KR101285899B1 - Manufacturing method of N, P free type Eco-Friendly Chelating agents - Google Patents

Abstract

The present invention has excellent biodegradability and does not contain nitrogen and phosphorus components, which are excellent biodegradable factors and eutrophication factors of aqueous pollution, in order to replace the hardly degradable chelating agents which are used in the textile, paper and leather industries, which are water consumption industries. It relates to the production of N, P free type environmentally friendly chelating agent of the structure.

Description

Manufacturing method of eco-friendly chelating agent that does not contain nitrogen and phosphorus component {Manufacturing method of N, P free type Eco-Friendly Chelating agents}

The present invention relates to EDTA (Ethylenediamine Tetra acetic acid sodium salt), DTPA (Diethylenetriamine pentaacetic acid penta sodium salt), DTPMPA (Diethyl-enetriamine penta) Methylenephosphonic acid hepta sodium salt) and N, P free type environmentally friendly chelating agent with chemical structure that does not contain nitrogen and phosphorus component that can replace STPP (Sodium Tripolyphosphate) which is phosphorus chelating agent. Compared to EDTA, DTPA and STPP, which are phosphorus chelating agents, it has excellent Chelating Value, hydroxide dispersibility of metal ions, residual excess amount, fiber whiteness and residual ratio, and has more than 90% COD, BOD reduction effect and biodegradation efficiency within 48 hours. Its main feature is that it can drastically reduce environmental hazards.

In the textile, paper and leather industry, which is a rather water-intensive industry, a large amount of water is used in all linking processes, from pretreatment to processing, in which processes minimize the effects of metal ions and accumulated impurities in the water. Although most of the chelating agents are used, most of the chelating agents are EDTA, which is a nitrogen-containing phosphorus chelating agent in most industries because of its functional effect despite the environmental damage of water pollution caused by structural characteristics that are difficult to decompose. , DTPA and STPP are widely used. Although the amount of industrial water used in the textile industry depends on the type of fiber and the processing process, it is known to use about 170 tons of water per 1000 pounds of textile products. In addition, more than 80% of this water is used in the pretreatment and dyeing process. The textile industry is a water-consuming industry where the water quality of the water greatly affects the product. Therefore, in the textile industry, water is the most used raw material and the most important process factor in all processes such as refining, bleaching, dyeing, printing and post processing of textile fabrics. In other words, the quality of water in each process acts as an important variable for the color and feel of the textile products. In the textile industry, pretreatment and dyeing processes, which use water most often, use surface water, groundwater, or industrial water. Among these, groundwater contains a lot of metal ions such as calcium (Ca ²⁺ ), magnesium (Mg ²⁺ ), and iron (Fe ³⁺ ) such that the hardness reaches 500 to 1,000 ppm. There is a severe effect of high organic decomposition products content, there is a problem that changes in turbidity and pH due to impurities such as acid or alkali is severe. On the other hand, industrial water has a hardness of about 60 to 90 ppm, but there is a problem in that the production cost increases due to the purification process. Industrial water contains a number of impurities such as various metal ions including heavy metals, carbonates, non-carbonates, organics, inorganics, turbidity-causing substances, and other insoluble solids, and as the industrial fields such as quality improvement and process refinement are advanced. The importance of water is becoming common in industries that use a large amount of water. Especially in the fine chemicals, textiles, paper and leather industries, the quality of water has a great influence on the products produced. Domestic household detergents are regulated for eutrophication and biodegradation of water quality for rivers and rivers. However, in the industrial sectors such as textiles and papermaking, there are still legal prohibitions for the production and sale of nitrogen-containing and phosphorus-based products. Since the situation is not made at all, the use of an environmentally friendly chelating agent is required more actively.

Therefore, in the present invention, after preparing a chelating agent of an environmentally friendly chemical structure, which is excellent in biodegradability and does not contain nitrogen and phosphorus, which is an eutrophication factor of water quality, the functional properties and environmental properties were evaluated.

Cellulose materials such as wood pulp, which manufactures paper, and cotton fiber, which manufactures fibers, require a bleaching process. Wood pulp bleaching is an Alkaline system using H ₂ O ₂ . An important factor of this bleaching process is metal ions and high alkalinity in water and pulp. Hydrogen peroxide and alkaline agents are inevitably used for uniform whiteness and removal of impurities. If metal ions are present in the solution in the bleaching process, the loss of useful oxygen components for bleaching occurs quickly by Peroxide and Interaction. Even if very small amounts of metal ions such as Fe ²⁺ 1.0 ppm and Cu ²⁺ 0.25 ppm exist in the bleach solution, peroxide decomposition proceeds rapidly. The source of metal ions is paper mill, wood, water, wood clip or pulp mill in the papermaking process of wood pulp. The main factors affecting the whiteness of pulp in the bleaching process are metal ion concentration, temperature, Density of pulp and uniform decomposition stability of hydrogen peroxide (H ₂ O ₂ ). Some of the metal ions are removed during the Deckering and Dewatering processes, but the others are removed using chelating agents. Chelating agent that can suppress peroxide decomposition by various metal ions in the solution to increase the stability of hydrogen peroxide used as bleaching agent in the process of paper making. Use Silicate is most commonly used as a water stabilizer during the bleaching process. In this process, insoluble Silicate is deposited on pulp fiber or machine, it gives a rough feeling to the paper, and the machine has a down or short life. Therefore, there are two kinds of stabilizers that are commonly used to use Silicate-free fruit stabilizers. One is Aminocarboxylate type such as EDTA, NTA, DTPA and the other is NTPO (Nitrilotrimethylenephosphonic acid), EDTPO (Ethylenediamine tetra methylene phosphonic acid), HEDP (Hydroethylidenediphosphonic acid). N and P compounds containing nitrogen and phosphorus are commonly used as the two strains, and are widely used as decomposition stabilizers in fruit or bleaching baths in the paper industry. However, the final product of the present invention is N, P free copolymer composites. I think that will achieve the goal.

Industrially used chelating agents include sequestration to form stoichiometric complexes with metal ions, deflocculation to disperse solids in solution, scale inhibition to prevent and remove scale deposits in the process, high temperature and rapid pH Hydrolytic Stability to maintain the stability of the solution from change. In addition, chelating agents soften hard water by dispersing organic and inorganic compounds, promoting cleaning power, preventing corrosion and complexing metal ions in water in various industrial processes. When impurities such as metal ions and organic decomposition products are contained in the water, problems such as deterioration of whiteness, pin hole generation, and reattachment of contaminants occur in the refining process.In the dyeing process, color discoloration, solubility of dye, dispersibility, etc. It causes problems of disproportionation and tarring due to deterioration. Chelating agents such as polyphosphate and Aminocarboxylate, which are used to solve this problem, have a great advantage in sequestering power, but most of the decomposition products are nitrogen (N) with the disadvantage of low water biodegradability which causes water pollution of rivers or rivers. ), It contains a large amount of phosphorus (P), there is a problem such as eutrophication, red tide caused by these nutrients.

Therefore, the present invention relates to the production of environmentally friendly chelating agent that does not contain nitrogen and phosphorus in the molecular structure starting from Sugar-base Alcohol as a natural base. The purpose of this study is to verify the performance and environmental performance through the evaluation of Chelating Value, hydroxide dispersibility of metal ions, residual excess, fiber whiteness, residual ratio and biodegradability.

Therefore, the present invention is a natural base having excellent biodegradability and alcohol-based sugar-based alcohol, and the mole ratio between polyhydric alcohols such as Mannitol, D-Sorbitol, Galactitol, Iditol, Erythritol, Arabitol, Xylitol, Pentaerythritol, Glycerol and Maleic anhydride and Acrylic acid. 1 to 1:10 to vary the conditions to proceed with the Ester reaction to complete the first reaction. In the second reaction, copolymerization is carried out using monomers containing carboxyl, that is, maleic anhydride, acrylic acid, methacrylic acid, etc., and the first reaction product, Ester Monomer, with mole ratio of 10: 1 to 0.01: 1.

N, P free chelating agent of the present invention is an environmentally friendly chemical structure with excellent biodegradability and quality evaluation such as Chelating Value, hydroxide dispersibility of metal ions, residual excess amount, fiber whiteness and residual ratio, etc. Since it does not contain nitrogen (N) and phosphorus (P), which are superior to phosphorus and especially cause decomposition of water, there are no problems such as eutrophication and red tide caused by these nutrients. have.

1 Experimental conditions of residual excess, fabric whiteness and residual ratio of the present invention
Figure 2 prototype-1 reaction scheme of the present invention
3 is a graph showing the change in total hardness of tap water according to the amount of chelating agent of the present invention

Phosphate-based and polyphosphonate-based metal ion sequestrants are organic phosphates, and their chemical main chains, phosphorus and carbon, are highly stabilized, resulting in relatively poor biodegradability and eutrophication in water. They are generally used as rust inhibitors or hydrogen peroxide stabilizers. In detergents, small amounts are used as additives for bleach to block heavy contaminants of laundry and water in order to prevent interference with bleaching effects. EDTA and NTA are widely used as additives for detergents and are generally mixed with zeolite A and sodium aluminum silicate salts. Their biodegradability is about 95%, but they slow down the growth of seaweeds when they are discharged and are already deposited in rivers. There is a disadvantage of forming a complex with a metal ion. EDTA has the ability to contain strong metal ions, but is not environmentally friendly due to the remobilization of metal ions. Organic phosphate also does not remobilize metal ions because it has high adsorption power and low formation ability index in neutral bath.

Patent WO2007025944, 'Chelating Formulation for machine Dishwashing Comprising Hydrophilically Modified Poly Carboxylates.' Filed by German multinational chemical company, summarizes the detergents for dishwashers comprising Carboxylates, a chelating agent that does not contain phosphorus. will be. Carboxylate polymers are N, P free eco-friendly chelating agents. It is necessary to pay attention to the effect that washing power is greatly enhanced in all materials by excellent dispersibility. Another advantage is that it is stable in acid and alkali baths and is a mild-induced metal such as calcium and magnesium ions. Bonding power and dispersibility are very good. In addition, according to Swiss multinational company Jungbunzlaeur, Gluconic acid made by oxidizing Glucose also has various chelating functions. Since this type of chelating agent exhibits high containment force only at limited acid alkali concentrations, metal ion containment efficiency is highly dependent on pH.

Here, it is worth paying attention to the raw materials of the above two chelating agents. If you fully understand the mechanism of the characteristics and effects of each of the above two chelating agents, N, P free type chelating agents with excellent biodegradability can be synthesized and applied in a wide range while providing various functions. When polycarboxylate polymer is used in water, it can chelate dissolved metal ions to soften water quality, inhibit corrosion of cooling water and boiler pipe, and prevent scale formation by dispersing organic and inorganic materials. It does not contain nitrogen and phosphorus. Therefore, water pollution can be minimized.

Prototype 1 of the present invention relates to the production of N, P free type eco-friendly chelating agent, which is a sugar-based alcohol as a natural base, polyhydric alcohols such as Mannitol, D-Sorbitol, Erythritol, Arabitol, Xylitol, Maleic anhydride and Acrylic The first reaction is completed by performing the Ester reaction, varying the mole ratio between 1: 1 and 1:10 between acids. In the second reaction, polymerization is carried out by varying the conditions of the monomers containing carboxyl, that is, maleic anhydride, acrylic acid, and methacrylic acid, and the ratio of the primary reaction product, Ester Monomer, to mole ratio from 10: 1 to 0.01: 1. Reaction initiator in the secondary copolymerization using Sodium persulfate (SPS) and the reaction temperature and time is proceeded for 5 hours at 40 ~ 100 ℃ and leave the aging time of 1 hour after the completion of the reaction. The final secondary reaction product is a copolymer of ester monomer and acrylic acid of Mannitol, D-Sorbitol, etc. and Maleic anhydride. The mole ratio is 2: 8, and the concentration is 50%.

Prototype-2, another method of the present invention, omits the first Ester reaction, and uses only 40% to 50% of the homopolymer, maleic anhydride, and acrylic by using only acrylic acid as the polymerization condition. The mole ratio between acids is 1: 1 to 1:10, and the polymerization is carried out by varying the conditions to synthesize a copolymer having a concentration of 40 to 50% as a primary reaction product. The first reactant was formulated at a rate of 1-99% and sugar-base Glucose Manni- tol and D-Sorbitol 0-80% to form a 50% N, P free eco-friendly chelating agent. Conduct quality and environmental assessment.

본 발명 시제품의 또 다른 제조과정 반응식으로 Sugar-base의 Alcohol인 D-Sorbitol과 Acrylic acid간의 Ester반응으로 제조된 Monomer와 Acrylic acid의 Copolymer 제조 및 Sodium 부가과정을 나타낸다.

시제품-2의 제조과정 반응식은 Maleic anhydride와 Acrylic acid간의 mole비를 1:1 ∼ 1:10으로 조건을 달리하며 공중합한 40 ~ 50% 농도의 Copolymer를 합성한다. 제조된 1차 공중합물 1~99%와 Sugar-base의 Alcohol인 D-Sorbitol을 1~80%함유한 비율로 Formulation을 하여 50% 농도의 N, P free형 킬레이트제의 제조과정을 나타낸다.

As a reaction scheme of the preparation of the present invention Prototype 1, it shows a process for preparing a copolymer and adding sodium to an acrylic acid after an ester reaction between D-Sorbitol, a sugar-based alcohol, and maleic anhydride.

As a reaction scheme of the preparation process of the present invention, the copolymer and monoaddition process of Monomer and Acrylic acid prepared by the ester reaction between D-Sorbitol and Acrylic acid, which are sugar-based alcohols, are shown.

Reproduction formula of Prototype-2 synthesizes copolymer of 40 ~ 50% of copolymer with different mole ratio of 1: 1 ~ 1: 10 between maleic anhydride and acrylic acid. The process of preparing N, P free type chelating agent with 50% concentration is shown by formulating 1 to 99% of the prepared primary copolymer and 1 to 80% of D-Sorbitol, an alcohol of sugar-base.

Physical properties of the N, P free type environmentally friendly chelating agent of the present invention are shown in Table 1 below.

The following examples illustrate the invention in more detail, but do not limit the scope of the invention.

(Example 1)

Completely remove the moisture in the reactor by drying and vacuum dehydration in a stainless reactor (SUS316; inner glass coating type), which is equipped with a reflux condenser, a cooling coil, and a jacket and is approved as a pressure vessel, and then prevents oxidation and reaction of reactants and products. In order to improve the yield, 1 mole of D-Sorbitol and 1 mole of maleic anhydride are added while replacing nitrogen gas, and then the Ester reaction is performed to complete the first reaction. The end point of the first reaction is determined based on the theoretical acid value corresponding to the remaining 0.5 mole of maleic anhydride by measuring the acid value. Copolymerization was carried out by titrating the first reaction product, Ester Monomer 1 mole and Acrylic acid 1 mole, followed by adding NaOH as a final step to prepare prototype 1, an N, P free type eco-friendly chelating agent. The reaction initiator in the second copolymerization is using sodium persulfate (SPS) and the reaction temperature and time is proceeded for 5 hours at 40 ~ 100 ℃ and leave the aging time of 1 hour after the completion of the reaction.

(Example 2)

Completely remove the moisture in the reactor by drying and vacuum dehydration in a stainless reactor (SUS316; inner glass coating type), which is equipped with a reflux condenser, a cooling coil, and a jacket, and is approved as a pressure vessel. For the purpose of yield improvement, after copolymerization with Titration of 0.1 mole of Maleic anhydride and 1 mole of Acrylic acid while replacing nitrogen gas, NaOH is added to complete the first reaction. The reaction initiator is using sodium persulfate (SPS), the reaction temperature and time is proceeded for 5 hours at 40 ~ 100 ℃ and leave the maturation time of 1 hour after the reaction. Prototype-2, a 50% concentration of N, P free eco-friendly chelating agent, is prepared by formulating a ratio containing 85% of the first reactant and 15% of D-Sorbitol.

Experimental Example 1

Using the N, P free type eco-friendly chelating agent Invention Prototype 1 prepared in Example 1, the cotton fabric (CW 30'S) was tested under the conditions of (FIG. 1) and the prescription of (Table 2), and (Table 3) Result was obtained.

As can be seen from Table 3, the result of excellent residual overflow, whiteness and residual ratio of the fabric can be seen.

Experimental Example 2

The COD for the environmental evaluation of the N, P free type environmental chelating agent obtained in Example 1 was tested based on the KSM 0115 test method and the BOD was tested based on the KSM 9137 test method. The results are shown. As it is N, P free type that contains no nitrogen and phosphorus, there is no environmental risk such as eutrophication. Environmental results such as BOD _and biodegradation rate also showed good results.

BOD is the amount of oxygen consumed when an organic substance undergoes biochemical oxidation at a certain temperature for a certain time. The biodegradability can be evaluated through the value of BOD. (Table 4) shows that the value of BOD decreases rapidly. Can be. The biodegradation recommended by the OECD requires 60 to 80% biodegradability, the N, P free eco-friendly chelating agent of the present invention has a high biodegradability of 97.2%.

Experimental Example 3

The Chelating Value was analyzed by using 0.5g / L, 1.0g / L, 2.0g / L with the following four chelating agents.The types were ethylene diamine tetra acetic acid tetra sodium salt (EDTA), sodium tripolyphosphate (STPP), A foreign product made by Gluconic acid and a prototype of N, P free invention, Prototype 1, were used. Table 5 shows the results of measuring the Chelating Value by type and amount of chelating agent.

Table 5 shows the change in the total hardness of tap water according to the amount of chelating agent based on the Chelating Value Check result (Figure 3), and the EDTA, N, and P free prototypes showed good results.

Experimental Example 4

Hydroxide dispersibility of metal ions was evaluated using N, P free type environmentally friendly chelating agents obtained in Example 1. Evaluate the effect of metal ions (Ca ²⁺ , Mg ²⁺ , Cu ²⁺ , Fe ²⁺ ) in the water on the formation and precipitation of hydroxides by caustic soda (NaOH) to disperse metal ions under high temperature strong alkali conditions of chelating agents The comparative items used were Ethylene diamine tetra acetic acid tetra sodium salt (EDTA), Sodium tripolyphosphate (STPP), and foreign C company's synthetic products using Gluconic acid. Table 6 shows the results of dispersibility by type and amount of chelating agent. N, P free prototype showed good dispersion effect in all metal ions. Foreign C company's product was only insufficient in Fe ³⁺ ion. The dissipation effect of the other ions was comparable with the present invention, but EDTA and STPP showed remarkably inferior dispersibility in all ions. Chelating value tested at pH 10 with nitrogen-containing (N) -based and phosphate-based (P) -based chelating agents showed good results, but high concentration alkali such as sodium hydroxide (NaOH) and hot water with high temperature above 90 ℃ In the paper, leather and leather industries, it is not suitable as a chelating agent in high temperature and alkaline conditions due to the lack of dispersibility.

Claims (3)

It is a natural sugar-base alcohol represented by Scheme 1. Method for preparing a liquid composition to be used as N, P free eco-friendly chelating agent for the production of copolymer of mole ratio of 10: 1 ~ 0.01: 1 of ester ester and acrylic acid. Reaction condition is using a sodium persulfate (SPS) as a catalyst and the copolymerization at 40 ~ 100 ℃ while Titration of Ester Monomer and Acrylic acid after the addition of NaOH to the final step of the manufacturing method of the chelating agent.
[Reaction Scheme 1]

Mole ratio between Homopolymer using only acrylic acid, maleic anhydride, and acrylic acid was changed to 1: 1 ~ 1:10, and the polymerized copolymer contained 1 ~ 99% based on the active ingredient, Mannitol, which is sugar-based Glucose. Liquid composition used as N, P free eco-friendly chelating agent containing 0 ~ 80% of tetravalent or higher polyhydric alcohols such as D-Sorbitol, Erythritol, Arabitol, Xylitol
[Reaction Scheme 2]

It is a natural sugar-based alcohol represented by Scheme 3. Method for preparing a liquid composition to be used as N, P free eco-friendly chelating agent for the production of copolymer of mole ratio of 10: 1 ~ 0.01: 1 of ester ester and acrylic acid. Reaction condition is using a sodium persulfate (SPS) as a catalyst and the copolymerization at 40 ~ 100 ℃ while Titration of Ester Monomer and Acrylic acid after the addition of NaOH to the final step of the manufacturing method of the chelating agent.
[Reaction Scheme 3]

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