EP0489781A1 - Procede de production de sels alcalins d'acides carboxyliques d'ether - Google Patents
Procede de production de sels alcalins d'acides carboxyliques d'etherInfo
- Publication number
- EP0489781A1 EP0489781A1 EP90912729A EP90912729A EP0489781A1 EP 0489781 A1 EP0489781 A1 EP 0489781A1 EP 90912729 A EP90912729 A EP 90912729A EP 90912729 A EP90912729 A EP 90912729A EP 0489781 A1 EP0489781 A1 EP 0489781A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ether
- oxygen
- oxidation
- reactor
- alkali 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.)
- Withdrawn
Links
- -1 alkali metal salts Chemical class 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title claims abstract description 24
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 8
- 239000002253 acid Substances 0.000 title description 4
- 150000007513 acids Chemical class 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 239000008346 aqueous phase Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000012071 phase Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000010419 fine particle Substances 0.000 claims abstract description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- 239000011541 reaction mixture Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- 229910000510 noble metal Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 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 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000012423 maintenance Methods 0.000 claims 1
- 150000001447 alkali salts Chemical class 0.000 abstract description 12
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 239000006260 foam Substances 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000036284 oxygen consumption Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
Definitions
- the invention relates to a process for the preparation of alkali metal salts of ether carboxylic acids of the general formula I.
- R is an alkyl group with 1 to 22 carbon atoms, an aryl group or an aralkyl group,
- n 2 and / or 3
- n is a number in the range from 0 to 20 and
- M is an alkali metal from the group formed by lithium, sodium and potassium
- Alkali salts of ether carboxylic acids are compounds with interesting surface-active properties, which in the form of their aqueous solutions e.g. be used in cosmetic formulations.
- Aqueous solutions of alkali salts of ether carboxylic acids foam too much when the water is removed by distillation.
- the cost-effectiveness of the process is greatly reduced by the energy required for the separation of water by distillation.
- the invention is directed to a process for the preparation of alkali salts of ether carboxylic acids of the type mentioned in the introduction, in which the above-mentioned disadvantages with regard to the increase in viscosity and the foaming of the reaction mixture are avoided and highly concentrated aqueous solutions of alkali salts of ether carboxylic acids, e.g. can be obtained with a concentration of 20 to 50 wt .-%, based on the total weight of the solution.
- an aqueous Solution of alkali metal hydroxide solution in a thin layer on a solid support or in the form of fine particles or droplets in contact with oxygen or the gases containing oxygen as a continuous phase, the concentration of the ether alcohols in the aqueous phase in the range from at least 0.1, in particular from 0.5 to 15 wt .-%, based on the total weight of the aqueous phase. Below the specified range, the reaction rate is generally too slow, so that this range should only be undercut at the end of the reaction after the ether alcohol supply has ended.
- the process of the invention can be used to prepare alkali metal salts of ether carboxylic acids of the general formula (I) in which the group R can be a straight-chain or branched alkyl group having 1 to 22 carbon atoms; typical examples of such alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and docosyl.
- the group R can be a straight-chain or branched alkyl group having 1 to 22 carbon atoms
- typical examples of such alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecy
- the method of the invention is particularly suitable for the production of alkali salts of ether carboxylic acids, the remainder of which R is derived from C 2 -C 8 fatty alcohols or technical mixtures thereof, obtainable from animal and / or vegetable fats and oils.
- the group R can also be an aryl radical be, for example a phenyl group, or an aralkyl radical, for example a phenylalkylene group having 1 to 3 carbon atoms in the alkylene radical.
- the compound of the general formula II is an adduct of ethylene oxide or ethylene oxide and propylene oxide onto alcohols of the formula ROH, where in the case of the ethylene oxide / propylene oxide adducts of the formula II the propylene glycol residues are randomly distributed in the alkoxylate chain. or block distribution, but there is always an ethylene glycol residue at the end.
- reaction solution is present in the form of thin layers on a solid support or in the form of fine particles in a continuous phase of gases containing oxygen or oxygen.
- the oxidation is carried out at temperatures in the range from 40 to 130 ° C., in particular 60 to 85 ° C.
- the reaction rate is too low below the specified range. You can work above the specified range, but only an insignificant increase in the reaction rate.
- the oxidation is carried out at an oxygen partial pressure of 0.1 to 5 bar abs. out.
- the foam formation is suppressed more and more as the system pressure increases and thus the effective gas throughput decreases.
- the reaction rate may increase with increasing partial pressure of oxygen.
- the oxidation is carried out with air.
- Suitable catalysts for use in the process of the invention are the noble metal catalysts known from the prior art mentioned above, in particular based on platinum or palladium.
- Palladium catalysts have proven particularly suitable for the process of the invention, for example palladium on carbon.
- the catalyst is preferably introduced into the process in the form of a suspension in the aqueous solution of the ether alcohols.
- activated carbon, graphite, diatomaceous earth, silica gel, spinels, aluminum oxide or ceramic materials can be used as carrier material.
- the catalysts can also contain combinations of several noble metals, for example mixtures of Pd and Pt, and further suitable activators such as lead, bismuth or cadmium in the form of their metals or their compounds, including combinations thereof.
- suitable catalysts are in the literature mentioned at the outset and in US Pat. No. 4,607,121.
- the catalyst in suspension form is used in a concentration of 0.2 to 3% by weight, based on the total weight of the suspension containing the ether alcohols and water.
- the process of the invention is carried out at pH values of at least 8. PH values of at least 9, in particular in the range from 9 to 11, are particularly advantageous.
- the oxidation of the ether alcohols is carried out in a reactor in which the oxygen or the gases containing oxygen and the ether phase, alkali metal hydroxide solution and, if appropriate, the aqueous phase containing the catalyst are added to the upper part of the reactor, the ether carboxylic acid salt, unreacted ether alcohol and, if appropriate, the reaction mixture containing the catalyst are removed at the lower part of the reactor and the reaction mixture is recycled to the upper part of the reactor for the further oxidation of unreacted ether alcohol.
- reaction mixture withdrawn from the lower part of the reactor is continuously subjected to alkali metal hydroxide to maintain the pH of at least 9, in particular 9 to 11, and ether alcohol to maintain the ether alcohol concentration before being returned to the upper part of at least 0.1, in particular from 0.5 to 15% by weight in the reaction mixture.
- packed columns of conventional design such as are used, for example, in Ullmann, Encyclopedia of Industrial Chemistry, 4th Edition, Volume 3, pp. 390 to 392 (1973), Verlag Chemie, Weinheim, are described as direct current packed columns.
- the packing to be used in the packed columns expediently have a large intermediate volume so that the gas velocity and the rate of foam formation do not become too high.
- suitable fillers are known from Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 2, page 529 (1972) and 5th edition, volume B3, pages 4-82 to 4-83 (1988); the use of Pall rings, Novalox saddles, Berl saddles, Intralox saddles and Interpack bodies is particularly preferred.
- Ordered packs as described in Volume 2 of the 4th edition of the aforementioned encyclopedia, pages 533-534, can also be used, e.g. of the Sulzer packing type.
- catalyst beds or fixed catalyst beds instead of a packed bed. Ordered catalyst packs, e.g. in honeycomb form, can be used.
- the reaction mixture withdrawn at the lower end of the column, after adjustment of the pH and the ether alcohol concentration, is returned to the upper part of the column for renewed reaction until the ether carboxylic acid salt has a concentration of 20 to 50% by weight .-%, based on the total weight of the solution, and the metered ether alcohol is converted.
- the system comprises a packed column 1, which is provided at its upper end with a supply line for oxygen or gases containing oxygen, in particular air.
- a line 3 is used to supply the water / ether alcohol mixture which may contain the suspended catalyst.
- a line 4 for removing the oxidized reaction mixture is arranged at the lower end of the packed column; the reaction mixture can be returned to the top of the packed column via a circulation pump 5, a valve 6 which is open during the reaction and is only closed in the filtration discussed below, and a heat exchanger 7 and via line 3.
- Aqueous sodium hydroxide solution is supplied via a line 8 and a metering pump 9, that of the ether alcohol to be oxidized via a line 10 and a metering pump 11.
- the exhaust air flowing from the packed column 1 is removed laterally via a line 12 and fed to an exhaust gas heater 13.
- the foam that arises, for example, when the system is operated incorrectly and carried along with the exhaust air can be destroyed and returned to the reactor as a liquid via a line 14.
- the air freed from the foam is fed to a cooler 16 via a line 15 and removed from the system via a valve 17 and a line 18; Any liquid droplets that are entrained or condensate are also returned to the reactor via a line 19.
- the aqueous suspension containing the end product is removed via a line 20 and a valve 21 and fed to a filter system 22, where the separation between the aqueous solution of the process products and the suspended catalyst takes place, which are carried away via lines 23 and 24, respectively.
- the catalyst is placed in a line 4, which is not shown.
- the system shown in Fig. 1 is operated as follows:
- the suspension of the powdered noble metal catalyst in water is recirculated from the bottom of the reactor to the top thereof by means of the circulation pump 5.
- a small amount of ether alcohol and sodium hydroxide solution in the form of an aqueous solution is metered into the circuit suspension by means of the metering pumps 9, 10.
- the nitrogen is then displaced by oxygen or a gas containing oxygen, and immediately after the desired pressure has been reached, the gas throughput required for the oxidation and the addition of sodium hydroxide solution and alcohol are adjusted via the metering pumps 9 and 11.
- Alcohol and aqueous sodium hydroxide solution are continuously metered in during the reaction, which can be recognized by an oxygen uptake.
- the metering rate is adjusted or varied and adapted to the reaction rate so that a low amount of unreacted ether alcohol and thus a low viscosity is ensured in the solution during the entire course of the reaction.
- the gas supply is interrupted and the catalyst is separated from the solution by filtration.
- a conventional packed column with an inner diameter of 50 mm and a height was used for this exemplary embodiment the packing of 1000 mm used; the column was filled with Interpack 15/40. loaded.
- the starting material was a commercially available fatty alcohol ethoxylate (adduct of approx. 4 mol of ethylene oxide with a technical fatty alcohol of chain length C 2 -C 4, molecular weight: 369).
- a palladium catalyst with 5% Pd on carbon was used as the catalyst, which had been reduced in the form of an aqueous suspension with hydrogen before use.
- the plant was initially charged with a suspension of, based on dry matter, 35 g of catalyst in 2400 g of demineralized water.
- 30 g of ether alcohol (approx. 1.2% by weight) and 3.3 g of NaOH (as 25% sodium hydroxide solution) were metered into the system.
- the respective free ether alcohol content was calculated from the amount of oxygen absorbed by the reaction solution up to that point and the amount of ether alcohol dosed up to that point.
- total amount of ether alcohol metered 720 g (1.95 gmol) total amount of NaOH added (as 100% NaOH): 78.0 g (1.95 gmol)
- Average or maximum content of unreacted ether alcohol 3 or 4% by weight
- Example 2 Analogously to the process of Example 1, an addition product of an average of 5 moles of ethylene oxide was oxidized to 1 mole of the technical fatty alcohol of the chain length C 1 -C 4 described in Example 1. After a reaction time of 6.7 hours, a 23.5% solution of the sodium salt of the corresponding ether carboxylic acid was obtained in a conversion of approximately 97%, calculated from the oxygen consumption. In the same way, an adduct of an average of 9 moles of ethylene oxide and 1 mole of a technical fatty alcohol of chain length C 2 -C 8 was oxidized. After a response time of 6.2 For hours, a 19.5% solution of the sodium salt of the corresponding ether carboxylic acid was obtained with a conversion of approx. 105% calculated from the oxygen consumption.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Un procédé permet d'obtenir des sels alcalins des acides carboxyliques d'éther par oxydation d'alcools d'éther dans une phase aqueuse avec de l'oxygène ou des gaz contenant de l'oxygène à des températures élevées, en présence d'hydroxydes de métaux alcalins et de catalyseurs en métaux précieux. A cet effet, on met en contact une couche mince d'une solution aqueuse des alcools d'éther contenant une lessive alcaline, appliquée sur un substrat solide ou sous forme de fines particules, avec de l'oxygène ou avec les gaz qui contiennent de l'oxygène sous forme d'une phase continue. La concentration d'alcools d'éther dans la phase aqueuse est comprise entre 0,1 et 15 % en poids du poids total de la phase aqueuse. Ce procédé permet d'obtenir des concentrations élevées de solutions aqueuses des sels alcalins des acides carboxyliques d'éther.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3929063A DE3929063A1 (de) | 1989-09-01 | 1989-09-01 | Verfahren zur herstellung von alkalisalzen von ethercarbonsaeuren |
| DE3929063 | 1989-09-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0489781A1 true EP0489781A1 (fr) | 1992-06-17 |
Family
ID=6388431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90912729A Withdrawn EP0489781A1 (fr) | 1989-09-01 | 1990-08-23 | Procede de production de sels alcalins d'acides carboxyliques d'ether |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0489781A1 (fr) |
| JP (1) | JPH05503686A (fr) |
| AU (1) | AU6288790A (fr) |
| CA (1) | CA2066452A1 (fr) |
| DE (1) | DE3929063A1 (fr) |
| WO (1) | WO1991003454A1 (fr) |
| ZA (1) | ZA906979B (fr) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5463114A (en) * | 1994-04-13 | 1995-10-31 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of ether carboxylic acids and salts thereof |
| DE10117222B4 (de) | 2001-04-06 | 2004-12-30 | Goldschmidt Ag | Verfahren zur Herstellung von Glycinderivaten |
| JP5511369B2 (ja) | 2009-12-28 | 2014-06-04 | 花王株式会社 | カルボン酸の製造方法 |
| JP5520088B2 (ja) * | 2010-03-10 | 2014-06-11 | 花王株式会社 | エーテルカルボキシレートの製造方法 |
| JP5520089B2 (ja) * | 2010-03-10 | 2014-06-11 | 花王株式会社 | エーテルカルボキシレートの製造方法 |
| JP2013067565A (ja) * | 2011-09-20 | 2013-04-18 | Kao Corp | カルボン酸塩の製造方法 |
| JP5985965B2 (ja) * | 2011-12-28 | 2016-09-06 | 花王株式会社 | ポリオキシアルキレンアルキルエーテルカルボン酸又はその塩の製造方法 |
| CN115894208B (zh) * | 2022-12-09 | 2024-11-12 | 万华化学集团股份有限公司 | 一种醇醚羧酸盐的制备方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2936123C2 (de) * | 1979-09-07 | 1987-04-09 | Hoechst Ag, 6230 Frankfurt | Verfahren zur Herstellung von Alkoxyessigsäuren |
| US4348509A (en) * | 1981-07-06 | 1982-09-07 | Shell Oil Company | Alkoxyalkanoic acid preparation |
| DE3135946A1 (de) * | 1981-09-10 | 1983-03-24 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von alkoxyessigsaeuren |
| IT1175314B (it) * | 1983-12-28 | 1987-07-01 | Anic Spa | Procedimento per la preparazione di sali di metallo alcalino di acidi polietossicarbossilici |
| DE3728222A1 (de) * | 1987-08-24 | 1989-03-09 | Henkel Kgaa | Verfahren zur herstellung von ethercarbonsaeuren |
-
1989
- 1989-09-01 DE DE3929063A patent/DE3929063A1/de not_active Withdrawn
-
1990
- 1990-08-23 CA CA002066452A patent/CA2066452A1/fr not_active Abandoned
- 1990-08-23 AU AU62887/90A patent/AU6288790A/en not_active Abandoned
- 1990-08-23 WO PCT/EP1990/001402 patent/WO1991003454A1/fr not_active Ceased
- 1990-08-23 JP JP2512142A patent/JPH05503686A/ja active Pending
- 1990-08-23 EP EP90912729A patent/EP0489781A1/fr not_active Withdrawn
- 1990-08-31 ZA ZA906979A patent/ZA906979B/xx unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9103454A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05503686A (ja) | 1993-06-17 |
| AU6288790A (en) | 1991-04-08 |
| CA2066452A1 (fr) | 1991-03-02 |
| ZA906979B (en) | 1991-06-26 |
| DE3929063A1 (de) | 1991-03-07 |
| WO1991003454A1 (fr) | 1991-03-21 |
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