CN117776949A - Chelating agent containing hydroxyamino carboxylic acid and preparation method and application thereof - Google Patents
Chelating agent containing hydroxyamino carboxylic acid and preparation method and application thereof Download PDFInfo
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- 239000002738 chelating agent Substances 0.000 title claims abstract description 92
- DRAJWRKLRBNJRQ-UHFFFAOYSA-N Hydroxycarbamic acid Chemical compound ONC(O)=O DRAJWRKLRBNJRQ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 110
- 239000000243 solution Substances 0.000 claims description 72
- 238000003756 stirring Methods 0.000 claims description 23
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000004471 Glycine Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 8
- DCEMCPAKSGRHCN-UHFFFAOYSA-N oxirane-2,3-dicarboxylic acid Chemical compound OC(=O)C1OC1C(O)=O DCEMCPAKSGRHCN-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 abstract description 6
- -1 hydroxylamino Chemical group 0.000 abstract description 6
- 239000011777 magnesium Substances 0.000 abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000006845 Michael addition reaction Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 24
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 20
- 238000004043 dyeing Methods 0.000 description 8
- 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 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000004061 bleaching Methods 0.000 description 6
- 239000002537 cosmetic Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 3
- 244000166124 Eucalyptus globulus Species 0.000 description 3
- 230000009920 chelation Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 125000002349 hydroxyamino group Chemical group [H]ON([H])[*] 0.000 description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 238000012430 stability testing Methods 0.000 description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- WYMDDFRYORANCC-UHFFFAOYSA-N 2-[[3-[bis(carboxymethyl)amino]-2-hydroxypropyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)CN(CC(O)=O)CC(O)=O WYMDDFRYORANCC-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 231100000175 potential carcinogenicity Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
Abstract
The invention provides a chelating agent containing hydroxyamino carboxylic acid, a preparation method and application thereof, belonging to the technical field of chelating agent preparation; the invention synthesizes epoxy succinic acid and iminodiacetic acid metal salt based on multi-step Michael addition reaction, cyclization and other technologies, and then carries out addition reaction on the epoxy succinic acid and iminodiacetic acid metal salt, thereby obtaining the chelating agent of hydroxyamino carboxylic acid; the chelating agent containing the hydroxyamino carboxylic acid has good chelating performance, and has good chelating performance on calcium, magnesium, iron, copper or other metals, and the application range is wide; the hydroxylamino-containing carboxylic acid chelating agent has high solubility in high-concentration alkaline water solution and high-concentration acidic water solution, and has excellent storage stability; the hydroxyl-containing amino carboxylic acid chelating agent has mild reaction conditions, basically no waste exists during production, and has good industrial application value and social value.
Description
Technical Field
The invention belongs to the technical field of chelating agent preparation, and particularly relates to a chelating agent containing hydroxyamino carboxylic acid, and a preparation method and application thereof.
Background
Currently, the most common chelating agents are mainly phosphates, hydroxycarboxylic acids, aminocarboxylic acids and carboxylic acid-containing polymers. Among them, phosphate chelating agents such as Sodium Tripolyphosphate (STPP) have excellent chelating effects, but phosphorus contained therein causes great pollution to the environment. The hydroxycarboxylic acid chelating agent mainly comprises sodium gluconate, sodium citrate and the like, and has lower cost performance due to poor chelating performance on common metal ions. The acrylic polymer is a high molecular chelating agent, and although it has both thickening and flocculating effects in addition to chelating ability, the acrylic polymer is settled in water after chelation, which has a disadvantage of being difficult to be bio-bound. The amino carboxylic acid chelating agent mainly comprises ethylenediamine tetraacetic acid (EDTA), hydroxyethyl ethylenediamine triacetic acid (HEDTA), diethylenetriamine pentaacetic acid (DTPA), nitrilotriacetic acid (NTA), iminodisuccinic acid (IDS), glutamic diacetic acid (GLDA), methylglycine diacetic acid (MGDA) and the like, but EDTA is not easy to biodegrade (OECD), NTA has potential carcinogenicity, IDS chelates metals with lower performance, GLDA and MGDA have high raw material toxicity, high equipment requirement, large industrialization difficulty, high production cost and high product price, and are difficult to be widely applied in industrial production.
Therefore, there is a need to develop a chelating agent which is non-toxic, phosphorus-free, low in chlorine, strong in chelating ability, good in degradability and low in cost.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a chelating agent containing hydroxyamino carboxylic acid, and a preparation method and application thereof; the invention synthesizes epoxy succinic acid and iminodiacetic acid metal salt based on multi-step Michael addition reaction, cyclization and other technologies, and then carries out addition reaction on the epoxy succinic acid and iminodiacetic acid metal salt, thereby obtaining the chelating agent of hydroxyamino carboxylic acid; the chelating agent containing the hydroxyamino carboxylic acid has good chelating performance, and has good chelating performance on calcium, magnesium, iron, copper or other metals, and the application range is wide; the hydroxylamino-containing carboxylic acid chelating agent has high solubility in high-concentration alkaline water solution and high-concentration acidic water solution, and has excellent storage stability; the hydroxyl-containing amino carboxylic acid chelating agent has mild reaction conditions, basically no waste exists during production, and has good industrial application value and social value.
The present invention achieves the above technical object by the following means.
The present invention first provides a chelating agent comprising a hydroxyamino carboxylic acid, the chelating agent having the formula C 9 H 9 NNa 4 O 9 The structural formula is as follows:
the invention also provides a preparation method of the chelating agent containing the hydroxyamino carboxylic acid, which specifically comprises the following steps:
(1) Dissolving maleic anhydride in deionized water, adding NaOH solution, mixing to obtain mixed solution, regulating the pH value of the mixed solution, and heating and stirring to react to obtain solution A;
(2) Adding sodium tungstate into the solution A, stirring for reaction, adding hydrogen peroxide solution and NaOH, adjusting the pH value of the mixed solution, and then heating for reaction to obtain solution B;
(3) Dissolving glycine in deionized water, adding NaOH solution into the glycine, stirring and mixing uniformly, adding acrylonitrile, reacting at a certain temperature 1, adding NaOH solution for the second time after the reaction is finished, and heating to react 2 to obtain solution C after the reaction is finished;
and (3) dropwise adding the solution B into the solution C, then heating the solution C for reaction 3, and cooling the solution C after the reaction is finished to obtain the chelating agent containing the hydroxyamino carboxylic acid.
Preferably, in the step (1), when the solution A is prepared, the mass ratio of the maleic anhydride to the deionized water to the NaOH solution is 190-220 g/190-220 g;
the temperature of the NaOH solution is not more than 45 ℃ when the NaOH solution is added, and the mass concentration of the NaOH solution is 35-50wt%;
the pH value of the system is regulated to 6.0-6.5;
the conditions of the heating and stirring reaction are that the temperature is raised to 45-65 ℃ and the stirring reaction is carried out for 15min.
Preferably, in the step (2), when the solution B is prepared, the dosage ratio of sodium tungstate, hydrogen peroxide solution, naOH and maleic anhydride in the step (1) is 12-18 g:320-380 g: 100-145 g: 180-200 g;
the stirring reaction condition is stirring for 45-60 min;
the mass concentration of the NaOH solution is 35-50wt%; the mass concentration of the hydrogen peroxide solution is 25-35 wt%;
the pH value of the system is regulated to 6.0-6.5;
the temperature rising reaction condition is that the temperature is raised to 25-40 ℃ and the stirring reaction is carried out for 1-5 h.
Preferably, in the step (3), when the solution C is prepared, the mass ratio of glycine to deionized water to the first NaOH solution, acrylonitrile to the second NaOH solution is 130-170 g/70-130 g/150-170 g/120-135 g/150-165 g;
the condition of the reaction 1 is that the reaction is carried out for 1 to 5 hours at the temperature of 50 to 70 ℃;
the condition of the temperature rising reaction 2 is that the reaction is carried out for 2 to 4 hours at the temperature of 90 ℃;
the mass concentration of the NaOH solution added for two times is 35-50wt%.
Preferably, in the step (3), the condition of the reaction 3 is that the reaction is carried out for 3 hours at 70-80 ℃.
The invention also discloses application of the chelating agent containing the hydroxyamino carboxylic acid in chelating heavy metal ions.
Compared with the prior art, the invention has the beneficial effects that:
the invention develops a non-toxic and non-toxicThe chelating agent has low phosphorus content, strong chelating ability, good degradability and low cost, and is a polyhydroxy amino carboxylic acid chelating agent with a molecular formula of C 9 H 9 NNa 4 O 9 . The chelating agent structure contains a plurality of hydroxyl, amino and carboxylate chelating groups, is different from the traditional chelating agent, has higher dispersion and solubility, higher chelating strength and higher electrostatic repulsion, can quickly generate water-soluble complex with calcium, magnesium, iron, lead, copper, manganese and the like, has strong complexing capacity especially for high-valence chromogenic metal, is widely applied to civil detergents, cosmetics fields, industrial cleaning agents, printing and dyeing auxiliaries, dyeing and finishing processes, textile industries, paper industry, photosensitive materials, ceramic industries, electroplating industries, extraction of soil heavy metal pollutants and the like, and can also be used as a scale inhibition dispersing agent in the traditional industrial circulating water field.
The chelating agent containing the hydroxyamino carboxylic acid can be used in the field of cosmetics, and forms stable water-soluble complexing molecules with heavy metal ions, so that the oxidation effect of the heavy metal ions on unsaturated fatty acids in the cosmetics is reduced, the risk of adverse reactions on skin is reduced, the quality stability of the cosmetics is improved, and the antibacterial effect is beneficial to ensuring the quality of the cosmetics in the process of using the cosmetics for a long time by a terminal customer.
The chelating agent containing the hydroxyamino carboxylic acid can be used in the field of papermaking application, and can be combined with metal ions to form chelate with a stable annular structure, so that the catalytic decomposition of the metal ions on hydrogen peroxide can be inhibited, the bleaching efficiency of the hydrogen peroxide can be improved, the metal ions can be prevented from being absorbed by paper pulp, the generation of colored compounds and metal ion lignin complexes can be avoided, and the whiteness of finished paper can be improved.
The chelating agent containing the hydroxyamino carboxylic acid can be used in the application field of printing and dyeing, and has wide application space in the working procedures of printing and dyeing water treatment, desizing, scouring, bleaching, dyeing, soaping and the like. In addition, the chelating agent containing hydroxyamino carboxylic acid has high dispersion, complexation and electrostatic repulsive force, and can help the dye to dissolve, increase the diffusion rate, and make the dye more suitable for use in the dyeAnd fully and uniformly spread in a short time and dissolved in the dye liquor, thereby dyeing the fiber. During dyeing, ca in the dye bath 2+ 、Mg 2+ 、Cu 2+ 、Fe 3+ 、Mn 2+ The existence of the plasma metal ions can denature the dye and influence the dyeing performance, the addition of the chelating agent can prevent the dye from acting, and complex some metal ions and impurities in the dye liquor to form a stable complex, so that the association of the dye is reduced, the generation of defects such as color spots and the like is avoided, and the effect of leveling is indirectly achieved.
The chelating agent containing hydroxyamino carboxylic acid has high solubility in high-concentration alkaline water solution and high-concentration acid water solution, and has excellent preservation stability; the hydroxyamino carboxylic acid chelating agent has mild reaction conditions, basically no waste exists during production, and has good industrial application value and social value.
Drawings
FIG. 1 is a graph showing the detection of chloride ions in a chelating agent containing hydroxyaminocarboxylic acid.
FIG. 2 is the solubility of a hydroxyamino-containing carboxylic acid chelating agent in concentrated sodium hydroxide solution.
FIG. 3 is a graph showing the solubility of a hydroxyamino-containing carboxylic acid chelator in water.
FIG. 4 is a graph showing the thermal stability of EDTA (a) and a chelating agent (b) containing hydroxyaminocarboxylic acid.
FIG. 5 is a graph of the chelation energy of a hydroxyamino-containing carboxylic acid chelator.
FIG. 6 is a graph of bleaching power of a hydroxyamino-carboxylic acid-containing chelating agent.
FIG. 7 is a graph of stability testing of a hydroxyamino-carboxylic acid-containing chelating agent.
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto. In the following examples, the synthetic schemes of the hydroxyamino-carboxylic acid-containing chelating agent are shown below.
The chelating agent described in example 4 was obtained commercially with the exception of the chelating agent containing hydroxyamino carboxylic acid according to the present invention.
Example 1:
(1) 196g of maleic anhydride is added into 200g of deionized water, hydrolysis is carried out for 1h at 25 ℃ to obtain mixed solution, then 200g of 50wt% NaOH solution is added at the temperature of not more than 45 ℃, the pH value of the reaction system is regulated to 6.0-6.5, and then the temperature is raised to 55 ℃ and stirring is carried out for 15min to obtain solution A.
(2) 14g of sodium tungstate is added into the solution A and stirred for 45min, then 360g of 30wt% hydrogen peroxide solution is added dropwise within 90min, 120g of 50wt% NaOH is added into the system to adjust the pH to 6.0-7.5, and then the temperature is raised to 65 ℃ and stirred for 3h, so as to obtain solution B.
(3) 150g glycine, 100g deionized water and 160g 50wt% NaOH are added into a 1L reaction kettle, stirred and dissolved, 125g acrylonitrile is added, the liquid temperature is about 60 ℃ for 3 hours, and then 160g 50wt% NaOH is added, the temperature is raised to about 100 ℃ for 3 hours, so that a solution C is obtained.
Dropwise adding a solution B into the solution C, controlling the temperature to be 70-80 ℃ after the dropwise adding of the solution B is completed, reacting for 3 hours, and cooling to obtain N- (2-carboxyethyl) -N- (carboxymethyl) -3-hydroxy-aspartic acid sodium salt (1:4), wherein the yield is: 98.33%.
In this example, the content of chloride ions in the chelating agent containing hydroxyaminocarboxylic acid was examined, and the examination results are shown in FIG. 1. As can be seen from FIG. 1, the hydroxylamine-containing carboxylic acid chelating agent product has low chlorine (20-150 ppm) or near chlorine-free standard, and can be used for cleaning large power station boilers, large stainless steel equipment of petrochemical systems and industrial circulating water treatment systems without chloride ions or low chloride ions, so that corrosion to the equipment is avoided, and the service life of the equipment is prolonged, and normal and effective operation of the system is protected.
The solubility of the hydroxyamino-carboxylic acid-containing chelating agent in concentrated sodium hydroxide solution was also examined in this example and the examination results are shown in FIG. 2. As can be seen from fig. 2, in the same high pH environment, the hydroxyamino-carboxylic acid-containing chelating agent is far more soluble than tetrasodium EDTA and trisodium MGDA, which suggests that the hydroxyamino-carboxylic acid-containing chelating agent can replace EDTA in extremely high alkaline environments, and the addition amount is smaller. Therefore, the chelating agent containing the hydroxyamino carboxylic acid can be used as the optimal chelating agent to prepare the cleaning agent with high cost performance.
The solubility of the hydroxyamino-carboxylic acid-containing chelating agent in water at 25℃was also examined in this example, and the examination results are shown in FIG. 3. As can be seen from fig. 3, the chelating agent containing hydroxyaminocarboxylic acid is far more soluble than tetra sodium EDTA, disodium EDTA and trisodium MGDA, which indicates that the chelating agent containing hydroxyaminocarboxylic acid can replace EDTA and MGDA in a highly concentrated environment, and the addition amount is smaller.
Example 2:
(1) Adding 232g of maleic acid into 200g of deionized water, hydrolyzing at 45 ℃ for 1h to obtain a mixed solution, then adding 220g of 50wt% NaOH solution at the temperature of not more than 50 ℃, adjusting the pH value of a reaction system to be 5.0-6.5, and then heating to 55 ℃ and stirring for 15min to obtain a solution A;
(2) Adding 16g of sodium tungstate into the solution A, stirring for 45min, then dropwise adding 450g of 30wt% hydrogen peroxide solution within 90min, simultaneously adding 180g of 50wt% NaOH into the system to adjust the pH to 6.0-7.0, heating to 65 ℃ and stirring for 3h to obtain a solution B;
(3) 150g glycine, 100g deionized water and 160g 50wt% NaOH are added into a 1L reaction kettle, stirred and dissolved, 125g acrylonitrile is added, the liquid temperature is about 60 ℃ for reaction for 5 hours, and then 160g 50wt% NaOH is added, the temperature is raised to about 100 ℃ for reaction for 5 hours, so that a solution C is obtained.
Dropwise adding a solution B into the solution C, controlling the temperature to be 70-80 ℃ after the dropwise adding of the solution B is completed, reacting for 5 hours, and cooling to obtain N- (2-carboxyethyl) -N- (carboxymethyl) -3-hydroxy-aspartic acid sodium salt (1:4), wherein the yield is: 96.63%.
The thermal stability of the hydroxyamino-carboxylic acid-containing chelating agent was examined in this example, and the examination results are shown in FIG. 4. As can be seen from FIG. 4, the temperature resistance of the chelating agent containing hydroxyamino carboxylic acid is higher than that of EDTA, and EDTA can hardly be used under the condition of high temperature use, especially at 250-350 ℃, but the chelating agent containing hydroxyamino carboxylic acid can be used continuously, and the residual rate of EDTA is about 28% and the residual rate of chelating agent containing hydroxyamino carboxylic acid is about 50%.
The chelating ability of the hydroxyaminocarboxylic acid-containing chelating agent was also examined in this example, and the examination results are shown in FIG. 5. As can be seen from FIG. 5, the chelating agent containing hydroxyaminocarboxylic acid has the capability of chelating calcium, magnesium and copper ions stronger than EDTA, only chelates iron ions lower than EDTA, and comprehensively evaluates the capability of chelating the four metals, and the chelating agent containing hydroxyaminocarboxylic acid is superior to EDTA, is an ideal chelating agent capable of replacing EDTA, and further considers the defects of high raw material toxicity, high equipment requirement, large industrialization difficulty, high production cost, high product price and the like in the GLDA and MGDA manufacturing processes. Therefore, the chelating agent containing the hydroxyamino carboxylic acid can replace EDTA, DPTA, NTA and other biodegradable chelating agents which are difficult to biodegrade and complex to produce and expensive.
Example 3:
(1) Adding 232g of maleic acid into 200g of deionized water, hydrolyzing at 45 ℃ for 1h to obtain a mixed solution, then adding 280g of 50wt% KOH solution at the temperature of not more than 50 ℃, adjusting the pH value of a reaction system to be 5.0-6.5, and then heating to 55 ℃ and stirring for 15min to obtain a solution A;
(2) Adding 15g of sodium tungstate into the solution A, stirring for 45min, then dropwise adding 450g of 30wt% hydrogen peroxide solution within 90min, simultaneously adding 168g of 50wt% KOH into the system, regulating the pH to 6.0-7.0, heating to 60-65 ℃ and stirring for 3h to obtain a solution B;
(3) 150g glycine, 100g deionized water and 300 g KOH/300 g were added to a separate 1L reactor, stirred and dissolved, then 125g acrylonitrile was added and reacted at about 60℃for 3 hours, and then 300 g KOH/300 g 30wt% was added and reacted at about 100℃for 3 hours to obtain a solution C.
Dropwise adding a solution B into the solution C, controlling the temperature to be 70-80 ℃ after the dropwise adding of the solution B is completed, reacting for 3 hours, and cooling to obtain N- (2-carboxyethyl) -N- (carboxymethyl) -3-hydroxy-aspartic acid potassium salt (1:4), wherein the yield is: 99.15%.
Example 4:
in this example, 100% eucalyptus pulp was used as a raw material, and EDTA, PP0124-2 (commercially available) and the chelating agent containing hydroxyamino carboxylic acid (denoted as New formulation-2) were used to bleach 100% eucalyptus pulp, respectively, to examine the bleaching ability of the chelating agent containing hydroxyamino carboxylic acid. Wherein, test concentration: the concentration of the bleached pulp is 25%; test environment: preserving heat for 90 minutes at 100 ℃, and kneading uniformly once every 30 minutes; the testing method and the dosage are as follows: the dosage of caustic soda and hydrogen peroxide is 100% of the effective content, other medicines are added by the finished goods, and the adding amount is the absolute dry weight of ton pulp.
Fig. 6 shows the chelation ability of the chelating agent containing hydroxyamino carboxylic acid, and it can be seen from the graph that the best bleaching effect is the formulation product containing the chelating agent containing hydroxyamino carboxylic acid, and EDTA is inferior, and the chelating agent containing hydroxyamino carboxylic acid is 4% higher than EDTA and 12.2% higher than the blank effect. Thus, from experimental results, the hydroxyamino-carboxylic acid-containing chelating agent may replace EDTA, while the formulation may replace a commercially available product formulation.
EDTA and other chelating agents in the prior art, such as acetic acid, benzoic acid, AP8101 (commercially available) and PP0124-2 (commercially available) are respectively adopted to examine the stability of the chelating agent containing the hydroxyamino carboxylic acid, and the specific examination steps are as follows:
the same dosage of EDTA, the chelating agent containing hydroxyamino carboxylic acid of the invention, AP8101 (commercially available), acetic acid, chelating agents containing hydroxyamino carboxylic acid of different batches, benzoic acid, ethylenediamine and PP0124-2 (commercially available) are respectively recorded as formulas 1-8, 100% eucalyptus pulp is used as raw materials, bleaching capability of formulas 1-8 is examined, and stability of each chelating agent is further described. Wherein, test concentration: the concentration of the bleached pulp is 25%; test environment: preserving heat for 90 minutes at 100 ℃, and kneading uniformly once every 30 minutes; the testing method and the dosage are as follows: the dosage of caustic soda and hydrogen peroxide is 100% of the effective content, other medicines are added by the finished goods, and the adding amount is the absolute dry weight of ton pulp.
FIG. 7 is a graph of stability testing of a hydroxyamino-carboxylic acid chelant, from which it can be seen that the formulation containing the hydroxyamino-carboxylic acid chelant bleach best, reflecting that the formulation containing the hydroxyamino-carboxylic acid chelant has better stability. In conclusion, the chelating agent containing the hydroxyamino carboxylic acid has high solubility in high-concentration aqueous alkali and aqueous acid, and has excellent storage stability; the hydroxyl-containing amino carboxylic acid chelating agent has mild reaction conditions, basically no waste exists during production, and has good industrial application value and social value.
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.
Claims (10)
1. A chelating agent containing hydroxyamino carboxylic acid, characterized in that the chelating agent has a molecular formula of C 9 H 9 NNa 4 O 9 The structural formula is as follows:
2. a process for preparing a chelating agent comprising a hydroxyamino carboxylic acid according to claim 1, comprising:
(1) Dissolving maleic anhydride in deionized water, adding NaOH solution, mixing to obtain mixed solution, regulating the pH value of the mixed solution, and heating and stirring to react to obtain solution A;
(2) Adding sodium tungstate into the solution A, stirring for reaction, adding hydrogen peroxide solution and NaOH, adjusting the pH value of the mixed solution, and then heating for reaction to obtain solution B;
(3) Dissolving glycine in deionized water, adding NaOH solution into the glycine, stirring and mixing uniformly, adding acrylonitrile, reacting at a certain temperature 1, adding NaOH solution for the second time after the reaction is finished, and heating to react 2 to obtain solution C after the reaction is finished;
and (3) dropwise adding the solution B into the solution C, then heating the solution C for reaction 3, and cooling the solution C after the reaction is finished to obtain the chelating agent containing the hydroxyamino carboxylic acid.
3. The method for preparing a chelating agent containing hydroxyamino carboxylic acid according to claim 2, wherein in the step (1), the mass ratio of maleic anhydride, deionized water and NaOH solution is 190-220 g:190-220 g;
the temperature of the NaOH solution is not more than 45 ℃ when the NaOH solution is added, and the mass concentration of the NaOH solution is 35-50 wt%.
4. The method for producing a chelating agent containing hydroxyamino carboxylic acid according to claim 2, wherein in the step (1), the pH of the system is adjusted to 6.0 to 6.5;
the conditions of the heating and stirring reaction are that the temperature is raised to 45-65 ℃ and the stirring reaction is carried out for 15min.
5. The method for preparing a chelating agent containing hydroxyamino carboxylic acid according to claim 2, wherein in the step (2), the solution B is prepared by using sodium tungstate, hydrogen peroxide solution, naOH and the maleic anhydride in the step (1) in a ratio of 12-18 g:320-380 g: 100-145 g: 180-200 g;
the stirring reaction condition is stirring for 45-60 min;
the mass concentration of the NaOH solution is 35-50wt%; the mass concentration of the hydrogen peroxide solution is 25-35 wt%.
6. The method for producing a chelating agent containing hydroxyamino carboxylic acid according to claim 2, wherein in the step (2), the pH of the system is adjusted to 6.0 to 6.5;
the temperature rising reaction condition is that the temperature is raised to 25-40 ℃ and the stirring reaction is carried out for 1-5 h.
7. The method for preparing a chelating agent containing hydroxyamino carboxylic acid according to claim 2, wherein in the step (3), the mass ratio of glycine, deionized water, the first NaOH solution, acrylonitrile and the second NaOH solution is 130-170 g/70-130 g/150-170 g/120-135 g/150-165 g.
8. The method for producing a chelating agent containing hydroxyamino carboxylic acid according to claim 2, wherein in the step (3), the condition of the reaction 1 is that the reaction is carried out at 50 to 70 ℃ for 1 to 5 hours;
the condition of the temperature rising reaction 2 is that the reaction is carried out for 2 to 4 hours at the temperature of 90 ℃;
the mass concentration of the NaOH solution added for two times is 35-50wt%.
9. The method for producing a chelating agent containing hydroxyamino carboxylic acid according to claim 2, wherein in the step (3), the condition of the reaction 3 is that the reaction is carried out at 70 to 80 ℃ for 3 hours.
10. Use of a chelating agent comprising a hydroxyamino carboxylic acid according to claim 1 for chelating heavy metal ions.
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