CN1184138C - Process and equipment for preparation of ultrapure hydrogen peroxide - Google Patents
Process and equipment for preparation of ultrapure hydrogen peroxide Download PDFInfo
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- CN1184138C CN1184138C CNB001253123A CN00125312A CN1184138C CN 1184138 C CN1184138 C CN 1184138C CN B001253123 A CNB001253123 A CN B001253123A CN 00125312 A CN00125312 A CN 00125312A CN 1184138 C CN1184138 C CN 1184138C
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- hydrogen peroxide
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Abstract
The present invention relates to a manufacture technology and a device for ultra-pure hydrogen peroxide (H2O2). The technology comprises the technologic steps of raw material liquid adsorption, ion exchange, filtration, etc. The operating pressure of the technologic process is controlled between 0.05 and 1.0MPa; the temperature is controlled between 5 and 41 DEG C. Compared with the prior art, the technology and the device of the present invention have the advantages of reasonable design and low cost. The obtained H2O2 has high purity and favorable stability.
Description
Technical field
The present invention relates to a kind of ultrapure hydrogen peroxide (H
2O
2) manufacturing process and equipment.
Background technology
The H of technical grade
2O
2Because its production technology inevitably contains a large amount of organic carbon harmonizing yinyang ionic impurities, and is not suitable for the requirement of some special industry (such as food, semiconductor) production technology.Yet H
2O
2A kind of material that is difficult for being cleaned, because it has strong oxidizing property, thermal sensitivity, unstability.The H that commonly uses at present
2O
2Purification has quartz towers continuous still method, but when the purity requirement of product is higher, requires less than 1PPb such as cations, and organic carbon content requires less than 1PPm, and is then very difficult; This method raw material H
2O
2Utilization rate is about 85%, and production cost is higher.Bigger, the lower-cost production method of output has hyperfiltration, and this method is to H
2O
2Organic carbon in the aqueous solution has good removal effect, and product stability is also very good.But be not suitable for producing the cations requirement less than the product of 50PPb, raw material H
2O
2Utilization rate is about 70%.Ultrapure H with ion-exchange production
2O
2Single anion can be less than 200PPb in the product, and single cation can be less than 1PPb; But ion-exchange is to H
2O
2Organic carbon removal effect in the aqueous solution is not good, and often affects its result of use because organic carbon causes negative resin to poison.The H of simultaneously ion-exchange and way of distillation production
2O
2Stability is bad, is not suitable for long-distance transportation and storage.
Summary of the invention
Purpose of the present invention is exactly to provide in order to overcome the defective that above-mentioned prior art exists that a kind of refining effect is good, the product stability is good, the manufacturing process and the equipment of lower-cost ultrapure hydrogen peroxide.
Purpose of the present invention can be by realizing by the following technical solutions:
A kind of manufacturing process of ultrapure hydrogen peroxide is characterized in that, comprises following processing step: at first with impure more raw material H
2O
2The aqueous solution carries out the absorption of organic carbon by pump input adsorption resin column, will remove then the H of organic carbon
2O
2Input anion-cation exchange resin post carries out ion-exchange, again will be through the H of ion-exchange
2O
2Input filter to be removing granule foreign, thereby obtains the ultrapure hydrogen peroxide product; The operating pressure of above-mentioned technical process is controlled at 0.05～1.0Mpa, and temperature is controlled at 5～41 ℃.
Described raw material H
2O
2The concentration of the aqueous solution is 20～35% weight.
The macroporous adsorbent resin that the polymeric adsorbent of described adsorption resin column selects for use copolymerization such as vinylbenzene, divinylbenzene to form.
Anionite-exchange resin contains bicarbonate radical in the described anion-cation exchange resin, and Zeo-karb is a Hydrogen.
Described impure more raw material H
2O
2The adsorption resin column that the aqueous solution is imported one or more series connection by pump carries out the absorption of organic carbon.
The described H that removes organic carbon
2O
2The anion-cation exchange resin post of importing one or more series connection carries out ion-exchange.
A kind of equipment of making ultrapure hydrogen peroxide, it is characterized in that, comprise raw material tank, organic carbon adsorption resin column, anion-cation exchange resin post, strainer, described raw material tank, organic carbon adsorption resin column, anion-cation exchange resin post, strainer connect successively by pipeline, on the connecting tube of raw material tank and organic carbon adsorption resin column, be provided with pump, on the import and export pipeline of each device, be provided with valve.
Direct and H in the described equipment
2O
2The part of contact adopts the fluorine resin material of few stripping impurity.
Compared with prior art, the present invention has adopted the method for purification that absorption, ion-exchange and filtration combine.It has overcome, and the hyperfiltration refining effect is not enough good, raw material H
2O
2Utilization rate is low, the way of distillation, ion-exchange energy consumption height and removal organic carbon and the imperfect defective of product stability, resulting H
2O
2The purity height, cost is low, stability good.
The ultrapure H that adopts the present invention to make
2O
2(20-35% weight) and the front raw material H that purifies
2O
2The result of laboratory test of (20-35% weight) impurity index is as shown in table 1.
Table 1
| Impurity index (PPb) | Raw material tank H 2O 2 | Pan tank H 2O 2 | Impurity index (PPb) | Raw material tank H 2O 2 | Pan tank H 2O 2 |
| Organic carbon (TOC) | 100000 | ＜1000 | Zn | 200 | 0.03 |
| Muriate (CL) | 4000 | ＜200 | Fe | 650 | 0.3 |
| Phosphoric acid salt (PO 4) | 4000 | ＜200 | Cu | 100 | 0.02 |
| Vitriol (SO 4) | 4000 | ＜200 | Mn | 100 | 0.1 |
| K | 600 | 0.2 | Ag | 50 | 0.02 |
| Ca | 800 | 0.1 | Pb | 200 | 0.02 |
| Na | 1100 | 0.3 | Ti | 50 | 0.2 |
| Mg | 330 | 0.1 | Ni | 50 | 0.1 |
| Al | 500 | 0.2 | Mo | 300 | 0.5 |
As can be seen from Table 1, the ultrapure H of the present invention's production
2O
2Meet following index: single anion is less than 200PPb, and single cation is less than 1PPb, and total organic carbon is less than 1PPm.The performance index of this product meet the production requirement of industries such as food, semi-conductor.
The present invention is provided with the strainer that is used to remove granule foreign in order to improve the stability of product in technology, make product more stable.Simultaneously, the utilization rate of raw material of the present invention reaches more than 99%, produces three-waste free discharge, has satisfied environmental requirement.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is described in further detail:
Embodiment 1
As shown in Figure 1,35% (weight) in the raw material tank 1 is contained more polymictic raw material H
2O
2, enter organic carbon adsorption resin column 3 by the effect of pump 2.In this post the macroporous adsorbent resin that is formed by copolymerization such as vinylbenzene, divinylbenzenes is housed, removes organic carbon herein the anionite-exchange resin in road, the back zwitterion exchange column is also shielded.Flow out from here the H that organic carbon content reduces
2O
2Flow into anion-cation exchange resin mixed column 4, mixed column can be regarded as does not have several single-stage yin and yang resin exchange column, so effect is especially obvious.Certainly also can adopt the combination of multiple tracks negative and positive post, or the combination of negative and positive post and mixed column.The organic carbon polymeric adsorbent that uses in the present embodiment is the LSA-5 macroporous adsorbent resin, and anion-cation exchange resin is 909 gel-types nuclear grade resins.In the present embodiment, adsorption column and exchange column diameter are 180mm, and macroporous adsorbent resin regulating YIN and YANG ion exchange resin resin layer height is 4000mm.Wherein anionite-exchange resin and Zeo-karb volume ratio are 1: 1, and wherein anionite-exchange resin contains bicarbonate radical, and Zeo-karb is a Hydrogen.
In the present embodiment, the pressure of operation is at 0.2Mpa, and temperature is controlled at 20 ℃, and production per hour is controlled at 5 times of anion-cation exchange resin volume, and output also can be according to raw material H certainly
2O
2Quality regulate.The H that flow out from this exchange column this moment
2O
2Obtained purification to a certain degree, but H
2O
2Granule foreign in the liquid is not yet removed.Former H
2O
2Destabilizing factor think to be caused by metal ion, light, heat institute, do not recognize that granule foreign is to H
2O
2Harm.Because the huge surface area of granule foreign makes H
2O
2Produce decomposing phenomenon, and be not suitable for long-distance transportation and storage.The precision of figure middle filtrator 5 is 0.1 μ m.This moment H
2O
2Comprehensively purified, less than 30, stability is improved greatly, can enter storage tank 6 and carry out the packing of product through filter 7 to baling line again greater than every milliliter of the particle of 0.1 μ m.In the present embodiment, raw material H
2O
2Utilization rate greater than 99%, above-mentioned used exchange column, pump and overcurrent partly adopt the polytetrafluoroethylmaterial material of few stripping impurity to make.
Embodiment 2
As shown in Figure 1,30% (weight) in the raw material tank 1 is contained more polymictic raw material H
2O
2, enter organic carbon adsorption resin column 3 by the effect of pump 2.In this post the macroporous adsorbent resin that is formed by copolymerization such as vinylbenzene, divinylbenzenes is housed, removes organic carbon herein the anionite-exchange resin in road, the back zwitterion exchange column is also shielded.Flow out from here the H that organic carbon content reduces
2O
2Flow into anion-cation exchange resin mixed column 4, the organic carbon polymeric adsorbent that uses in the present embodiment is HZ 902 macroporous absorbent resins, and anion-cation exchange resin is AMBERLITE IRN160 Nuclear grade resin.In the present embodiment, adsorption column and exchange column diameter are 150mm, and macroporous adsorbent resin regulating YIN and YANG ion exchange resin resin layer height is 3000mm.Wherein anionite-exchange resin and Zeo-karb volume ratio are 1: 1.2, and wherein anionite-exchange resin contains bicarbonate radical, and Zeo-karb is a Hydrogen.
In the present embodiment, the pressure of operation is at 1.0Mpa, and temperature is controlled at 41 ℃, and production per hour is controlled at 5 times of anion-cation exchange resin volume.The H that flow out from this exchange column this moment
2O
2Obtained purification to a certain degree, but H
2O
2Granule foreign in the liquid is not yet removed.Because the huge surface area of granule foreign makes H
2O
2Produce decomposing phenomenon, and be not suitable for long-distance transportation and storage.The precision of figure middle filtrator 5 is 0.2 μ m.This moment H
2O
2Comprehensively purified, less than 20, stability is improved greatly, can enter storage tank 6 and carry out the packing of product through filter 7 to baling line again greater than every milliliter of the particle of 0.2 μ m.In the present embodiment, raw material H
2O
2Utilization rate greater than 99%, above-mentioned used exchange column, pump and overcurrent partly adopt the polytetrafluoroethylmaterial material of few stripping impurity to make.
Embodiment 3
As shown in Figure 1,20% (weight) in the raw material tank 1 is contained more polymictic raw material H
2O
2, enter organic carbon adsorption resin column 3 by the effect of pump 2.In this post the macroporous adsorbent resin that is formed by copolymerization such as vinylbenzene, divinylbenzenes is housed, removes organic carbon herein the anionite-exchange resin in road, the back zwitterion exchange column is also shielded.Flow out from here the H that organic carbon content reduces
2O
2Flow into anion-cation exchange resin mixed column 4, the organic carbon polymeric adsorbent that uses in the present embodiment is the LSA-5 macroporous absorbent resin, and anion-cation exchange resin is the high-purity resin of AMBERLITE UP604.In the present embodiment, adsorption column and exchange column diameter are 200mm, and macroporous adsorbent resin regulating YIN and YANG ion exchange resin resin layer height is 4500mm.Wherein anionite-exchange resin and Zeo-karb volume ratio are 1.2: 1, and wherein anionite-exchange resin contains bicarbonate radical, and Zeo-karb is a Hydrogen.
In the present embodiment, the pressure of operation is at 0.05Mpa, and temperature is controlled at 5 ℃, and production per hour is controlled at 5 times of anion-cation exchange resin volume.The H that flow out from this exchange column this moment
2O
2Obtained purification to a certain degree, but H
2O
2Granule foreign in the liquid is not yet removed, because the huge surface area of granule foreign makes H
2O
2Produce decomposing phenomenon, and be not suitable for long-distance transportation and storage.The precision of figure middle filtrator 5 is 0.05 μ m.This moment H
2O
2Comprehensively purified, less than 50, stability is improved greatly, can enter storage tank 6 and carry out the packing of product through filter 7 to baling line again greater than every milliliter of the particle of 0.05 μ m.In the present embodiment, raw material H
2O
2Utilization rate greater than 99%.Above-mentioned used exchange column, pump and overcurrent partly adopt the polytetrafluoroethylmaterial material of few stripping impurity to make.
Claims (8)
1. the manufacturing process of a ultrapure hydrogen peroxide is characterized in that, comprises following processing step: at first with impure more raw material H
2O
2The aqueous solution carries out the absorption of organic carbon by pump input adsorption resin column, will remove then the H of organic carbon
2O
2Input anion-cation exchange resin post carries out ion-exchange, again will be through the H of ion-exchange
2O
2Input filter to be removing granule foreign, thereby obtains the ultrapure hydrogen peroxide product; The operating pressure of above-mentioned technical process is controlled at 0.05～1.0Mpa, and temperature is controlled at 5～41 ℃.
2. the manufacturing process of ultrapure hydrogen peroxide according to claim 1 is characterized in that, described raw material H
2O
2The concentration of the aqueous solution is 20～35% weight.
3. the manufacturing process of ultrapure hydrogen peroxide according to claim 1 is characterized in that, the macroporous adsorbent resin that the polymeric adsorbent of described adsorption resin column selects for use vinylbenzene, divinylbenzene copolymerization to form.
4. the manufacturing process of ultrapure hydrogen peroxide according to claim 1 is characterized in that, anionite-exchange resin contains bicarbonate radical in the described anion-cation exchange resin, and Zeo-karb is a Hydrogen.
5. the manufacturing process of ultrapure hydrogen peroxide according to claim 1 is characterized in that, described impure more raw material H
2O
2The adsorption resin column that the aqueous solution is imported one or more series connection by pump carries out the absorption of organic carbon.
6. the manufacturing process of ultrapure hydrogen peroxide according to claim 1 is characterized in that, the described H that removes organic carbon
2O
2The anion-cation exchange resin post of importing one or more series connection carries out ion-exchange.
7. equipment of making ultrapure hydrogen peroxide, it is characterized in that, comprise raw material tank, organic carbon adsorption resin column, anion-cation exchange resin post, strainer, described raw material tank, organic carbon adsorption resin column, anion-cation exchange resin post, strainer connect successively by pipeline, on the connecting tube of raw material tank and organic carbon adsorption resin column, be provided with pump, on the import and export pipeline of each device, be provided with valve.
8. the equipment of manufacturing ultrapure hydrogen peroxide according to claim 7 is characterized in that, direct and H in the described equipment
2O
2The part of contact adopts the fluorine resin material of few stripping impurity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001253123A CN1184138C (en) | 2000-09-21 | 2000-09-21 | Process and equipment for preparation of ultrapure hydrogen peroxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001253123A CN1184138C (en) | 2000-09-21 | 2000-09-21 | Process and equipment for preparation of ultrapure hydrogen peroxide |
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|---|---|
| CN1285311A CN1285311A (en) | 2001-02-28 |
| CN1184138C true CN1184138C (en) | 2005-01-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001253123A Expired - Fee Related CN1184138C (en) | 2000-09-21 | 2000-09-21 | Process and equipment for preparation of ultrapure hydrogen peroxide |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347078C (en) * | 2004-09-27 | 2007-11-07 | 上海哈勃化学技术有限公司 | Hydrogen peroxide concentration process |
| CN100420625C (en) * | 2006-08-18 | 2008-09-24 | 上海华谊微电子化学品有限公司 | Process for preparation of ultrapure hydrogen peroxide |
| CN101817511B (en) * | 2010-04-02 | 2012-01-11 | 赫格雷(大连)制药有限公司 | Device for producing low-carbon environment-friendly super clean high-purity H2O2 |
| CN102095617B (en) * | 2010-11-29 | 2014-07-09 | 上海化学试剂研究所 | Pretreatment method for determining organic carbon in high-purity hydrogen peroxide |
| CN102556976A (en) * | 2010-12-08 | 2012-07-11 | 上海华谊微电子材料有限公司 | Method for continuous production of ultrapure hydrogen peroxide |
| CN103466557B (en) * | 2013-09-11 | 2015-07-22 | 杭州精欣化工有限公司 | Preparation method of ultra-pure hydrogen peroxide aqueous solution |
| CN109850851B (en) * | 2019-02-26 | 2020-11-24 | 苏州晶瑞化学股份有限公司 | Method for controlling particles in ultra-high-purity hydrogen peroxide |
| CN109911858A (en) * | 2019-04-24 | 2019-06-21 | 广州市天夫美新材料科技有限公司 | The production equipment of One-step production super-clean high-purity microelectronics grade hydrogen peroxide |
| CN113942979A (en) * | 2021-11-11 | 2022-01-18 | 河南慧泽生物工程有限公司 | Preparation method of ultra-pure 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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|---|---|
| CN1285311A (en) | 2001-02-28 |
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Owner name: SHANGHAI HABO CHEMICAL TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: SHANGHAI HARBO CHEMICAL CO., LTD. Effective date: 20060811 |
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Effective date of registration: 20060811 Address after: Songjiang export processing zone of Shanghai City, No. 300 Cao Nong Lu 201613 Patentee after: Shanghai Habo Chemical Technology Co.,Ltd. Address before: 200120 No. 855 South Pudong Road, Shanghai, 33D Patentee before: Shanghai Harbo Chemical Co., Ltd. |
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Granted publication date: 20050112 Termination date: 20120921 |