CN103102273B - A kind of purification process of organic amine electroplating additive - Google Patents

Abstract

The invention discloses a method for purifying organic amine electroplating additives. The anion and cation impurities in organic amine electroplating additives are removed through an electrodeionization device; The cathode or anode connected to the DC power supply, several parallel purification chambers and concentrated water chambers are arranged alternately between the two end plates, and each purification chamber and concentrated water chamber are separated by cation exchange membranes or anion exchange membranes ;The purification chamber is filled with ion exchange resin, and the concentrated water chamber and the extreme water chamber are respectively filled with organic ammonium salt solution with a concentration of 0.3%-1%; the flow rate of the purification chamber is 1-100L/h, and the flow rate of the concentrated water chamber and the extreme water chamber 1-100L/h; the voltage of the DC power supply is 0-100V, the voltage of the purification process is constant and the temperature of the solution is kept at 20-70°C; the recovery rate of organic amine electroplating additives after purification is greater than 80%. The purification method of the organic amine electroplating additive provided by the invention has a simple and easy-to-control process, and the purification degree can reach the fine electronic grade standard.

Description

A kind of purification method of organic amine electroplating additive

technical field

The invention relates to a method for purifying organic amine compounds, in particular to a method for purifying organic amine electroplating additives, mainly aimed at the removal of metal ion impurities and anion impurities in industrial-grade and electronic-grade organic amine electroplating additives.

Background technique

Organic amine electroplating additives refer to the key additives used in high-purity copper sulfate or high-purity copper methanesulfonate electroplating, such as: triethanolamine, triisopropanolamine, diglycolamine, triethylenediamine, N, N-diethylpropynylamine, tetramethylammonium hydroxide, etc. Its general formula is as follows:

R ₁ -R ₃ represent H or 1-10 carbon chain alkyl, alkenyl, alkynyl, alkoxy, alkanol, acetyl, benzyl, etc.

Organic amine electroplating additives, such as tetramethylammonium hydroxide (TMAH) and triethanolamine, belong to organic bases and have a very wide range of uses in the field of industrial scientific research. For example, tetramethylammonium hydroxide is mainly used in organic Catalysts for silicon series products and polyester polymers, textiles, plastic products, food, leather, wood processing and other fields. With the development of the electronics industry, these organic amine compounds can also be used as excellent electroplating additives in the semiconductor industry. For example: Chinese patent CN10381313 reports a method for synthesizing electroplating additive N,N-diethylpropynylamine, and Chinese patent CN101298688A uses amine compounds as the main additives of electronic electroplating solutions. At present, most of the domestically produced organic amine compounds are of industrial grade, and commercially available industrial-grade organic amine compounds contain more metal ion impurities and anion impurities, which are not suitable for application in the field of electronic electroplating, especially for semiconductor crystal Round plating. Taking tetramethylammonium hydroxide as an example, a commercial industrial-grade tetramethylammonium hydroxide sample is now analyzed for trace metals. The analysis report is shown in Table 1. Na, K, Ca, Cr, Cu, Mn, Mg, The contents of Ni, Zn, Pb, Fe, Al, Ag metal ions are determined by ICP-AES method and expressed in ppb (1ppb=1μg/kg). At the same time, chloride ions and carbonate ions in industrial-grade TMAH were detected using DIONEXDX120 dual-channel ion chromatography. The results are shown in Table 1, which shows that the concentration of metal ions, chloride ions and carbonate ions in TMAH exceeds that of fine electronic grade (SEMIStandardC46- 0306) level standards.

Table 1 shows the content of anion and cation impurities in a commercially available technical-grade TMAH raw material.

As we all know, when IC chips are polluted by metal ions such as Fe, Cu, and Na, OISF (Oxidation-Induced Stacking Faults, Oxidation-Induced Stacking Faults) will be generated, thus increasing the leakage current of p-n combination and reducing the lifetime of minority carriers. Therefore, it is an urgent problem to develop a good method to purify organic amine electroplating additives to make them more suitable for the use of highly precise semiconductor devices. At present, most of the researches on the purification of organic amines focus on rectification or electrolysis. For example, U.S. Pat. No. 4,714,530 has developed a method for purifying TMAH by electrolysis. However, none of them have been able to propose a general, simple, green and environmentally friendly purification scheme for organic amine compounds.

Electrodeionization technology (ElectroDeionization), referred to as EDI technology, can organically combine electrodialysis technology and ion exchange resin technology, and has the advantages of continuous desalination of electrodialysis technology and deep desalination of ion exchange resin, and can avoid electrolysis Concentration polarization of dialysis technology and acid-base regeneration of ion exchange resin. Usually, EDI technology is used for the production of high-purity water. In the Chinese patent CNCN201770477U, an EDI production device for preparing ultra-clean and high-purity H ₂ O ₂ was invented. In addition, in the Chinese patent CN101993387A, the method of combining rectification and EDI is used for purification Electronic grade N,N-dimethylformamide, but its application to the purification of organic amine electroplating additives has not been reported in the literature.

Contents of the invention

The purpose of the present invention is to provide a method for removing metal ions and chloride ion impurities in industrial-grade organic amine electroplating additives, and to provide a purification method with simple process, easy control of conditions, and environmental protection and greenness. In the obtained organic amine additive solution, The impurity content of each metal ion and anion can reach the fine electronic grade standard, so as to overcome the shortcomings of the prior art such as high impurity content and unstable quality control.

In order to achieve the above object, the present invention provides a method for purifying organic amine electroplating additives, wherein the method is to remove anion and cation impurities in organic amine electroplating additives through an electrodeionization device; End plates are respectively provided at one end plate, a cathode connected to a DC power supply is provided on one end plate, an anode connected to a DC power supply is provided on the other end plate, an electrode water chamber is provided on the inner side of the two end plates, and two A number of parallel purification chambers and concentrated water chambers are arranged alternately between the extreme water chambers, and each purification chamber and concentrated water chamber are separated by a cation exchange membrane or an anion exchange membrane; the cation exchange membrane and the anion exchange The membranes are arranged alternately so that the side of each purification chamber near the anode end plate is a cation exchange membrane, and the side near the cathode end plate is an anion exchange membrane; the purification chamber is filled with a mixture of anion exchange resin and cation exchange resin; The concentrated water chamber and the polar water chamber are respectively added with 0.3%-1% organic ammonium salt solution as the electrolyte; the liquid flow rate of the purification chamber is 1-100L/h, and the flow rate of the concentrated water chamber and the polar water chamber is 1-100L/h; the initial voltage of the DC power supply is 0-100V, the voltage is constant during the purification process and the solution temperature is kept at 20-70°C; the recovery rate of the purified organic amine electroplating additive is greater than 80%.

Under the action of an electric field, anions and cations migrate through the ion exchange membrane, reducing impurity ions in the purification chamber, thereby achieving the effect of purifying organic amine compounds. At the same time, for organic ammonium salt compounds, since the concentration of organic ammonium salt is 10 ⁵ -10 ⁶ times the concentration of impurity ions, the dissociation loss of a small amount of organic ammonium salt under the action of electric field can be ignored, and at the same time enter the concentrated water chamber The organic ammonium salt in it can be recycled after entering the industrial production system, thereby reducing the cost.

The above-mentioned method for purifying organic amine electroplating additives, wherein the anion exchange membrane is a heterogeneous or homogeneous ion exchange membrane of one of polyethylene, polypropylene, polyvinyl chloride, polyether or fluorine-containing high polymer , the cation exchange membrane is one of heterogeneous ion exchange membrane, polyethylene homogeneous ion exchange membrane, sulfonic acid membrane or perfluorosulfonic acid membrane.

The purification method of the above-mentioned organic amine electroplating additive, wherein, described anion exchange resin and cation exchange resin comprise styrene-based ion-exchange resin, polyacrylic acid-based ion-exchange resin, aminophosphoric acid or iminodiacetic acid chelating resin One of.

The above-mentioned method for purifying organic amine electroplating additives, wherein the ratio of the anion exchange resin to the cation exchange resin is 10:1 to 1:10, preferably 1:4 to 2:3.

The method for purifying the above-mentioned organic amine electroplating additives, wherein the cathode and the anode use one of graphite, 316L stainless steel, titanium, platinum or iridium-plated titanium plate, preferably iridium-plated titanium wire mesh plate. Under the action of a DC electric field, the anion and cation impurities in the industrial-grade organic amine electroplating additives enter the concentrated water chamber through the anion and cation membranes on both sides respectively, so as to achieve the purpose of purification.

The above-mentioned method for purifying organic amine electroplating additives, wherein, the outside of the concentrated water chamber and the polar water chamber are respectively provided with partitions, and are fixed with the entire electrodeionization device through the partitions; the electrodeionization Each joint of the device is sealed with a silicone rubber gasket.

The above-mentioned method for purifying organic amine electroplating additives, wherein, the electrodeionization device further includes a feed port and a discharge port of organic amine electroplating additives, a concentrated water/polar water inlet, a concentrated water outlet, and a polar water outlet , are respectively connected with the upper and lower parts of the purification chamber, the upper part of the polar water chamber and the concentrated water chamber, the lower part of the concentrated water chamber and the lower part of the polar water chamber.

The method for purifying the above-mentioned organic amine electroplating additives, wherein, the concentrated water/polar water inlet, the concentrated water outlet, the polar water outlet, and the inlet and outlet of the organic amine electroplating additives of the electrodeionization device are respectively It is connected with a conveying pipe, and gate valves are respectively arranged on the conveying pipe; the conveying pipe connected with the feed inlet is also provided with a first pressure gauge, a safety valve, a first flow meter and a raw material pump in sequence from the feed inlet to the outside; A second pressure gauge, a second flow meter, and a concentrated water/polar water pump are provided on the delivery pipe connected to the water/polar water inlet from the concentrated water/polar water inlet to the outside; A third pressure gauge, a third flow meter and a sampling valve are arranged in sequence outward from the feed port; a fourth pressure gauge, a gate valve and a concentrated water circulation pump are arranged in sequence from the concentrated water outlet outward on the conveying pipe connected to the concentrated water outlet. , the other end of the conveying pipe is respectively connected with the conveying pipe between the second flow meter and the concentrated water/polar water pump and the concentrated water discharge tank.

The above method for purifying organic amine electroplating additives, wherein the method includes: step 1, assembling an electrodeionization device and filling ion exchange resin; step 2, filtering the raw material solution of organic amine electroplating additives, and filtering out particulate matter , fibrous impurities, etc., the filtrate is transparent and clear, without visible particles, and then the filtrate is diluted to a pH value of 10-13.5, and pumped into the electrodeionization device; Step 3, add 0.3% Organic ammonium salt solution with a concentration of -1% is used as electrolyte; step 4, the raw material pump, concentrated water/polar water pump and concentrated water circulation pump are started at the same time, and a cyclic electrodeionization process is performed; step 5, change the device material and reaction conditions, and record The concentration of impurity metal ions and anions in the organic amine electroplating additive solution in the purification chamber when the electrodeionization device reaches a steady state operation is used to determine the optimized process conditions, for example, with a gradient of 10 volts, the operating voltage is gradually increased from 0 volts to 100V, record the ion concentration of impurities in the purification chamber under each operating voltage, and also investigate the current and the concentration of metal ions in the concentrated water and other parameter values; step 6, carry out the purification of organic amine electroplating additives with the optimized process conditions determined in step 5. During the purification process, the temperature of the raw material solution is detected by a thermometer, and the temperature is controlled not to be higher than 20°C-70°C, preferably 45°C-60°C; at the same time, the discharge is sampled every 15 minutes to detect the anion and cation concentrations of impurities in it. When the concentration of anions and cations in the sample reaches the standard requirements of the fine electronic grade, the purified organic amine electroplating additive solution is collected; step 7, the purified organic amine electroplating additive solution is then passed through a 0.1-0.22 μm microfiltration membrane The final product is obtained by filtration. In order to ensure that the product quality is not affected by the environment such as air, the filtration process is carried out in a 100-level ultra-clean environment. The organic ammonium salt solution in the concentrated water chamber can be recycled and reused. The method may further include step 8, wherein the purified organic amine electroplating additive is dehydrated and concentrated by vacuum distillation.

The above purification method of organic amine electroplating additives, wherein, the electrodeionization device is a thick chamber mixed bed electrodeionization device, a thin chamber mixed bed electrodeionization device, a layered bed electrodeionization device, a separate bed electrodeionization device One of a deionization unit or a bipolar membrane electrodeionization unit.

The purification method of the organic amine electroplating additive provided by the invention has the following advantages:

The invention provides a production process with good purification effect, low energy consumption and continuous production of electronic-grade purity organic amine electroplating additives. It can well reduce the content of metal ions and anions in the organic amine electroplating additives, and the purified organic amine electroplating additives can reach the standard of fine electronic grade.

The characteristics of organically combining electrodialysis and ion exchange by using electrodeionization technology not only retains the advantages of electrodialysis can continuously remove anion and cation impurity ions and ion exchange resin can deeply remove anion and cation impurities, but also overcomes electrodialysis. It cannot deeply remove anion and cation impurities and adverse effects caused by concentration polarization.

The purification method can not only effectively purify industrial-grade organic amine electroplating additives to electronic grade, but also has low energy consumption, is green and environmentally friendly, occupies an area, can effectively reduce the discharge of industrial three wastes, and is suitable for large-scale industrial production. Therefore the present invention has good adaptability and market prospect.

Description of drawings

Fig. 1 is the schematic diagram of the electrodeionization device of the purification method of the organic amine electroplating additive of the present invention.

Fig. 2 is a schematic diagram of equipment connection of the purification method of the organic amine electroplating additive of the present invention.

detailed description

The specific embodiments of the present invention will be further described below in conjunction with the accompanying drawings.

The method for purifying organic amine electroplating additives provided by the present invention uses an electrodeionization device 15 to remove anion and cation impurities in organic amine electroplating additives.

Electrodeionization (EDI) device 15 includes 2 pairs of electrodes and 30 pairs of ion exchange membranes, the size of which is 200mm×100mm. The anion exchange membrane 12 is a heterogeneous or homogeneous ion exchange membrane such as polyethylene, polypropylene, polyvinyl chloride, polyether or fluorine-containing high polymer, and the cation exchange membrane 11 is a heterogeneous ion exchange membrane. membrane, sulfonic acid membrane or perfluorosulfonic acid membrane. The designed production flow is 1-100L/h.

As shown in Figure 1, the two ends of the EDI device 15 are respectively provided with end plates 8, one end plate 8 is provided with a cathode 1 connected with a DC power supply, and the other end plate 8 is provided with an anode 2 connected with a DC power supply, both The inner side of the block end plate 8 is respectively provided with a polar water chamber 9, between the two polar water chambers 9, parallel purification chambers 7 and concentrated water chambers 10 are arranged alternately in sequence, between each purification chamber 7 and concentrated water chamber 10 Separated by cation exchange membrane 11 or anion exchange membrane 12 respectively. Cation exchange membranes 11 and anion exchange membranes 12 are arranged alternately so that the side of each purification chamber 7 close to the end plate 8 of the anode 2 is the cation exchange membrane 11 and the side close to the end plate 8 of the cathode 1 is the anion exchange membrane 12 .

The anion exchange resin and cation exchange resin are mixed or layered in the purification chamber 7, and the used resins include styrene-based ion-exchange resin, polyacrylic acid-based ion-exchange resin, aminophosphonic acid and iminodiacetic acid chelating resin. The ratio of anion exchange resin to cation exchange resin in the mixed bed resin is 10:1 to 1:10, preferably 1:4 to 2:3.

One of graphite, 316L stainless steel, titanium, platinum, and iridium-plated titanium plate is used as the anode 2 and the cathode 1, preferably an iridium-plated titanium wire mesh plate. Under the action of a DC electric field, anion and cation impurities in industrial-grade organic amine electroplating additives enter the concentrated water chamber 10 through the cation exchange membrane 11 or anion exchange membrane 12 on both sides respectively, so as to achieve the purpose of purification.

The concentrated water chamber 10 is separated from the cation exchange membrane 11 or anion exchange membrane 12 by a PP (Polypropylene, polypropylene) partition 13, and the partition 13 is fixed to the entire EDI device 15 by means of screws or the like. The joints of the entire EDI device 15 are sealed with silicon rubber gaskets to prevent leakage of the feed liquid.

The EDI device 15 also includes a feed port 3 and a discharge port 4 of organic amine electroplating additives, a concentrated water/polar water inlet 5, a concentrated water outlet 6, and a polar water outlet 14, respectively connected to the upper and lower parts of the purification chamber 7, the polar water The upper part of the chamber 9 and the concentrated water chamber 10 , the lower part of the concentrated water chamber 10 and the lower part of the polar water chamber 9 are connected.

As shown in Figure 2, the concentrated water/polar water inlet 5, the concentrated water outlet 6, the polar water outlet 14 of the EDI device 15, and the feed port 3 and the discharge port 4 of the organic amine electroplating additive are respectively connected with a delivery pipe 16 , the delivery pipe 16 is respectively provided with a gate valve 17; the delivery pipe 16 connected to the feed port 3 is also provided with a first pressure gauge 18, a safety valve 19, a first flow meter 20 and a raw material Pump 21; a second pressure gauge 22, a second flow meter 23 and a concentrated water/polar water pump 24 are provided on the delivery pipe 16 connected to the concentrated water/polar water inlet 5 outwardly from the concentrated water/polar water inlet 5; A third pressure gauge 25, a third flowmeter 26 and a sampling valve 27 are also arranged in sequence from the outlet 4 outwards on the delivery pipe 16 connected to the discharge port 4; Concentrated water outlet 6 is also provided with a fourth pressure gauge 28 and a concentrated water circulation pump 29 in sequence. The water discharge tanks 30 are connected.

Now take the purification of tetramethylammonium hydroxide as an example to illustrate the purification process. The industrial grade TMAH is prepared into a solution with a concentration of 1%-25% using ultrapure water, and the concentration is preferably 2.38%-25%. Then use a microfiltration membrane with a pore size of 0.22-5 μm to filter the solution. The material of the microfiltration membrane is PP, PFA (Polyfluoroalkoxy, perfluoroalkoxy resin), PTFE (Polytetrafluoroethene, polytetrafluoroethylene), HDPE (HighDensityPolyethylene, high-density polyethylene) Ethylene) and other acid and alkali resistant materials, preferably PP. The TMAH flow rate is controlled to be 6-100L/h by the raw material pump 21, and the material of the whole delivery pipe 16 system is acid and alkali resistant materials such as PP, PFA, PTFE, HDPE, preferably PP. EDI device 15 is equipped with cation exchange membrane 11 and anion exchange membrane 12, and the purification chamber 7 is filled with anion exchange resin and cation exchange resin according to the mixed bed or layered bed mode, and the concentrated water/polar water pump 24 and the concentrated water circulation pump 29 are turned on, and the purification chamber 7 Set the flow rate to 1-100L/h, set the flow rate of concentrated water chamber 10 and electrode water chamber 9 to 1-100L/h, set the initial voltage to 0-100V, preferably 30-90V, turn on the DC power supply, and perform electrodeionization Operation, the optimal temperature for operation is 45°C-60°C, after running for about 60-300min, open the sampling valve 27 to take samples Use inductively coupled atomic emission spectrometer ICP-AES (ThermoFisher company) and DIONEXDX120 dual-channel ion chromatography to detect and detect the purified TMAH Concentrations of anion and cation impurities (metal ions, chloride ions and carbonate ions) in the When the test result reaches the SEMI standard, the EDI operation can be stopped and the samples can be collected; otherwise, the EDI operation can be continued until the concentration of anion and cation impurities reaches the electronic grade standard. During the production process, the liquid in the concentrated water chamber 10 is regularly monitored for anion and cation concentration and TMAH concentration, and replacement and supplementation of fresh liquid is performed when necessary. Finally, the purified TMAH is filtered through a 0.1μm-0.22μm microfiltration membrane to obtain the final product. If the TMAH concentration is less than 25% after acid-base titration, vacuum distillation can be performed to remove water to concentrate TMAH to a concentration of 25%.

Example 1

Take 100kg of industrial-grade TMAH pentahydrate, use ultrapure water to prepare a 25% concentration of TMAH solution, use a microfiltration membrane with a pore size of 2 μm to filter the solution to obtain a clear and transparent liquid, put the filtrate into a PP material storage tank, and use a raw material pump 21 The TMAH is input into the electrodeionization device 15, and the purification chamber 7 is equipped with a commercial brand D261 strong basic styrene-based anion exchange resin and Amberlite252Na strong acidic styrene-based cation exchange resin, and the ratio of the anion and cation exchange resins is 2:3 (V: V), cation exchange membrane 11 and anion exchange membrane 12 are polyethylene sulfonic acid type cation membrane 3361W polyethylene tertiary ammonia type anion membrane 3362W (Shanghai Chemical Water Treatment Plant), turn on the DC power supply, operate at constant voltage, and set the initial voltage 70V, conduct electrodeionization operation, control the temperature of the system below 45 degrees Celsius, and monitor the anion and cation concentration of the sample when the EDI operation lasts for 90 minutes, reaching the SEMI standard. As shown in Table 2, after concentration conversion, all metal ions The concentrations are all lower than 2-10ppb, the chloride ion concentration is lower than 0.1ppm, and the carbonate ion is lower than 100ppm. The concentration of TMAH obtained by acid-base titration is 20.07%, and the recovery rate of TMAH can reach 80.3% without considering the electrolytic separation of water.

Example 2

Process conditions and equipment are the same as in Example 1, except that the cation-exchange membrane 11 and anion-exchange membrane 12 in the EDI device 15 are changed into ethylene-propylene rubber homogeneous cationic membrane KM ethylene-propylene rubber homogeneous anion membrane AM (Shandong Tianwei membrane Co., Ltd.), when the EDI operation reaches 60 minutes, the anion and cation concentration of the sample is monitored and meets the SEMI standard. As shown in Table 2, the concentration of all metal ions is lower than 2-10ppb, the concentration of chloride ion is lower than 0.1ppm, and the concentration of carbonate Ions below 100ppm. The concentration of TMAH obtained by acid-base titration is 21.67%. Without considering other factors such as electrolytic separation of water, the recovery rate of TMAH can reach 86.7%.

Example 3:

Process condition and equipment are the same as embodiment 2, the difference is that the ion exchange resin in the EDI unit 15 uses JK204 strong base gel type anion exchange resin and D001 macroporous strongly acidic styrene cation exchange resin to be packed in the mixed bed mode instead Purification chamber 7, the ratio of anion exchange resin and cation exchange resin in purification chamber 7 is 2:3 (V:V). When the reaction reaches 60min, take a sample for inspection. After testing, as shown in Table 2, after concentration conversion, all metal ion concentrations are lower than 2-10ppb, chloride ion concentrations are lower than 0.1ppm, and carbonate ions are lower than 100ppm. SEMI standard. The concentration of TMAH at this time was determined to be 21.34% by acid-base titration. Without considering other factors such as electrolytic separation of water, the recovery rate of TMAH was calculated to reach 85.4%.

From the results of the above examples, it can be seen that the time spent by TMAH reaching the SEMI standard in Example 1 is longer than that of Example 2 and Example 3, and the yield is also lower. The negative and positive ions in the chamber are easy to reverse osmosis, resulting in prolonged operation time. In addition, because the homogeneous membrane has good compactness and strong pressure resistance, it is not easy to cause TMAH leakage in the purification chamber 7, thereby reducing the loss rate of TMAH. Therefore, in this invention, the homogeneous membrane EDI is used to purify TMAH faster. The yield is higher. At the same time, from the comparative results of Example 2 and Example 3, the change of the ion exchange resin model has little influence on the experimental results.

Table 2: Anion and cation impurity content in EDI purified TMAH.

The data in Table 2 shows that the TMAH purified by the TMAH purification method provided by the present invention can fully meet the electronic grade standard of SEMI. This method can also be well applied to the purification of other organic amine additives.

Although the content of the present invention has been described in detail through the above preferred embodiments, it should be understood that the above description should not be considered as limiting the present invention. Various modifications and alterations to the present invention will become apparent to those skilled in the art upon reading the above disclosure. Therefore, the protection scope of the present invention should be defined by the appended claims.

Claims (6)

1. a purification process for organic amine electroplating additive, is characterized in that, the method is the zwitterion impurity removed by electric deionizer (15) in organic amine electroplating additive; Described organic amine electroplating additive is Tetramethylammonium hydroxide;

Described electric deionizer (15) two ends are respectively equipped with end plate (8), one piece of end plate (8) is provided with the negative electrode (1) be connected with direct supply, another block end plate (8) is provided with the anode (2) be connected with direct supply, the inner side of two end plates is respectively equipped with a pole hydroecium (9), be arranged alternately some parallel purifying rooms (7) and dense hydroecium (10) between two pole hydroeciums (9) successively, separate respectively by cationic exchange membrane (11) or anion-exchange membrane (12) between each purifying room (7) and dense hydroecium (10);

Described cationic exchange membrane (11) and anion-exchange membrane (12) are arranged alternately makes each purifying room (7) be cationic exchange membrane (11) near the side of anode (2) end plate (8), be anion-exchange membrane (12) near the side of negative electrode (1) end plate (8);

The mixture of anionite-exchange resin and Zeo-karb is filled with in described purifying room (7); Described anionite-exchange resin and Zeo-karb all select the ion exchange resin of polystyrene, the ion exchange resin of polyacrylic, the one in phosphoramidic acid or iminodiethanoic acid resin; Described anionite-exchange resin and the ratio of Zeo-karb are 1:4 to 2:3; Be respectively equipped with dividing plate (13) outside described dense hydroecium (10) and the surrounding of pole hydroecium (9), and fixed by dividing plate (13) and whole electric deionizer (15); Each junction of described electric deionizer (15) is respectively by silicon rubber gasket seal; The organic ammonium salt solution of 0.3%-1% concentration is added with respectively as ionogen in described dense hydroecium (10) and pole hydroecium (9);

The liquid flow rate of described purifying room (7) is 1-100L/h, and dense hydroecium (10) and pole hydroecium (9) flow are 1-100L/h; The initial voltage of direct supply is 0-100V, and voltage constant in purge process also keeps solution temperature to be 20-70 DEG C; The rate of recovery of the organic amine electroplating additive after purifying is greater than 80%;

Described method also comprises: use ultrapure water to be mixed with the solution of concentration 1%-25% described organic amine electroplating additive, then the micro-filtrate membrane filtration solution in 0.22-5 μm of aperture is used, the filtrate pH value of gained is adjusted to 10-13.5, then pumps into described electric deionizer; The material acid and alkali-resistance of the microfiltration membrane in 0.22-5 μm of described aperture, it is selected from any one in polypropylene, perfluoroalkoxy resin, tetrafluoroethylene, high density polyethylene(HDPE).

2. the purification process of organic amine electroplating additive as claimed in claim 1, it is characterized in that, described anion-exchange membrane (12) is polyethylene, polypropylene, polyvinyl chloride, polyethers or fluorine-containing high polymers one of them out-phase or homogeneous ion-exchange membrane, described cationic exchange membrane (11) is heterogeneous ion-exchange membrane, polyethylene homogeneous ion-exchange membrane, sulfonate film or perfluoro sulfonic acid membrane one of them.

3. the purification process of organic amine electroplating additive as claimed in claim 1, is characterized in that, described negative electrode (1) and anode (2) adopt the one in graphite, 316L stainless steel, titanium, platinum or plating iridium titanium plate.

4. the purification process of organic amine electroplating additive as claimed in claim 1, it is characterized in that, described electric deionizer (15) also comprises the opening for feed (3) of organic amine electroplating additive and discharge port (4), dense water/pole water inlet (5), dense water out (6) and pole water out (14), is connected respectively with purifying room (7) top with below, pole hydroecium (9) and the below of the top of dense hydroecium (10), dense hydroecium (10) and the below of pole hydroecium (9).

5. the purification process of organic amine electroplating additive as claimed in claim 4, it is characterized in that, the opening for feed (3) of the dense water/pole water inlet (5) of described electric deionizer (15), dense water out (6), pole water out (14) and organic amine electroplating additive and discharge port (4) are connected with transfer lime (16) respectively, transfer lime (16) are respectively equipped with gate valve (17);

The transfer lime (16) be connected with opening for feed (3) is outwards also provided with the first tensimeter (18), safety valve (19), first-class gauge (20) and feedstock pump (21) successively by opening for feed (3);

The transfer lime (16) be connected with dense water/pole water inlet (5) is outwards also provided with the second tensimeter (22), second gauge (23) and dense water/pole water pump (24) successively by dense water/pole water inlet (5);

The transfer lime (16) be connected with discharge port (4) is outwards also provided with the 3rd tensimeter (25), the 3rd under meter (26) and sampling valve (27) successively by discharge port (4);

The transfer lime (16) be connected with dense water out (6) is outwards also provided with the 4th tensimeter (28) and dense water-circulating pump (29) successively by dense water out (6), and the other end of this transfer lime (16) is connected with the transfer lime (16) between second gauge (23) and dense water/pole water pump (24) and concentrated water discharge groove (30) respectively.

6. the purification process of organic amine electroplating additive as claimed in claim 5, it is characterized in that, described method comprises:

Step 1, carries out the filling of electric deionizer (15) assembling and ion exchange resin;

Step 2, filter organic amine electroplating additive material solution, then filtrate being diluted to pH value is 10-13.5, pumps into electric deionizer (15);

Step 3, the organic ammonium salt solution adding 0.3%-1% concentration in dense hydroecium (10) and pole hydroecium (9) does ionogen;

Step 4, feedstock pump (21), dense water/pole water pump (24) and dense water-circulating pump (29) startup optimization simultaneously, carries out electrodeionization process;

Step 5, modifier material and reaction conditions, the concentration of foreign metal ion and negatively charged ion in purifying room (7) interior organic amine electroplating additive solution when record electric deionizer (15) reaches steady-state operation, to determine the processing condition of optimization;

Step 6, the Optimizing Technical determined with step 5 carries out organic amine electroplating additive purifying, and in this purge process, detect material solution temperature by temperature measurer, control temperature is not higher than 20 DEG C-70 DEG C; Once every 15 minutes to discharging sampling, detect the zwitterion concentration of wherein impurity, after the zwitterion concentration in sample reaches the standard-required of fine electronic level, the organic amine electroplating additive solution after purifying is collected simultaneously;

Step 7, the organic amine electroplating additive solution after purifying obtains the finished product through 0.1-0.22 μm of micro-filtrate membrane filtration again, and this filtration procedure carries out in 100 grades of super-clean environments.