CA2790161C - Process for preparing aminocarboxylates low in by-products - Google Patents
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- CA2790161C CA2790161C CA2790161A CA2790161A CA2790161C CA 2790161 C CA2790161 C CA 2790161C CA 2790161 A CA2790161 A CA 2790161A CA 2790161 A CA2790161 A CA 2790161A CA 2790161 C CA2790161 C CA 2790161C
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- aminocarboxylates
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- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000006227 byproduct Substances 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000013922 glutamic acid Nutrition 0.000 claims abstract description 8
- 239000004220 glutamic acid Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 11
- 235000004279 alanine Nutrition 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000003880 polar aprotic solvent Substances 0.000 claims description 2
- 239000003586 protic polar solvent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 abstract description 6
- 238000007046 ethoxylation reaction Methods 0.000 abstract description 5
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 abstract description 4
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 abstract description 3
- 101100345345 Arabidopsis thaliana MGD1 gene Proteins 0.000 abstract description 3
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 3
- 150000007513 acids Chemical class 0.000 abstract description 3
- 150000001414 amino alcohols Chemical class 0.000 abstract description 3
- 239000008139 complexing agent Substances 0.000 abstract description 3
- OHOTVSOGTVKXEL-UHFFFAOYSA-K trisodium;2-[bis(carboxylatomethyl)amino]propanoate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C(C)N(CC([O-])=O)CC([O-])=O OHOTVSOGTVKXEL-UHFFFAOYSA-K 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 239000010949 copper Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- -1 alkaline earth metal salts Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- GMKMEZVLHJARHF-UHFFFAOYSA-N (2R,6R)-form-2.6-Diaminoheptanedioic acid Natural products OC(=O)C(N)CCCC(N)C(O)=O GMKMEZVLHJARHF-UHFFFAOYSA-N 0.000 description 1
- PGNYNCTUBKSHHL-UHFFFAOYSA-N 2,3-diaminobutanedioic acid Chemical compound OC(=O)C(N)C(N)C(O)=O PGNYNCTUBKSHHL-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000008133 Iron-Binding Proteins Human genes 0.000 description 1
- 108010035210 Iron-Binding Proteins Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005027 hydroxyaryl group Chemical group 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- GMKMEZVLHJARHF-SYDPRGILSA-N meso-2,6-diaminopimelic acid Chemical compound [O-]C(=O)[C@@H]([NH3+])CCC[C@@H]([NH3+])C([O-])=O GMKMEZVLHJARHF-SYDPRGILSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The present invention relates to a method for producing aminocarboxylates starting from amines using a reaction sequence of ethoxylation to form amino alcohols and subsequent oxidative dehydrogenation to form the corresponding aminocarboxylates, in particular the alkali or alkaline earth salts of the complexing agents MGDA (methylglycinediacetic acid), EDTA (ethylenediaminetetraacetic acid) and GLDA (glutamic acid diacetic acid) or the free acids thereof.
Description
=
= CA 02790161 2012-08-16 Process for preparing aminocarboxylates low in by-products The present invention relates to a process for preparing aminocarboxylates proceeding from the amines 1 and 4 by employing a reaction sequence composed of ethoxylation to the amino alcohols 2 and 5 and subsequent oxidative dehydrogenation to the corresponding aminocarboxylates 3 and 6 (for example the alkali metal or alkaline earth metal salts of the complexing agents MGDA (methylglycinediacetic acid), EDTA
(ethylenediaminetetraacetic acid) or GLDA (glutamic acid diacetic acid) or the free acids thereof).
N, 1-12 XOH
R' RR.
HO
0 Nee \ N rj.-1-"Nõ.0H
1-12144.-R.\
1---r-coox - Hz X0 OC) OH
R = alkyl, alkenyl, alkynyl, aryl, aralkyl, alkylenecarboxyl, hydroxyalkyl, hydroxyaralkyl, alkylenesulfonate rcoox NCOOX
where A = Cl to C12 alkylene bridge or a chemical bond coox R' = COOX, CH2OH
= alkylene X = alkali metals or alkaline earth metals, preferably sodium and potassium N=1-10 The ethoxylation of amines is performed on the industrial scale, typically at temperatures greater than 120 C. For instance, ethanolamines are prepared proceeding from ammonia (solution of 20 to 30% by mass in water) and ethylene oxide at temperatures around 150 C and at pressures of 30 to 150 bar (H.-J. Arpe, lndustrielle Organische Chemie [Industrial Organic Chemistry]). N-Alkylethanolamines are even prepared at temperatures up to 170 C (Ullmann's Encyclopedia). WO
98/38153 describes the ethoxylation of ethylenediamine in isopropanol as a solvent with 4 equivalents of ethylene oxide at standard pressure and a reaction temperature of 140 to 180 C. The corresponding ethoxylation in pure substance is described in US
3 907 745, at somewhat lower temperatures of 120 to 130 C.
The oxidative dehydrogenation of amino alcohols with alkali metal hydroxides is typically performed under pressure and at temperatures of 140 to 220 C using copper I I
= CA 02790161 2012-08-16 Process for preparing aminocarboxylates low in by-products The present invention relates to a process for preparing aminocarboxylates proceeding from the amines 1 and 4 by employing a reaction sequence composed of ethoxylation to the amino alcohols 2 and 5 and subsequent oxidative dehydrogenation to the corresponding aminocarboxylates 3 and 6 (for example the alkali metal or alkaline earth metal salts of the complexing agents MGDA (methylglycinediacetic acid), EDTA
(ethylenediaminetetraacetic acid) or GLDA (glutamic acid diacetic acid) or the free acids thereof).
N, 1-12 XOH
R' RR.
HO
0 Nee \ N rj.-1-"Nõ.0H
1-12144.-R.\
1---r-coox - Hz X0 OC) OH
R = alkyl, alkenyl, alkynyl, aryl, aralkyl, alkylenecarboxyl, hydroxyalkyl, hydroxyaralkyl, alkylenesulfonate rcoox NCOOX
where A = Cl to C12 alkylene bridge or a chemical bond coox R' = COOX, CH2OH
= alkylene X = alkali metals or alkaline earth metals, preferably sodium and potassium N=1-10 The ethoxylation of amines is performed on the industrial scale, typically at temperatures greater than 120 C. For instance, ethanolamines are prepared proceeding from ammonia (solution of 20 to 30% by mass in water) and ethylene oxide at temperatures around 150 C and at pressures of 30 to 150 bar (H.-J. Arpe, lndustrielle Organische Chemie [Industrial Organic Chemistry]). N-Alkylethanolamines are even prepared at temperatures up to 170 C (Ullmann's Encyclopedia). WO
98/38153 describes the ethoxylation of ethylenediamine in isopropanol as a solvent with 4 equivalents of ethylene oxide at standard pressure and a reaction temperature of 140 to 180 C. The corresponding ethoxylation in pure substance is described in US
3 907 745, at somewhat lower temperatures of 120 to 130 C.
The oxidative dehydrogenation of amino alcohols with alkali metal hydroxides is typically performed under pressure and at temperatures of 140 to 220 C using copper I I
2 catalysts. The catalysts consist, for example, of doped or undoped Raney Cu (described, for example, in EP 1 125 633, EP 1 125 634, WO 04/24091, WO 00/066539, EP 1 067 114, WO
00/032310). The dopants used are generally one or more metals, for example Pt, Fe, Cr (EP 1 125 633, EP 1 125 634) Cr, Mo, V, Bi, Sn, Sb, Pb, Ge (WO 04/24091) or Ag (EP 1 067 114).
In other examples, Cu is applied to alkali-stable supports directly or via anchor metals (e.g. Os, Ir, Rh, Pt, Pd) (e.g. WO 01/77054, WO 03/022140, WO 98/50150). Precipitated Cu catalysts with further metal oxides have also been described (e.g. WO 03/051513 (Cu, Fe), EP 0 506 973, WO 98/13140 (Cu, Zr, Ca)). There have also been isolated reports about conversion over noble metal systems (e.g. EP 0 201 957).
A problem in the preparation especially of complexing agents such as MGDA
(methylglycinediacetic acid), EDTA (ethylenediaminetetraacetic acid) or GLDA
(glutamic acid diacetic acid) and salts thereof is that relatively high contents of by-products are obtained in a simple performance of the two process steps. In order to keep the content of such by-products in the end product low, expensive operations, which are complex in terms of apparatus, to purify the end product and/or the intermediate are required.
It is therefore an object of the present invention to provide a process which does not have the disadvantage mentioned, i.e. which affords an end product with a low by-product content and in which operations to purify the end product and/or intermediate are dispensable.
According to the invention, the object is achieved by a process for preparing aminocarboxylates, in which, in a first stage, an amine is ethoxylated at a reaction temperature in the range from 30 to 100 C to give an alkanolamine, and the alkanolamine thus formed is dehydrogenated in a second stage oxidatively to give an aminocarboxylate, where the salts which form can also be converted to the corresponding aminocarboxylic acids.
Preference is given to a process in which the amine is selected from the group of the amines of the formula 1 or 4 j,R"
NH H,N-R/L, W
where
00/032310). The dopants used are generally one or more metals, for example Pt, Fe, Cr (EP 1 125 633, EP 1 125 634) Cr, Mo, V, Bi, Sn, Sb, Pb, Ge (WO 04/24091) or Ag (EP 1 067 114).
In other examples, Cu is applied to alkali-stable supports directly or via anchor metals (e.g. Os, Ir, Rh, Pt, Pd) (e.g. WO 01/77054, WO 03/022140, WO 98/50150). Precipitated Cu catalysts with further metal oxides have also been described (e.g. WO 03/051513 (Cu, Fe), EP 0 506 973, WO 98/13140 (Cu, Zr, Ca)). There have also been isolated reports about conversion over noble metal systems (e.g. EP 0 201 957).
A problem in the preparation especially of complexing agents such as MGDA
(methylglycinediacetic acid), EDTA (ethylenediaminetetraacetic acid) or GLDA
(glutamic acid diacetic acid) and salts thereof is that relatively high contents of by-products are obtained in a simple performance of the two process steps. In order to keep the content of such by-products in the end product low, expensive operations, which are complex in terms of apparatus, to purify the end product and/or the intermediate are required.
It is therefore an object of the present invention to provide a process which does not have the disadvantage mentioned, i.e. which affords an end product with a low by-product content and in which operations to purify the end product and/or intermediate are dispensable.
According to the invention, the object is achieved by a process for preparing aminocarboxylates, in which, in a first stage, an amine is ethoxylated at a reaction temperature in the range from 30 to 100 C to give an alkanolamine, and the alkanolamine thus formed is dehydrogenated in a second stage oxidatively to give an aminocarboxylate, where the salts which form can also be converted to the corresponding aminocarboxylic acids.
Preference is given to a process in which the amine is selected from the group of the amines of the formula 1 or 4 j,R"
NH H,N-R/L, W
where
3 R is an alkyl, alkenyl, alkynyl, aryl, aralkyl, alkylenecarboxyl, hydroxyalkyl, hydroxy-aralkyl, alkylenesulfonate or a substituent ,coox A N COOX
y coox where A = Cl to C12 alkylene bridge, or a chemical bond R' is COOX or CH2OH, R* is an alkylene radical, X is an alkali metal or alkaline earth metal and n is from 1 to 10.
R is more preferably relatively long alkyl or alkenyl radicals of Cl to C30 alkyl and C2 to C30 alkenyl, alkylenecarboxylates or else alkylenesulfonates, hydroxyalkyl or hydroxyaryl groups and double alkylglycinediacetic acids such as diaminosuccinic acid (A = "chemical bond") or diaminopimelic acid (A = -(CH2)3-) with (Coax Ay N COOX
R= coox where A = a Cl to C12 alkylene bridge or a chemical bond.
Particular preference is given to a process in which the amine is selected from the group consisting of alanine, glutamic acid and salts thereof, and ethylenediamine.
With regard to the process parameters, there are preferred embodiments.
Preference is thus given to a process in which the reaction temperature in the first stage is in the range from 40 to 90 C, preferably in the range from 60 to 80 C.
With regard to the temperature profile too, there are preferred variants.
Preference is thus given to a process in which the reaction temperature in the first stage varies by less than 60 C, preferably by less than 40 C, over the reaction time.
The performance of the process as a batchwise, semibatchwise or continuous process is preferred. A process in which (at least) one reactor selected from the group consisting of stirred tank reactor, loop reactor and tubular reactor is used is particularly preferred.
This is possible using various reactor models such as stirred tank reactors of various designs, loop reactors (gas circulation reactor, plunging jet reactor, jet nozzle reactor or high-loading packed column) or tubular reactors (gas phase-free or with gas phase).
=
y coox where A = Cl to C12 alkylene bridge, or a chemical bond R' is COOX or CH2OH, R* is an alkylene radical, X is an alkali metal or alkaline earth metal and n is from 1 to 10.
R is more preferably relatively long alkyl or alkenyl radicals of Cl to C30 alkyl and C2 to C30 alkenyl, alkylenecarboxylates or else alkylenesulfonates, hydroxyalkyl or hydroxyaryl groups and double alkylglycinediacetic acids such as diaminosuccinic acid (A = "chemical bond") or diaminopimelic acid (A = -(CH2)3-) with (Coax Ay N COOX
R= coox where A = a Cl to C12 alkylene bridge or a chemical bond.
Particular preference is given to a process in which the amine is selected from the group consisting of alanine, glutamic acid and salts thereof, and ethylenediamine.
With regard to the process parameters, there are preferred embodiments.
Preference is thus given to a process in which the reaction temperature in the first stage is in the range from 40 to 90 C, preferably in the range from 60 to 80 C.
With regard to the temperature profile too, there are preferred variants.
Preference is thus given to a process in which the reaction temperature in the first stage varies by less than 60 C, preferably by less than 40 C, over the reaction time.
The performance of the process as a batchwise, semibatchwise or continuous process is preferred. A process in which (at least) one reactor selected from the group consisting of stirred tank reactor, loop reactor and tubular reactor is used is particularly preferred.
This is possible using various reactor models such as stirred tank reactors of various designs, loop reactors (gas circulation reactor, plunging jet reactor, jet nozzle reactor or high-loading packed column) or tubular reactors (gas phase-free or with gas phase).
=
4 A process in which the reactor consists essentially of a material with a thermal conductivity coefficient greater than 5 W/K*m is particularly suitable.
"Essentially"
means that more than 50%, preferably more than 80% and more preferably more than 90% of the reactor material consists of a material with a corresponding thermal conductivity coefficient.
Particularly suitable materials for this purpose are found to include 1.4541 (V2A steel), 1.4571 (V4A steel), 2.4610 (HC4) with a thermal conductivity coefficient greater than
"Essentially"
means that more than 50%, preferably more than 80% and more preferably more than 90% of the reactor material consists of a material with a corresponding thermal conductivity coefficient.
Particularly suitable materials for this purpose are found to include 1.4541 (V2A steel), 1.4571 (V4A steel), 2.4610 (HC4) with a thermal conductivity coefficient greater than
5 W/K*m, in order to enable efficient removal of heat in the industrial process.
Equally preferred is a process in which the solvent of the first stage is selected from protic solvents such as water, alcohols, preferably short-chain alcohols, and especially methanol, ethanol, 2-propanol and/or polar aprotic solvents such as dimethyl sulfoxide, dimethylformamide or N-methylpyrrolidone.
A process in which the alkanolamine formed in the first stage is dehydrogenated directly constitutes a further preferred embodiment. Direct dehydrogenation means that preference is given to those processes in which there is no apparatus for removing substances with boiling points greater than 200 C (at standard pressure), on the basis of different boiling points, between the first and second stages. This is simpler in apparatus terms and hence saves one process step with comparably good end product quality.
Particular preference is given to a process in which the end product too is not purified further, but is used directly in the corresponding applications, for example as an additive for industrial cleaning formulations for hard surfaces of metal, plastic, coating material or glass, in alkaline cleaning formulations for the drinks and foods industry, especially for bottle cleaning in the drinks industry and in apparatus cleaning in dairies, in breweries, in the preserves industry, in the bakery industry, in the sugar industry, in the fat-processing industry and in the meat-processing industry, in dishware cleaning formulations, especially in phosphate-free compositions for machine dishwashing in machine dishwashers in the household or in commercial premises, for example large kitchens or restaurants, in bleaching baths in the paper industry, in photographic bleaching and bleach fixing baths, in pretreatment and bleaching in the textile industry, in electrolytic baths for masking of contaminating heavy metal cations, and also in the field of plant foods for remedying heavy metal deficits as copper, iron, manganese and zinc complexes. In principle, use is advantageous anywhere where precipitations of calcium, magnesium or heavy metal salts disrupt industrial processes and should be prevented (prevention of deposits and encrustations in tanks, pipelines, spray nozzles or generally on smooth surfaces), and also for stabilization of phosphates in alkaline degreasing baths and prevention of the precipitation of lime soaps, in order thus to prevent the tarnishing of non-iron surfaces and to prolong the service life of alkaline cleaning baths. In addition, they find use in pulverulent or liquid detergent formulations for textile washing as builders and preservatives. In soaps, they prevent metal-catalyzed oxidative decompositions, and also in pharmaceuticals, cosmetics and foods.
The dehydrogenation is effected with the aid of a base from the group of the alkali metal and alkaline earth metal hydroxides, preferably NaOH or KOH, particular preference being given to NaOH. The temperature of the second stage is typically in the range from 140 to 240 C, preferably in the range from 150 to 210 C and more preferably in the range from 160 to 200 C. The pressure is typically in the range from standard pressure to 100 bar, preferably from 5 to 50 bar and more preferably in the range from 8 to 20 bar and even more preferably from 10 to 20 bar.
A process in which the dehydrogenation is performed with a catalyst, the main and secondary constituents of which is/are selected from groups 4 to 12 of the Periodic Table, is particularly preferred; very particular preference is given to a process in which the dehydrogenation is performed with a catalyst which comprises (at least) one metal which is selected from the group consisting of: Cu, Fe, Co, Ni, Zr, Hf, Ag, Pd and Pt.
The catalyst can be used, for example, in the form of powder or shaped bodies (e.g.
extrudates, tablets etc.), or in the form of an unsupported catalyst or supported catalyst, and may consist of metals and metal oxides.
A process in which the NTA content in the direct product of the second stage is less than 1% by mass, based on the main product, forms a further part of the subject matter of the present invention.
In addition to the salts (aminocarboxylates) themselves, the corresponding amino-carboxylic acids are also obtainable after acidification. The direct product of the second stage is understood to mean the reaction discharge as obtained in the oxidative dehydrogenation. Thereafter, in the case of a suspension method, the catalyst can be sedimented and filtered off. In addition, a desired water content can subsequently be established or a bleaching can be carried out, for example with hydrogen peroxide or UV light.
The present invention is illustrated in detail hereinafter by nonlimiting examples:
Example 1:
3.743 kg (20.00 mol) of glutamic acid monosodium salt monohydrate are suspended in 5.599 kg of water and admixed with 1.578 kg (20.00 mol) of 50.7% by mass sodium hydroxide solution. The resulting mixture was charged into a 20 I autoclave (2.4610 material) and, after appropriate inertization, nitrogen was injected to 20 bar.
Subsequently, 2.026 kg (46.00 mol) of ethylene oxide were metered in at 40-45 C
Equally preferred is a process in which the solvent of the first stage is selected from protic solvents such as water, alcohols, preferably short-chain alcohols, and especially methanol, ethanol, 2-propanol and/or polar aprotic solvents such as dimethyl sulfoxide, dimethylformamide or N-methylpyrrolidone.
A process in which the alkanolamine formed in the first stage is dehydrogenated directly constitutes a further preferred embodiment. Direct dehydrogenation means that preference is given to those processes in which there is no apparatus for removing substances with boiling points greater than 200 C (at standard pressure), on the basis of different boiling points, between the first and second stages. This is simpler in apparatus terms and hence saves one process step with comparably good end product quality.
Particular preference is given to a process in which the end product too is not purified further, but is used directly in the corresponding applications, for example as an additive for industrial cleaning formulations for hard surfaces of metal, plastic, coating material or glass, in alkaline cleaning formulations for the drinks and foods industry, especially for bottle cleaning in the drinks industry and in apparatus cleaning in dairies, in breweries, in the preserves industry, in the bakery industry, in the sugar industry, in the fat-processing industry and in the meat-processing industry, in dishware cleaning formulations, especially in phosphate-free compositions for machine dishwashing in machine dishwashers in the household or in commercial premises, for example large kitchens or restaurants, in bleaching baths in the paper industry, in photographic bleaching and bleach fixing baths, in pretreatment and bleaching in the textile industry, in electrolytic baths for masking of contaminating heavy metal cations, and also in the field of plant foods for remedying heavy metal deficits as copper, iron, manganese and zinc complexes. In principle, use is advantageous anywhere where precipitations of calcium, magnesium or heavy metal salts disrupt industrial processes and should be prevented (prevention of deposits and encrustations in tanks, pipelines, spray nozzles or generally on smooth surfaces), and also for stabilization of phosphates in alkaline degreasing baths and prevention of the precipitation of lime soaps, in order thus to prevent the tarnishing of non-iron surfaces and to prolong the service life of alkaline cleaning baths. In addition, they find use in pulverulent or liquid detergent formulations for textile washing as builders and preservatives. In soaps, they prevent metal-catalyzed oxidative decompositions, and also in pharmaceuticals, cosmetics and foods.
The dehydrogenation is effected with the aid of a base from the group of the alkali metal and alkaline earth metal hydroxides, preferably NaOH or KOH, particular preference being given to NaOH. The temperature of the second stage is typically in the range from 140 to 240 C, preferably in the range from 150 to 210 C and more preferably in the range from 160 to 200 C. The pressure is typically in the range from standard pressure to 100 bar, preferably from 5 to 50 bar and more preferably in the range from 8 to 20 bar and even more preferably from 10 to 20 bar.
A process in which the dehydrogenation is performed with a catalyst, the main and secondary constituents of which is/are selected from groups 4 to 12 of the Periodic Table, is particularly preferred; very particular preference is given to a process in which the dehydrogenation is performed with a catalyst which comprises (at least) one metal which is selected from the group consisting of: Cu, Fe, Co, Ni, Zr, Hf, Ag, Pd and Pt.
The catalyst can be used, for example, in the form of powder or shaped bodies (e.g.
extrudates, tablets etc.), or in the form of an unsupported catalyst or supported catalyst, and may consist of metals and metal oxides.
A process in which the NTA content in the direct product of the second stage is less than 1% by mass, based on the main product, forms a further part of the subject matter of the present invention.
In addition to the salts (aminocarboxylates) themselves, the corresponding amino-carboxylic acids are also obtainable after acidification. The direct product of the second stage is understood to mean the reaction discharge as obtained in the oxidative dehydrogenation. Thereafter, in the case of a suspension method, the catalyst can be sedimented and filtered off. In addition, a desired water content can subsequently be established or a bleaching can be carried out, for example with hydrogen peroxide or UV light.
The present invention is illustrated in detail hereinafter by nonlimiting examples:
Example 1:
3.743 kg (20.00 mol) of glutamic acid monosodium salt monohydrate are suspended in 5.599 kg of water and admixed with 1.578 kg (20.00 mol) of 50.7% by mass sodium hydroxide solution. The resulting mixture was charged into a 20 I autoclave (2.4610 material) and, after appropriate inertization, nitrogen was injected to 20 bar.
Subsequently, 2.026 kg (46.00 mol) of ethylene oxide were metered in at 40-45 C
6 within 8 h, and the mixture was stirred at this temperature for a further 2 h.
After the removal of the unconverted residues of ethylene oxide, the autoclave was emptied. In this way, 12.862 kg of aqueous reaction discharge were obtained as a clear, colorless, viscous solution.
418 g (0.650 mol based on glutamic acid monosodium salt monohydrate) of this crude product were initially charged with 53.0 g (1.33 mol) of sodium hydroxide powder, 12.7 g of water and 7.5 g of a copper-iron catalyst prepared according to WO
03/051513 in a 1.21 autoclave (2.4610 material). The reactor was closed, nitrogen was injected to 5 bar, and the reactor was then heated to 190 C. The temperature was held for 6 h. The stirrer speed over the entire experimental duration was 700 rpm.
The hydrogen which formed was removed continuously through a 15 bar pressure-regulating valve. After the end of the experiment, the reactor was purged with nitrogen at room temperature and then emptied. The product was obtained as a clear, colorless, viscous solution. By iron binding capacity, a glutamic acid-/V,N-diacetic acid tetrasodium salt (GLDA-Na4) content of 42.2% by mass was determined, which corresponds to a yield of 88.6% of theory based on glutamic acid monosodium salt monohydrate used.
Example 2:
4.365 kg (49.00 mol) of alanine were suspended in 2.600 kg of water and admixed with 3.920 kg (49.00 mol) of 50% by mass sodium hydroxide solution. The resulting mixture was charged into a 20 I autoclave (2.4610 material) and, after appropriate inertization, nitrogen was injected to 20 bar. Subsequently, 4.749 kg (107.8 mol) of ethylene oxide were metered in at 40-45 C within 8 h, and the mixture was stirred at this temperature for a further 2 h. After the removal of the unconverted residues of ethylene oxide, the autoclave was emptied. In this way, 15.597 kg of aqueous reaction discharge were obtained as a clear, colorless, viscous solution.
328 g (1.03 mol based on alanine) of this crude produce were initially charged with 197 g (2.46 mol) of 50% by mass sodium hydroxide solution, 18 g of water and 45 g of Raney copper (from Evonik Degussa GmbH) in a 1.71 autoclave (2.4610 material).
The reactor was closed, nitrogen was injected to 5 bar, and the reactor was then heated to 190 C within 2.25 h. This temperature was held for 16 h. The stirrer speed over the entire experimental duration was 500 rpm. The hydrogen which formed was removed continuously through a 10 bar pressure-regulating valve. After the end of the experiment, the reactor was purged with nitrogen at room temperature, the reaction discharge was diluted with 484 g of water and the reactor was then emptied.
The product was obtained as a clear, colorless, viscous solution. By means of HPLC, a yield of methylglycine-N,N-diacetic acid trisodium salt (MGDA-Na3) of 92.0% of theory based on alanine used was determined.
After the removal of the unconverted residues of ethylene oxide, the autoclave was emptied. In this way, 12.862 kg of aqueous reaction discharge were obtained as a clear, colorless, viscous solution.
418 g (0.650 mol based on glutamic acid monosodium salt monohydrate) of this crude product were initially charged with 53.0 g (1.33 mol) of sodium hydroxide powder, 12.7 g of water and 7.5 g of a copper-iron catalyst prepared according to WO
03/051513 in a 1.21 autoclave (2.4610 material). The reactor was closed, nitrogen was injected to 5 bar, and the reactor was then heated to 190 C. The temperature was held for 6 h. The stirrer speed over the entire experimental duration was 700 rpm.
The hydrogen which formed was removed continuously through a 15 bar pressure-regulating valve. After the end of the experiment, the reactor was purged with nitrogen at room temperature and then emptied. The product was obtained as a clear, colorless, viscous solution. By iron binding capacity, a glutamic acid-/V,N-diacetic acid tetrasodium salt (GLDA-Na4) content of 42.2% by mass was determined, which corresponds to a yield of 88.6% of theory based on glutamic acid monosodium salt monohydrate used.
Example 2:
4.365 kg (49.00 mol) of alanine were suspended in 2.600 kg of water and admixed with 3.920 kg (49.00 mol) of 50% by mass sodium hydroxide solution. The resulting mixture was charged into a 20 I autoclave (2.4610 material) and, after appropriate inertization, nitrogen was injected to 20 bar. Subsequently, 4.749 kg (107.8 mol) of ethylene oxide were metered in at 40-45 C within 8 h, and the mixture was stirred at this temperature for a further 2 h. After the removal of the unconverted residues of ethylene oxide, the autoclave was emptied. In this way, 15.597 kg of aqueous reaction discharge were obtained as a clear, colorless, viscous solution.
328 g (1.03 mol based on alanine) of this crude produce were initially charged with 197 g (2.46 mol) of 50% by mass sodium hydroxide solution, 18 g of water and 45 g of Raney copper (from Evonik Degussa GmbH) in a 1.71 autoclave (2.4610 material).
The reactor was closed, nitrogen was injected to 5 bar, and the reactor was then heated to 190 C within 2.25 h. This temperature was held for 16 h. The stirrer speed over the entire experimental duration was 500 rpm. The hydrogen which formed was removed continuously through a 10 bar pressure-regulating valve. After the end of the experiment, the reactor was purged with nitrogen at room temperature, the reaction discharge was diluted with 484 g of water and the reactor was then emptied.
The product was obtained as a clear, colorless, viscous solution. By means of HPLC, a yield of methylglycine-N,N-diacetic acid trisodium salt (MGDA-Na3) of 92.0% of theory based on alanine used was determined.
7 Example 3:
178 g (2.00 mol) of alanine were suspended in 1069 of water and admixed with (2.00 mol) of 50% by mass sodium hydroxide solution. The resulting mixture was charged into a 2.5 I autoclave (1.4571 material) and, after appropriate inertization, nitrogen was injected to 1 bar. Subsequently, 189 g (4.30 mol) of ethylene oxide were metered in at 80-89 C within 2 h, and the mixture was stirred at this temperature for a = further 3 h. After the removal of the unconverted residues of ethylene oxide, the autoclave was emptied. In this way, 624 g of aqueous reaction discharge were obtained as a clear, colorless, viscous solution.
328 g (1.05 mol based on alanine) of this crude produce were initially charged with 208 g (2.60 mol) of 50% by mass sodium hydroxide solution, 39 g of water and 45 g of Raney copper (from Evonik Degussa GmbH) in a 1.7 I autoclave (2.4610 material). The reactor was closed, nitrogen was injected to 5 bar, and the reactor was then heated to 190 C within 2.25 h. This temperature was held for 16 h. The stirrer speed over the entire experimental duration was 500 rpm. The hydrogen which formed was removed continuously through a 10 bar pressure-regulating valve. After the end of the experiment, the reactor was purged with nitrogen at room temperature, the reaction discharge was diluted with 403 g of water and the reactor was then emptied.
The product was obtained as a clear, colorless, viscous solution. By means of HPLC, a yield of methylglycine-N,N-diacetic acid trisodium salt (MGDA-Na3) of 91.3% of theory based on alanine used was determined.
Comparative example:
267 g (3.00 mol) of alanine were suspended in 159 g of water and admixed with 240 g (3.00 mol) of 50% by mass sodium hydroxide solution. The resulting mixture was charged into a 2.5 I autoclave (1.4571 material) and, after appropriate inertization, nitrogen was injected to 20 bar. Subsequently, 291 g (6.60 mol) of ethylene oxide were metered in at 140-145 C within 5 h, and the mixture was stirred at this temperature for a further 2 h. After the removal of the unconverted residues of ethylene oxide, the autoclave was emptied. In this way, 930 g of aqueous reaction discharge were obtained as a clear, yellowish, viscous solution.
322 g (1.04 mol based on alanine) of this crude produce were initially charged with 208 g (2.60 mol) of 50% by mass sodium hydroxide solution, 40 g of water and 45 g of Raney copper (from Evonik Degussa GmbH) in a 1.71 autoclave (2.4610 material).
The reactor was closed, nitrogen was injected to 5 bar, and the reactor was then heated to 190 C within 2.25 h. This temperature was held for 16 h. The stirrer speed over the entire experimental duration was 500 rpm. The hydrogen which formed was removed continuously through a 10 bar pressure-regulating valve. After the end of the experiment, the reactor was purged with nitrogen at room temperature, the reaction discharge was diluted with 424 g of water and the reactor was then emptied.
The , =
178 g (2.00 mol) of alanine were suspended in 1069 of water and admixed with (2.00 mol) of 50% by mass sodium hydroxide solution. The resulting mixture was charged into a 2.5 I autoclave (1.4571 material) and, after appropriate inertization, nitrogen was injected to 1 bar. Subsequently, 189 g (4.30 mol) of ethylene oxide were metered in at 80-89 C within 2 h, and the mixture was stirred at this temperature for a = further 3 h. After the removal of the unconverted residues of ethylene oxide, the autoclave was emptied. In this way, 624 g of aqueous reaction discharge were obtained as a clear, colorless, viscous solution.
328 g (1.05 mol based on alanine) of this crude produce were initially charged with 208 g (2.60 mol) of 50% by mass sodium hydroxide solution, 39 g of water and 45 g of Raney copper (from Evonik Degussa GmbH) in a 1.7 I autoclave (2.4610 material). The reactor was closed, nitrogen was injected to 5 bar, and the reactor was then heated to 190 C within 2.25 h. This temperature was held for 16 h. The stirrer speed over the entire experimental duration was 500 rpm. The hydrogen which formed was removed continuously through a 10 bar pressure-regulating valve. After the end of the experiment, the reactor was purged with nitrogen at room temperature, the reaction discharge was diluted with 403 g of water and the reactor was then emptied.
The product was obtained as a clear, colorless, viscous solution. By means of HPLC, a yield of methylglycine-N,N-diacetic acid trisodium salt (MGDA-Na3) of 91.3% of theory based on alanine used was determined.
Comparative example:
267 g (3.00 mol) of alanine were suspended in 159 g of water and admixed with 240 g (3.00 mol) of 50% by mass sodium hydroxide solution. The resulting mixture was charged into a 2.5 I autoclave (1.4571 material) and, after appropriate inertization, nitrogen was injected to 20 bar. Subsequently, 291 g (6.60 mol) of ethylene oxide were metered in at 140-145 C within 5 h, and the mixture was stirred at this temperature for a further 2 h. After the removal of the unconverted residues of ethylene oxide, the autoclave was emptied. In this way, 930 g of aqueous reaction discharge were obtained as a clear, yellowish, viscous solution.
322 g (1.04 mol based on alanine) of this crude produce were initially charged with 208 g (2.60 mol) of 50% by mass sodium hydroxide solution, 40 g of water and 45 g of Raney copper (from Evonik Degussa GmbH) in a 1.71 autoclave (2.4610 material).
The reactor was closed, nitrogen was injected to 5 bar, and the reactor was then heated to 190 C within 2.25 h. This temperature was held for 16 h. The stirrer speed over the entire experimental duration was 500 rpm. The hydrogen which formed was removed continuously through a 10 bar pressure-regulating valve. After the end of the experiment, the reactor was purged with nitrogen at room temperature, the reaction discharge was diluted with 424 g of water and the reactor was then emptied.
The , =
8 product was obtained as a clear, colorless, viscous solution. By HPLC, in spite of full conversion, a yield of methylglycine-N,N-diacetic acid trisodium salt (MGDA-Na3) of only 74.4% of theory based on alanine used was determined.
Claims (10)
1. A process for preparing aminocarboxylates, in which, in a first stage, an amine is ethoxylated at a reaction temperature in the range from 30 to 100°C to give an alkanolamine, and the alkanolamine thus formed is dehydrogenated in a second stage oxidatively to give an aminocarboxylate.
2. The process according to claim 1, in which the amine is selected from the group consisting of alanine, glutamic acid and salts thereof, and ethylenediamine.
3. The process according to claim 1 or 2, in which the reaction temperature in the first stage varies by less than 60°C over the reaction time.
4. The process according to any one of claims 1 to 3, which is performed as a batchwise, semibatchwise or continuous process.
5. The process according to any one of claims 1 to 4, in which a reactor selected from the group consisting of stirred tank reactor, loop reactor and tubular reactor is used.
6. The process according to claim 5, in which the reactor consists essentially of a material with a thermal conductivity coefficient greater than 5 W/K*m.
7. The process according to any one of claims 1 to 6, in which the first stage comprises a solvent which is a protic solvent, a polar aprotic solvent or a mixture thereof.
8. The process according to any one of claims 1 to 7, in which the alkanolamine formed in the first stage is dehydrogenated directly.
9. The process according to any one of claims 1 to 8, in which the dehydrogenation is performed with a catalyst which comprises a metal which is selected from the group consisting of: Cu, Fe, Co, Ni, Zr, Hf, Ag, Pd and Pt.
10. The process according to any one of claims 1 to 9, in which the NTA
content in the direct product of the second stage is less than 1% by mass, based on the main product.
content in the direct product of the second stage is less than 1% by mass, based on the main product.
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US8609894B2 (en) | 2011-05-23 | 2013-12-17 | Basf Se | Process for preparing aminopolycarboxylates |
EP2714645B1 (en) * | 2011-05-23 | 2015-08-05 | Basf Se | Method for producing aminopolycarboxylates |
CN112028785B (en) * | 2020-09-01 | 2023-01-31 | 河南清水源科技股份有限公司 | Preparation method of green chelating agent glutamic acid diacetic acid sodium salt |
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DE10028636A1 (en) * | 2000-06-09 | 2001-12-13 | Basf Ag | Production of at least one alkanolamine by reaction of ammonia with alkylene oxide, in a reactor, in the presence of a catalyst, is regulated by the temperature profile in the reactor |
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DE10161674A1 (en) * | 2001-12-14 | 2003-06-26 | Basf Ag | Catalysts for the production of carboxylic acid salts from alcohols, useful as chelates in detergents and pharmaceuticals, comprise copper and are prepared by precipitation of copper salt solutions with a base and reduction with hydrogen |
JP2003252839A (en) * | 2002-03-04 | 2003-09-10 | Nippon Shokubai Co Ltd | Method for producing n-bishydroxyalkylamino acid |
WO2004024091A2 (en) | 2002-09-12 | 2004-03-25 | Cyternex, Inc. | Expanded porphyrin compositions for tumor inhibition |
-
2011
- 2011-03-15 CN CN201180013685.8A patent/CN102791676B/en active Active
- 2011-03-15 BR BR112012021940A patent/BR112012021940A2/en not_active IP Right Cessation
- 2011-03-15 ES ES11710452T patent/ES2426165T3/en active Active
- 2011-03-15 CA CA2790161A patent/CA2790161C/en active Active
- 2011-03-15 WO PCT/EP2011/053869 patent/WO2011113822A1/en active Application Filing
- 2011-03-15 RU RU2012144218/04A patent/RU2552535C2/en active
- 2011-03-15 AU AU2011229202A patent/AU2011229202A1/en not_active Abandoned
- 2011-03-15 JP JP2012557524A patent/JP2013522269A/en active Pending
- 2011-03-15 KR KR1020127027173A patent/KR20130006481A/en not_active Application Discontinuation
- 2011-03-15 EP EP11710452.1A patent/EP2547648B1/en active Active
- 2011-03-15 SG SG2012060547A patent/SG183805A1/en unknown
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- 2011-03-15 MX MX2012010036A patent/MX2012010036A/en active IP Right Grant
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Also Published As
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MX2012010036A (en) | 2012-09-21 |
ZA201207741B (en) | 2013-12-23 |
CN102791676B (en) | 2015-12-16 |
ES2426165T3 (en) | 2013-10-21 |
AU2011229202A1 (en) | 2012-09-06 |
KR20130006481A (en) | 2013-01-16 |
RU2012144218A (en) | 2014-04-27 |
WO2011113822A1 (en) | 2011-09-22 |
RU2552535C2 (en) | 2015-06-10 |
BR112012021940A2 (en) | 2016-05-31 |
SG183805A1 (en) | 2012-10-30 |
EP2547648A1 (en) | 2013-01-23 |
JP2013522269A (en) | 2013-06-13 |
EP2547648B1 (en) | 2013-07-10 |
PL2547648T3 (en) | 2013-12-31 |
CN102791676A (en) | 2012-11-21 |
TW201144259A (en) | 2011-12-16 |
CA2790161A1 (en) | 2011-09-22 |
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