CN103102273B - A kind of purification process of organic amine electroplating additive - Google Patents
A kind of purification process of organic amine electroplating additive Download PDFInfo
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Abstract
The invention discloses a kind of purification process of organic amine electroplating additive, remove the zwitterion impurity in organic amine electroplating additive by electric deionizer; Electric deionizer two ends are respectively equipped with end plate, end plate is respectively equipped with the negative electrode or anode that are connected with direct supply, be arranged alternately some parallel purifying rooms and dense hydroecium between two end plates successively, separate respectively by cationic exchange membrane or anion-exchange membrane between each purifying room and dense hydroecium; Purifying indoor are filled with ion exchange resin, are added with the organic ammonium salt solution of 0.3%-1% concentration in dense hydroecium and pole hydroecium respectively; Purifying room flow is 1-100L/h, and dense hydroecium and pole hydroecium flow are 1-100L/h; The voltage of direct supply is 0-100V, and purge process voltage constant also keeps solution temperature to be 20-70 DEG C; After purifying, the rate of recovery of organic amine electroplating additive is greater than 80%.The purification process of organic amine electroplating additive provided by the invention, technique is simple and easy to control, and degree of purification can reach fine electronic grade standard.
Description
Technical field
The present invention relates to a kind of method of purification of organic amine compound, particularly, relate to a kind of purification process of organic amine electroplating additive, mainly for the removal of impurity metal ion and anionic impurity in technical grade and electronic-grade organic amine electroplating additive.
Background technology
Organic amine electroplating additive refers to the crucial additive used in high-purity copper or the plating of high-purity methanesulfonic acid copper, such as: trolamine, and tri-isopropanolamine, diglycolamine, triethylenediamine, N, N-diethyl propargylamine, Tetramethylammonium hydroxide etc.Its general formula is as follows:
R
1-R
3represent the alkyl of H or 1-10 carbochain, thiazolinyl, alkynyl, alkoxyl group, silane alcohol base, ethanoyl, benzyl etc.
Organic amine electroplating additive, for Tetramethylammonium hydroxide (TMAH), trolamine etc., belong to organic bases, purposes very is widely had, such as: Tetramethylammonium hydroxide is mainly used in the field such as catalyzer and polyester polymer, weaving, plastics, food, leather, wood working of organosilicon series product in industrial scientific field.Along with the development of electronic industry, these organic amine compounds also can be applied to semiconductor industry as extremely excellent electroplating additive.Such as: Chinese patent CN10381313 reports a kind of synthetic method of electroplating additive N, N-diethyl propargylamine, Chinese patent CN101298688A uses aminated compounds as the main additive of electronics finishing liquid.At present, the organic amine compound of domestic production is main mainly with technical grade, and commercially available technical grade organic amine compound can contain more impurity metal ion and anionic impurity, is not suitable for being applied to electronics finishing field, in the plating of especially semiconductor crystal wafer.For Tetramethylammonium hydroxide, now carry out trace metal analysis to a kind of technical grade Tetramethylammonium hydroxide sample of business, analysis report is in Table 1.Na, K, Ca, Cr, Cu, Mn, Mg, Ni, Zn, Pb, Fe, Al, Ag metal ion content adopts ICP-AES method to measure, and with ppb(1ppb=1 μ g/kg) represent.Simultaneously, chlorion in technical grade TMAH and carbanion use DIONEXDX120 two channels chromatography of ions to detect, result, see table 1, wherein shows the standard that concentration of metal ions in TMAH, chlorion and carbon acid ion concentration have all exceeded fine electronic level (SEMIStandardC46-0306) rank.
Zwitterion foreign matter content in a kind of technical grade TMAH raw material that table 1 is commercially available.
As everyone knows, when IC wafer is subject to the metal ion pollutions such as Fe, Cu, Na, can OISF(Oxidation-InducedStackingFaults be caused, Oxidation induced stacking fualt) generation, thus increase the leakage current that p-n junction closes, reduce life-span of minority carrier.So develop a kind of good method to organic amine electroplating additive of purifying, be problem in the urgent need to address to make its use more meeting high-precision semiconducter device.At present, the purification research for organic amine compound focuses mostly in rectification method or electrolytic process, and such as: U.S.Pat.NO.4,714,530 just develop a kind of method utilizing electrolytic process purification TMAH.But all do not have well to propose a kind of general, easy, the organic amine compound purification scheme of environmental protection.
Electrodeionization technology (ElectroDeionization) is called for short EDI technology, electrodialytic technique and ion-exchange resin technique can be combined, with the advantage of the advanced desalination of the continuous desalination of electrodialytic technique and ion exchange resin, the acid-alkali regeneration problem of electrodialytic technique concentration polarization and ion exchange resin can also be avoided.Usually, EDI technology is all the production for high purity water, has invented one and prepare super-clean high-purity H in Chinese patent CNCN201770477U
2o
2eDI production equipment, in addition, the Methods For Purification electronic-grade DMF using rectifying and EDI to combine in Chinese patent CN101993387A, but not yet have pertinent literature to report its purification being applied to organic amine electroplating additive.
Summary of the invention
The object of this invention is to provide a kind of for removing metal ion in technical grade organic amine electroplating additive and chloride ion impurities, there is provided a kind of technique simple, condition is easy to control, the method of purification of environment-friendly and green, in the organic amine additive solution of gained, every metal ion species and anionic impurity content can reach fine electronic grade standard, high to overcome prior art foreign matter content, the shortcomings such as quality control is unstable.
In order to achieve the above object, the invention provides a kind of purification process of organic amine electroplating additive, wherein, the method is the zwitterion impurity removed by electric deionizer in organic amine electroplating additive; Described electric deionizer two ends are respectively equipped with end plate, one piece of end plate is provided with the negative electrode be connected with direct supply, another block end plate is provided with the anode be connected with direct supply, the inner side of two end plates is respectively equipped with a pole hydroecium, be arranged alternately some parallel purifying rooms and dense hydroecium successively between two pole hydroeciums, separate respectively by cationic exchange membrane or anion-exchange membrane between each purifying room and dense hydroecium; Described cationic exchange membrane and anion-exchange membrane are arranged alternately makes each purifying room be cationic exchange membrane near the side of anode end plate, be anion-exchange membrane near the side of cathode end plate; Described purifying indoor are filled with the mixture of anionite-exchange resin and Zeo-karb; The organic ammonium salt solution of 0.3%-1% concentration is added with respectively as ionogen in described dense hydroecium and pole hydroecium; The liquid flow rate of described purifying room is 1-100L/h, and dense hydroecium and pole hydroecium 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%.
Under electric field action, zwitterion moves respectively by ion-exchange membrane, the foreign ion in purifying room is reduced, thus reaches the effect of purification organic amine compound.Simultaneously for organic ammonium salt compounds, the concentration due to organic ammonium salt is 10 of concentration impurity ion
5-10
6doubly, the dissociate loss of a small amount of organic ammonium salt under the effect of electric field, negligible, the organic ammonium salt simultaneously entered in dense hydroecium can be recycled entering industrial production system, thus reduce costs.
The purification process of above-mentioned organic amine electroplating additive, wherein, described anion-exchange membrane be polyethylene, polypropylene, polyvinyl chloride, polyethers or fluorine-containing high polymers one of them out-phase or homogeneous ion-exchange membrane, described cationic exchange membrane is one of them of heterogeneous ion-exchange membrane, polyethylene homogeneous ion-exchange membrane, sulfonate film or perfluoro sulfonic acid membrane.
The purification process of above-mentioned organic amine electroplating additive, wherein, described anionite-exchange resin and Zeo-karb comprise the ion exchange resin of polystyrene, the ion exchange resin of polyacrylic, the one in phosphoramidic acid or iminodiethanoic acid resin.
The purification process of above-mentioned organic amine electroplating additive, wherein, described cloudy exchange resin and the ratio of Zeo-karb are 10:1 to 1:10, are preferably 1:4 to 2:3.
The purification process of above-mentioned organic amine electroplating additive, wherein, described negative electrode and anode adopt the one in graphite, 316L stainless steel, titanium, platinum or plating iridium titanium plate, preferably plating iridium titanium wire network plate.Under DC electric field effect, the zwitterion impurity in technical grade organic amine electroplating additive enters dense hydroecium respectively by the zwitterion film of two sides, thus reaches purification object.
The purification process of above-mentioned organic amine electroplating additive, wherein, is respectively equipped with dividing plate outside described dense hydroecium and the surrounding of pole hydroecium, and is fixed by dividing plate and whole electric deionizer; Each junction of described electric deionizer is respectively by silicon rubber gasket seal.
The purification process of above-mentioned organic amine electroplating additive, wherein, described electric deionizer also comprises opening for feed and discharge port, dense water/pole water inlet, dense water out and the pole water out of organic amine electroplating additive, is connected respectively with above purifying room with the below of below, pole hydroecium and the top of dense hydroecium, the below of dense hydroecium and pole hydroecium.
The purification process of above-mentioned organic amine electroplating additive, wherein, the opening for feed of the dense water/pole water inlet of described electric deionizer, dense water out, pole water out and organic amine electroplating additive and discharge port are connected with transfer lime respectively, transfer lime is respectively equipped with gate valve; The transfer lime be connected with opening for feed is outwards also provided with the first tensimeter, safety valve, first-class gauge and feedstock pump successively by opening for feed; The transfer lime be connected with dense water/pole water inlet is outwards also provided with the second tensimeter, second gauge and dense water/pole water pump successively by dense water/pole water inlet; The transfer lime be connected with discharge port is outwards also provided with the 3rd tensimeter, the 3rd under meter and sampling valve successively by discharge port; The transfer lime be connected with dense water out is outwards also provided with the 4th tensimeter, gate valve and dense water-circulating pump successively by dense water out, and the other end of this transfer lime is connected with the transfer lime between second gauge and dense water/pole water pump and concentrated water discharge groove respectively.
The purification process of above-mentioned organic amine electroplating additive, wherein, described method comprises: step 1, carries out the filling of electric deionizer assembling and ion exchange resin; Step 2, filter organic amine electroplating additive material solution, elimination particulate matter, fibrous impurity etc., transparent clear shape in filtrate, without naked eyes visible particle thing, then filtrate being diluted to pH value is 10-13.5, pumps into electric deionizer; Step 3, the organic ammonium salt solution adding 0.3%-1% concentration in dense hydroecium and pole hydroecium does ionogen; Step 4, feedstock pump, dense water/pole water pump and dense water-circulating pump be startup optimization simultaneously, carries out circulating electrodeionization process; Step 5, modifier material and reaction conditions, foreign metal ion and anion concentration in purifying indoor organic amine electroplating additive solution when record electric deionizer reaches steady-state operation, to determine the processing condition optimized, be such as a gradient with 10 volts, increase operating voltage step by step to 100V from 0 volt, record the ionic concn of the indoor impurity of purifying under each operating voltage, electric current can also be investigated and dense underwater gold belongs to the parameter values such as ionic concn; Step 6, the Optimizing Technical determined with step 5 carries out organic amine electroplating additive purifying, in this purge process, detect material solution temperature by temperature measurer, control temperature not higher than 20 DEG C-70 DEG C, preferably 45 DEG C-60 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 in order to ensure that quality product is not subject to the impact of the environment such as air, this filtration procedure carries out in 100 grades of super-clean environments.Organic ammonium salt solution in dense hydroecium can recycle and reuse.The method can also comprise step 8 further, and the organic amine electroplating additive after purifying dewaters concentrated by the mode of underpressure distillation.
The purification process of above-mentioned organic amine electroplating additive, wherein, described electric deionizer is thick room mixed bed electric deionizer, thin room mixed bed electric deionizer, stratified bed electric deionizer, the wherein one of point bed electric deionizer or Bipolar Membrane electric deionizer.
The purification process of organic amine electroplating additive provided by the invention has the following advantages:
The invention provides a kind of refining effect good, energy consumption is low, the production technique of energy continuous prodution electronic-grade purity organic amine electroplating additive.Can reduce metal ion content and anion-content in organic amine electroplating additive very well, the organic amine electroplating additive after purification reaches fine electronic grade standard.
Utilize the feature that electrodeionization technology organically combines electrodialysis and ion-exchange, both remained electroosmose process to remove zwitterion foreign ion and ion exchange resin continuously and the degree of depth can remove the advantage of zwitterion impurity, and overcome again electroosmose process and the degree of depth can not remove the detrimentally affect that zwitterion impurity and concentration polarization cause.
Technical grade organic amine electroplating additive not only effectively can be purified to electronic-grade by this method of purification, and energy consumption is low, environmental protection, and floor space effectively can reduce the discharge of three industrial wastes, is applicable to large-scale industrial production.Therefore the present invention has good adaptability and market outlook.
Accompanying drawing explanation
Fig. 1 is the electric deionizer schematic diagram of the purification process of organic amine electroplating additive of the present invention.
Fig. 2 is the equipment connection schematic diagram of the purification process of organic amine electroplating additive of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is further described.
The purification process of organic amine electroplating additive provided by the invention, removes the zwitterion impurity in organic amine electroplating additive by electric deionizer 15.
Electrodeionization (EDI) device 15 is containing 2 pairs of electrodes, and 30 pairs of ion-exchange membranees, film is of a size of 200mm × 100mm.Anion-exchange membrane 12 is out-phase or the homogeneous ion-exchange membranes such as polyethylene, polypropylene, polyvinyl chloride, polyethers or fluorine-containing high polymers, and cationic exchange membrane 11 is heterogeneous ion-exchange membrane, polyethylene homogeneous ion-exchange membrane, sulfonate film or perfluoro sulfonic acid membrane.It is 1-100L/h that flow is produced in design.
As shown in Figure 1, EDI device 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 8 is respectively equipped with a pole hydroecium 9, be arranged alternately parallel purifying room 7 and dense hydroecium 10 successively between two pole hydroeciums 9, separate respectively by cationic exchange membrane 11 or anion-exchange membrane 12 between each purifying room 7 and dense hydroecium 10.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.
In purifying room 7, anionite-exchange resin and Zeo-karb are filled in mixing or layering, and resin used comprises the ion exchange resin of polystyrene, the ion exchange resin of polyacrylic, aminophosphonic acid and iminodiethanoic acid resin.In mixed-bed resin, the ratio of anionite-exchange resin and Zeo-karb is 10:1 to 1:10, preferred 1:4 to 2:3.
One in use graphite, 316L stainless steel, titanium, platinum, plating iridium titanium plate, as anode 2 and negative electrode 1, preferably plates iridium titanium wire network plate.Under DC electric field effect, the zwitterion impurity in technical grade organic amine electroplating additive enters dense hydroecium 10 respectively by the cationic exchange membrane 11 of both sides or anion-exchange membrane 12, thus reaches purification object.
PP(Polypropylene is used, polypropylene between dense hydroecium 10 and cationic exchange membrane 11 or anion-exchange membrane 12) dividing plate 13 of material separates, and dividing plate 13 is fixed by the modes such as screw and whole EDI device 15.The combining site of whole EDI device 15 all uses silicon rubber pad to seal, and prevents the seepage of feed liquid.
EDI device 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 above purifying room 7 with the below of below, pole hydroecium 9 and the top of dense hydroecium 10, the below of dense hydroecium 10 and pole hydroecium 9.
As shown in Figure 2, the opening for feed 3 of the dense water/pole water inlet 5 of EDI device 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.
Now for Tetramethylammonium hydroxide purification, purifying technique is described.Ultrapure water is used to be mixed with the solution of concentration 1%-25%, concentration preferred 2.38%-25% technical grade TMAH.Then the micro-filtrate membrane filtration solution in 0.22-5 μm of aperture is used, the material of microfiltration membrane is PP, PFA(Polyfluoroalkoxy, perfluoroalkoxy resin), PTFE(Polytetrafluoroethene, tetrafluoroethylene), HDPE(HighDensityPolyethylene, high density polyethylene(HDPE)) etc. the material of acid and alkali-resistance, preferred PP.Be 6-100L/h by feedstock pump 21 control TMAH flow, the material of whole transfer lime 16 system is the material of the acid and alkali-resistances such as PP, PFA, PTFE, HDPE, preferred PP.EDI device 15 installs cationic exchange membrane 11 and anion-exchange membrane 12, anionite-exchange resin and Zeo-karb are filled by mixed bed or stratified bed mode in purifying room 7, open dense water/pole water pump 24 and dense water-circulating pump 29, purifying room 7 flow is set to 1-100L/h, dense hydroecium 10 and pole hydroecium 9 flow are set to 1-100L/h, setting initial voltage is 0-100V, preferred 30-90V, open direct supply, carry out electrodeionization operation, operation optimum temps is at 45 DEG C-60 DEG C, after about operation 60-300min, open sampling valve 27 sample use jigger coupling Atomic Emission SpectrometerAES ICP-AES(ThermoFisher company) and DIONEXDX120 two channels chromatography of ions detect zwitterion impurity (metal ion in the TMAH after purification, chlorion and carbanion) concentration.After detected result reaches SEMI standard, EDI can be stopped to operate, collect sample, otherwise, proceed EDI operation, until the concentration of zwitterion impurity reaches electronic-grade standard.In process of production, the liquid of dense hydroecium 10 regularly carries out zwitterion concentration measurement and control and TMAH concentration measurement and control, and the replacement carrying out fresh liquid if desired supplements.Finally, the TMAH of purification obtains the finished product through 0.1 μm of-0.22 μm of micro-filtrate membrane filtration again, if TMAH concentration is less than 25% after acid base titration, can carries out underpressure distillation water removal operation and carry out concentrated TMAH and reach 25% concentration.
Embodiment 1
Get 100kg technical grade five hydration TMAH, ultrapure water is used to prepare the TMAH solution of 25% concentration, use the micro-filtrate membrane filtration solution in 2 μm of apertures, obtain clear liquid, filtrate is loaded the reservoir of PP material, use feedstock pump 21 that TMAH is inputted electric deionizer 15, trade names D261 strong-basicity styrene series anion exchange resin and Amberlite252Na strongly acidic styrene type cation exchange resin are equipped with in purifying room 7, cloudy, the ratio 2:3(V:V of Zeo-karb), cationic exchange membrane 11 and anion-exchange membrane 12 are chemical industry water treatment plant, polyvinyl sulfonic acid type cationic membrane 3361W polyethylene tertiary ammonia type anionic membrane 3362W(Shanghai respectively), open direct supply, constant voltage operates, setting initial voltage is 70V, carry out electrodeionization operation, hierarchy of control temperature is below 45 degrees Celsius, when EDI operates 90min, monitor the zwitterion concentration of sample, reach SEMI standard, as shown in table 2, after concentration conversion, all metal ions concentration is all lower than 2-10ppb, chlorine ion concentration is lower than 0.1ppm, carbanion is lower than 100ppm.Measuring through acid base titration the TMAH concentration obtained is 20.07%, does not consider the electrolytic separation of water, and the rate of recovery calculating TMAH can reach 80.3%.
Embodiment 2
Processing condition and equipment are with embodiment 1, ethylene-propylene rubber(EPR) homogeneous phase cation film KM ethylene-propylene rubber(EPR) homogeneous-phase anion film AM(Shandong Tian Weimo company limited is changed into) unlike the cationic exchange membrane 11 in EDI device 15 and anion-exchange membrane 12, when EDI operates 60min, monitor the zwitterion concentration of sample, reach SEMI standard, as shown in table 2, all metal ions concentration is all lower than 2-10ppb, chlorine ion concentration is lower than 0.1ppm, and carbanion is lower than 100ppm.Measuring through acid base titration the TMAH concentration obtained is 21.67%, does not consider other factors such as the electrolytic separation of water, and the rate of recovery calculating TMAH can reach 86.7%.
Embodiment 3:
Processing condition and equipment are with embodiment 2, changing into unlike the ion exchange resin in EDI device 15 uses JK204 highly basic gel-type anion exchange resin and D001 macropore strong acid vinylbenzene Zeo-karb to be loaded on purifying room 7 in mixed bed mode, and in purifying room 7, the ratio of anionite-exchange resin and Zeo-karb is 2:3(V:V).When reaction reaches 60min, sampling censorship, after testing, as shown in table 2, after concentration conversion, all metal ions concentration is all lower than 2-10ppb, and chlorine ion concentration is lower than 0.1ppm, and carbanion, lower than 100ppm, reaches SEMI standard.The TMAH concentration measured now through acid base titration is 21.34%, and do not consider the other factorses such as the electrolytic separation of water, the rate of recovery calculating TMAH reaches 85.4%.
From the result of above-described embodiment, in embodiment 1, TMAH reaches SEMI standard spent time and is longer than embodiment 2 and embodiment 3, and yield is also lower, and this is because heterogeneous membrane does not have homogeneous membrane fine and close, make the easy reverse osmosis of the zwitterion in dense hydroecium, cause the operating time to extend.In addition, because the compactness of homogeneous membrane is good, carrying capacity is strong, is not easy the TMAH seepage caused in purifying room 7, thus decreases TMAH rate of loss, so adopt homogeneous membrane EDI purification TMAH speed faster in this invention, yield is higher.Meanwhile, from the comparing result of embodiment 2 and embodiment 3, the ion exchange resin type alternation of signs is less on experimental result impact.
Zwitterion foreign matter content in the TMAH that table 2:EDI purifies.
The data of table 2 show, the TMAH purified by TMAH purification process provided by the invention can reach the electronic-grade standard of SEMI completely.The method also can well be applied to the purification of other organic amine additive.
Although content of the present invention has done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple amendment of the present invention and substitute will be all apparent.Therefore, protection scope of the present invention should be limited to 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.
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| CN108176233A (en) * | 2018-03-01 | 2018-06-19 | 天津城建大学 | Novel three Room electrodialysis desalination device |
| CN108392986A (en) * | 2018-05-11 | 2018-08-14 | 梁小朝 | A kind of purifying plant of tetramethyl ammonium carbonate |
| CN109433279A (en) * | 2018-10-24 | 2019-03-08 | 南京元亨化工科技有限公司 | Diffusive separation device for tetramethylammonium hydroxide purifying |
| CN109761818A (en) * | 2019-03-13 | 2019-05-17 | 东莞市乔科化学有限公司 | A kind of electron level polyethylene polyamine fine work, preparation method and application |
| KR20230034935A (en) * | 2020-04-08 | 2023-03-10 | 다우 글로벌 테크놀로지스 엘엘씨 | Purification method of organic amines |
| JP2024520315A (en) * | 2021-05-19 | 2024-05-24 | ダウ グローバル テクノロジーズ エルエルシー | Process for purifying organic amines |
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