Patent Application
20200223786
The present invention relates to a process for in situ the preparation of mixtures of chelating agents by catalyzed reactions of diethanolamine with maleic acid and then with 2-halocarboxylic acid, mixtures obtainable using said process and mixtures of chelating agents. In addition, the invention relates to methods where such mixtures are used.
In pulp bleaching liquors, iron and manganese are desired to be trapped by a chelating agent, thereby inhibiting these metal ions from catalyzing the decomposition of the bleaching agents, hydrogen peroxide or peroxy acids. Because there is naturally a high concentration of calcium ions in the bleaching liquors, a chelating agent effectively chelating calcium would be consumed by calcium ions. Therefore, chelating agents to selectively complex iron and manganese ions are desired.
WO 97/45396 discloses N-bis- and N-tris-[(1,2-dicarboxy-ethoxy)-ethyl]-amine derivatives including N-bis-[(1,2-dicarboxy-ethoxy)-ethyl]-aspartic acid (also called aspartic acid diethoxy succinate or AES), and the use of these derivatives as chelating agents of metals, especially in connection with pulp bleaching. These derivatives can be prepared by reacting di- or triethanolamine with an alkali metal or alkaline earth metal salt of maleic acid in the presence of a catalyst such as lanthanoid compounds, a nickel compound or alkaline earth metal compounds, e.g. calcium hydroxide or magnesium hydroxide.
A drawback with the above-mentioned synthesis of e.g. AES is that the reaction is relatively slow, the reaction time being about 12 to 16 hours, and that the reaction does not go to completion. A typical obtainable conversion from diethanol amine to AES products is about 60 to 70%. This means that a significant amount, up to about 40 mol-%, of the diethanol amine (DEA) used as a starting material is left unreacted.
In order to simultaneously complex different metal ions in aqueous solutions, it is essential in many applications to have a mixture of chelating agents having different ligand structure. Therefore, there is a need to develop a method for the preparation of mixtures of chelating agents in situ in the same reaction mixture. In addition, there is a continuous need for a process where the starting materials are efficiently converted into chelating agents.
According to the present invention it was surprisingly found that the unreacted diethanolamine can easily and effectively be converted into other reactive ingredients by the addition of a 2-haloalkyl carboxylic acid compound into the reaction containing a lanthanoid catalyst to yield an amino acid derivative, thereby utilizing the unreacted diethanol amine.
It has now been surprisingly found that mixtures of chelating agents having a diethanol amine backbone can be effectively prepared by lanthanoid catalysed reaction of diethanol amine with maleate followed by a lanthanoid-catalyzed reaction of 2-halocarboxylic acid. Alternatively, mixtures of chelating agents can effectively be prepared by a lanthanoid catalyzed reaction of diethanol amine with 2-halocarboxylic acid followed by addition of maleate.
The first aspect of the present invention is a process for the preparation of a mixture of chelating agents comprising a compound of Formula (I)
wherein at least one of R1, R2 and R3 is a succinic acid group or a salt thereof and at least one of R1, R2 and R3 is a carboxymethyl or 1-carboxyethyl group or a salt thereof. According to the invention said reaction comprises reacting maleic acid or a salt thereof with diethanol amine under alkaline conditions in the presence of a lanthanoid catalyst to form at least one compound having a general formula (I) where at least one of R1, R2 and R3 is a succinic acid group or a salt thereof followed by adding of 2-halocarboxylic acid or a salt thereof which reacts with unreacted diethanol amine and/or with intermediates containing hydroxyl groups or secondary amino groups to form a mixture comprising compounds having a general formula (I) where at least one of R1, R2 and R3 is succinic acid group or a salt thereof and at least one of R1, R2 and R3 is carboxymethyl or 1-carboxyethyl group or a salt thereof.
The second aspect of this invention is a mixture of chelating agents obtained as described here.
The third aspect of this invention is a mixture of chelating agents. According to the invention said mixture comprises at least 30% (w/w) of AES6 and at least 2% (w/w) of AES5 or GES5 or combination of AES5 and GES5.
The fourth aspect of this invention is a method of chelating metals by contacting the mixture here described with aqueous slurry comprising the metals.
The fifth aspect of this invention is a method of bleaching pulp comprising treating the pulp with the mixture described here or adding the mixture described here to the bleaching stage.
As used here expression “a mixture of chelating agents” means a mixture comprising at least two differently substituted chelating agents synthesized starting from diethanolamine.
Maleate as used herein means maleic acid or a salt thereof.
As used herein the expression intermediate(s) means compounds having a diethanolamine backbone and a general formula (I) where at least one of R1, R2 and R3 is a succinic acid group, carboxymethyl or carboxyethyl group, and the compound contains at least one unreacted/free hydroxyl group or a secondary amino group.
As used herein the expression succinic acid group means a substituent formed in the Michael-addition of a maleate to a hydroxyl group or the hydroamination reaction of a maleate and a secondary amine including both carboxylic acids and salts thereof.
As used herein the term 2-halocarboxylic acid means saturated carboxylic acids substituted with a halogen atom in the 2-position. The carboxylic acid is preferably acetic acid or propionic acid. The halogen is preferably bromine or chlorine.
As used herein the term equilibrium means an ordinary chemical equilibrium of a reaction.
A method for the preparation of mixtures of chelating agents in situ is described here. This method accomplishes the conversion of most of the starting materials to chelating agents. A mixture comprising chelating agents with different capability to complex metal cations is many times advantageous for a complete deactivation of the metal ions in for example pulp bleaching applications. In addition, it is economically and environmentally advantageous to have the starting materials of the chelating agent synthesis reacted as completely as possible to form useful reaction products. In addition, the mixture comprising products obtained using the method here described is essentially free of diethanol amine that could form harmful or toxic nitrosamines. The composition of the metal complexing molecules can be easily adjusted by varying the ratios of the reagents used in the synthesis of the mixtures of chelating agents.
The metal complexing ability of mixtures of chelating agents is usually better than the complexing ability of individual chelating agents. This is especially noticed in the pulp bleaching applications, where iron, manganese, calcium and magnesium ions are present in the bleaching liquor.
Compared to traditionally used chelating agents such as ethylenediamine tetraacetic acid (EDTA) and diethylenetriamine pentaacetic acid (DTPA), the chelating agents prepared by the method described here, are more biodegradable. Some of the compounds obtained by this method are readily biodegradable (e.g. ethylenedisuccinic acid EDDS and iminodisuccinic acid IDS) and generally the diethanolamine originated polycarboxylic acids are at least inherently biodegradable.
An aspect of the present invention is the process for preparation of a mixture of chelating agents comprising a compound of Formula (I)
wherein at least one of R1, R2 and R3 is a succinic acid group or a salt thereof and at least one of R1, R2 and R3 is a carboxymethyl or 1-carboxyethyl group or a salt thereof. Said process comprises reacting maleic acid or a salt thereof with diethanol amine under alkaline conditions in the presence of a lanthanoid catalyst to form at least one compound having a general formula (I) wherein at least one of R1, R2 and R3 is a succinic acid group or a salt thereof followed by addition of 2-halocarboxylic acid or a salt thereof which reacts with unreacted diethanol amine and/or with intermediates containing hydroxyl groups or secondary amino groups to form a mixture comprising compounds having a general formula (I) wherein at least one of R1, R2 and R3 is a succinic acid group or a salt thereof and at least one of R1, R2 and R3 is a carboxymethyl or 1-carboxyethyl group or a salt thereof.
In this connection expression “carboxymethyl or 1-carboxyethyl group or a salt thereof” means a monocarboxylic acid group (or a salt thereof) derived from the reaction of a hydroxyl group or a secondary amine with a 2-haloalkylcarboxylic acid or a salt thereof.
In one embodiment unreacted diethanol amine (in practice diethanol amine that has not reacted with maleic acid in the first reaction step), is N-alkylated with a halocarboxylic acid to form a tertiary amine group, such as bis-(2-hydroxyethyl)glycine or bis-(2-hydroxyethyl)methyl glycine. Such reaction catalyzed as described here provides a reaction mixture essentially free of diethanol amine. Unreacted diethanol amine could form harmful nitrosamines.
In one embodiment the reaction is continued until the reaction mixture comprises at least one compound of Formula (I) wherein at least one of R1, R2 and R3 is a carboxymethyl or 1-carboxyethyl group or a salt thereof and wherein the two remaining of R1, R2 and R3 are succinic acid groups or salts thereof (AES5 or GES5), and at least one compound with Formula (I) wherein R1, R2 and R3 are succinic acid groups (AES6), and bis-(2-hydroxyethyl)glycine or bis-(2-hydroxyethyl)methyl glycine.
2-halocarboxylic acid as used herein includes 2-halocarboxylic acids as acids and salts. Said acid can be any carboxylic acid containing 2 to 3 carbon atoms, typically haloacetic acid or 2-halopropionic acid. The halogen is usually bromine or chlorine, the latter being preferred for environmental reasons.
One possible simplified reaction scheme is illustrated in
In one embodiment the 2-halocarboxylic acid is bromo- or chloroacetic acid, preferably 2-chloroacetic acid. In another embodiment the 2-halocarboxylic acid can be 2-chloro- or 2-bromopropionic acid, preferably 2-chloropropionic acid.
Chlorine-containing starting materials are preferred due to the difficulties in recycling the hydrobromic acid formed in the reaction. Furthermore, colored bromine-containing side-products which are undesirable in pulping applications are formed.
The non-catalyzed reaction of 2-halocarboxylic acids with an amino group is known in the literature. This reaction is usually carried out in an alkaline aqueous solution. Side reactions, e.g. hydrolysis of 2-halocarboxylic acid to the respective 2-hydroxycarboxylic acids are also well-known. A conversion of the unreacted amino or hydroxyl groups of the chelating agent intermediates by non-catalyzed alkylation after the incomplete reaction result in a sluggish and incomplete reaction. The alkylation of hydroxyl groups with 2-halocarboxylic acids usually requires strong bases and again, the reactions proceed incompletely.
Lanthanoid-catalyzed Michael additions of hydroxyl groups to maleate are known in the past literature. It has now been surprisingly found that it is possible to convert the free hydroxyl groups in a complex mixture of polycarboxylic acids to the respective carboxymethyl derivatives by a lanthanoid catalyzed alkylation of the hydroxyl group with 2-halocarboxylic acids. Also, the previous efforts of the inventors to convert diethanolamine derivatives to the corresponding O-alkylated carboxymethyl derivatives have failed when 2-haloalkyl carboxylic acids were used in the absence of a lanthanoid catalyst.
The lanthanoid (previously named lanthanide) series comprises the fifteen elements with atomic numbers from 57 to 71. Preferred lanthanoid catalysts are lanthanum (La), praseodymium (Pr), neodymium (Nd), europium (Eu), dysprosium Dy), Erbium (Er) and ytterbium (Yb). The elements of the lanthanoid series may be used in the form of oxides or salts including carbonates, nitrates, chlorides, maleates and octanates.
Residual lanthanide ions/salts are removed from the reaction mixture by methods known in the literature. Such methods can be precipitation as carbonates or oxalates followed by the removal of the precipitate by filtration or centrifugation.
In one embodiment the catalyst is a lanthanoid catalyst including lanthanum(III)oxide and lanthanum(III)salts, such as lanthanum carbonate, lanthanum maleate, lanthanum nitrate, lanthanum chloride or lanthanum octanoate. Michael additions of hydroxyl groups to maleate proceed to some extent without a catalyst. Lanthanoids also catalyze hydroamination of maleates. The reaction time of the addition of maleate for example to ethylenediamine has been shortened from 16 hours to one hour by using lanthanoids as catalysts.
The reactions described here are catalyzed by a lanthanoid catalyst. Thus there is no need to remove or change the catalyst during the process.
In one embodiment the initial molar ratio of the lanthanoid catalyst to diethanol amine is 0.5:1 to 1.5:1. The relatively large amount of catalyst is needed as some of the lanthanide is chelated by the formed products.
In one embodiment 2-halocarboxylic acid or a salt thereof is added after at least 10 mol-% preferably at least 30 mol-%, more preferably at least 50 mol-% of DEA has reacted with maleic acid or a salt thereof. In one embodiment the reaction between maleic acid or a salt thereof and DEA is continued until an equilibrium is reached before adding 2-halocarboxylic acid or a salt thereof in order to ensure the largest possible percentage of chelating agents with at least two succinic acid groups. The progression of the reaction may be monitored using ordinary analytical methods used in organic chemistry, for example gas chromatography (after derivatization), 1H-NMR spectroscopy and 13C-NMR spectroscopy.
In one embodiment the ratio of added 2-halocarboxylic acid or a salt thereof to unreacted hydroxyl and/or amine is 1:1, preferably 1.2:1. Such ratios enable complete conversion of unreacted hydroxyl groups and secondary amines into carboxylic acid groups.
In one embodiment the initial molar ratio of diethanol amine to maleic acid or a salt thereof is 1:1.5 to 1:3.2.
One possible simplified reaction scheme is illustrated in
A mixture comprising aspartic acid diethoxy succinate (AES) and glycine diethoxy succinate (GES5) is obtained by reacting maleate with diethanol amine under alkaline conditions in the presence of a lanthanoid catalyst to form aspartic acid diethoxy succinate followed by adding 2-haloacetic acid or its salt which reacts with the side-product N-bis-[(1,2-dicarboxy-ethoxy)-ethyl]-amine (BCA4) to form glycine diethoxysuccinate (GES5).
In addition to the above-mentioned reactions, other intermediates present in the reaction mixture, containing hydroxyl groups are reacting with 2-haloacetic acid in the presence of lanthanoid catalyst to form appropriate derivatives. Such derivatives are for example N-[2-(1,2-dicarboxyethoxy)ethyl]-N-[(2-carboxymethoxy)ethyl]glycine (GES 5) and N-[2-(1,2-dicarboxyethoxy)ethyl]-N-[2-(carboxymethoxy)ethyl]aspartic acid (AES5).
Respectively a mixture comprising aspartic acid diethoxy succinate and methylglycine diethoxysuccinate is prepared by adding 2-chloropropionic acid or 2-bromopropionic acid, preferably 2-chloropropionic acid to the reaction mixture which reacts with unreacted secondary amines to form methylglycine diethoxysuccinate.
In addition to the above-mentioned reactions, other intermediates present in the reaction mixture, containing hydroxyl groups are reacting with 2-chloropropionic acid or 2-bromopropionic acid, preferably 2-chloropropionic acid to form appropriate derivatives. Such derivatives are for example 2-(2-((2-(1-carboxyethoxy)ethyl)(1-carboxyethyl)amino)ethoxy) succinic acid (MGES 4) and 2-(2-((2-(1-carboxyethoxy)ethyl)(1,2-dicarboxyethyl)amino)ethoxy) succinic acid (AES5b).
The intermediates containing secondary amino groups are reacting with 2-haloacetic acid or 2-halopropionic acid in the presence of lanthanoid catalyst to form polycarbocylic acids capable of forming metal complexes. Such intermediate reacting with 2-haloacetic acid is for example N-bis-[(1,2-dicarboxy-ethoxy)-ethyl]-amine (BCA4), a compound existing in the known AES solution produced by prior art methods and being capable of complexing effectively only earth alkali metals.
With the process described here, BCA4 was reacted completely with 2-chloroacetic acid to produce an effective chelating agent, GES5. According to the experience of the inventors, the conversion of BCA4 to GES5 has not been possible in the absence of lanthanoid catalyst. This conversion is possible by using 2-haloacetic or 2-halopropionic acid in the presence of lanthanoid catalyst.
One embodiment described here is the process for preparation of a mixture of aspartic acid diethoxy succinate and glycine diethoxysuccinate (GES), wherein the process comprises reacting maleate with diethanol amine under alkaline conditions in the presence of a lanthanoid catalyst to form aspartic acid diethoxy succinate. In this reaction, a partially alkylated diethanolamine derivative AES 4 is formed as a side-product. Furthermore, BCA4, a side-product resulting from an anti-Michael reaction of AES6 is formed. BCA4 is converted quantitatively to GES5 by a lanthanoid catalyzed N-alkylation of BCA4. Respectively, the partially reacted intermediates are O-alkylated.
In another embodiment, a mixture comprising aspartic acid diethoxysuccinate and glycine diethoxysuccinate in molar ratios from 10:1 to 1:10 is prepared by addition of 2-haloacetic acid, preferably chloroacetic acid, into the reaction mixture after only a partial reaction of maleate with diethanolamine.
Another embodiment described here relates to the preparation of a mixture comprising aspartic acid diethoxy succinate and methyl glycine diethoxysuccinate (MGES), comprising reacting maleate with diethanol amine under alkaline conditions in the presence of a lanthanoid catalyst to form aspartic acid diethoxy succinate followed by adding 2-halopropionic acid, preferably 2-chloropropionic acid which reacts with unreacted diethanol amine to form methyl glycine diethoxysuccinate (MGES). Respectively, the partially reacted intermediates are O-alkylated.
In another embodiment diethanolamine is reacted with maleate, followed by a catalyzed addition of 2-haloacetic acid followed by a reaction of aspartic acid or ethylene diamine in order to consume the unreacted maleate from the reaction mixture to produce to the reaction mixture iminodisuccininc acid (IDS) or ethylenediamine disuccinic acid (EDDS), respectively. The conversion of maleate to EDDS or IDS is described in the previous patent publication of the authors.
In one embodiment the amount of the diethanol amine is substoichiometric in relationship to the amount of the maleate. By varying this ratio is possible to obtain a desired amount of GES or MGES in the end product mixture. The molar ratio of diethanol amine to maleic acid or a salt thereof may be between 5:1 and 1:5, preferably between 1:1 and 1:3.
However, it is also possible to use e.g. a stoichiometric amount of diethanol amine in relationship to the amount of the maleate and add chloroacetic acid or chloropropionic acid after or before the maleate addition reaction has reached its equilibrium.
Preferably the maleate and diethanol amine are reacted for a period of time long enough for at least 30 mol-% of the original diethanol amine to be converted into aspartic acid diethoxy succinate. After that 2-halocarboxylic acid is added.
The molar ratio of unreacted diethanol amine and/or intermediates containing hydroxyl groups or secondary amino groups and 2-halocarboxylic acid may be between 10:1 and 1:10, preferably between 1:1 and 1:3.
The initial molar ratio of the lanthanoid catalyst to maleate is preferably between 0.01:2.5 to 1:5, more preferably between 1:3 and 1:6. Expression “initial molar ratio” herein means the ratio when the reaction between diethanol amine and maleate is started.
The initial molar ratio of the lanthanoid catalyst to 2-halocarboxylic acid is preferably between 0.01:2.5 to 1:5, more preferably between 1:3 and 1:6. Expression “initial molar ratio” herein means the ratio when the reaction between unreacted diethanol amine and/or with intermediates containing hydroxyl groups or secondary amino groups and 2-halocarboxylic acid is starter, i.e. when said 2-halocarboxylic acid is added to the reaction mixture.
After completing the reaction, the catalyst is separated using methods known within the field. The catalyst can by separated from the reaction mixture by precipitation as a carbonate by the addition a carbonate salt or carbon dioxide, or as precipitation as an oxalate by the addition of oxalic acid. The formed precipitation can be separated by filtration or centrifugation followed by collecting the supernatant.
The individual components (intermediates or final reaction products) of the mixture are preferably obtained as alkali metal salts or alkaline earth metal salts, but the components may also be obtained in acid form or may be converted from salts into acids.
The present disclosure relates also to a mixture of chelating agents obtained by the process here described.
Further the present disclosure relates to a mixture of chelating agents comprising at least AES6 and GES5 or AES5. In one embodiment the mixture comprises at least 30% (w/w) of AES6 and at least 2% (w/w) of AES5 or GES5 or combination of AES5 and GES5. In one embodiment the mixture further comprises at least 3% (w/w) of AES4.
In one embodiment the mixture comprises less than 1% (w/w) of DEA, preferably less than 0.5% (w/w) of DEA, more preferably less than 0.1% (w/w) of DEA. In one embodiment the mixture is essentially free of DEA.
Table below shows one illustrative composition of the mixture described here.
When oxygen or peroxide compounds are used in bleaching of pulp it is important to remove the transition metals from the fiber before bleaching, since transition metal ions catalyze the decomposition of peroxy compounds, thus forming radical compounds. As a consequence of these reactions the strength properties of the fiber are deteriorated. The decomposition of hydrogen peroxide is catalyzed by transition metals; iron, manganese, and copper are of particular importance in pulp bleaching. The use of chelating agents to remove some of these metal ions from the pulp prior to adding peroxide allows peroxide to be used more efficiently. A chelating agent can be used directly in the bleaching or as a pretreatment before the bleaching proper. This is especially the case when a multistage peroxide bleaching is employed.
The present disclosure relates also to a method of chelating metals by contacting a mixture of chelating agents described here with an aqueous slurry comprising the metals.
The present disclosure relates also to a method of bleaching pulp comprising treating the pulp by a mixture of chelating agents here described or adding the mixture here described to the bleaching state.
It should be understood, that the embodiments given in the description above are for illustrative purposes only, and that various changes and modifications are possible within the scope of the disclosure. It is also to be understood that the terminology employed herein is for the purpose of description and should not be regarded as limiting. The features described here as separate embodiments may also be provided in combination in a single embodiment. Also various features described here in the context of a single embodiment, may also be provided separately or in any suitable sub-combination.
The invention is described below with the help of examples. The examples are given only for illustrative purpose and they do not limit the scope of the invention.
A solution of maleic acid was prepared by addition of maleic anhydride (75.6 g, 0.77 mol) to deionized water at 55° C. Lanthanum oxide (42.03 g, 0.129 mol) was added to the maleic acid solution and the reaction mixture was heated to 70° C. The resulting lanthanum-maleate solution was added into a solution of diethanolamine (31.54 g, 0.768 mol). The resulting reaction mixture was stirred at 90° C. for 16 hours at pH 8.5-9.5.
Lanthanum catalyst was precipitated out from the reaction mixture by addition of sodium carbonate and the reaction mixture was analyzed as by gas-chromatography after silyl derivatization. The final composition of the reaction mixture is presented in Table 1.
The reaction product from example 1 was divided into two portions. One portion was heated at 75° C. at pH 9.6 and 2-chloroacetic acid (12.11 g, 0.128 mol) was added over 45 minutes. The pH was adjusted to 8.1 and the reaction mixture was stirred at 90° C. for 4 hours.
Lanthanum catalyst was precipitated out from the reaction mixture by addition of sodium carbonate and the reaction mixture was analyzed as by gas-chromatography after silyl derivatization. The composition of the active ingredients of obtained reaction mixture is presented in Table 2.
The other portion of the reaction product from example 1 was treated in order to precipitate the lanthanum catalyst from the reaction mixture, followed by a treatment of 2-chloroacetic acid as described in example 2A. The reaction mixture was analyzed as by gas-chromatography after silyl derivatization. The final composition of the active ingredients of obtained reaction mixture is presented in Table 2. No conversion of BCA4 to AES5 was obtained. This result clearly shows that the alkylation of the amino group in this reaction product only occurs in the presence of lanthanum catalyst. Furthermore, the O-alkylation of AES4 did not proceed in this reaction in the absence of a lanthanum catalyst.
Example 1 discloses the first reaction step of the process described here. As can be seen from the results, a mixture of AES6 and AES4 are the main products with almost 3% concentration of unreacted diethanolamine. Furthermore, 2.84% of a poor chelating agent, BCA4, is formed.
Example 2B discloses the second reaction step according to this invention. AES synthesis was run as in Example 1), followed by addition of 2-chloroacetic acid in the presence of Lanthanum catalyst. The total percentage of the effective chelating agent is increased. BCA4 is converted quantitatively to AES5, an effective chelating agent for iron and manganese. Diethanolamine is converted almost quantitatively to bicine and effective chelating agents GES3 and GES5. It should be noted that these reactions are non-optimized reactions. Better conversions could be obtained by optimizing the reaction conditions.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20175631 | Jun 2017 | FI | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/FI2018/050504 | 6/27/2018 | WO | 00 |
