TWI229146B - Regenerating method for cleaning solution of metallic product - Google Patents
Regenerating method for cleaning solution of metallic product Download PDFInfo
- Publication number
- TWI229146B TWI229146B TW090118911A TW90118911A TWI229146B TW I229146 B TWI229146 B TW I229146B TW 090118911 A TW090118911 A TW 090118911A TW 90118911 A TW90118911 A TW 90118911A TW I229146 B TWI229146 B TW I229146B
- Authority
- TW
- Taiwan
- Prior art keywords
- waste liquid
- acid waste
- fluoric acid
- fluoride ion
- concentration
- Prior art date
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims description 19
- 230000001172 regenerating effect Effects 0.000 title claims description 17
- 239000002699 waste material Substances 0.000 claims abstract description 128
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 95
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims description 140
- 229960002050 hydrofluoric acid Drugs 0.000 claims description 84
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 54
- 238000004519 manufacturing process Methods 0.000 claims description 40
- 239000012535 impurity Substances 0.000 claims description 39
- 238000005406 washing Methods 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 230000008929 regeneration Effects 0.000 claims description 14
- 238000011069 regeneration method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 239000011737 fluorine Substances 0.000 abstract description 5
- -1 fluorine ions Chemical class 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 238000007689 inspection Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 239000010436 fluorite Substances 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000001223 reverse osmosis Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PBZHKWVYRQRZQC-UHFFFAOYSA-N [Si+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical group [Si+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PBZHKWVYRQRZQC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical class OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5036—Azeotropic mixtures containing halogenated solvents
- C11D7/5068—Mixtures of halogenated and non-halogenated solvents
- C11D7/5077—Mixtures of only oxygen-containing solvents
- C11D7/5086—Mixtures of only oxygen-containing solvents the oxygen-containing solvents being different from alcohols, e.g. mixtures of water and ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/16—Metals
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/40—Specific cleaning or washing processes
- C11D2111/48—Regeneration of cleaning solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Detergent Compositions (AREA)
Abstract
Description
12291461229146
發明之技術領域 本發明是有關為了清洗不銹鋼管等之金屬產品，以在各 種工業產品製程中所排出之氟酸廢液做為金屬產品洗淨液 的再生方法。 先前技術 在金屬產品表面，由於製程的熱處理中或與空氣中之氧 =觸而產生氧化膜，此氧化膜因會導致產品品質下降所以 需要清洗除去，例如，舉不銹鋼管等之例子來說明時，將 表面有氧化膜之數枝不銹鋼管以電線纏著吊下，將其浸潰 到貯存有稀氟酸之水槽中數分鐘，氧化膜被清洗除去，而 成為表面有光澤之不鱗鋼管。 如此用來清洗不銹鋼管之稀氟酸，一般是經如圖7所示 之流程圖製程來製造。也就是說，首先，在營石·硫酸攪 拌步驟S 11中混合攪捽螢石和硫酸，其次在反應爐投入步 驟S12中將其投入旋轉窯爐等之反應爐内，在6〇(rc以上之 溫度條件下起化學反應生成氟化氫酸。之後，經由吸收精 製步驟S13，在濃度調整步驟S14中，於氟化氫酸中加入 多I足純水，稀釋氟離子濃度到3%程度而得到稀氟酸。 發明所欲解決之課題 然而，如上述般所製造之做為洗淨液的稀氟酸，若洗淨 之金屬產品越是變得大型的話則使用量就越是膨大，稀釋 用足純水使用量因變得更膨大量之故，稀氟酸製造成本在 金屬產品洗淨步驟中占有很大的分量，期望有任何之解決 策略。 -4 - 本紙張尺度適用中國國家標準(CNS) 1229146Technical Field of the Invention The present invention relates to a method for regenerating metal products such as stainless steel pipes and the like, using a fluoric acid waste liquid discharged from various industrial product processes as a cleaning solution for metal products. In the prior art, an oxide film was generated on the surface of a metal product due to heat treatment during the process or in contact with oxygen in the air. This oxide film will cause product quality degradation and needs to be cleaned and removed. For example, take the example of a stainless steel pipe to illustrate Several stainless steel pipes with an oxide film on the surface were hung by wires and immersed in a water tank storing dilute hydrofluoric acid for several minutes. The oxide film was cleaned and removed to become a non-scale steel pipe with a shiny surface. The dilute hydrofluoric acid used for cleaning stainless steel pipes is generally manufactured by a flow chart process as shown in FIG. 7. That is, first, fluorite and sulfuric acid are mixed and stirred in the campstone-sulfuric acid stirring step S 11, and then, they are placed in a reaction furnace such as a rotary kiln in a reaction furnace putting-in step S12. A chemical reaction occurs under temperature conditions to generate hydrofluoric acid. After that, through absorption and purification step S13, in a concentration adjustment step S14, more than one foot of pure water is added to the hydrofluoric acid, and the fluoride ion concentration is diluted to about 3% to obtain dilute hydrofluoric acid. Problems to be Solved by the Invention However, the diluted fluoric acid produced as a cleaning solution as described above, the larger the size of the metal product to be washed, the larger the amount of use will be. Use diluted pure water for dilution. As the volume becomes more bulky, the manufacturing cost of dilute fluoric acid occupies a large part in the washing step of metal products, and any solution is expected. -4-This paper standard applies Chinese National Standard (CNS) 1229146
五、發明説明（2 ) 又，在上述稀氟酸製造工程中，於為了得到新氟化氯酸 液而經過之反應爐投入步騾Sl2中，有所謂的消費大量能 源之問題，再I，有做為原料之勞石及硬酸或純水之資源匕 消費問題。再加上，為了螢石及硫酸在6〇〇t：以上之溫产 條件下起化學反應，也會有產生煤煙等所謂之環境惡1 = 題。 本發明有鑑於上述相關點，做為其目的的是，有效利用 本來要廢棄物處理之廢液，於不使用消費大量能源、成為 環境惡化原因之反應爐而可以得到便宜之洗淨液。 課題之解決手段 為了·達成上述目的，本發明的特徵是以，在半導體製造 工程等之各種工業產品製程中，混合調整所排出之廢液做 為金屬產品之洗淨液再利用，具體的是如下所述之解決手 段。 即，發明申請專利範圍第1項之特徵是，相對於1公升氟 離子濃度3%以上之氟酸廢液，藉由添加1〇〜2〇〇毫升比率 之硝酸，獲得pH值已調整在ι·2〜5.0之再生洗淨液。 由上述之構成，在發明申請專利範圍第丨項中，是恢復 氟離子濃度3%以上之氟酸廢液做為再生洗淨液。 此再生洗淨液’因是從本來要廢棄處理之廢液所得，所 以不需要為了製造洗淨液之螢石或硫酸，並且在洗淨液產 生步驟中，不使用反應爐所以不會有大量消費能源之問 題，可以得到便宜之洗淨液。又，也因為不使用反應爐所 以不會產生煤煙之環境惡化問題。 -5- 1229146 A7V. Description of the invention (2) In the above dilute fluoric acid production process, the reactor that was passed to obtain a new fluorinated chloric acid solution was put into step S12, which had the problem of consuming a large amount of energy. There is a problem with the consumption of resources such as hard rock or hard acid or pure water as raw materials. In addition, for the chemical reaction of fluorite and sulfuric acid at a temperature of 600t: above, so-called environmental evils such as soot may also be caused. The present invention has been made in view of the above-mentioned related points, and its purpose is to effectively use the waste liquid originally intended for waste treatment, and to obtain a cheap cleaning liquid without using a reaction furnace that consumes a large amount of energy and causes environmental degradation. Means for Solving the Problem In order to achieve the above-mentioned object, the present invention is characterized in that, in various industrial product manufacturing processes such as semiconductor manufacturing engineering, the waste liquid discharged is mixed and adjusted as a cleaning liquid for metal products and reused. Specifically, Solution as described below. That is, the first feature of the scope of the patent application for invention is that the pH value is adjusted to ι by adding nitric acid at a ratio of 10 to 2000 milliliter to the fluoric acid waste liquid having a fluoride ion concentration of 3% or more. · 2 ~ 5.0 regeneration cleaning solution. With the above structure, in the first item of the patent application scope of the invention, the fluoride acid waste liquid with a fluoride ion concentration of more than 3% is recovered as the regeneration cleaning liquid. This regenerating cleaning solution is obtained from the waste liquid that is to be discarded. Therefore, it is not necessary to manufacture fluorite or sulfuric acid for the cleaning solution, and there is no large amount of reaction furnace in the cleaning solution generation step. The problem of energy consumption can get cheap cleaning solution. In addition, because the reactor is not used, there is no problem of environmental degradation of soot. -5- 1229146 A7
再^如上述般因氟酸廢液和硝酸混合比率，硝酸廢液之 添加量和pH關係成直線變化，因應金屬產品之材質pH調 整變得很容#，因應要求洗淨時間及洗淨能力可以自由自 在控制。 申請專利範圍第2項之特徵是，在申請專利範圍第丨項之 發明中，於添加硝酸之前，自氟離子濃度3%以上之氟酸 廢液中除去雜質。 藉由上述之構成，在申請專利範圍第2項中，是恢復本 雜質之氟離子濃度3 %以上之氟酸廢液以做為再生洗 液。 申請專利範圍第3項之特徵是，在申請專利範圍第2項之 發明中，自氟離子濃度3%以上之氟酸廢液中除去雜質之 刖，將此氟酸廢液稀釋成氟離子濃度不滿3%，濃縮自此As mentioned above, due to the mixing ratio of fluoric acid waste liquid and nitric acid, the relationship between the amount of nitric acid waste liquid and the pH changes linearly, and the pH adjustment of the metal product becomes very content #, according to the required cleaning time and cleaning ability Freedom to control. The second feature of the scope of patent application is that in the invention of the first scope of patent application, impurities are removed from the fluoric acid waste liquid with a fluoride ion concentration of 3% or more before adding nitric acid. With the above structure, in the second item of the scope of the patent application, the fluoride acid waste liquid with a fluorine ion concentration of 3% or more of the impurity is recovered as the regeneration washing liquid. The third feature of the scope of the patent application is that in the invention of the second scope of the patent application, the impurities of the fluoride acid waste liquid with a fluoride ion concentration of 3% or more are removed, and the fluoride acid waste liquid is diluted to a fluoride ion concentration. Less than 3%, concentrated since then
稀釋氟酸廢液除去雜質後之稀釋氟酸廢液，做成氟離予濃 度在3%以上之氟酸廢液。 I 由上述之構成，在發明申請專利範圍第3項中，含雜質 之氟離子濃度3%以上之氟酸廢液一旦被稀釋，以自所稀 釋之氟酸廢液除去雜質可很快地恢復成再生洗淨液。 發明申请專利範圍第4項之特徵是，濃縮氟離子濃度不 滿3%之氟酸廢液做成氟離子濃度在3%以上之氣酸廢液 相對於1公升此氟離子濃度為3%以上之氟酸廢液，藉由添 加10〜200毫升比率之硝酸，獲得pH值已調整在i 2〜5 〇之 再生洗淨液。 由上述之構成，在發明申請專利範圍第4項，是復越敦 -6-Dilute the fluoric acid waste liquid after removing the impurities, and make a fluoric acid waste liquid with a fluorine ion concentration of 3% or more. I consists of the above. In item 3 of the scope of the patent application for invention, the fluoric acid waste liquid containing impurities with a fluoride ion concentration of 3% or more can be recovered quickly by removing impurities from the diluted fluoric acid waste liquid. Into regeneration washing solution. The fourth feature of the scope of the patent application for invention is that concentrated fluoric acid waste liquid with a fluoride ion concentration of less than 3% is made into a gas acid waste liquid with a fluoride ion concentration of 3% or more. For 1 liter, the fluoride ion concentration is 3% or more. By adding 10 to 200 ml of nitric acid to the fluoric acid waste liquid, a regeneration washing liquid whose pH value has been adjusted to i 2 to 50 is obtained. Consisting of the above, the fourth item in the scope of patent application for invention is Fu Yuedun -6-
12291461229146
離子辰度不滿3%之氟酸廢液而做成再生洗淨液。 發明申請專利範圍第5项之特徵是，在申請專利範圍第4 ^又發明中，於濃縮氟離子濃度不滿3%之氟酸廢液之 前’除去此氟酸廢液之雜質。 由上述足構成，在發明申請專利範圍第5項中，是復甦 含雜質 < 氟離子濃度不滿3%之氟酸廢液而做成再生洗淨 發明之實施形態 以下，在本發明之實施形態中，相關金屬產品之再生洗 乎液製造方法例舉不銹鋼管來說明，但本發明並不限制只 有此而已，其它金屬產品也可以適用。 如以往之例來說明般，不銹鋼管在製造工程中因與空氣 中的氧接觸，表面會生成氧化膜，在洗淨液貯存水槽中浸 潰除去氧化膜，，而回復光澤。 在此發明之最大特徵是，做為為了洗淨除去上述氧化膜 之洗淨液者，為利用各種工業產品之製程中所排出之廢 液。具體列舉時，例如， ① 在半導體製程中，於矽晶元洗淨步驟有經純水稀釋過 之排出稀釋氟酸廢液。 ② 在液晶平板製程中，於液晶平板之洗淨及蝕刻步驟所 排出之氟酸廢液。 ③ 太陽電池產品製程中，於太陽電池之洗淨及蝕刻步騾 所排出之氟酸廢液。 ④ 玻璃產品製程中，於玻璃之洗淨及蝕刻步驟所排出之 1229146Recycled cleaning solution made of fluoric acid waste liquid with ion degree less than 3%. The fifth feature of the patent application scope of the invention is that in the fourth invention of the patent application scope, impurities of the fluoride acid waste solution are removed before the concentrated fluoride acid waste solution with a fluoride ion concentration of less than 3%. Consisting of the above-mentioned foot, in the fifth item of the scope of the patent application for invention, the embodiment of the invention for regenerating and washing the waste liquid containing fluoride <3% fluoride ion concentration is recovered, and the invention is described below. In the embodiment of the present invention, In the manufacturing method of the regenerating washing liquid of related metal products, a stainless steel tube is used as an example, but the present invention is not limited to this, and other metal products can also be applied. As explained in the previous examples, during the manufacturing process of the stainless steel tube, due to the contact with oxygen in the air, an oxide film is formed on the surface, and the oxide film is immersed in the cleaning solution storage water tank to restore the gloss. The most significant feature of the invention is that the cleaning liquid used for cleaning and removing the oxide film is a waste liquid discharged from the manufacturing process of various industrial products. For specific enumeration, for example, ① In the semiconductor manufacturing process, in the silicon wafer cleaning step, the diluted fluoric acid waste liquid is discharged after being diluted with pure water. ② In the liquid crystal panel manufacturing process, the fluoric acid waste liquid discharged during the cleaning and etching steps of the liquid crystal panel. ③ During the solar cell product manufacturing process, the fluoric acid waste liquid discharged during the cleaning and etching steps of the solar cell. ④ 1229146 discharged during the glass washing and etching steps during the glass product manufacturing process
氣酸廢液。 、〇毛燈產品製程中，於内面消豔步騾及洗淨步騾所排出 之氟酸廢液。 ⑥電視產品製程中，於顯像管内面洗淨步驟所排出之氟 酸廢液。 、⑦石材產品製程中，於石材表面洗淨步驟有排出氟酸廢 ⑧印刷基板產品製程中，於印刷基板表面洗淨及脫脂步 驟有排出氟酸廢液。 ^⑨/飞車製造工程中，於汽車車體塗裝之脫脂步驟有排出 鼠酸廢液。 (實施之形態 、圖1表示本發明之實施形態1中相關再生洗淨液之製造方 ，製程的流程圖。在此列舉半導體製造工程的石英破璃洗 淨步驟例子來說明。 、、做t上述石英玻璃洗淨步驟丨次洗淨水所排出之氟酸廢 硬：疋不含雜質之高濃度氟酸廢液，以下，高濃度氟酸廢 液疋指所謂之氟離子濃度在3%以上之氟酸廢液。 X先將上述不含雜質之高濃度氟酸廢液移入水質簡易 =查步驟（步驟s 1-1)中，在此使用混有檢知劑之滴管式水 質簡易檢查器，相對於上述高濃度氟酸廢液，在每一=次 2仃有菩物質之含有檢查。只是，如上述由石英破璃洗 '驟所排出之氟酸廢液因不含雜質之故，通常是檢不出 有荃物質，移入其次步驟之硝酸廢液添加步驟（步驟U- -8 - 1229146 A7Gas acid waste. In the manufacturing process of wool lamp products, the fluoric acid waste liquid discharged from the inner step and the washing step is eliminated. ⑥ During the TV product manufacturing process, the fluoric acid waste liquid discharged during the washing step of the inner surface of the picture tube. 2. In the manufacturing process of stone products, the waste of hydrofluoric acid is discharged during the washing step of the stone surface. In the manufacturing process of printed substrate products, the waste liquid of fluoride is discharged in the cleaning and degreasing steps of the printed substrate surface. ^ ⑨ / Flying car manufacturing process, the degreasing step of car body coating has exhausted lysate. (Implementation mode, FIG. 1 shows a flowchart of a manufacturing method and a manufacturing process of a related regenerating cleaning solution according to Embodiment 1 of the present invention. Here is an example of a quartz glass cleaning step for semiconductor manufacturing process for illustration. The above-mentioned quartz glass washing step 丨 The fluoric acid waste discharged from the washing water is hard: 疋 High-concentration fluoric acid waste liquid containing no impurities, hereinafter, the high-concentration fluoric acid waste liquid means the so-called fluoride ion concentration above 3% Fluoric acid waste liquid. X First move the above-mentioned high-concentration fluoric acid waste liquid without impurities into the water quality simple = check step (step s 1-1), and use a dropper-type water quality test with mixed detection agent here. Device, compared with the above-mentioned high-concentration fluoric acid waste liquid, there is an inspection of the content of the boron substance every 2 times. However, the fluoric acid waste liquid discharged from the quartz glass washing step as described above does not contain impurities. ， Usually the nitric acid waste solution addition step (step U- -8-1229146 A7) is not detected
2)。 接著’在硝酸廢液添加步驟（步驟s u)中，如 上沭合、曲* 相對於1公升 、呵破度氟酸廢液，藉由添加10〜2〇〇毫升比率、" 獲得PH值已調整在丨.2〜5.〇之酸性度範圍中之再生\=淨 液。在此之硝酸，是使用半導體製造工程中矽晶元蝕刻: 驟所排出之硝酸廢液’此硝酸廢液之添加量換算酸 度時為相當100%之10〜200毫升。 ‘ 如此’氟離子濃度設定在以上者，是因未滿3%時自 不務鋼表面洗淨除去氧化膜很花費時間，不可能很快除 又，.相對於氟酸廢液，硝酸之添加量與pH之關係設定如 上述者，從圖6之資料可以明白，在上述設定範圍中硝酸 廢液之添加量與pH間之關係，與鹽酸廢液及硫酸廢液相 比有直線的變化之故，對應不銹鋼管材質可以很容易調整 PH，因應洗淨時間及洗淨能力之要求可以自由自在= 制。 工 再者，從圖5之可資料判斷··相對於丨公升高濃度氟酸廢 液，藉由添加30毫升之硝酸，氟離子濃度保持在3%以上 原樣，可以使pH值下降到3·〇以下之事實，由此，可以在 短時間内進行洗淨處理。 又，在以往之例子由螢石和硫酸製造稀氟酸，因有以純 水薄薄地稀釋氟酸，ρ Η值上昇酸性度下降，洗淨能力雖 不可能提高，但此發明之再生洗淨液，是在氟酸廢液中添 加硝酸廢液因可以變化ρ Η值，即使能提昇氟離子濃度而 • 9 -2). Next, in the step of adding nitric acid waste liquid (step su), as above, it is mixed with Koji * with respect to 1 liter of fluoric acid waste liquid, by adding a ratio of 10 ~ 200 ml, " Adjust the regeneration in the acidity range of 丨 .2 ~ 5.0. The nitric acid used here is silicon nitrate etched in the semiconductor manufacturing process: the nitric acid waste liquid discharged from the step 'is added to the acidic acid solution in an amount of 10 to 200 ml which is equivalent to 100%. 'So' the fluoride ion concentration is set to the above, because it is time-consuming to clean and remove the oxide film from the surface of the stainless steel when it is less than 3%, and it is impossible to remove it quickly. Compared to the fluoride acid waste liquid, the addition of nitric acid The relationship between the amount and pH is set as described above. It can be understood from the data in Figure 6 that the relationship between the amount of nitric acid waste liquid and pH in the above setting range has a linear change compared with the hydrochloric acid waste liquid and sulfuric acid waste liquid. Therefore, it is easy to adjust the pH according to the stainless steel pipe material, and it can be freely made according to the requirements of the cleaning time and cleaning capacity. Working again, judging from the data available in Figure 5 ... Relative to the elevated concentration of fluoric acid waste liquid, by adding 30 ml of nitric acid, the fluoride ion concentration is kept above 3% as it is, and the pH value can be reduced to 3 · 〇 The following facts make it possible to perform the cleaning process in a short time. Moreover, in the conventional example, dilute fluoric acid was produced from fluorite and sulfuric acid. Due to the thin dilution of fluoric acid with pure water, the ρ value increased and the acidity decreased. Although the cleaning ability could not be improved, the regeneration cleaning liquid of this invention It is because adding nitric acid waste liquid to fluoric acid waste liquid can change the ρ Η value, even if it can increase the fluoride ion concentration. • 9-
1229146 A7 B7 五、發明説明（7 ) 酸性度也沒有大幅度調整，在一定氟離子濃度之原樣下可 以大幅度調整酸性度。又，依照圖5之資料時，在鹽酸廢 液及硫酸廢液中，因顯示有減少氟離子濃度之傾向，所以 判斷氟離子濃度不適於保持在3%以上。 此等事實，由下面之化學反應式也能判斷，鹽酸廢液及 硫酸廢液是被認為因在氟離子之外有產生氟化氫離子之 故，而認為會減少氟離子。 <硝酸廢液與氟酸廢液之反應> HN〇3 + HF H2N〇3+ + F*1229146 A7 B7 5. Description of the invention (7) The acidity has not been adjusted significantly, and the acidity can be adjusted significantly under a certain fluoride ion concentration. In addition, according to the data in Fig. 5, since the hydrochloric acid waste liquid and the sulfuric acid waste liquid showed a tendency to reduce the fluoride ion concentration, it was judged that the fluoride ion concentration was not suitable to be maintained at 3% or more. These facts can also be judged from the following chemical reaction formulas. The hydrochloric acid waste liquid and the sulfuric acid waste liquid are considered to reduce fluoride ions because hydrogen fluoride ions are generated in addition to fluoride ions. < Reaction of nitric acid waste liquid and hydrofluoric acid waste liquid > HN〇3 + HF H2N〇3 + + F *
HF — H+ + F <鹽酶廢液與氟酸廢液之反應> HC1 + HF H2C1+ + F* HF H+ + F* 2HF + H+ — H+ + HF2-<硫酸廢液與氟酸廢液之反應> h2so4 + hf->h3so4+ + f HF H+ + F· 2HF + H+ H1 + HF2* 如此即使將硝酸廢液加入氟酸廢液中，氟離子濃度大致 不會下降，保持安定之氟離子濃度的硝酸添加氟酸廢液， 即可以得到不銹鋼管之洗淨液。 如此只要將本來要廢棄處理之氟酸廢液再利用就可以， 所以不需要以往之螢石或硫酸，並且洗淨液產生步驟中， 不用使用反應爐所以不會有大量消費能源之問題，可以便 -10- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐） 1229146HF — H + + F < Reaction of salt enzyme waste liquid and fluoric acid waste liquid > HC1 + HF H2C1 + + F * HF H + + F * 2HF + H + — H + + HF2- < Sulfuric acid waste liquid and fluoric acid waste liquid Reaction > h2so4 + hf- > h3so4 + + f HF H + + F · 2HF + H + H1 + HF2 * So even if the nitric acid waste liquid is added to the fluoric acid waste liquid, the fluoride ion concentration will not decrease and the stable fluorine will be maintained. Adding fluoric acid waste liquid to nitric acid with ion concentration can obtain the cleaning liquid of stainless steel tube. In this way, as long as the fluoric acid waste liquid to be discarded is reused, the conventional fluorite or sulfuric acid is not needed, and in the cleaning liquid generating step, the reaction furnace is not used, so there is no problem of large energy consumption. -10- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1229146
置，造洗淨液。又，也不會有因使用反應爐而產生煤煙引 起環境惡化之問題。 (實施之形態2) /2表示在此發明之實施形態2中，相關的再生洗淨液製 ^•方法的製&步驟流程圖’在此’列舉半導體製造工程之 碎晶元洗淨步驟加以說明。 、自^上述以元洗淨步㈣排出之氟酸錢，是含有雜質 之咼濃度氟酸廢液。 首先將上述含有雜質足高濃度氟酸廢液移入稀釋步驟 (步^ S2-1)中’在此時大致不含有純水或雜質之氟離子濃 度藉由添力口不滿3%之氟酸錢，稀釋成氣離子濃度在不 滿3%之^度，以下，將氟離子濃度不滿3%之氟酸廢液稱 為低濃度鼠酸廢液。 如此將高濃度氟酸廢液稀釋成氟離子濃度在不滿3%之程 度，在其次步驟（步驟S 2-2)中以過濾材除去雜質之際，氟 酸廢液為高濃度時黏度變高所以過濾速度下降。 同時，在上述稀釋步驟(步驟S2屮中，所添加之大致不 含有雜質之低濃度氟酸廢液者，是指雜質 質污濁防止法，在排水基準值以下㈤毫克 者。 其次，在上述氟酸廢液除去雜質步驟（步驟82_2)中，由 通過過濾材將稀釋氟酸廢液雜質除去。同時，在過濾材之 外，也可以使用、經特別選定之吸著螯合劑可以除=溶解 性之有機物及無機物等之雜質。 -11-Set to make a washing solution. In addition, there is no problem of environmental degradation caused by the use of soot in the reaction furnace. (Embodiment 2) / 2 indicates that in the second embodiment of the present invention, the method of manufacturing a related regeneration cleaning liquid ^ • method manufacturing & step flow chart 'here' enumerates the broken wafer cleaning steps of the semiconductor manufacturing process Explain. 2. The fluorinated acid discharged from the above washing step is a fluorinated fluoric acid waste solution containing impurities. First, the above-mentioned high-concentration fluoric acid waste liquid containing impurities is transferred to the dilution step (step ^ S2-1). At this time, the fluorine ion concentration that contains substantially no pure water or impurities is less than 3% of the fluoric acid by Timlikou. , Diluted to a gas ion concentration of less than 3%, hereinafter, a fluoride acid waste liquid with a fluoride ion concentration of less than 3% is referred to as a low-concentration rat acid waste liquid. In this way, the high-concentration fluoric acid waste liquid is diluted to a fluoride ion concentration of less than 3%. When the impurities are removed by the filter material in the next step (step S 2-2), the viscosity of the fluoric acid waste liquid becomes high when the concentration is high. So the filtering speed drops. At the same time, in the above-mentioned dilution step (step S2 屮), the low-concentration fluoric acid waste liquid containing substantially no impurities is the impurity pollution prevention method, which is ㈤mg below the drainage reference value. Second, in the above-mentioned fluorine In the step of removing impurities from the acid waste liquid (step 82_2), the impurities of the diluted fluoric acid waste liquid are removed by the filter material. At the same time, the filter material can also be used, and the specially selected adsorption chelating agent can be removed = solubility Organic and inorganic impurities. -11-
12291461229146
五、發明説明（9 、後將通過上述過濾材之稀釋氟酸廢液移入濃縮步 (步驟S 2-3)中，通過離子交換樹脂或逆滲透膜做戶 氟酸溶液。 辰度 ▲在$ 離子交換樹脂，例如使用陽離子交換樹脂等將溶 解丨％離子（金屬類大致為陽離子）吸著在樹脂内，氟離予 因f陰離子之故並不被吸著’以原樣通過樹脂内收集氟離 子可ス濃縮。另一方面，在逆滲透膜中加上滲透壓以上之 壓力丄結果只有水透過因而有可能濃縮，與吸著有限界艾 ::父換？脂相比有適當之高濃度氟酸廢液。因此，含； 質I多之高濃度氟酸廢液以使用逆滲透膜濃縮，另一方面 含雜質量少之低濃度氟酸廢液以使用離子交換樹脂濃縮較 裴 但並不一定有此限制…一般乙酸纖維素系或“ 族胺系等做為逆滲透膜之素材，肖甲基丙缔 缔酸等做為離子交換樹脂之素材相比，在成本上有便宜 優點。 訂 然後，將濃縮之高濃度氟酸廢液搬入水質簡易檢查步驟 (:驟S 2-4)中’在此’使用混有檢知劑之滴管式水質簡易 檢查器，相對於上述濃縮之高濃度氟酸廢液，在每一批★ 中進行有害物質之含有檢查。只是，在上 = ㈣叫已除去所含之雜質，所以不再含有之 Γ步害物質’移入其次步驟之確酸廢液添加步驟 接著，在硝酸廢液添加步驟（步驟S2_5)中相對於1公升 上述高濃度氟酸廢液，藉由添加1〇〜2〇〇毫升比率之硝^， -12- 1229146 A7 _____ B7 五、發明說明（1〇 ) 獲得PH值已調整在ι·2〜5.0之酸性度範圍中之再生洗淨 液。此時，是使用硝酸作為硝酸廢液，與實施形態1相 同。 因此，在實施形態2中可以得到與實施形態1相同之作用 效果。 (實施之形態3) 圖3表示本發明之實施形態3中相關再生洗淨液之製造方 法的製程流程圖。在此列舉半導體製造工程的石英玻璃洗 淨步驟之例子來說明。 自上述石英玻璃洗淨步驟所排出2次洗淨水後之氟酸廢 液’是不含雜質之低濃度氟酸廢液。 首先，將此低濃度氟酸廢液移入濃縮步驟（步驟S 3β1) 中’使通過離子交換樹脂或逆滲透膜做成高濃度氟酸廢 液。 其次將濃縮之高濃度氟酸廢液移入水質簡易檢查步驟（步 驟S 3·2)中，在此使用混有檢知劑之滴管式水質簡易檢查 器’相對於上述高濃度氟酸廢液，在每一批次中進行有害 物質之含有檢查。只是，如上述自石英玻璃洗淨步驟所排 出之氟酸廢液因不含雜質之故，通常是檢不出有害物質， 移入其次步驟之硝酸廢液添加步驟（步驟S 3-3)。 之後’硝酸廢液添加步驟（步驟S3-3)中，相對於1公升上 述高濃度氟酸廢液，藉由添加1〇〜200毫升比率之硝酸，獲 得PH值已調整在Κ2〜5.0之酸性度範圍中之再生洗淨液。 此時，使用硝酸做為硝酸廢液是與實施形態1相同。 -13- 本紙張尺度適用中國國家標準(CNS)人4規格(210><297公爱) 一- 1229146V. Description of the invention (9. After that, the diluted fluoric acid waste liquid passing through the above-mentioned filter material is transferred to the concentration step (step S 2-3), and the fluoric acid solution is made by ion exchange resin or reverse osmosis membrane. Ion exchange resins, such as cation exchange resins, dissolve 丨% ions (metals are approximately cations) in the resin, and the fluorine ion is not adsorbed because of the f anion. The fluorine ions are collected through the resin as it is. It can be concentrated. On the other hand, when the pressure above the osmotic pressure is added to the reverse osmosis membrane, only water permeates and thus it is possible to concentrate. Compared with the adsorption limit Ai :: Father exchange? Fat has a suitable high concentration of fluorine Acid waste liquid. Therefore, high-concentration fluoric acid waste liquid containing high quality I is concentrated using reverse osmosis membrane, on the other hand, low-concentration fluoric acid waste liquid with low impurity content is concentrated using ion exchange resin but not There must be this limitation ... Generally, cellulose acetate or "family amines" are used as materials for reverse osmosis membranes, and compared with materials used as ion exchange resins, they are cheaper in cost. Ordering, will Condensed high-concentration fluoric acid waste liquid is carried into the simple check step of water quality (: step S 2-4). Here, a dropper-type simple water quality checker mixed with a detection agent is used, compared with the concentrated high-concentration fluoric acid The waste liquid is checked for the content of harmful substances in each batch of ★. However, the above = tweets that the contained impurities have been removed, so the Γ step harmful substances that are no longer contained are moved to the next step. Next, in the nitric acid waste liquid adding step (step S2_5), the nitric acid waste liquid with a concentration of 10 to 2000 ml is added to 1 liter of the high-concentration fluoric acid waste liquid, -12-1229146 A7 _____ B7 V. Invention Explanation (10) Obtain a regeneration washing liquid whose pH value has been adjusted in the acidity range of ι · 2 to 5.0. At this time, nitric acid is used as the nitric acid waste liquid, which is the same as Embodiment 1. Therefore, Embodiment 2 The same functions and effects as those of Embodiment 1 can be obtained in (Embodiment 3) Fig. 3 shows a process flow chart of a method for manufacturing a regenerating cleaning solution according to Embodiment 3 of the present invention. Here, quartz glass for semiconductor manufacturing process is listed. Examples of washing steps The fluoric acid waste liquid 'after washing water discharged twice from the quartz glass washing step described above is a low-concentration fluoric acid waste liquid containing no impurities. First, this low-concentration fluoric acid waste liquid is transferred to a concentration step ( In step S 3β1), a high-concentration fluoric acid waste liquid is made through an ion exchange resin or a reverse osmosis membrane. Next, the concentrated high-concentration fluoric acid waste liquid is moved to a simple water quality inspection step (step S 3 · 2), here Use a dropper-type simple water quality checker mixed with a detection agent 'to check the content of harmful substances in each batch with respect to the above-mentioned high-concentration fluoric acid waste liquid. However, it is discharged from the quartz glass washing step as described above. Because the fluoric acid waste liquid does not contain impurities, usually no harmful substances can be detected, and the nitric acid waste liquid addition step of the next step is moved (step S 3-3). After that, in the step of adding nitric acid waste liquid (step S3-3), relative to 1 liter of the above-mentioned high-concentration fluoric acid waste liquid, by adding nitric acid at a ratio of 10 to 200 ml, the acidity of which has been adjusted to a pH value of κ2 to 5.0 Regeneration cleaning solution in the degree range. At this time, using nitric acid as the nitric acid waste liquid is the same as in the first embodiment. -13- This paper size applies to China National Standard (CNS) Person 4 specifications (210 > < 297 public love) a-1229146
因此在實施形怨3也可以得到與實施形態丨相同之作用效 果。 (實施之形態4) 圖4表不在此發明之實施形態4中，相關的再生洗淨液製 U方法的製造步驟流程圖，在此，列舉半導體製造工程中 碎曰曰元之氧化膜餘刻步驟之洗淨步驟而加以說明。 自上述洗淨步驟所排出之氟酸廢液，為含有雜質之低濃 度氟酸廢液。 首先’將上述低濃度氟酸廢液於雜質除去步驟（步驟S 4-1) 中，使通過過濾材，自低濃度氟酸廢液除去雜質。同時， 在過濾材之外，也可以使用經選定之特定離子吸著螯合劑 除去不溶解性之有機物及無機物等之雜質，與實施形態2 相同。 其次’移入濃縮步驟（步驟S4-2)中，通過離子交換樹脂 或逆滲透膜做成高濃度氟酸溶液。考慮要使用之任一種作 業效率等而作適當選擇的話較好。 之後，將濃縮之高濃度氟酸廢液移入水質簡易檢查步驟 (步驟S 4-3)中，在此，使用混有檢知劑之滴管式水質簡易 檢查器，相對於上述高濃度氟酸廢液，在每一批次中進行 有害物質之含有檢查。只是，雜質在上述雜質除去步驟 (步驟S 4-1)中除去，所以不含有雜質，通常是檢不出有堂 物質，移入其次步驟之硝酸廢液添加步驟（步驟。 然後，在硝酸廢液添加步驟（步驟S4-4)中，相對於丨公升 上述咼濃度氟酸廢液，藉由添加1〇〜2〇〇毫升比率之硝酸 -14- A7 B7 12 )Therefore, the same effects as in the implementation mode can also be obtained in the implementation of Form 3. (Embodiment 4) FIG. 4 is a flowchart showing the manufacturing steps of a method for producing a U in a regenerating cleaning solution, which is not included in Embodiment 4 of the present invention. Here, the oxide film remaining on the chip in the semiconductor manufacturing process is listed. The step of washing is explained. The fluoric acid waste liquid discharged from the above washing step is a low-concentration fluoric acid waste liquid containing impurities. First, in the step of removing the low-concentration fluoric acid waste liquid (step S4-1), the impurities are removed from the low-concentration fluoric acid waste liquid through a filter medium. At the same time, in addition to the filter material, insoluble impurities such as organic matter and inorganic matter can also be removed using a selected specific ion-adsorbing chelating agent, which is the same as the second embodiment. Next, it is transferred to the concentration step (step S4-2), and a high-concentration fluoric acid solution is prepared by an ion exchange resin or a reverse osmosis membrane. It is better to make an appropriate selection considering the efficiency of any kind of operation to be used. After that, the concentrated high-concentration fluoric acid waste liquid is transferred to a simple water quality inspection step (step S 4-3). Here, a dropper-type simple water quality checker mixed with a detection agent is used, compared with the high-concentration fluoric acid Waste liquids are checked for the content of hazardous substances in each batch. However, impurities are removed in the above-mentioned impurity removal step (step S 4-1), so they do not contain impurities, and usually there is no detectable substance, and the nitric acid waste liquid addition step (step) is moved to the next step. Then, in the nitric acid waste liquid In the adding step (step S4-4), nitric acid-14- A7 B7 12 is added at a ratio of 10 ~ 200 ml to 丨 liter of the above-mentioned rhenium concentration fluoric acid waste liquid.
1229146 五、發明説明（ 獲得pH值已調整在1·2〜5.0之酸性度範圍中之再生洗、淨 液。此時，使用硝酸做為硝酸廢液是與實施形態丨相同。 因此在實施形態4也可以得到與實施形態1相同之作 果。 發明之效果 如上述說明般，依發明申請專利範圍第1項的話，相對 於1公升氟離子濃度為3%以上之氟酸廢液，藉由添加 10〜200毫升比率之硝酸獲得pH值已調整在12〜5 〇之再^ 洗淨液。此時，在含雜質之情形，希望要經過雜質除去步 驟（申請專利範圍第2項），再者，經過稀釋步驟（申請專利 範圍第.3項）。另一方面，在氟離子濃度為未滿3%之氟酸廢 液的情形，如申請專利範圍第4項般，於濃縮到氟離子濃 度在3%以上之後，相對於丨公升此濃縮之氟酸廢液，藉由 添加10〜200毫升比率之硝酸，獲得調整pH值已調整在 1.2〜5.0間之再生洗淨液。此時，於含雜質之情形，是要經 過雜質除去步驟（申請專利範圍第5項）。因此，洗淨液是不 使用螢石、硫酸及反應爐，可以製造便宜且不會招至環境 惡化’同時，容易因應金屬產品之材質由調整pH可以自 由自在控制洗淨時間及洗淨能力。 圖式說明（元件符號說明） 圖1表示本發明實施形態1相關之再生洗淨液製造方法之 製程流程圖。 圖2表示本發明實施形態2相關之再生洗淨液製造方法之 製程流程圖。1229146 V. Description of the invention (Obtaining the regeneration washing and cleaning solution whose pH value has been adjusted in the acidity range of 1.2 to 5.0. At this time, using nitric acid as the nitric acid waste liquid is the same as the embodiment 丨. Therefore, in the implementation mode 4 can also obtain the same results as in Embodiment 1. The effect of the invention is as described above. According to the first item of the scope of the patent application for invention, the fluoride acid waste liquid having a fluoride ion concentration of 3% or more relative to 1 liter of Adding nitric acid at a ratio of 10 ~ 200 ml to obtain a pH value adjusted to 12 ~ 50. ^ Wash solution. At this time, in the case of impurities, it is desirable to go through the impurity removal step (item 2 of the scope of patent application), and then For example, after the dilution step (the scope of the patent application. Item 3.), on the other hand, in the case of a fluoride acid waste liquid with a fluoride ion concentration of less than 3%, it is concentrated to the fluoride ion as in the scope of the patent application. After the concentration is above 3%, with respect to 丨 liter of this concentrated fluoric acid waste liquid, by adding 10 to 200 ml of nitric acid, a regenerating washing liquid having an adjusted pH value adjusted between 1.2 and 5.0 is obtained. At this time, In the case of impurities, it is necessary to Through the impurity removal step (No. 5 in the scope of patent application). Therefore, the cleaning liquid does not use fluorite, sulfuric acid, and a reaction furnace, which can be manufactured cheaply without causing environmental degradation. At the same time, it is easy to adjust according to the material of the metal product. The pH can freely control the washing time and washing ability. Schematic description (element symbol description) FIG. 1 shows a process flow chart of a method for manufacturing a regenerating cleaning liquid according to Embodiment 1 of the present invention. FIG. 2 shows Embodiment 2 of the present invention Process flow chart of related manufacturing method of regenerating cleaning liquid.
裝 訂 -15-Binding -15-
1229146 A7 B7 五、發明説明（13 ) 圖3表示本發明實施形態3相關之再生洗淨液製造方法之 製程流程圖。 圖4表示本發明實施形態4相關之再生洗淨液製造方法之 製程流程圖。 圖5表示在氟酸廢液中添加硝酸、鹽酸及硫酸之情形的 pH和氟進子濃度關係資料。 圖6表示相對於氟酸廢液中硝酸、鹽酸及硫酸之添加量 與p Η間的關係資料。 圖7表示往例之洗淨液製造方法之製程流程圖。 符號之說明 S 1-1 水質簡易檢查步驟 S 1-2 硝酸廢液添加步驟 S2-1 稀釋步驟 S2-2 雜質除去步驟 S2-3 濃縮步驟 S2-4 水質簡易檢查步驟 S2-5 硝酸廢液添加步驟 S3-1 濃縮步驟 S3-2 水質簡易檢查步驟 S3-3 硝酸廢液添加步驟 S4-1 雜質除去步驟 S4-2 濃縮步驟 S4-3 水質簡易檢查步驟 S4-4 硝酸廢液添加步驟 -16- 本紙張尺度適用中國國家標準(CNS) Α4規格(210 X 297公釐）1229146 A7 B7 V. Description of the invention (13) FIG. 3 shows a process flow chart of a method for manufacturing a regenerating cleaning liquid according to Embodiment 3 of the present invention. Fig. 4 is a flowchart showing a manufacturing process of a method for producing a regenerating cleaning liquid according to a fourth embodiment of the present invention. Fig. 5 is a graph showing the relationship between pH and fluorine ion concentration when nitric acid, hydrochloric acid, and sulfuric acid are added to a fluoric acid waste liquid. Fig. 6 shows the relationship between the amount of nitric acid, hydrochloric acid, and sulfuric acid added to the hydrofluoric acid waste solution and pΗ. FIG. 7 shows a process flow chart of the conventional cleaning liquid manufacturing method. Explanation of symbols S 1-1 Simple water quality inspection step S 1-2 Nitric acid waste liquid addition step S2-1 Dilution step S2-2 Impurity removal step S2-3 Concentration step S2-4 Simple water quality inspection step S2-5 Nitric acid waste liquid addition Step S3-1 Concentration step S3-2 Simple water quality inspection step S3-3 Nitric acid waste liquid addition step S4-1 Impurity removal step S4-2 Concentration step S4-3 Simple water quality inspection step S4-4 Nitric acid waste liquid addition step -16- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000234286 | 2000-08-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TWI229146B true TWI229146B (en) | 2005-03-11 |
Family
ID=36071000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW090118911A TWI229146B (en) | 2000-08-02 | 2001-08-02 | Regenerating method for cleaning solution of metallic product |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100502589B1 (en) |
| TW (1) | TWI229146B (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0969509A (en) * | 1995-09-01 | 1997-03-11 | Matsushita Electron Corp | Cleaning/etching/drying system for semiconductor wafer and using method thereof |
-
2001
- 2001-08-02 TW TW090118911A patent/TWI229146B/en not_active IP Right Cessation
- 2001-08-02 KR KR10-2001-0046708A patent/KR100502589B1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| KR100502589B1 (en) | 2005-07-22 |
| KR20020011904A (en) | 2002-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3600834B2 (en) | Recirculation of wafer cleaning materials | |
| KR101514863B1 (en) | Cleaning water for electronic material, method of cleaning electronic material, and system for supplying water containing dissolved gases | |
| CN104649335A (en) | Method and device for recycling ferrous chloride crystal and hydrochloric acid from chlorohydric acid pickling waste solution | |
| JP6165882B2 (en) | Anion exchanger, mixture of anion exchanger and cation exchanger, mixed bed comprising anion exchanger and cation exchanger, method for producing them, and method for purifying hydrogen peroxide water | |
| TWI229146B (en) | Regenerating method for cleaning solution of metallic product | |
| CN106621757B (en) | Chlorosilane analysis waste gas recovery treatment device and treatment method | |
| JP4361056B2 (en) | Ozone treatment method and ozone treatment apparatus | |
| JP3413411B2 (en) | Method for producing reclaimed cleaning solution for metal products | |
| JP2010135810A (en) | METHOD OF CONTROLLING pH VALUE OF SOLUTION AND OXIDATION-REDUCTION POTENTIAL, AND APPARATUS | |
| CN112062089A (en) | Preparation process of electronic grade hydrochloric acid | |
| JP2005144209A (en) | Fluorine-containing waste water treatment method | |
| JPH11186207A (en) | Cleaning water for electronic material | |
| JP2013138097A (en) | Acid mixture liquid recovery system, acid mixture liquid recovery method, and silicon material cleaning method | |
| WO1996039264A1 (en) | On-site manufacture of ultra-high-purity hydrochloric acid for semiconductor processing | |
| JP4203776B2 (en) | Cleaning liquid for electronic materials | |
| JP2000262992A (en) | Substrate washing method | |
| RU2065488C1 (en) | Detergent for polymeric surface washing off and a method of washing off | |
| JPH09234379A (en) | Method for regenerating or purifying anion exchange resin | |
| TWI815364B (en) | Electronic-grade isopropanol recovery and purification method and system | |
| TW201731772A (en) | Method for treating high concentration of hydrofluoric acid | |
| JP2008145384A (en) | Method for evaluating ion-exchange resin | |
| JPH0919661A (en) | Method and apparatus for washing electronic parts and the like | |
| Spiegelman et al. | Alternative Method and Device to Purify and Deliver Water Vapor | |
| JP2005187245A (en) | Method for recycling fluorine | |
| JPH11181493A (en) | Cleaning water for electronic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK4A | Expiration of patent term of an invention patent |