CN103466557A - Preparation method of ultra-pure hydrogen peroxide aqueous solution - Google Patents
Preparation method of ultra-pure hydrogen peroxide aqueous solution Download PDFInfo
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Abstract
The invention relates to a preparation method of ultra-pure hydrogen peroxide aqueous solution, aiming at providing a method which is capable of providing the ultra-pure hydrogen peroxide aqueous solution and has the characteristics of high safety and good reproducibility. The technical scheme of the invention is as follows: filtering food grade hydrogen peroxide containing many impurities as a raw material in a membrane prefilter, and then removing the organic impurities by at least one group of adsorption resin columns which are connected in series; then removing the ion impurities by at least one group of cation exchange resin columns and at least one group of anion exchange resin columns which are connected in series, or removing the ion impurities by at least one group of mixed cation and anion exchange resin columns; finally, filtering the product by a membrane fine filter, and collecting the target product ultra-pure hydrogen peroxide.
Description
Technical field
The present invention relates to a kind of preparation method of the ultrapure hydrogen peroxide aqueous solution; The preparation method who particularly meets the ultrapure hydrogen peroxide aqueous solution of SEMI C12 standard.
Background technology
Ultrapure hydrogen peroxide is one of indispensable key basic chemical industry material in electronic technology microfabrication making processes, mainly be used as the remover of clean-out system, etching reagent and the photoresist material of semiconductor crystal sheet, electronic industry is produced the premium insulation layer, is removed inorganic impurity in electroplate liquid, and the processing of copper, copper alloy and semiconductor material gallium, germanium and picture tube manufacturing process etc., its purity has very important impact to yield rate, electrical property and the reliability of unicircuit.In recent years, along with the development of electronic industry, the demand of the ultrapure hydrogen peroxide aqueous solution is also growing.
Ultrapure hydrogen peroxide is generally that to take technical grade hydrogen peroxide product cheap and easy to get be raw material, through a series of purification, scavenging process and obtain.The at present almost anthraquinone preparation of employing without exception of technical grade hydrogen peroxide.The technical grade hydrogen peroxide of anthraquinone production contains a certain amount of organic impurities and inorganics impurity, these organic impurities are mainly derived from the processes such as additive in production, materiel machining, transportation, storage, comprise anthraquinone compounds, ester, alcohol, phenol, ketone compounds etc., general organic content is in the 100-500mg/L scope; Inorganics impurity from the material that forms reactor used and synthesis device, comprises silicon compound, aluminium, iron, chromium, nickel etc. usually.Electronic applications has strict requirement to the foreign matter content of hydrogen peroxide, and therefore, aqueous hydrogen peroxide solution need to pass through purification processes, removes these impurity, reaches the specification of quality of realistic application.
In order to remove these impurity in technical grade hydrogen peroxide product, since the 1950's, people have developed many purifying methods in succession, mainly comprise the combination of distillation under vacuum, reverse osmosis method, ion exchange method and several method; But all there is some problems in these methods, wherein the distillation method vapor-liquid separation not exclusively reaches fog-like liquid and carries, and makes the purity of hydrogen peroxide generally can not reach very high, and energy consumption is high, and hydrogen peroxide decomposes very fast, and material consumption is high, poor stability, and production cost is higher; Reverse osmosis purifying hydrogen peroxide technological operation pressure is high, and film is short work-ing life, and production cost is higher, and technology is also immature; At present, though there is at home report can obtain meeting the ultrapure hydrogen peroxide product of semiconductor equipment and material structure SEMI C12 standard by exchange resin method, but in the conventional ion exchange process, hydrogen peroxide contacts with negative resin easily and decomposes and formation danger, and there is potential safety hazard in production process; And bicarbonate radical type negative resin selectivity is poor, in regenerative process, be difficult to make other negatively charged ion that adsorb in resin fully to replace, affect the regeneration effect of resin, produce a large amount of bubbles in purification process, hydrogen peroxide and resin contact area are descended and affect refining effect, when resin contacts with hydrogen peroxide, also easily decompose and have in process of production a potential safety hazard.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned background technology, a kind of preparation method of the ultrapure hydrogen peroxide aqueous solution is provided, the method should be able to provide the ultrapure hydrogen peroxide aqueous solution, and has characteristics safe, that reproducibility is good.
The present invention is achieved through the following technical solutions:
A kind of preparation method of the ultrapure hydrogen peroxide aqueous solution, comprise the steps:
First by the film prefilter, filter impure more food grade hydrogen peroxide as raw material, then by the adsorption resin column of at least one group of series connection, remove organic impurities; And then remove ionic impurity by least one group of cation exchange resin column and at least one group of anion-exchange resin column that are connected in series, or mix the anion-cation exchange resin post by least one group again and remove ionic impurity; Finally enter the film fine filter and filter, collect the target product ultrapure hydrogen peroxide.
Polymeric adsorbent in described adsorption resin column is macroporous adsorbent resin.
Further, described macroporous adsorbent resin is nonpolar macroporous adsorption resin and polar macroporous adsorption resin, and adopts two kinds of adsorption resin column series connection to be used in conjunction with.
Described at least one group refers to 1～8 group; Preferred 2-7 group.
Described nonpolar macroporous adsorption resin and polar macroporous adsorption resin, all configure two kinds of apertures; Be respectively
with
.
The styrene diethylene benzene copoly mer that described macroporous adsorbent resin material is amide-containing or cyano group or phenolic hydroxyl group polar group.
Described anionite-exchange resin is the weak base anion-exchange resin that chlorion type anionite-exchange resin changes into hydroxyl.
The volume ratio of the anion-cation exchange resin in described mixing anion-cation exchange resin post is 1:3～1.
The operating pressure of above-mentioned preparation process is at 0.1-0.5Mpa, and temperature is at 5-30 ℃, and the production flow control is at 300-500kg/h.
Described ultrapure hydrogen peroxide refers to that in the aqueous solution, concentration of hydrogen peroxide is 27.5%-50%, preferably 30-50%.
The preparation method of the weak base anion-exchange resin of described hydroxyl is:
1) a certain amount of strong alkali aqueous solution is inputted to chlorion type anion-exchange resin column and this strong alkali aqueous solution uniflux is processed through this ion exchange resin column, standing 6-24h; Then input again a certain amount of strong alkali aqueous solution and its equidirectional this ion exchange resin column of mobile process is processed; Then input pure water and make it continue this ion exchange resin column of equidirectional process and flow to this ion exchange resin column cleaning; Strong alkali aqueous solution in this step is identical with the flow direction of pure water;
2) the chlorion type anion-exchange resin column of a certain amount of strong alkali aqueous solution input being processed through step 1) also makes this strong alkali aqueous solution uniflux be processed through this ion exchange resin column, standing 6-24h; Then input again a certain amount of strong alkali aqueous solution and its equidirectional this ion exchange resin column of mobile process is processed; Then input pure water and make it continue this ion exchange resin column of equidirectional process and flow to this ion exchange resin column cleaning; Strong alkali aqueous solution in this step is all contrary with step 1) with the flow direction of pure water.
The invention has the beneficial effects as follows: adopt the ultrapure hydrogen peroxide aqueous solution content that preparation method of the present invention obtains to be greater than 30%, organic carbon content is lower than 5ppm, single cations is lower than 0.1ppb, single anion-content is lower than 30ppb, be greater than the dust granules of 0.5 μ m lower than 25/milliliter, meet SEMI C12 standard.And the present invention has also solved hydrogen peroxide in the purification operations and has contacted the technical barrier that the interior temperature rising of tower and pressure are raise with anionite-exchange resin, thereby has guaranteed the security that aqueous hydrogen peroxide solution is purified.The aqueous hydrogen peroxide solution of purifying by method of the present invention in addition, has good and stable reproducibility on the degree of removing organic impurity and ionic impurity.
The accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
In Fig. 1,1 is raw material storage tank, 2 is pump, 3 prefilters that are precision 0.5 μ m, 4,5,6,7 be adsorption resin column, 8 is cation exchange resin column, and 9 is anion-exchange resin column, and 10 is Zeo-karb/mixture iron exchange resin post, 11 fine filters that are precision 0.1 μ m, 12 is finished product storage tank.
Embodiment
[polymeric adsorbent processing]
In the preparation method of the ultrapure hydrogen peroxide aqueous solution of the present invention, with before ion exchange resin contacts, first need to make aqueous hydrogen peroxide solution to contact with polymeric adsorbent.
As polymeric adsorbent, use the macroporous adsorbent resin that there is no ion-exchange capacity.Macroporous adsorbent resin adopts the styrene diethylene benzene copoly mer of amide-containing or cyano group or phenolic hydroxyl group polar group.Desirable macroporous adsorbent resin, the aperture under anhydrous state is about
macroporous adsorbent resin can be selected not containing the nonpolar adsorption resin of any ion-exchange group and the Polar Adsorbent Resin that contains hydrophilic radical.Nonpolar macroporous adsorption resin comprises Rohm& The XAD series product such as Amberlite XAD2, XAD4, XAD8, XAD16N, XAD16HP, XAD18, XAD1600N and XAD1180N that Haas company produces; Float that Lai Te company produces
the PAD series product such as PAD350, PAD400, PAD500, PAD550, PAD700, PAD900 and PAD910; HP10, HP20, HP30, HP40, HP50, SP800, SP850 and SP900 that Mitsubishi compound probability company produces.Polar macroporous adsorption resin comprises the MN series product such as Macronet MN100, MN150, MN200, MN202, MN220, MN250, MN270, MN300, MN400 and MN500 that float the production of Lai Te company; The resin of the commodity of Mitsubishi compound probability company " SEPABEADS SP207 and SP825 " by name; The resin of the commodity " Bofazit EP63, Wofazit EP63, bophachett EP63 " by name that also have Bayer company to produce.
The present invention adopts that nonpolar adsorption resin and Polar Adsorbent Resin are used in conjunction with, the different pore size resin is used in conjunction with, by this treating processes, can remove in a large number the organic impurities in aqueous hydrogen peroxide solution, thereby reduce the total content of organic carbon (TOC) in aqueous hydrogen peroxide solution.
As recommendation, the most handy alkali, the sour and pure aqueous solution are processed polymeric adsorbent as regenerator and are regenerated, and after manipulation of regeneration completes, with ultrapure water, clean.
Alkali can be used sodium hydroxide, potassium hydroxide, the preferred 2-10% of the concentration of alkali aqueous solution, especially preferably 4-8%; Acid can be used sulfuric acid, hydrochloric acid, the preferred 2-10% of the concentration of aqueous acid, especially preferably 4-8%; Alcohol can be used methyl alcohol, ethanol and propyl alcohol, the preferred 50-100% quality of the concentration of alcohol solution, especially preferably 60-80%.
Adopt repeatedly repetition methods (preferably 2-5 time) regeneration polymeric adsorbent, the volume of the regenerator volume used and pending polymeric adsorbent should be quite or is larger, the 2-10 of preferred resin volume times.The method that polymeric adsorbent is contacted with regenerator is the process of a continuous flow, wherein makes regenerator with 2-5Hr
-1(under defined terms, the bolus volume that enters resin column in unit time is equivalent to several times of resin volumes, unit per hour is) the SV(space velocity) and the BV(bed volume of 3-5L/L-R, the liquor capacity of expression by resin is how many times of the resin volume processed, unit representation becomes L/L-R, L rises, L-R is the resin volume, with liter, mean) first downwards by filling the adsorption resin column of polymeric adsorbent, regenerator is soaked to polymeric adsorbent 6-24h, preferably 12-18h, then make progress by filling the adsorption resin column of polymeric adsorbent.After every kind of regenerator has been regenerated, repeat the polymeric adsorbent after pure water cleaning process (comprise and be downward through and upwards flow through) is carried out further cleaning and regeneration for 2-5 time.Ultrapure water flows preferably with 5-20Hr
-1sV and the BV of 3-5L/L-R.Preferably with the ultrapure water of resin volume 10-50 times, cleaned.
[Zeo-karb processing]
In the preparation method of the ultrapure hydrogen peroxide aqueous solution, after processing aqueous hydrogen peroxide solution with polymeric adsorbent, continue to make aqueous hydrogen peroxide solution and H
+type sun resin or hybrid resin contact.
The H that the present invention uses
+type sun resin is a kind of resin that is commonly referred to storng-acid cation exchange resin.General storng-acid cation exchange resin preferably has network structure, wherein in styrene-divinylbenzene copolymerzation with cross-linking body, has introduced sulfonic acid group.
H
+the type Zeo-karb comprises Rohm& Amberlite IRN77, Amberlite IRN160, AMBERJET1200H, AMBERLITETM FPC11Na, AMBERLITETM FPC14Na, AMBERLITETM FPC22H, AMBERLITETM FPC22Na, AMBERLITETM FPC23 that Haas company produces; Float that Lai Te company produces
the C series product; Also have PK216, SK1B, the IR-120B that can buy on market.
Adopt repeatedly repetition methods (preferably 2-5 time) regeneration H
+the type Zeo-karb, use the inorganic acid aqueous solution (regenerator) of regenerating resin given volume multiple (preferably 1-2 doubly) through described cation exchange resin column (from top to bottom flowing), standing 6-24h, preferably 12-18h; Follow the pure water of inlet flow a certain amount of (resin volume certain multiple) on this resin column, pure water from top to bottom flows and cleans; Then use the inorganic acid aqueous solution of regenerating resin given volume multiple (preferably 1-2 doubly) to flow through this resin column from bottom to top, standing 6-24h, preferably 12-18h; Again with the pure water of regenerating resin given volume multiple from bottom to top through the cleaning of flowing of this resin column, processing Zeo-karb.In the present invention, repeat twice of the circulation that flow/ultrapure water of regenerator cleans or be repeatedly best.By repeating flowing of regenerator/ultrapure water, impel resin shrinkage and expansion, can be effectively and the exchange resin of regenerating uniformly, and resin capable of washing inside.
The mineral acid used is conventional mineral acid, as sulfuric acid, hydrochloric acid.
The preferred 4-10% of inorganic acid concentration in the regenerator aqueous solution, more preferably 5-8%.The regenerator volume used is preferably treated 3 times or more times of regenerating resin, and the 5-15 of preferred pending resin volume doubly.
Regenerator should be with 1-3Hr
-1sV and the BV of 1-2L/L-R flow through resin, then ultrapure water is with 5-20Hr
-1sV and the BV of 0.1-0.5L/L-R flow through resin, for cleaning.Finally repeat ultrapure water cleaning (comprise and be downward through and upwards flow through) 5-10 time, further the ion exchange resin after cleaning and regeneration.Preferably ultrapure water is with 5-20Hr
-1sV and the BV of 3-5L/L-R pass through.Preferred resin volume 10-50 is doubly cleaned.
The raw material hydrogen peroxide aqueous solution is with method and the H used in the present invention of continuous flow
+the contact of type Zeo-karb, aqueous hydrogen peroxide solution is with 10-50Hr
-1, preferred 20-40Hr
-1sV by cation exchange resin layer or hybrid resin layer.
As stated above, use H
+the type Zeo-karb is processed, and just can remove the positive impurity metal ion in aqueous hydrogen peroxide solution.
[anion exchange process]
In the present invention, the aqueous hydrogen peroxide solution through Zeo-karb then contacts with anionite-exchange resin.As anionite-exchange resin, the present invention uses hydroxyl type (OH
-) weak base anion-exchange resin (being the weak base anion-exchange resin of hydroxyl).
Hydroxyl type (OH in the present invention
-) weak base anion-exchange resin is to be transformed with a kind of usually known anionite-exchange resin.The known anionite-exchange resin of this routine is derived from the styrene-divinylbenzene cross-linking copolymer, and has primary amine, secondary amine and the tertiary amine weak base anion-exchange resin as ion-exchange group.
Weak base anion-exchange resin (chlorion type anionite-exchange resin) comprises Rohm& Amberlite IRC84, AMBERLITE IRA93, AMBERLITE IRA96RF, AMBERLITE FPA51 etc. that Haas company produces; Float that Lai Te company produces
a100, A103S, A105, A830 and A845 etc.; Wofatit AD-41, the Lewatit MP-60 that can buy on market in addition, Diaion WA-30, Duolite A305, AH-89 * 77 II, Zerolite MPH etc.
For chlorion type anionite-exchange resin is changed into to hydroxyl type (OH
-) weak base anion-exchange resin, adopted the preparation method who repeatedly repeats (preferably 2-5 time); Wherein first with the processing that flows downward of the strong alkali aqueous solution of chlorion type anionite-exchange resin given volume multiple, standing 6-24h, preferred 12-18h, then again input the strong alkali aqueous solution of chlorion type anionite-exchange resin given volume multiple, continue equidirectional flow and processed, then with the pure water cleaning that flows downward; Then the strong alkali aqueous solution with chlorion type anionite-exchange resin given volume multiple upwards flows, standing 6-24h, preferred 12-18h, then again input the strong alkali aqueous solution of chlorion type anionite-exchange resin given volume multiple, continuing equidirectional flowing is processed), then with pure water, upwards flow and clean.In the present invention, flow/ultrapure water cleans to repeat strong alkali aqueous solution, circulates twice or is repeatedly best.By repeating flowing of strong alkali aqueous solution/ultrapure water, impel resin shrinkage and expansion, can effectively He equably to chlorion type anionite-exchange resin, be transformed, and resin capable of washing inside.Obviously, this preparation method is equally for the regeneration of hydroxyl type (OH-) weak base anion-exchange resin.
As highly basic, can use known highly basic usually, as sodium hydroxide, potassium hydroxide.
The preferred 4-10% of the concentration of contained highly basic, more preferably 5-8% in strong alkali aqueous solution.The strong alkali aqueous solution volume used preferably pending resin 3-20 doubly, the 5-15 of preferred pending resin volume is doubly.
Strong alkali aqueous solution should be with 1-3Hr
-1sV and the BV of 1-2L/L-R flow through resin, then ultrapure water is with 5-20Hr
-1sV and the BV of 0.1-0.5L/L-R flow through resin, for cleaning.Finally repeat ultrapure water cleaning (comprise and be downward through and upwards flow through) 5-10 time, further clean chlorion type anionite-exchange resin.Preferably ultrapure water is with 5-20Hr
-1sV and the BV of 3-5L/L-R pass through.Preferred resin volume 10-50 is doubly cleaned.
The raw material hydrogen peroxide aqueous solution contacts with hydroxyl type used in the present invention (OH-) weak base anion-exchange resin with the method for continuous flow, and aqueous hydrogen peroxide solution is with 10-50Hr
-1, preferred 20-40Hr
-1sV by hydroxyl type (OH-) weak base anion-exchange resin.
Common chlorion type anionite-exchange resin (CO3
-or HCO3
-type anionite-exchange resin) with the aqueous hydrogen peroxide solution contact need, carry out at low temperatures, this is because CO3
-or HCO3
-during type anionite-exchange resin contact aqueous hydrogen peroxide solution, aqueous hydrogen peroxide solution decomposes can produce reacted gas, decomposes and also can produce heat, has potential safety hazard.The present invention uses hydroxyl type (OH-) weak base anion-exchange resin can avoid well the generation of these phenomenons, greatly improves the security of producing.
By aforesaid operations, can prepare the ultrapure hydrogen peroxide aqueous solution, wherein the concentration after organic impurities, ionic impurity removal all reaches SEMI C12 standard level.And, adopt the aqueous hydrogen peroxide solution of purifying of the present invention to there is good and stable reproducibility on the degree of removing organic impurity and ionic impurity.
In addition, can also in the aqueous hydrogen peroxide solution obtained according to method provided by the invention, add ultrapure water (preferred heights has been removed the ultrapure water of impurity), regulate concentration of hydrogen peroxide.
Below in conjunction with embodiment, the present invention is more specifically described.Yet the present invention is not limited only to these embodiment.(TOC: total organic carbon) content adopts the TOC analyser to detect to gained aqueous hydrogen peroxide solution organic impurities, and positively charged ion adopts ICP-MS to analyze, and negatively charged ion adopts ion chromatography, and dust granules adopts the laser calculating instrument to be measured.
Embodiment 1
35% food grade hydrogen peroxide, its TOC content is 72ppm, contain a large amount of ionic impurities, first filtered pre-treatment, then the effect by pump enters PAD700, XAD4, MN200 and the MN150 adsorption resin column (totally four groups of adsorption resin columns) that four series connection are used in conjunction with successively.The organic carbon content flowed out from here then flows into one group of cationic exchange coloum and one group of anion-exchange column successively lower than the superoxol of 5ppm, then filters through fine filter, thereby obtains target product.The nonpolar macroporous adsorption resin that in the present embodiment, adsorption resin column is used is to float Lai Te company to produce
pAD700 and Rohm & The XAD4 that Haas company produces; Polar macroporous adsorption resin is to float Macronet MN200 and the MN150 that Lai Te company produces; The sun resin is used Rohm& The Amberlite IRN77 that Haas company produces; Negative resin is used Rohm& The AMBERLITE IRA96RF that Haas company produces.In the present embodiment, the diameter of every group of adsorption resin column and every group of ion exchange column is 300mm, and aspect ratio is 8:1; Wherein Zeo-karb is hydro-strong acidic cation exchange resin, and anionite-exchange resin is the hydroxyl type weak base anion-exchange resin.
In the present embodiment, the pressure of operation is at 0.2Mpa, and temperature is controlled at 25 ℃, and the production flow is 400kg/h; Certainly flow also can be according to raw material H
2o
2quality regulated.After aqueous hydrogen peroxide solution is by each adsorption column and ion exchange column, dilute purified aqueous hydrogen peroxide solution with ultrapure water (its camber has been removed impurity), preparation has the ultrapurity aqueous hydrogen peroxide solution that concentration of hydrogen peroxide is 31%.
Embodiment 2
50% food grade hydrogen peroxide, its TOC content is 93ppm, contain a large amount of ionic impurities, first filtered pre-treatment, then by the effect of pump, enter the adsorption resin column (totally four groups of adsorption resin columns) that MN500, PH20, MN150 and the PAD300 of four series connection are used in conjunction with.The organic carbon content flowed out from here flows into one group of cationic exchange coloum, one group of anion-exchange column and one group of cationic exchange coloum successively lower than the superoxol of 5ppm, then filters through fine filter, thereby obtains target product.The nonpolar macroporous adsorption resin that in the present embodiment, adsorption resin column is used is the PH20 that Mitsubishi compound probability company produces and floats that Lai Te company produces
pAD300; What polar macroporous adsorption resin was used is to float Macronet MN500 and the MN150 that Lai Te company produces; The production of Lai Te company is floated in the use of sun resin
c150; The production of Lai Te company is floated in the negative resin use
a100.In the present embodiment, the diameter of adsorption resin column and ion exchange column is 300mm, and aspect ratio is 10:1; Wherein Zeo-karb is hydro-strong acidic cation exchange resin, and anionite-exchange resin is the hydroxyl type weak base anion-exchange resin.
In the present embodiment, the pressure of operation is at 0.3Mpa, and temperature is controlled at 20 ℃, and the production flow is 300kg/h; Certainly flow also can be according to raw material H
2o
2quality regulated.After aqueous hydrogen peroxide solution is by each adsorption column and ion exchange column, dilute purified aqueous hydrogen peroxide solution with ultrapure water (its camber has been removed impurity), preparation has the ultrapurity aqueous hydrogen peroxide solution that concentration of hydrogen peroxide is 31%.
35% food grade hydrogen peroxide, its TOC content is 68ppm, contain a large amount of ionic impurities, first filtered pre-treatment, then by the effect of pump, enter the adsorption resin column (totally four groups of adsorption resin columns) that XAD16N, SP850, MN200 and the MN250 of four series connection are used in conjunction with.The organic carbon content flowed out from here flows into two groups of mixing cation and anion exchange posts of series connection lower than the superoxol of 5ppm.The nonpolar macroporous adsorption resin used in the present embodiment is Rohm& The SP850 that the XAD16N that Haas company produces and Mitsubishi compound probability company produce; Polar macroporous adsorption resin is all used and floats M1cronet MN200 and the MN250 that Lai Te company produces; Zeo-karb is used Rohm& The Amberlite IRN77 that Haas company produces; Anionite-exchange resin is used Rohm& The AMBERLITE IRA93 that Haas company produces.In the present embodiment, the diameter of adsorption resin column and ion exchange column is 300mm, and aspect ratio is 6:1; Wherein the volume ratio of anion-exchange resin column and cation exchange resin column is 2:1, and wherein Zeo-karb is hydro-strong acidic cation exchange resin, and anionite-exchange resin is the hydroxyl type weak base anion-exchange resin.
In the present embodiment, the pressure of operation is at 0.1Mpa, and temperature is controlled at 30 ℃, and the production flow is 500kg/h; Certainly flow also can be according to raw material H
2o
2quality regulated.After aqueous hydrogen peroxide solution is by each adsorption column and ion exchange column, dilute purified aqueous hydrogen peroxide solution with ultrapure water (its camber has been removed impurity), preparation has the ultrapurity aqueous hydrogen peroxide solution that concentration of hydrogen peroxide is 31%.
The purified aqueous hydrogen peroxide solution impurities amount obtained in three embodiment is meaned by following table.
The purified aqueous hydrogen peroxide solution impurities scale obtained in three embodiment
Claims (10)
1. the preparation method of a ultrapure hydrogen peroxide aqueous solution, comprise the steps:
First by the film prefilter, filter impure more food grade hydrogen peroxide as raw material, then by the adsorption resin column of at least one group of series connection, remove organic impurities; And then remove ionic impurity by least one group of cation exchange resin column and at least one group of anion-exchange resin column that are connected in series, or mix the anion-cation exchange resin post by least one group again and remove ionic impurity; Finally enter the film fine filter and filter, collect the target product ultrapure hydrogen peroxide.
2. the preparation method of the ultrapure hydrogen peroxide aqueous solution according to claim 1 is characterized in that: the polymeric adsorbent in described adsorption resin column is macroporous adsorbent resin.
3. the preparation method of the ultrapure hydrogen peroxide aqueous solution according to claim 2, it is characterized in that: described macroporous adsorbent resin is nonpolar macroporous adsorption resin and polar macroporous adsorption resin, and adopts two kinds of adsorption resin columns series connection to be used in conjunction with.
4. according to the preparation method of the described ultrapure hydrogen peroxide aqueous solution of claim 2 or 3, it is characterized in that: described at least one group refers to 1～8 group.
5. the preparation method of the ultrapure hydrogen peroxide aqueous solution according to claim 4, it is characterized in that: described nonpolar macroporous adsorption resin and polar macroporous adsorption resin all configure two kinds of apertures; Be respectively
with
.
6. the preparation method of the ultrapure hydrogen peroxide aqueous solution according to claim 5, is characterized in that: the styrene diethylene benzene copoly mer that described macroporous adsorbent resin material is amide-containing or cyano group or phenolic hydroxyl group polar group.
7. the preparation method of the ultrapure hydrogen peroxide aqueous solution according to claim 6, is characterized in that: the weak base anion-exchange resin that described anionite-exchange resin is hydroxyl.
8. the preparation method of the ultrapure hydrogen peroxide aqueous solution according to claim 7, it is characterized in that: the volume ratio of the anion-cation exchange resin in described mixing anion-cation exchange resin post is 1:3～1.
9. the preparation method of the ultrapure hydrogen peroxide aqueous solution according to claim 8, it is characterized in that: the operating pressure of preparation process is at 0.1-0.5Mpa, and temperature is at 5-30 ℃, and the production flow control is at 300-500kg/h.
10. the preparation method of the ultrapure hydrogen peroxide aqueous solution according to claim 9, it is characterized in that: the preparation method of the weak base anion-exchange resin of described hydroxyl is:
1) a certain amount of strong alkali aqueous solution is inputted to chlorion type anion-exchange resin column and this strong alkali aqueous solution uniflux is processed through this ion exchange resin column, standing 6-24h; Then input again a certain amount of strong alkali aqueous solution and its uniflux is processed through this ion exchange resin column; Then input pure water and make it continue this ion exchange resin column of equidirectional process and flow to this ion exchange resin column cleaning; Strong alkali aqueous solution in this step is all identical with the flow direction of pure water;
2) the chlorion type anion-exchange resin column of a certain amount of strong alkali aqueous solution input being processed through step 1) also makes this strong alkali aqueous solution uniflux be processed through this ion exchange resin column, standing 6-24h; Then input again a certain amount of strong alkali aqueous solution and its uniflux is processed through this ion exchange resin column; Then input pure water and make it continue this ion exchange resin column of equidirectional process and flow to this ion exchange resin column cleaning; Strong alkali aqueous solution in this step is all contrary with step 1) with the flow direction of pure water.
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| CN111921263A (en) * | 2020-07-23 | 2020-11-13 | 江苏理文化工有限公司 | Novel purification process of hydrogen peroxide |
| CN114671408A (en) * | 2022-04-12 | 2022-06-28 | 杭州精欣化工有限公司 | Method for removing B, Si element in semiconductor grade hydrogen peroxide solution |
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| CN116673075B (en) * | 2023-08-03 | 2023-09-26 | 甘肃华隆芯材料科技有限公司 | Preparation method and application of high-purity perfluoropolyether sulfonic acid |
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