CN103102273A - Method for purifying organic amine electroplating additive - Google Patents
Method for purifying organic amine electroplating additive Download PDFInfo
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Abstract
The invention discloses a method for purifying an organic amine electroplating additive. Anion and cation impurities in the organic amine electroplating additive are eliminated by using an electric deionization device; end plates are respectively arranged on two ends of the electric deionization device; cathodes and anodes which are connected with a direct-current power supply are respectively arranged on the end plates; a plurality of purifying chambers and concentrated water chambers are sequentially and alternatively arranged in parallel between two end plates; each purifying chamber and the concentrated water chamber are respectively isolated from each other through cation exchange membranes or anion exchange membranes; the purifying chambers are filled with ion exchange resin; the concentrated water chamber and an electrode water chamber are respectively filled with 0.3-1% organic ammonium salt solutions; the flow of the purifying chamber is 1-100L/h; the flows of the concentrated water chamber and the electrode water chamber are 1-100L/h; the voltage of the direct-current power supply is 0-100V; the voltage is constant and the solution temperature is kept be at 20-70 DEG C in the purification process; and the recovery rate of the organic amine electroplating additive after being purified is greater than 80%. The method for purifying the organic amine electroplating additive, disclosed by the invention, is simple in process and easy to control, and the purification degree can achieve the 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
The organic amine electroplating additive refers to the crucial additive that uses in high-purity sulphuric acid copper or high-purity methanesulfonic acid copper are electroplated, for example: trolamine, tri-isopropanolamine, diglycolamine, triethylenediamine, N, N-diethyl propargylamine, Tetramethylammonium hydroxide etc.Its general formula is as follows:
R
1-R
3Represent alkyl, thiazolinyl, alkynyl, alkoxyl group, silane alcohol base, ethanoyl, benzyl of a H or 1-10 carbochain etc.
The organic amine electroplating additive, take Tetramethylammonium hydroxide (TMAH), trolamine etc. as example, belong to organic bases, at industrial scientific research field, purposes is very widely arranged, mainly be used in the fields such as the catalyzer of organosilicon series product and polyester polymer, weaving, plastics, food, leather, wood working such as: Tetramethylammonium hydroxide.Along with the development of electronic industry, these organic amine compounds also can be used as extremely good electroplating additive and are applied to semiconductor industry.For example: Chinese patent CN10381313 has reported a kind of electroplating additive N, the synthetic method of N-diethyl propargylamine, and Chinese patent CN 101298688A uses aminated compounds as the main additive of electronics electroplate 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 the electronics field of electroplating, especially in the plating of semiconductor crystal wafer.Take Tetramethylammonium hydroxide as example, existing technical grade Tetramethylammonium hydroxide sample to a kind of business carries out trace metal analysis, and analysis report sees Table 1.Na, K, Ca, Cr, Cu, Mn, Mg, Ni, Zn, Pb, Fe, Al, Ag metal ion content adopt the ICP-AES method to measure, and with ppb(1ppb=1 μ g/kg) represent.Simultaneously, chlorion in technical grade TMAH and carbanion use DIONEX DX120 two channels chromatography of ions to detect, result shows wherein that referring to table 1 concentration of metal ions in TMAH, chlorion and carbon acid ion concentration have all surpassed other standard of fine electronic level (SEMI Standard C46-0306) level.
Zwitterion foreign matter content in the commercially available a kind of technical grade TMAH raw material of table 1.
As everyone knows, when being subject to the metal ion pollutions such as Fe, Cu, Na when the IC wafer, can cause OISF(Oxidation-Induced Stacking Faults, the oxidation induced fault) generation, thereby increase the leakage current that p-n junction closes, the life-span of reducing minority carrier.So develop a kind of good method organic amine electroplating additive of purifying, so that its use that more meets high-precision semiconducter device is problem in the urgent need to address.At present, the purification research for organic amine compound focuses mostly in rectification method or electrolytic process, for example: U.S. Pat. NO.4,714,530 just develop a kind of method of 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 (Electro Deionization) is called for short the 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, can also avoid the acid-alkali regeneration problem of electrodialytic technique concentration polarization and ion exchange resin.Usually, the EDI technology is all the production for high purity water, has invented a kind of super-clean high-purity H for preparing in Chinese patent CNCN201770477U
2O
2The EDI production equipment, in addition, the Methods For Purification electronic-grade DMF that uses rectifying and EDI to combine in Chinese patent CN101993387A, but its purification that is applied to the organic amine electroplating additive is not yet had the pertinent literature report.
Summary of the invention
The purpose of this invention is to provide a kind of metal ion and chloride ion impurities for removing technical grade organic amine electroplating additive, provide 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 the fine electronic grade standard, high to overcome the prior art foreign matter content, the shortcoming 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 to remove zwitterion impurity in the organic amine electroplating additive by electric deionizer; Described electric deionizer two ends are respectively equipped with end plate, an end plate is provided with the negative electrode that is connected with direct supply, another piece end plate is provided with the anode that is connected with direct supply, the inboard of two end plates is respectively equipped with a utmost point hydroecium, be arranged alternately successively some parallel purifying chambers and dense hydroecium between two utmost point hydroeciums, separate by cationic exchange membrane or anion-exchange membrane respectively between each purifying chamber and dense hydroecium; Described cationic exchange membrane and anion-exchange membrane are arranged alternately and make each purifying chamber be cationic exchange membrane, be anion-exchange membrane near a side of cathode end plate near a side of anode end plate; The indoor mixture that is filled with anionite-exchange resin and Zeo-karb of described purifying; Be added with respectively the organic ammonium salt solution of 0.3%-1% concentration in described dense hydroecium and utmost point hydroecium as ionogen; The liquid flow rate of described purifying chamber is 1-100 L/h, and dense hydroecium and utmost point hydroecium flow are 1-100 L/h; The initial voltage of direct supply is 0-100V, voltage constant and to keep solution temperature be 20-70 ℃ in purge process; The rate of recovery of the organic amine electroplating additive after purifying is greater than 80%.
Under electric field action, zwitterion moves by ion-exchange membrane respectively, and the foreign ion in the purifying chamber is reduced, thereby reaches the effect of purification organic amine compound.Simultaneously for the organic ammonium salt compounds, because the concentration of 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 can be ignored, and the organic ammonium salt that enters simultaneously in dense hydroecium can be recycled entering industrial production system, thereby reduces costs.
The purification process of above-mentioned organic amine electroplating additive, wherein, described anion-exchange membrane is one of them out-phase or homogeneous ion-exchange membrane of polyethylene, polypropylene, polyvinyl chloride, polyethers or fluorine-containing high polymers, and 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, a kind of in phosphoramidic acid or iminodiethanoic acid resin.
The purification process of above-mentioned organic amine electroplating additive, wherein, the ratio that described Yinchiao (abdomen, Ren 7) changes resin and Zeo-karb is 10:1 to 1:10, is preferably 1:4 to 2:3.
The purification process of above-mentioned organic amine electroplating additive, wherein, described negative electrode and anode adopt a kind of in graphite, 316L stainless steel, titanium, platinum or plating iridium titanium plate, preferably plate iridium titanium wire network plate.Under the DC electric field effect, the zwitterion impurity in technical grade organic amine electroplating additive enters dense hydroecium by the zwitterion film of two sides respectively, thereby reaches the purification purpose.
The purification process of above-mentioned organic amine electroplating additive wherein, is respectively equipped with dividing plate outside the surrounding of described dense hydroecium and utmost point hydroecium, and fixes by dividing plate and whole electric deionizer; Each junction of described electric deionizer is respectively by the sealing of silicon rubber pad.
The purification process of above-mentioned organic amine electroplating additive, wherein, described electric deionizer also comprises opening for feed and discharge port, dense water/utmost point water inlet, dense water out and the utmost point water out of organic amine electroplating additive, is connected with the below of below, utmost point hydroecium and the top of dense hydroecium, dense hydroecium and the below of utmost point hydroecium with top, purifying chamber respectively.
The purification process of above-mentioned organic amine electroplating additive, wherein, be connected with respectively transfer lime on the opening for feed of the dense water of described electric deionizer/utmost point water inlet, dense water out, utmost point water out and organic amine electroplating additive and discharge port, be respectively equipped with gate valve on transfer lime; With outwards also be provided with successively the first tensimeter, safety valve, first flow meter and feedstock pump by opening for feed on transfer lime that opening for feed is connected; With outwards also be provided with successively the second tensimeter, the second under meter and dense water/utmost point water pump by dense water/utmost point water inlet on transfer lime that dense water/utmost point water inlet is connected; With outwards also be provided with successively the 3rd tensimeter, the 3rd under meter and sampling valve by discharge port on transfer lime that discharge port is connected; With outwards also be provided with successively the 4th tensimeter, gate valve and dense water-circulating pump by dense water out on transfer lime that dense water out is connected, the other end of this transfer lime respectively with the second under meter and dense water/utmost point water pump between transfer lime and concentrated water discharge groove be connected.
The purification process of above-mentioned organic amine electroplating additive, wherein, described method comprises: step 1, carry out the filling of electric deionizer assembling and ion exchange resin; Step 2 is filtered organic amine electroplating additive material solution, elimination particulate matter, fibrous impurity etc., and transparent clear shape in filtrate without naked eyes visible particle thing, then is diluted to filtrate the pH value for 10-13.5, pumps into electric deionizer; Step 3 adds the organic ammonium salt solution of 0.3%-1% concentration to do ionogen in dense hydroecium and utmost point hydroecium; Step 4, feedstock pump, dense water/utmost point water pump and dense water-circulating pump start operation simultaneously, carry out circulating electrodeionization process; Step 5, modifier material and reaction conditions, foreign metal ion and anion concentration in the indoor organic amine electroplating additive of purifying solution when recording electric deionizer and reaching steady-state operation, with the processing condition of determining to optimize, for example take 10 volts as a gradient, increase step by step operating voltage to 100V from 0 volt, record the ionic concn of the indoor impurity of purifying under each operating voltage, can also investigate electric current and dense underwater gold belongs to the parameter values such as ionic concn; Step 6, the Optimizing Technical of determining with step 5 carries out organic amine electroplating additive purifying, detects the material solution temperature by temperature measurer in this purge process, controls temperature not higher than 20 ℃-70 ℃, preferred 45 ℃-60 ℃; Every 15 minutes to the discharging sampling once, detect the wherein zwitterion concentration of impurity simultaneously, after the zwitterion concentration in sample reaches the standard-required of fine electronic level, the organic amine electroplating additive solution after purifying is collected; Step 7, the organic amine electroplating additive solution after purifying obtain the finished product through 0.1-0.22 μ m micro-filtrate membrane filtration again, are not subject to the impact of the environment such as air in order to guarantee quality product, and 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 further comprise step 8, 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 chamber mixed bed electric deionizer, thin chamber mixed bed electric deionizer, the stratified bed electric deionizer divides the wherein a kind of of 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, and the production technique of electronic-grade purity organic amine electroplating additive is produced in the energy serialization.Metal ion content and anion-content in can fine reduction organic amine electroplating additive, the organic amine electroplating additive after purification reaches the fine electronic grade standard.
The characteristics of utilizing the electrodeionization technology that electrodialysis and ion-exchange are organically combined, both kept electroosmose process and can remove continuously the advantage that zwitterion foreign ion and ion exchange resin can the degree of depth be removed zwitterion impurity, and overcome again electroosmose process and can not the degree of depth have removed the detrimentally affect that zwitterion impurity and concentration polarization cause.
This method of purification not only can effectively be purified to electronic-grade with technical grade organic amine electroplating additive, and energy consumption is low, environmental protection, and floor space can effectively reduce the discharging of three industrial wastes, is fit to large-scale industrial production.Therefore the present invention has good adaptability and market outlook.
Description of drawings
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 is by the zwitterion impurity in electric deionizer 15 removal organic amine electroplating additives.
Electrodeionization (EDI) device 15 contains 2 pairs of electrodes, 30 pairs of ion-exchange membranees, and 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 1-100 L/h that flow is produced in design.
As shown in Figure 1, EDI device 15 two ends are respectively equipped with end plate 8, an end plate 8 is provided with the negative electrode 1 that is connected with direct supply, another piece end plate 8 is provided with the anode 2 that is connected with direct supply, the inboard of two end plates 8 is respectively equipped with a utmost point hydroecium 9, be arranged alternately successively parallel purifying chamber 7 and dense hydroecium 10 between two utmost point hydroeciums 9, separate by cationic exchange membrane 11 or anion-exchange membrane 12 respectively between each purifying chamber 7 and dense hydroecium 10.Cationic exchange membrane 11 and anion-exchange membrane 12 are arranged alternately and make each purifying chamber 7 be cationic exchange membrane 11, be anion-exchange membrane 12 near a side of negative electrode 1 end plate 8 near a side of anode 2 end plates 8.
Anionite-exchange resin and Zeo-karb are filled in the interior mixing in purifying chamber 7 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.
Use a kind of as anode 2 and negative electrode 1 in graphite, 316L stainless steel, titanium, platinum, plating iridium titanium plate, preferably plate iridium titanium wire network plate.Under the DC electric field effect, the zwitterion impurity in technical grade organic amine electroplating additive enters dense hydroecium 10 by cationic exchange membrane 11 or the anion-exchange membrane 12 of both sides respectively, thereby reaches the purification purpose.
Using PP(Polypropylene, 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 fixing by the mode such as screw and whole EDI device 15.The combining site of whole EDI device 15 all uses the silicon rubber pad to seal, and prevents the seepage of feed liquid.
As shown in Figure 2, be connected with respectively transfer lime 16 on the opening for feed 3 of the dense water of EDI device 15/utmost point water inlet 5, dense water out 6, utmost point water out 14 and organic amine electroplating additive and discharge port 4, be respectively equipped with gate valve 17 on transfer lime 16; With outwards also be provided with successively the first tensimeter 18, safety valve 19, first flow meter 20 and feedstock pump 21 by opening for feed 3 on transfer lime 16 that opening for feed 3 is connected; With outwards also be provided with successively the second tensimeter 22, the second under meter 23 and dense water/utmost point water pump 24 by dense water/utmost point water inlet 5 on transfer lime 16 that dense water/utmost point water inlet 5 is connected; With outwards also be provided with successively the 3rd tensimeter 25, the 3rd under meter 26 and sampling valve 27 by discharge port 4 on transfer lime 16 that discharge port 4 is connected; With outwards also be provided with successively the 4th tensimeter 28 and dense water-circulating pump 29 by dense water out 6 on transfer lime 16 that dense water out 6 is connected, the other end of this transfer lime 16 respectively with the second under meter 23 and dense water/utmost point water pump 24 between transfer lime 16 and concentrated water discharge groove 30 be connected.
Now take the Tetramethylammonium hydroxide purification as example, purifying technique is described.Technical grade TMAH use ultrapure water is mixed with the solution of concentration 1%-25%, the preferred 2.38%-25% of concentration.Then use the micro-filtrate membrane filtration solution in 0.22-5 μ m aperture, the material of microfiltration membrane is PP, PFA(Polyfluoroalkoxy, perfluoroalkoxy resin), PTFE(Polytetrafluoroethene, tetrafluoroethylene), HDPE(High Density Polyethylene, high density polyethylene(HDPE)) material of acid and alkali-resistance such as, preferred PP.Controlling the TMAH flows by feedstock pump 21 is 6-100 L/h, and the material of whole transfer lime 16 systems 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 chamber 7, open dense water/utmost point water pump 24 and dense water-circulating pump 29, purifying chamber 7 flows are made as 1-100 L/h, dense hydroecium 10 and utmost point hydroecium 9 flows are made as 1-100 L/h, the setting initial voltage is 0-100V, preferred 30-90V, open direct supply, carry out the electrodeionization operation, the operation optimum temps is at 45 ℃-60 ℃, approximately after operation 60-300 min, open sampling valve 27 sampling and use jigger coupling Atomic Emission SpectrometerAES ICP-AES(Thermo Fisher company) and DIONEX DX120 two channels chromatography of ions detect zwitterion impurity (metal ion in TMAH after purification, chlorion and carbanion) concentration.After detected result reaches the SEMI standard, can stop the EDI operation, collect sample, otherwise, proceed the EDI operation, until the concentration of zwitterion impurity reaches the 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 of carrying out in case of necessity fresh liquid replenishes.At last, the TMAH of purification obtains the finished product through 0.1 μ m-0.22 μ m micro-filtrate membrane filtration again, if TMAH concentration after acid base titration less than 25%, can carry out the underpressure distillation water removal operation and concentrate TMAH and reach 25% concentration.
Embodiment 1
get 100 kg technical grade five hydration TMAH, use the TMAH solution of ultrapure water preparation 25% concentration, use the micro-filtrate membrane filtration solution in 2 μ m apertures, get clear liquid, with pack into the reservoir of PP material of filtrate, use feedstock pump 21 that TMAH is inputted electric deionizer 15, trade names D261 strong-basicity styrene series anion exchange resin and Amberlite 252Na strongly acidic styrene type cation exchange resin are equipped with in purifying chamber 7, cloudy, the ratio 2:3(V:V of Zeo-karb), cationic exchange membrane 11 and anion-exchange membrane 12 are respectively chemical industry water treatment plants, polyvinyl sulfonic acid type cationic membrane 3361W polyethylene uncle's ammonia type anionic membrane 3362W(Shanghai), open direct supply, the constant voltage operation, setting initial voltage is 70 V, carry out the electrodeionization operation, hierarchy of control temperature is below 45 degrees centigrade, when EDI operates 90 min, monitor the zwitterion concentration of sample, reach the SEMI standard, as shown in table 2, after concentration conversion, all metal ions concentration is all lower than 2-10 ppb, chlorine ion concentration is lower than 0.1 ppm, carbanion is lower than 100 ppm.Measuring through acid base titration the TMAH concentration that obtains is 20.07%, does not consider the electrolytic separation of water, and the rate of recovery of calculating TMAH can reach 80.3%.
Embodiment 2
Processing condition and equipment are with embodiment 1, cationic exchange membrane 11 in different EDI devices 15 and anion-exchange membrane 12 change ethylene-propylene rubber(EPR) homogeneous phase cation film KM ethylene-propylene rubber(EPR) homogeneous-phase anion film AM (sky, Shandong dimension film company limited) into, when EDI operates 60 min, monitor the zwitterion concentration of sample, reach the SEMI standard, as shown in table 2, all metal ions concentration is all lower than 2-10 ppb, chlorine ion concentration is lower than 0.1 ppm, and carbanion is lower than 100 ppm.Measuring through acid base titration the TMAH concentration that obtains is 21.67%, does not consider other factors such as electrolytic separation of water, and the rate of recovery of calculating TMAH can reach 86.7%.
Embodiment 3:
Processing condition and equipment are with embodiment 2, ion exchange resin in different EDI devices 15 changes into and uses JK204 highly basic gel-type anionite-exchange resin and D001 macropore strong acid vinylbenzene Zeo-karb to be loaded on purifying chamber 7 in the mixed bed mode, and in purifying chamber 7, the ratio of anionite-exchange resin and Zeo-karb is 2:3(V:V).When reaction reaches 60 min, the sampling censorship, as shown in table 2 after testing, after concentration conversion, all metal ions concentration is all lower than 2-10 ppb, and chlorine ion concentration is lower than 0.1 ppm, and carbanion reaches the SEMI standard lower than 100 ppm.The TMAH concentration of measuring this moment through acid base titration is 21.34%, does not consider the other factorses such as electrolytic separation of water, and the rate of recovery that calculates TMAH reaches 85.4%.
From the result of above-described embodiment as seen, 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 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 to cause the TMAH seepage in purifying chamber 7, thereby has reduced the TMAH rate of loss, so adopt in this invention homogeneous membrane EDI purification TMAH speed faster, yield is higher.Simultaneously, from the comparing result of embodiment 2 and embodiment 3, the ion exchange resin type alternation of signs is less on the experimental result impact.
Zwitterion foreign matter content in the TMAH that table 2:EDI purifies.
The data of table 2 show, can reach the electronic-grade standard of SEMI fully by the TMAH of TMAH purification process purification provided by the invention.The method also can well be applied to the purification of other organic amine additive.
Although content of the present invention has been 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 modification of the present invention with to substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (9)
1. the purification process of an organic amine electroplating additive, is characterized in that, the method is by the zwitterion impurity in electric deionizer (15) removal organic amine electroplating additive;
Described electric deionizer (15) two ends are respectively equipped with end plate (8), an end plate (8) is provided with the negative electrode (1) that is connected with direct supply, another piece end plate (8) is provided with the anode (2) that is connected with direct supply, the inboard of two end plates is respectively equipped with a utmost point hydroecium (9), be arranged alternately successively some parallel purifying chambers (7) and dense hydroecium (10) between two utmost point hydroeciums (9), separate by cationic exchange membrane (11) or anion-exchange membrane (12) respectively between each purifying chamber (7) and dense hydroecium (10);
Described cationic exchange membrane (11) and anion-exchange membrane (12) are arranged alternately and make each purifying chamber (7) be cationic exchange membrane (11), be anion-exchange membrane (12) near a side of negative electrode (1) end plate (8) near a side of anode (2) end plate (8);
Be filled with the mixture of anionite-exchange resin and Zeo-karb in described purifying chamber (7);
Be added with respectively the organic ammonium salt solution of 0.3%-1% concentration as ionogen in described dense hydroecium (10) and utmost point hydroecium (9);
The liquid flow rate of described purifying chamber (7) is 1-100 L/h, and dense hydroecium (10) and utmost point hydroecium (9) flow are 1-100 L/h; The initial voltage of direct supply is 0-100V, voltage constant and to keep solution temperature be 20-70 ℃ in purge process; The rate of recovery of the organic amine electroplating additive after purifying is greater than 80%.
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 one of them out-phase or homogeneous ion-exchange membrane of polyethylene, polypropylene, polyvinyl chloride, polyethers or fluorine-containing high polymers, and described cationic exchange membrane (11) is one of them of heterogeneous ion-exchange membrane, polyethylene homogeneous ion-exchange membrane, sulfonate film or perfluoro sulfonic acid membrane.
3. the purification process of organic amine electroplating additive as claimed in claim 1, it is characterized in that, described anionite-exchange resin and Zeo-karb are all selected the ion exchange resin of polystyrene, the ion exchange resin of polyacrylic, a kind of in phosphoramidic acid or iminodiethanoic acid resin.
4. the purification process of organic amine electroplating additive as claimed in claim 3, is characterized in that, the ratio of described anionite-exchange resin and Zeo-karb is 10:1 to 1:10.
5. 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 a kind of in graphite, 316L stainless steel, titanium, platinum or plating iridium titanium plate.
6. the purification process of organic amine electroplating additive as claimed in claim 1, it is characterized in that, be respectively equipped with dividing plate (13) outside the surrounding of described dense hydroecium (10) and utmost point hydroecium (9), and fixing by dividing plate (13) and whole electric deionizer (15); Each junction of described electric deionizer (15) is respectively by the sealing of silicon rubber pad.
7. the purification process of organic amine electroplating additive as claimed in claim 6, it is characterized in that, described electric deionizer (15) also comprises the opening for feed (3) and discharge port (4), dense water/utmost point water inlet (5), dense water out (6) and utmost point water out (14) of organic amine electroplating additive, is connected with the below of below, utmost point hydroecium (9) and the top of dense hydroecium (10), dense hydroecium (10) and the below of utmost point hydroecium (9) with top, purifying chamber (7) respectively.
8. the purification process of organic amine electroplating additive as claimed in claim 7, it is characterized in that, be connected with respectively transfer lime (16) on the opening for feed (3) of the dense water of described electric deionizer (15)/utmost point water inlet (5), dense water out (6), utmost point water out (14) and organic amine electroplating additive and discharge port (4), be respectively equipped with gate valve (17) on transfer lime (16);
The transfer lime (16) that is connected with opening for feed (3) is upper outwards also is provided with the first tensimeter (18), safety valve (19), first flow meter (20) and feedstock pump (21) successively by opening for feed (3);
The transfer lime (16) that is connected with dense water/utmost point water inlet (5) is upper outwards also is provided with the second tensimeter (22), the second under meter (23) and dense water/utmost point water pump (24) successively by dense water/utmost point water inlet (5);
The transfer lime (16) that is connected with discharge port (4) is upper outwards also is provided with the 3rd tensimeter (25), the 3rd under meter (26) and sampling valve (27) successively by discharge port (4);
The transfer lime (16) that is connected with dense water out (6) is upper outwards also is provided with the 4th tensimeter (28) and dense water-circulating pump (29) successively by dense water out (6), the other end of this transfer lime (16) respectively with the second under meter (23) and dense water/utmost point water pump (24) between transfer lime (16) and concentrated water discharge groove (30) be connected.
9. the purification process of organic amine electroplating additive as claimed in claim 8, is characterized in that, described method comprises:
Step 1 is carried out the filling of electric deionizer (15) assembling and ion exchange resin;
Step 2 is filtered organic amine electroplating additive material solution, then filtrate is diluted to the pH value for 10-13.5, pumps into electric deionizer (15);
Step 3 adds the organic ammonium salt solution of 0.3%-1% concentration to do ionogen in dense hydroecium (10) and utmost point hydroecium (9);
Step 4, feedstock pump (21), dense water/utmost point water pump (24) and dense water-circulating pump (29) start operation simultaneously, carry out the electrodeionization process;
Step 5, modifier material and reaction conditions record the concentration of foreign metal ion and negatively charged ion in purifying chamber (7) the interior organic amine electroplating additive solution of electric deionizer (15) when reaching steady-state operation, with the processing condition of determining to optimize;
Step 6, the Optimizing Technical of determining with step 5 carries out organic amine electroplating additive purifying, detects the material solution temperature by temperature measurer in this purge process, controls temperature not higher than 20 ℃-70 ℃; Every 15 minutes to the discharging sampling once, detect the wherein zwitterion concentration of impurity simultaneously, after the zwitterion concentration in sample reaches the standard-required of fine electronic level, the organic amine electroplating additive solution after purifying is collected;
Step 7, the organic amine electroplating additive solution after purifying obtain the finished product through 0.1-0.22 μ m micro-filtrate membrane filtration again, and this filtration procedure carries out in 100 grades of super-clean environments.
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| 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 |
| WO2021203255A1 (en) * | 2020-04-08 | 2021-10-14 | Dow Global Technologies Llc | Organic amine purification method |
| WO2022241690A1 (en) * | 2021-05-19 | 2022-11-24 | Dow Global Technologies Llc | Processes for purifying organic amines |
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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 |
| WO2021203255A1 (en) * | 2020-04-08 | 2021-10-14 | Dow Global Technologies Llc | Organic amine purification method |
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| EP4341240A4 (en) * | 2021-05-19 | 2025-03-26 | Dow Global Technologies LLC | PROCESSES FOR THE PURIFICATION OF ORGANIC AMINES |
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