A1831§ Α7 Β7 五、發明説明（） 1.發明背景 煉油工業之媒裂、重油加氫脱硫等工場，製 程中所產生的酸水含有氰酸根離子（CN')成份， 為避免CN—造成管件、設備腐蝕及堵塞，必需準 確定量CN_，作為抗腐蚀劑如Polysulfide添加量 之依據。 由於酸水中含有高濃度硫化氫（H2S > 2 0 0 0 ppm)，會嚴重干擾CN_分析，一般分析方法必需 加以前處理，耗時且處理過程常造成誤差，乃重 新檢討e rr之定量分析方法。 一般CN·分析方法有硝酸銀（AgN03 )滴定法、 離予層析法、Merck比色法（MerckSpectroquant 14800)、Cheveroii比色法（Cheveron HCN 分析法） 及標準方法（ASTM D 2 0 3 6 - 9 1 )等。 其中硝酸銀（AgN03)滴定法，係先行將試樣添 加碳酸鉛（PbC03)，使產生PbS沈澱物以去除H2S 之干擾，再過遽、加指示劑，以AgN03滴定。惟 PbC03為固體物，溶解度低，反應慢，對高濃度 H2S樣品之前處理，需耗時二小時以上。且反應 產生大量PbS污泥沈積，過濾不易，部份HCN會附 著於PbS污泥上，造成分析誤差。另對於低濃度 HCN樣品，滴定點之顏色變化不易辨識，而除CN-外，銀離子亦會與其它離子反應*造成分析誤 差0 3 83.110,000 (請先聞讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） 經濟部中央榇準局貝工消費合作社印製 _ Λ 1 8 3 2 5 Α7 _ Β7_ 五、發明説明（） 離子層析法之前處理步騾與硝酸銀（AgN〇3) 滴定法相同，故會造成相同的誤差，過濾所得之 遽液直接以離子層析儀分析，由於CN-的導電度 不佳，故以離子層析儀分析感度差。A1831§ Α7 Β7 V. Description of the invention (1) Background of the invention The acid water produced in the refinery industry's media cracking and heavy oil hydrodesulfurization process contains cyanate ion (CN ') component. For equipment corrosion and blockage, CN_ must be accurately quantified as a basis for the amount of anticorrosives such as Polysulfide added. Because the acid water contains high concentration of hydrogen sulfide (H2S > 2000 ppm), it will seriously interfere with CN_ analysis. The general analysis method must be added to the previous processing, which is time-consuming and often causes errors in the processing process. The quantitative analysis of e rr is re-examined. Analytical method. General CN analysis methods include silver nitrate (AgN03) titration, ion chromatography, Merck colorimetry (Merck Spectroquant 14800), Cheveroii colorimetry (Cheveron HCN analysis), and standard methods (ASTM D 2 0 3 6-9 1) Wait. Among them, the silver nitrate (AgN03) titration method is to first add lead carbonate (PbC03) to the sample to generate PbS precipitates to remove the interference of H2S, and then pass the tritium and indicator to titrate with AgN03. However, PbC03 is a solid, with low solubility and slow response. It takes more than two hours to process the high-concentration H2S sample beforehand. Moreover, the reaction produced a large amount of PbS sludge deposition, which was not easy to filter. Part of the HCN would attach to the PbS sludge, causing analysis errors. In addition, for low-concentration HCN samples, the color change at the titration point is not easy to identify, and in addition to CN-, silver ions will also react with other ions * causing analysis errors 0 3 83.110,000 (Please read the precautions on the back before filling in this Page) This paper size is applicable to China National Standards (CNS) A4 (210X297 mm) Printed by the Central Laboratories Bureau of the Ministry of Economic Affairs, Pai Gong Consumer Cooperative _ Λ 1 8 3 2 5 Α7 _ Β7_ V. Description of the invention () Ionic layer The processing steps before analysis are the same as those of the silver nitrate (AgN〇3) titration method, which will cause the same error. The filtered solution is directly analyzed by an ion chromatograph. Due to the poor conductivity of CN-, the ion layer is used. Analyzer analysis sensitivity is poor.
Merk比色法係將試樣先行將CN-轉換成 C1CN，再與顯色劑反應，反應五分鐘後於波長 585nm比色定量，若試樣中含有、h2s2〇3，吸光 會產生干擾，造成誤差。實際應用時，仍需將H2S、 H2S203去除，才能準確定量HCN。 而Che ver on比色法，反應步騾繁雜，分析原 理係先將HCN轉化為HSCN，酸化後汽提h2S，再過 濾去除硫項沈澱物，再添加溴水使樣品中S c N完 全轉化為BrSCN ，另缓慢添加Potassium Tetrathionate去除多餘的溴分子，最後加顯色 劍，以分光光度計於510nm下定量分析。 至於標準方法（ASTM D 2 0 3 6 - 9 1 )，其前處理 步驟亦與硝酸銀滴定法相同，即會產生相同的誤 差。過濾除去PbS沈澱物後所得的濾液，取5〇〇ml 經酸化、蒸餾，以l%NaOH溶液吸收被蒸餾出來的 HCN，再加反應劑、顯色劑，以分光光度計於波 長578nm下定量分析，本方法除了前處理步驟户斤 造成的誤差外，分析亦費時，每支樣品需四小# 以上。 4 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 83· 3· 10,000 _ I ^-- (請先閲讀背面之注意事項再填寫本頁) -訂—1 線 A7 _B7 五、發明説明（） --------------~^衣 ~_ (請先閲讀背面之注意事項再填寫本頁 針對前述所提及耗時、樣品前處理造成.誤差、步 騾繁雜、感度不佳等缺失。本發明建立一種操作 簡便，且高感度、準確性佳，又可避免硫化氫等 雜質干擾的H C N分析方法。本H C N分析方法除可應 用於製程中之H C Ν分析，亦可應用於一般樣品中 之HCN、CN—分析，有利於工廠之操作管理及排放 水水質管制。 2 .發明概述： 本發明為一種新的H C N / C Ν -分析方法，此方法 之分析原理係在過量S·2下，於含有HCN或/及CN-之試樣中，在pH大於約1 0之反應條件下，加入Η202 或其·它適用氧化劑如Cl2、Br2、12·..等，將HCN 或/及CN完全轉化成HSCN，反應式如下： 線 H2S + HCN + H202— HSCN +2H20 此反應液再直接以離子層析儀定量分析SCN· 含量，進而計算得到HCN或/及CN—含量·’。若試樣 中未含足量H2S或完全不含，則可外加NaS後，再 以相同步騾進行HCN或/及CN'分析。 本發明具有如下優點：（1 )省略前處理去除 H2S干擾步驟，避免分析誤差。（2 )本分析方法係 將CN-先行轉化成SCN-，由於SCN-導電度佳，以 離子層析儀分析，感度可達lQppb以下。（3)於 離子層析儀之管柱中，SCN —、S 20 3,2、S·2、S04_2·.. 5 本紙張尺度適用_國國家標準（CNS ) A4規格（2Ϊ0Χ297公釐） S3. 3.丨0 000 4⑽ 4⑽ 經濟部中央標牟局員工消咋；良 A 7 B7 五、發明説明（） 等離子可完全分離，故可避免干擾。（4)分析快 速，一支酸水樣品分析時間約2 5分鐘即可。 另SCIT之生成，亦可經由CN-和多硫化合物反應 生成.，所用之多硫化合物如、（NH4)2Sx(x=3~5)…+。 本方法除可應用於煉油製程酸水樣品中之 HCN或/及CN-分析，以控制抗腐蚀劑之添加量外， 其它含有HCN或/及CN—之樣品亦可引用，有利於 業者應用於製程管理，或樣品中CN—含量之環保 管制。 3 .發明的詳細説明： . 本發明是一種簡易快速、南感度且準確 性佳之氰酸（HCN)或/及氰酸根離子（CN·)之分析 方法。本發明的分析原理係先將試樣中之H C Ν或/ 及C Ν_，於過量S-2存在下，加入適當氧化劑如Η 20 2、 C 12、B r 2、12· . ·等，在ρ Η大於約1 0之反應條件下， 反應約20分鐘以上，將HCN或/及CN-轉化成SCN—， 反應液再直接以離子層析儀分析，由於SCfr之導 電性佳，因此以離子層析儀（1C)分析，其感度可 達 lOppb以下 〇 另 SCN-與 S20 3-2、S-2、S04·2、SO,2·.· 等離子於離子層析儀管柱中可完全分離，而避免 干擾，SCN·之1C分析圖譜如圖一所示。 6 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） S3. 3.10,000 .~. 裝-- (請先閱讀背面之注意事項再填寫本頁) '17 線 • 41 ft” 5 A7 _B7_^_ 五、發明説明（） 而S C ΓΓ之生成，亦可經由c N -和多硫化合物反 應生成，所用之多硫化合物如Na2Sx、（NH^Sx^-5)·.· 等0 為詳述本發明對於HCN或/及CIT之分析準確 性及操作方便性，特以下列闡述性而非限制性之 試驗實例説明： 例一：於人工配製之（^-1.72又10匆（約0_447 mg/L)試樣中，分別加入 9 3 3、1 867、2 8 0 0mg/L 等不同濃度之S·2,於pH = 12 土 0 . 5及H202/S'2莫耳比 1.0至2.5之反應條件下，反應30分鐘後，反應液 注入離子層析儀分析，得知CIT回收率為98%_ 1 0 2 %。証實可利用本發明準確分析C1Γ。 例二：人工配製試樣，CN·濃度為0.419mg/L (1.61x10-510，加入 S-2 2000 mg/L ，另加入不 同濃度及種類的離子，其C1T回收率誤差皆小於 ±3%，顯示利用本發明分析c『，可不受其它離 : .1'I 痒-- (請先聞讀背面之注意事項再填寫本頁) .線 示 所 1 表 如 果 結 驗 試 ο 擾 干 的 子 經濟部中央標準局員工消費合作，社¥裂 83. 3.10,000 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A18325 A7 B7 五、發明説明（） 表一：外來離子對於C ΓΓ分析準確性的影響 外來離子_ 添加濃度，mg/L CN- ,mg/L 回收率，％ None — 0.419 一 Br' 1000 0.419 101.2 100 0.419 -99.2 Cl· 100 0.419 -98.9 HC03* 100 0.419 101.5 Γ 1000 0.419 100.6 100 0 . 419 100.7 νη4+ 100 0.419 100.4 NO/ 1000 0.419 100.3 100 0.419 100.9 Ρ04-3· 1000 0.419 101.7 S20 3'2 1000 0.419 102.4 100 0.419 -99.9 S 0 3_2 1000 0.419 100.0 100 0.419 -99.0 S04'2 1000 0.419 100.2 100 0.419 -98.8 Fe(CN)6'3 200 0.419 101.5 例三：某一廢水樣品，加入S—2 2 0 0 0 01 g / L、 H2〇2 4 2 5 0 mg/L ，於pH 11下，反應40分鐘後， 取反應液2 0 u 1注入離子層析儀分析，測得C N _含 (請先閲讀背面之注意事項再填寫本頁) "衣 訂The Merk colorimetric method converts the sample into CN-C1CN first, and then reacts with the developer. After five minutes of reaction, the colorimetric measurement is performed at a wavelength of 585nm. If the sample contains, h2s203, light absorption will cause interference, causing error. In actual application, H2S and H2S203 need to be removed to accurately quantify HCN. The Che ver on colorimetric method has complicated reaction steps. The principle of analysis is to first convert HCN to HSCN, strip the h2S after acidification, filter to remove sulfur precipitates, and then add bromine water to completely convert S c N in the sample into BrSCN, and slowly add Potassium Tetrathionate to remove excess bromine molecules, and finally add a color sword, and quantitative analysis at 510nm by spectrophotometer. As for the standard method (ASTM D 2 0 3 6-9 1), the pre-treatment steps are the same as the silver nitrate titration method, which will produce the same error. The filtrate obtained after the removal of the PbS precipitate was filtered, and 500 ml of it was acidified and distilled, and the distilled HCN was absorbed in a 1% NaOH solution. Then, a reactant and a developer were added, and the amount was spectrophotometrically measured at a wavelength of 578 nm Analysis, in addition to the error caused by the households in the pre-processing step, the analysis is also time-consuming, and each sample requires more than four small #. 4 This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 83 · 3 · 10,000 _ I ^-(Please read the precautions on the back before filling this page)-Order-1 line A7 _B7 V. Description of the invention () -------------- ~ ^ 衣 ~ _ (Please read the precautions on the back before filling out this page for the aforementioned time-consuming and sample pre-treatment. Errors, The steps are complicated, the sensitivity is not good, etc. The invention establishes an HCN analysis method that is easy to operate, has high sensitivity and accuracy, and can avoid the interference of impurities such as hydrogen sulfide. This HCN analysis method can be applied to HC in the manufacturing process. Ν analysis can also be applied to HCN and CN-analysis in general samples, which is beneficial to the operation and management of the factory and the quality control of the discharged water. 2. Summary of the invention: The present invention is a new HCN / CN-analysis method. This method The principle of analysis is to add Η202 or its suitable oxidizing agent such as Cl2, Br2, 12 · in a sample containing HCN or / and CN- under reaction conditions with a pH greater than about 10 under excess S · 2. .. etc., completely convert HCN or / and CN into HSCN, the reaction formula is as follows: line H2S + HCN + H202— HSCN + 2H20 This reaction solution is then directly analyzed by quantitative analysis of the content of SCN · with an ion chromatograph, and then calculated HCN or / and CN—content · '. If the sample does not contain sufficient H2S or does not contain it at all, Then, after adding NaS, HCN or / and CN 'analysis is performed in phase synchronization. The present invention has the following advantages: (1) omitting the pre-processing to remove H2S interference steps to avoid analysis errors. (2) This analysis method is based on CN -Converted into SCN- in advance, because SCN- has good conductivity, it can be analyzed by ion chromatography with sensitivity up to lQppb. (3) In the column of ion chromatography, SCN —, S 20 3, 2, S · 2, S04_2 · .. 5 This paper size applies _ National Standard (CNS) A4 specification (2Ϊ0 × 297mm) S3. 3. 丨 0 000 4⑽ 4⑽ Employees of the Central Standards Bureau of the Ministry of Economic Affairs; good A 7 B7 5 Explanation of the invention () The plasma can be completely separated, so interference can be avoided. (4) The analysis is fast, and the analysis time of a sample of acid water can be about 25 minutes. In addition, the generation of SCIT can also be reacted via CN- and polysulfide compounds. The formation of polysulfide compounds such as (NH4) 2Sx (x = 3 ~ 5) ... +. For the analysis of HCN or / and CN- in acid water samples of the refining process to control the amount of anti-corrosive added, other samples containing HCN or / and CN- can also be cited, which is beneficial to the application of process management, or Environmental protection control of CN content in the sample 3. Detailed description of the invention: The invention is a simple, fast, highly sensitive and highly accurate analysis method for cyanic acid (HCN) or / and cyanate ion (CN ·). The analysis principle of the present invention is to first add HC Ν or / and C Ν_ in a sample in the presence of an excess of S-2, and add an appropriate oxidant such as 2 、 20 2, C 12, B r 2, 12 ... Under reaction conditions where ρ Η is greater than about 10, the reaction is performed for about 20 minutes, and HCN or / and CN- is converted into SCN-. The reaction solution is directly analyzed by ion chromatography. Because SCfr has good conductivity, Chromatograph (1C) analysis, the sensitivity can reach less than 10ppb. In addition, SCN- and S20 3-2, S-2, S04 · 2, SO, 2 ... Plasma can be completely separated in the column of ion chromatography. , And to avoid interference, the 1C analysis spectrum of SCN · is shown in Figure 1. 6 This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) S3. 3.10,000. ~. Packing-(Please read the precautions on the back before filling this page) '17 Lines • 41 ft ”5 A7 _B7 _ ^ _ 5. Description of the invention () And the formation of SC ΓΓ can also be generated by the reaction of c N-with polysulfide compounds, such as Na2Sx, (NH ^ Sx ^ -5), etc. 0 In order to detail the analysis accuracy and operation convenience of the present invention for HCN or / and CIT, the following illustrative but non-limiting test examples are used to illustrate: Example 1: Prepared manually (^ -1.72 and 10 hurdles (about 0_447 mg / L), add S · 2 at different concentrations such as 9 3 3, 1 867, 2 8 0 mg / L, etc., at pH = 12 soil 0.5 and H202 / S'2 mole ratio 1.0 Under the reaction conditions of 2.5, after 30 minutes of reaction, the reaction solution was injected into an ion chromatograph for analysis, and the CIT recovery rate was 98% _102%. It was confirmed that the present invention can accurately analyze C1Γ. Example 2: Manual preparation test For example, the concentration of CN · is 0.419mg / L (1.61x10-510, S-2 2000 mg / L is added, and different concentrations and types of ions are added. The C1T recovery error is less than ± 3%. Shows that using the present invention to analyze c ", can not be affected by other factors: .1'I itch-(Please read the precautions on the back before filling out this page). The line shows the table 1 if the test is completed ο disturbed sub-economy Employees' cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs, 83. 3.10,000 This paper size applies to Chinese National Standards (CNS) A4 specifications (210X297 mm) A18325 A7 B7 V. Description of the invention () Table 1: Foreign ions for C ΓΓ Impact of analysis accuracy Foreign ions _ added concentration, mg / L CN-, mg / L recovery,% None — 0.419 a Br '1000 0.419 101.2 100 0.419 -99.2 Cl · 100 0.419 -98.9 HC03 * 100 0.419 101.5 Γ 1000 0.419 100.6 100 0. 419 100.7 νη4 + 100 0.419 100.4 NO / 1000 0.419 100.3 100 0.419 100.9 P04-3 · 1000 0.419 101.7 S20 3'2 1000 0.419 102.4 100 0.419 -99.9 S 0 3_2 1000 0.419 100.0 100 0.419 -99.0 S04'2 1000 0.419 100.2 100 0.419 -98.8 Fe (CN) 6'3 200 0.419 101.5 Example 3: A sample of wastewater, adding S-2 2 0 0 0 01 g / L, H2 02 2 4 50 mg / L, in After reaction at pH 11, after 40 minutes, reverse 2 0 u 1 was injected into the ion chromatograph analysis, including the measured C N _ (Read Notes on the back and then fill the page) " Custom clothing
L .線_ 8 83. 3.10, 本紙張尺度適用t國國家標準（CNS ) A4規格（210X297公釐） AU325 A7 B7 五、發明説明（） 量 0.028mg/L。同一樣品外加 CN，0.38mg/L’ 以 相同之分析步驟操作，亦測得外加C ΪΓ之回收率 為 9 7% 0 例四：某一煉油嚴之酸水樣品’因樣品本身 已含有S-2 900 mg/L，故不再外加S·2，直接加入 兩倍莫耳量的H 202，於pH12下，反應4G分鐘後， 取2 0 _u 1注入離子層析儀分奸，測得C N -含量0 3 2 9 tng/L 〇同一酸水樣品，但外加CN'0.219 mg/L， 以相同之分析步騾操作，亦測得外加CN-之回收 率為9 9 %。 利用本發明分析HCN或/及CN —，樣品無需前處 理，*操作簡便，分析時間可於30分鐘内完成，分 析感度可達〇.〇〇4mg/L CN-，且準確性佳’誤差 僅為± 3%，為一具實用性之分析方法，可應用 於工廠中之製程管理，如：抗腐蝕劑添加量的控 制，亦可應用於一般之CN·環保管制。 ；—^-- (請先閲讀背面之注意事項再填寫本貫) ii bj. 訂 線. 本紙張尺度適用中國國家標準（CNS ) A4規格（2】0X297公釐） 83. 3. 10,000 mw5 A7 __B7 _ 五、發明説明（） 圖式簡單説明： 圖一為含err樣品利用本發明之分析方法，將CN 轉化成S C N -後，注入離子層析儀分析所得到的圖 譜。 ' 離子層析儀的操作條件如下： 樣品注入量：20~100ul 溶洗液_(eluent):0·]·% NaOH l‘〇ml/min· 偵測器（Detector) :Coductivity type 管拄：Dionex AS- 1 1 I--------- —裝------訂-----ί線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 83, 3. 10,000L .line_ 8 83. 3.10, this paper size is applicable to national standard (CNS) A4 specification (210X297 mm) AU325 A7 B7 V. Description of the invention () Amount 0.028mg / L. The same sample was added with CN, 0.38mg / L 'was operated in the same analysis procedure, and the recovery rate of added CΪΓ was also measured. 9 7% 0 Example 4: A refining acid water sample' because the sample itself already contains S- 2 900 mg / L, so no additional S · 2, and directly add twice the molar amount of H 202. After reacting at pH 12 for 4G minutes, take 2 0_u 1 and inject it into an ion chromatograph to measure the CN. -Content 0 3 2 9 tng / L 〇 The same acid water sample, but with the addition of CN '0.219 mg / L, the same analysis steps were performed, and the recovery rate of the additional CN- was also determined to be 99%. Utilizing the present invention to analyze HCN or / and CN —, the sample does not require pretreatment, * easy operation, analysis time can be completed within 30 minutes, the analysis sensitivity can reach 0.004mg / L CN-, and the accuracy is good. The error is only It is ± 3%, which is a practical analysis method, which can be applied to the process management in the factory, such as the control of the amount of anti-corrosive agent added, and it can also be applied to the general CN · environmental control. ; ^-(Please read the notes on the back before filling in this book) ii bj. Thread setting. This paper size applies to China National Standard (CNS) A4 specification (2) 0X297 mm 83. 3. 10,000 mw5 A7 __B7 _ 5. Description of the invention () Brief description of the diagram: Figure 1 shows the chromatogram obtained by analyzing the sample containing err by converting the CN into SCN using the analysis method of the present invention and then injecting it into an ion chromatograph. 'The operating conditions of the ion chromatograph are as follows: Sample injection volume: 20 ~ 100ul Eluent_ (eluent): 0 ·] ·% NaOH l'〇ml / min · Detector: Coductivity type tube: Dionex AS- 1 1 I --------- —install ------ order ----- ί line (please read the precautions on the back before filling out this page) The paper size printed by the Industrial and Consumer Cooperatives applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 83, 3. 10,000