> x1 00% mole of FV in the feedstock The following examples are intended to illustrate the process and the advantages of the present invention more fully without limiting its scope, since numerous modifications and variations will be apparent to those skilled in the art.
Example 1 130 g of aluminum hydroxide (Al(OH)3), 1-7.5 g of calcium carbonate calcium carbonate (CaC)3), and 500 ml of deionized were mixed. 14 g of titania (TiO2, titanium dioxide) was added slowly to the mixture under reflux at 100 C to form a solution A.
20 g of silica (S'02) was added to 120 ml of de-ionized water and then 20 g of potassium hydroxide (KOH) was added. The mixture was stirred and heated to form a solution B.
The solution B was added to the solution A under reflux at 100 C. Then, 230 g of 85% H3204 solution was added at a rate of 18.3 g/min and the mixture was stirred at 100 C for 8 hours. The solution was concentrated at 100 C to give a sticky white product, which was then dried in an oven at 120 C to give a solid white product. The solid white product was then cracked to form particles with a size of 30-40 mesh. Thus, a solid acid/base catalyst A15Si1Cao.5Tio.5P6K10x was obtained.
20 of the obtained solid acid/base catalyst and 30 ml of 0.05 M Pd (NH3),C12 solution (pH=10) were stirred for 1 hour. Then, the solution dried under reduced pressure, and calcined in the presence of air at 500 C for 6 hours to give a pale yellow solid, that is, 1wt%Pd/A15Si1Cao.5Tio.5P6K10x, which can serve as a dehydrocarbonylation catalyst with selectivity.
7 ml of the obtained dehydrocarbonylation catalyst was placed in a 3/8" stainless steel tube to form, a fixed bed reactor. Methyl formylvalerate, methanol, and water (33/57/10 in weight ratio) were mixed with the air and then charged from the upper portion of the reactor to the reactor at a liquid hour space velocity (hHSV) of 1 hr-1- The fixed bed was controlled at 180 C and the reactor was maintained at atmospheric pressure. After the reaction was completed, the reaction product was allowed to flow out from the reactor, cooled, and collected. The liquid product was analyzed by gas chromatography and the results are shown in Table 1.
Table 1 Reaction temperature ( C) 180 Feedstock composition (wt%) Formylvaleric ester 33 Methanol 57 Water 10 Molar ratio of 2.5 oxygen/formylvaleric ester Conversion of 92.55 formylvaleric ester (%) Selectivity of 80.81 pentenoic ester (%) Example <U>2</U> 78 g of aluminum hydroxide, 19.8 g of magnesium nitrate (Mg(N03)2), and 500 ml of deionized were mixed. 16 g of titanic was added slowly to the mixture under reflux at 100 C to form a solution A.
20 g of silica was added to 120 ml of deionized water and then 20 g of potassium hydroxide was added. The mixture was stirred and heated to form a solution B.
The solution B was added to the solution A under reflux at 100 C. Then, 192 g of 85% H3P04 solution was added at a rate of 18.3 g/min and the mixture was stirred at 100 C for 8 hours. The solution was concentrated at 100 C to give a sticky white product, which was then dried in an oven at 120 C to give a solid white product. The solid white product was then cracked to form particles with a size of 30-40 mesh. Thus, a solid acid/base catalyst A13Si1Mgo.4Tio.spsK,Ox was obtained, 20 of the obtained solid acid/base catalyst and 30 ml of 0.05 M Pd (NH3),Cl2 solution (pH=10) were stirred for 1 hour. Then, the solution dried under reduced pressure, and calcined in the presence of air at 500 C for 6 hours to give a pale yellow solid, that is, 1wt%Pd/A13Si1Mga.,Tio.6P5KjOX, which can serve as a dehydrocarbonylation catalyst with selectivity.
ml of the obtained dehydrocarbonylation catalyst was placed in a 3/8" stainless steel tube to form a fixed bed reactor. Methyl formylvalerate, methanol, and water (33/57/10 in weight ratio) were mixed with the air and then charged from the upper portion of the reactor to the reactor at a liquid hour space velocity (LHSV) of 1 hr-1. The fixed bed was controlled at 180 C and the reactor was maintained at atmospheric pressure. After the reaction was completed, the reaction product was allowed to flow out from the reactor; cooled, and collected- The liquid product was analyzed by gas chromatography and the res?:lts are shown in Table 2.
Table 2 Reaction temperature ( C) 180 Feedstock composition (wt%) Formylvaleric ester 33 Methanol 57 Water 10 Molar ratio of 2.0 oxygen/formylvaleric ester Conversion of 90.76 formylvaleric ester (%) Selectivity of 85.40 pentenoic ester (%) Examples 3-7 The procedures for preparing the catalyst were employed as described in Example 1. ml of the obtained dehydrocarbonylation catalyst was placed in a 3/8" stainless steel tube to form a fixed bed reactor. Methyl formylvalerate, methanol, and water with various weight ratios were mixed with the air and then charged from the upper portion of the reactor to the reactor at various liquid hour space velocities (LYSV) . -the fixed bed was controlled at various temperature and the reactor was maintained at atmospheric pressure. After the reaction was completed, the reaction product was allowed to flow out from the reactor, cooled, and collected. The liquid product was analyzed by gas chromatography and the results are shown in Table 3.
Table 3 Example 3 4 5 6 7 Reaction Condition Temperature ( C) 140 160 180 180 180 Feedstock composition (wt%) FV 23 23 23 23 33 methanol 67 67 67 67 59 water 10 10 10 10 8 Molar ratio of oxygen/FV 4.8 4.8 3.2 2.4 1.7 Conversion of FV (%) 74.15 67.40 76.51 74.71 80.57 Selectivity of 64.62 38.60 77.94 85.13 F 92.24 pentenoic ester (%) FV = formylvaleric ester Example 8 The procedures for preparing the catalyst were employed as described in Example 1. 50 ml of the obtained dehydrocarbonylation catalyst was placed in a 1" stainless steel tube to form a fixed bed reactor. Methyl formylvalerate, methanol, and water (33/59/8 in weight ratio) were mixed with the air and then- charged from the upper portion of the reactor to the reactor at a liquid hour space velocity (LHSV) of 2 hr-1. The fixed bed was controlled at 180 C and the reactor was maintained at atmospheric pressure. After the reaction was completed, the reaction product was allowed to flow out from the reactor, cooled, and collected. The liquid product was analyzed by gas chromatography and the results are shown in Table 4.
Table 4 Reaction temperature ( C) 180 Feedstock Composition (wt%) formylvaleric ester 33 methanol <B>59</B> water g Molar ratio of 1.25 oxygen/formylvaleric ester Conversion of 90.43 formylvaleric ester (%) Selectivity of pentenoic ester (%) 98.95 4-pentenoic ester 42 3-pentenoic ester 46 2-pentenoic ester and others 12 From the above results, it can be seen that by means of the specific mixed oxide-supported noble metal as the catalyst according to the present invention, the formylvaleric ester has a high conversion, and the selectivity of the 3- and 4-pentenoic esters can be increased and that of the '2-pentenoic ester can be decreased to below 20$.
The foregoing description of the preferred embodiments of this invention has been presented for purposes of illustration and description. Obvious modifications or variations are possible in light of the above teaching. The embodiments were chosen and described to provide the best illustration of the principles of this invention and its practical application to thereby enable those skilled in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. A11 such modifications and variations are within the scope of the present invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled.
Claims (17)
- WHAT IS CLAIMED IS: 1 1. A process for preparing a pentenoic ester 2 comprising heating a 3-, 4-formylvaleric ester or 3 mixtures thereof at 50 C to 400 C in the presence of a 4 supported noble metal catalyst, 5 wherein the noble metal catalyst is supported on a 6 mixed oxide (M1)a(M2)b(M3)cPdA1cSiOx, wherein M' is an alkali 7 metal, M2 is an alkaline earth metal, M3 is a Group IVB e metal, a=0.5~1.5, b=0.2~0.8, c=0.2~0.8, d=2~8, e=3~10, 9 and x is the stoichiometric value. 1
- 2. The process as claimed in claim 1, wherein M2 is 2 Li, Na, or K. 1
- 3. The process as claimed in claim 1, wherein M2 is 2 Be, Mg, or Ca. 1
- 4. The process as claimed in claim 1, wherein M3 is 2 Ti, Zr, or Hf. 1
- 5. The process as claimed in claim 1, wherein 2 a=0.7~1.3, b=0.4~0.7, c=0.9~0.7, d=4~7, and e=4~8. 3 1
- 6. The process as claimed in claim 1, wherein the 2 noble metal catalyst contains a Group VIIIB metal. 1
- 7. The process as claimed in claim 6, wherein the 2 Group VIIIB metal is Pd, Pt, Rh, or Ru. 1
- 8. The process as claimed in claim 1, wherein the 2 noble metal catalyst is present in an amount of 0.01 to 3 10 wt% based on the total weight of the noble metal 4 catalyst and the mixed oxide. 1
- 9. The process as claimed in claim 8, wherein the 2 noble metal catalyst is present in an amount of 0.1 to 5 3 wt% based on the total weight of the noble metal catalyst 4 and the mixed oxide. 1
- 10. The process as claimed in claim 1, which is 2 conducted at 100 C to 250 C. 1
- 11. The process as claimed in claim 1, which is 2 conducted in the presence of an oxygen-containing gas. 1
- 12. The process as claimed in claim 11, which is 2 conducted in the presence of air. 1
- 13. The process as claimed in claim 11, which is 2 conducted in the presence of oxygen. 1
- 14. The process as claimed in claim 1, wherein the 2 3- and 4-formylvaleric esters are independently an ester 3 of alkyl having from l to 3 carbon atoms. 1
- 15. The process as claimed in claim 14, wherein 2 methyl 3-formylvalerate and/or methyl 4-formylvalerate 3 are used as the starting material. 1
- 16. The process as claimed in claim 1, wherein the 2 formylvaleric ester has an LHSV of 0.1 to 10 hr-l. 1
- 17. The process as claimed in claim 16, wherein the 2 formylvaleric ester has an LHSV of 0.5 to 5 hr-1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0007676A GB2360770B (en) | 1999-07-21 | 2000-03-29 | Process for preparing pentinoic esters |
| DE10017111A DE10017111A1 (en) | 1999-07-21 | 2000-04-06 | Production of pentenoic acid esters comprises heating formylvaleric acid esters in the presence of a supported precious metal catalyst in mixed oxide form |
| FR0005786A FR2808524B1 (en) | 1999-07-21 | 2000-05-05 | PROCESS FOR PREPARING PENTENOATE ESTERS |
| JP2000220594A JP2001064232A (en) | 1999-07-21 | 2000-07-21 | Method for producing pentenoic acid ester |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW088112374A TW473471B (en) | 1999-07-21 | 1999-07-21 | Process for preparing pentenoic ester |
| GB0007676A GB2360770B (en) | 1999-07-21 | 2000-03-29 | Process for preparing pentinoic esters |
| FR0005786A FR2808524B1 (en) | 1999-07-21 | 2000-05-05 | PROCESS FOR PREPARING PENTENOATE ESTERS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB0007676D0 GB0007676D0 (en) | 2000-05-17 |
| GB2360770A true GB2360770A (en) | 2001-10-03 |
| GB2360770B GB2360770B (en) | 2002-04-24 |
Family
ID=27248657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0007676A Expired - Lifetime GB2360770B (en) | 1999-07-21 | 2000-03-29 | Process for preparing pentinoic esters |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2001064232A (en) |
| DE (1) | DE10017111A1 (en) |
| FR (1) | FR2808524B1 (en) |
| GB (1) | GB2360770B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3719937A1 (en) * | 1987-06-15 | 1988-12-29 | Basf Ag | METHOD FOR THE PRODUCTION OF PENTENSIC ACID ESTERS FROM FORMYLVALERICANIC ACID ESTERS |
| DE3719935A1 (en) * | 1987-06-15 | 1988-12-29 | Basf Ag | METHOD FOR THE PRODUCTION OF PENTENIC ACID ESTERS |
-
2000
- 2000-03-29 GB GB0007676A patent/GB2360770B/en not_active Expired - Lifetime
- 2000-04-06 DE DE10017111A patent/DE10017111A1/en not_active Withdrawn
- 2000-05-05 FR FR0005786A patent/FR2808524B1/en not_active Expired - Lifetime
- 2000-07-21 JP JP2000220594A patent/JP2001064232A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001064232A (en) | 2001-03-13 |
| DE10017111A1 (en) | 2001-01-25 |
| FR2808524A1 (en) | 2001-11-09 |
| FR2808524B1 (en) | 2002-09-27 |
| GB0007676D0 (en) | 2000-05-17 |
| GB2360770B (en) | 2002-04-24 |
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| PE20 | Patent expired after termination of 20 years |
Expiry date: 20200328 |