一,加入点部位：初馏塔,常压塔,减压塔顶挥发线/Vapor line of top of Initial distillation column, atmospheric distillation column and vacuum distillation column
二,投加注入量/dosage amount：
初馏塔15-20 ppm,常压塔15-20 ppm,减压塔5-10 ppm.(均是以装置处理量计算)
the initial distillation tower: 15-20ppm,
the atmosphere distillation tower: 15-20ppm,
the vacuum distillation tower: 5-10ppm
all above data is based on the plant's processing capacity.
三,使用效果指标/the results after dosing neutralization corrosion inhibitor
1.塔顶流出污水 PH6-7.
The sewage from top of the tower: pH is 6-7
2.污水中铁离子含量小于3毫克/升.(邻菲罗啉分光光度法)
The content of the iron ions in sewage is less than 3 mg/l (phenanthroline spectrophotometry)
四,中和缓蚀剂产品指标的检测/the Detection methods of neutralization corrosion inhibitor
这个产品重要的指标有俩个,分别是碱值(产品中和能力大小衡量指标),缓蚀率(产品缓蚀能力大小的直观衡量),这俩个指标直接关系到产品质量的好坏,其余的理化指标只是表征产品的基本性能,与效果并无直接关系.如密度,外观,粘度等,只是表述产品的理化指标,这些指标能帮助我们对产品有个直观的了解,但与效果并无直接关系.
There are two important indicators of this product, respectively, the alkali value (product neutralization capacity measurement indicators), corrosion inhibition rate (product corrosion inhibition capacity intuitive measurement), these two indicators are directly related to the quality of the product, the rest of the physical and chemical indicators only characterize the basic performance of the product, and the effect has no direct relationship. Such as density, appearance, viscosity, etc., only describe the physical and chemical indicators of the product, these indicators can help us to have an intuitive understanding of the product, but there is no direct relationship with the effect.
邻菲啰啉分光光度法
Phenanthroline spectrophotometry
1.方法原理/Methods and principals
亚铁离子在Ph3~9之间的溶液中与邻菲啰啉生成稳定的橙红色络合物,其反应式为：
Ferrous ions form stable orange-red complexes with phenanthrene in solutions between Ph 3 and 9, with the formula 2+
此络合物在避光时可稳定半年.测量波长为510nm,其摩尔吸光系数为1.1X104L•mol-1•cm-1.若用还原剂(如盐酸羟胺)将高铁离子还原,则本法可测高铁离子及总铁含量.
This complex can be stable for half a year when it is shielded from light. The measurement wavelength is 510nm, and the molar absorption coefficient is 1.1X104L•mol-1•cm-1. If the ferric ion is reduced by a reducing agent (such as hydroxylamine hydrochloride), the content of ferric ion and total iron can be measured by this method.
2.干扰及消除/Interference and elimination
强氧化剂,氰化物,亚硝酸盐,焦磷酸盐,偏聚磷酸盐及某些重金属离子会干扰测定.经过加酸煮沸可将氰化物及亚硝酸盐除去,并使焦磷酸,偏聚磷酸盐转化为正磷酸盐以减轻干扰.加入盐酸羟胺则可消除强氧化剂的影响.
Strong oxidants, cyanide, nitrite, pyrophosphate, metaphosphate and some heavy metal ions can interfere with the determination. After acid boiling, cyanide and nitrite can be removed, and pyrophosphoric acid and metaphosphate can be converted into orthophosphate to reduce interference. The addition of hydroxylamine hydrochloride can eliminate the effect of the strong oxidant.
邻菲啰啉能与某些金属离子形成有色络合物而干扰测定.但在乙酸-乙酸铵的缓冲溶液中,不大于铁浓度10倍的铜,锌,钴,铬及小于2mg/L的镍,不干扰测定,当浓度再高时,可加入过量显色剂予以消除.汞,镉,银等能与邻菲啰啉形成沉淀,若浓度低时,可加过量邻菲啰啉来消除;浓度高时,可将沉淀过滤出去.水样有底色,可用不加邻菲啰啉的试液作参比,对水样的底色进行校正.
Phenanthroline can form colored complexes with some metal ions and interfere with the determination. However, in the buffer solution of acetic acid-ammonium acetate, copper, zinc, cobalt, chromium and nickel less than 2mg/L, which are not greater than 10 times the concentration of iron, do not interfere with the determination, and when the concentration is higher, excessive color development agent can be added to eliminate. Mercury, cadmium, silver, etc. can precipitate with phenanthroline, if the concentration is low, excess phenanthroline can be added to eliminate; When the concentration is high, the precipitation can be filtered out. The base color of water sample can be corrected by using the test solution without phenanthroline as reference
3.方法的适用范围/The scope of application of the method
此法适用于一般环境水和废水中铁的测定,最低检出浓度为0.03mg/L,测定上限为5.00mg/L.对铁离子大于5.00mg/L的水样,可适当稀释后再按本方法进行测定.
This method is suitable for the determination of iron in general environmental water and wastewater. The minimum detected concentration is 0.03mg/L, and the upper limit is 5.00mg/L.
Water samples with iron ions greater than 5.00mg/L can be properly diluted and then determined according to this method.
4.仪器/instrument
分光光度计,10mm比色皿.
Spectrophotometer, 10mm colorimetric dish.
5.试剂/reagent
(1)铁标准贮备液,准确称取0.7020g硫酸亚铁铵((NH4)2Fe(SO4)2·6H2O),溶于(1+1)硫酸50ml中,转移至1000ml容量瓶中,加水至标线,摇匀.此溶液每毫升含100 .0μg铁.
Iron standard reserve liquid, accurately weigh 0.7020g ammonium ferrous sulfate ((NH4) 2Fe (SO4) 2·6H2O), dissolve in (1+1) 50ml sulfuric acid, transfer to 1000ml volume bottle, add water to the line, shake well. This solution contains 100.0μg iron per milliliter.
(2)铁标准使用液：准确移取标准贮备液25.00ml置100ml容量瓶中,加水至标线,摇匀.此溶液每毫升含铁25.0μg.
Iron standard liquid: accurately remove the standard reserve liquid 25.00ml into a 100ml volumetric bottle, add water to the line, and shake well. This solution contains 25.0μg of iron per milliliter.
(3)(1+3)盐酸.(1+3) hydrochloric acid.
(4)10%盐酸羟胺溶液.10% hydroxylamine hydrochloride solution.
(5)缓冲溶液：40g乙酸铵加50ml冰乙酸用水稀释至100ml.
Buffer solution: 40g ammonium acetate and 50ml glacial acetic acid diluted with water to 100ml.
(6)0.5%邻菲啰啉(1,10-phenanthroline)水溶液,加数滴盐酸帮助溶解.
0.5% aqueous solution of 1, 10-phenanthroline, with several drops of hydrochloric acid added to help dissolve..
6.步骤/procedures
(1)校准曲线的绘制/Calibration curve drawing
依次移取铁标准使用液0,2.00,4.00,6.00,8.00 ,10.0ml置锥形瓶中,加入蒸馏水至50.0ml,再加(1+3)盐酸1ml,10%盐酸羟胺1ml,玻璃珠两粒.加热煮沸至溶液剩15ml左右,冷却至室温,定量转移至50ml具塞比色管中.加一小片刚果红试纸,滴加饱和乙酸钠溶液至试纸变红,加入5ml缓冲溶液,0.5%邻菲啰啉溶液2ml,加水至标线,摇匀.显色15分钟后,用10mm比色皿,以水为参比,在510nm处测量吸光度,由经过空白校正的吸光度对铁的微克数作图.
Remove the standard iron liquid 0, 2.00, 4.00, 6.00, 8.00, 10.0ml in a conical bottle, add distilled water to 50.0ml, add 1ml of (1+3) hydrochloric acid, 1ml of 10% hydroxylamine hydrochloride, and two glass beads. Heat and boil until about 15ml of the solution remains, cool to room temperature, and transfer to a 50ml stopper colorimetric tube. Add a small piece of Congo red test paper, add saturated sodium acetate solution to the test paper until it turns red, add 5ml buffer solution, 2ml 0.5% o-phenylene solution, add water to the line, shake well. After 15 minutes of color development, the absorbance was measured at 510nm using a 10mm colorimetric dish with water as the reference, and the microgram number of iron was plotted by the absorbance after blank correction.
(2) 总铁的测定/Determination of total iron
采样后立即将样品用盐酸酸化至PH<1,分析时取50.0ml混匀水样于150ml锥形瓶中,加(1+3)盐酸1ml,盐酸羟胺1ml,加热煮沸至体积减少到15ml左右,以保证全部铁的溶解和还原,若仍有沉淀应过滤除去.以下按绘制校准曲线同样操作,测量吸光度并作空白校正.
Immediately after sampling, the sample was acidified with hydrochloric acid to PH<1. During analysis, 50.0ml mixed water sample was taken into a 150ml conical bottle, 1ml of (1+3) hydrochloric acid and 1ml hydroxylamine hydrochloride were added, and heated and boiled until the volume was reduced to about 15ml to ensure the dissolution and reduction of all iron. If there was still precipitation, it should be filtered out. Perform the same operation as drawing the calibration curve below to measure the absorbance and make a blank correction.
(3)亚铁的测定/Determination of ferrous iron
采样时将2ml盐酸放在一个100ml具塞的水样瓶内,直接将水样注满样品瓶,塞好瓶塞以防氧化,一直保存到进行显色和测量(最好现场测定或显色).分析时只需取适量水样,直接加入缓冲溶液与邻菲啰啉溶液,显色5-10分钟,在510nm处以水为参比测量吸光度,并作空白校正.
Place 2ml hydrochloric acid in a 100ml stoppered water sample bottle, fill the sample bottle directly with water sample, plug the bottle to prevent oxidation, and store until color development and measurement (preferably field determination or color development). During the analysis, just take an appropriate amount of water sample, directly add buffer solution and o-phenanthroline solution, develop color for 5-10 minutes, measure absorbance at 510nm with water as the reference, and make blank correction.
(4)可过滤铁的测定/Determination of filtrable iron
在采样现场,用0.45μm滤膜过滤水样,并立即用盐酸酸化过滤水至pH<1,准确吸取样品50ml置与150ml锥形瓶中,以下操作与步骤(1)相同.
At the sampling site, filter the water sample with 0.45μm filter membrane, and immediately acidify the water with hydrochloric acid to pH<1. Accurately absorb 50ml of the sample and place it in a
150ml conical bottle.
The following operations are the same as step (1).
7.计算/calculation
铁(Fe,mg/L)=m/v
曲线x为A. Y为m. 得回归方程.
式中： m---由校准曲线查得的铁量(μg);
V---水样体积(ml).
Iron (Fe,mg/L)=m/v
The curve x is A. Y is m. The regression equation is obtained.
Where: m-- iron content obtained by calibration curve (μg);
V-- Water sample volume (ml).
8.精密度和准确度/Precision and accuracy
一个实验室测定铁离子的浓度为0.5,2.5,4.5mg/L的水样,相对标准偏差分别为1.0%,0.44%和0.33%.
对于0.5,2.5mg/L浓度的铁溶液按1：1的比例加标进行回收实验,回收率分别为102.6%和97.4%.
In one laboratory, the relative standard deviations of water samples with concentrations of 0.5, 2.5 and 4.5mg/L iron ions were 1.0%, 0.44% and 0.33%, respectively.
For 0.5 and 2.5mg/L concentration of iron solution, the recovery rate was 102.6% and 97.4%, respectively.
9.注意事项/Precautions
(1)各批试剂的铁含量如不同,每新配一次试液,都需重新绘制校准曲线.
If the iron content of each batch of reagents is different, the calibration curve needs to be redrawn for each new test solution
(2)含硫离子的水样酸化时,必须小心进行,因为会产生有毒气体.
When acidifying water samples containing sulfur ions, care must be taken because toxic gases are produced
(3)若水样含铁量较高,可适当稀释;浓度低时可换用30mm或50mm的比色皿.
If the water sample contains high iron content, it can be diluted appropriately; When the concentration is low, use 30mm or 50mm cuvette
缓蚀率测定方法(详情见Q/ SHCG109-2017)
Method for determination of corrosion inhibition rate (see Q/ SHCG109-2017 for details)
试剂与仪器/Reagents and instruments：
盐酸：分析纯,用于配制腐蚀液(警示：盐酸对皮肤或纤维有灼伤腐蚀.
Hydrochloric acid: Analytically pure, used to prepare corrosive fluids (Warning: Hydrochloric acid can burn and corrode skin or fibers
石油醚：60℃~90℃,分析纯(警示：石油醚易燃).
Petroleum ether: 60℃~90℃, analytically pure (warning: petroleum ether is flammable)
无水乙醇：分析纯(警示：无水乙醇易燃).
Anhydrous ethanol: Analytically pure (Warning: Anhydrous ethanol is flammable)
六亚甲基四胺(乌洛托品)：配成质量分数为0.5%水溶液.
Hexamethylenetetramine (hexamethylenetetramine) : prepared into an aqueous solution with a
mass fraction of 0.5%
水：符合GB/T6682中三级水的要求.
Water: Meet the requirements of GB/T6682 Level 3 water
缓蚀剂：待测样品.
Corrosion inhibitor: sample to be tested
盐酸溶液：质量分数为10%(用于清洗挂片).
Hydrochloric acid solution: mass fraction of 10% (for cleaning hanging film)
试片规格：35mm×10mmX2mm的20"碳钢(符合GB/T699-2015).
Specimen size: 20" carbon steel 35mm×10mmX2mm (GB/ T699-2015)
仪器和设备
Instruments and equipment
恒温水浴：或与之类似的试验仪器,温度控制精度为士0.5℃.
Constant temperature water bath: or similar test instrument, temperature control accuracy of 0.5℃
注：测定温度时温度计应在检定有效期内.
Note: When measuring temperature, the thermometer should be within the validity period of verification
电子天平：最小分度值0.1mg.
Electronic balance: minimum division value 0.1mg
试验容器：烧杯或其他
Test container: beaker or other
实验步骤/Experimental procedure：
试片的准备：对购置到的试片进行检查,试片应有编号,选择表面光滑无毛刺的试片.
Preparation of the test piece: check the purchased test piece, the test piece should be numbered, and choose the test piece with a smooth surface and no burrs
试片的预清洗：先用石油醚浸泡擦拭,后用无水乙醇清洗,吸干,置于干燥器中保存 24h备用.测定前称量,准确至0.1mg,不应用手直接接触钢片表面.
Pre-cleaning of the test piece: first soak and wipe with petroleum ether, then clean with anhydrous ethanol, blot dry, and store in a dryer for 24h for use. Before measuring, weigh accurately to 0.1mg, and do not directly touch the surface of the steel sheet by hand
腐蚀溶液的制备：在20℃±2℃条件下,制备足量的1000mg/LHCl水溶液
Preparation of corrosion solution: under the condition of 20℃±2℃, a sufficient amount of 1000mg/LHCl aqueous solution is prepared
缓蚀样品溶液的准备：水溶性的缓蚀剂用蒸馏水稀释,配制成50mL~100 mL质量分数为10%的缓蚀剂溶液.
Preparation of corrosion inhibition sample solution: the water-soluble corrosion inhibitor is diluted with distilled water and prepared into 50mL~ 100mL corrosion inhibitor solution with a mass fraction of 10%
采用四个试验容器,在四个实验容器中分别加入1000mg/LHCl水溶液做为腐蚀液,其中两个试验容器用作空白腐蚀试验,在另两个实验容器中加入缓蚀剂,使腐蚀溶液中缓蚀剂浓度为100mg/L.
Four test vessels were used, in which 1000mg/LHCl aqueous solution was added as corrosion solution, two test vessels were used as blank corrosion test, and corrosion inhibitor was added in the other two experimental vessels, so that the corrosion inhibitor concentration in the corrosion
solution was 100mg/L
当温度稳定在85℃±2℃时,把准备好的装有腐蚀溶液(1000mL)的试验容器放入水浴中,每个试验容器中置入三片待测试片,试片悬挂的位置水平面角120°分布,试片在腐蚀液液面10mm下,且距离试验容器壁的水平距离不小于20mm,开始记录腐蚀测定时间.
When the temperature is stable at 85 ° C ±2 ° C, the prepared test container with corrosion solution (1000mL) is put into the water bath, and three pieces to be tested are placed in each test container. The water plane Angle of the test plate is distributed at the position where the test plate is suspended, and the test plate is 10mm below the surface of the corrosion liquid, and the horizontal distance from the test container wall is not less than 20mm. Start recording corrosion measurement time
试验开始后,若因温升引起水浴中水分蒸发量较大时(影响实验),应补充适量同温
直至实验6h后结束,取出试片观察其表面情况并记录.
After the start of the test, if the evaporation of water in the water bath is large due to temperature rise (affecting the experiment), an appropriate amount of the same temperature should be added
Until the end of the experiment 6h later, take out the test piece to observe its surface conditions and record
试片的处理：试片上腐蚀沉积物用质量分数为1O%HICI 溶液冲洗并再用脱脂棉蘸质量分数为0.5%乌洛托品水溶液(A.3.4)将试片擦洗干净,并用水冲洗干净;
Treatment of the test piece: Wash the corrosion deposits on the test piece with 1O%HICI solution and then scrub the test piece with absorbent cotton dipped in 0.5% Ulotropine aqueous solution (A.3.4), and rinse with water
最后用无水乙醇清洗后用滤纸吸干,置入干燥器 24h 后取出称量,准确至 0.lmg.
Finally, clean with anhydrous ethanol, blot with filter paper, put in dryer for 24h, take out and weigh, accurate to 0.lmg
注1：整个测定过程应在通风橱内进行.
Note 1: The entire measurement process should be carried out in the fume hood
注2：在配制测定用腐蚀溶液的过程中应遵守国家对危险品的相关规定.
Note 2: In the process of preparation of corrosion solution for determination, relevant national regulations on dangerous goods shall be observed
挂片腐蚀试验应在相同条件下做平行试验,每个试验容器内挂置三个试片.
The hanging corrosion test should be carried out in parallel under the same conditions, and three test pieces should be hung in each test container
测定结果的计算/Calculation of measurement results
计算三个试片的平均腐蚀失重值
缓蚀率按下式计算：
n=(1-△Wx /△Wn)X100%
n-缓蚀率(%);
△Wx--加缓蚀剂条件下试片的腐蚀失重数值,单位为克(g);
△Wn--空白条件下试片的腐蚀失重数值,单位为克(g)
The average corrosion weight loss of the three test pieces was calculated
The corrosion inhibition rate is calculated as follows:
n=(1-△Wx /△Wn)X100%
n - corrosion inhibition rate (%);
△Wx -- the corrosion weight loss value of the test piece under the condition of adding corrosion inhibitor, in grams (g);
△Wn -- the corrosion weight loss value of the test piece under blank conditions, in grams (g)
碱值的测定(高氯酸电位滴定法)
Determination of alkali content (perchlorate potentiometric titration)
主题内容与适用范围/Subject content and scope of application：
适用于测定石油产品和使用过的油以及添加剂的碱性组分,这些组分包括有机碱,无机碱,
胺基化合物,弱酸盐(皂类),多元酸碱式盐和重金属盐类.
Suitable for the determination of alkaline components of petroleum products and used oils and additives, including organic bases, inorganic bases, amino compounds, weak acid salts (soaps), multi-acid base salts and heavy metal salts
碱值：在规定的试验条件下,用标准滴定溶液滴定1g试样所用的高氯酸量,以 mgKOH/g为单位表示.
Alkaline value: The amount of perchloric acid used to titrate a 1g sample with a standard titration solution under specified test conditions, expressed in mgKOH/g.
方法概要/method summary
正滴定方法：试样溶解于滴定溶剂中,以高氯酸冰乙酸标准滴定溶液为滴定剂,以玻璃电极为指示
电极,甘汞电极为参比电极进行电位滴定,用电位滴定曲线的电位突跃判断终点.
返滴定方法：试样溶解于滴定溶剂中,加入过量的高氯酸冰乙酸标准滴定溶液,反应完成后,用乙酸钠冰乙酸标准滴定溶液进行滴定,以电位滴定曲线的电位突跃判断终点.
Positive titration method: The sample was dissolved in the titration solvent, the standard titration solution of perchloric acid and glacial acetic acid was used as the titration agent, the glass electrode was used as the indicator electrode, and the calomel electrode was used as the reference electrode for potentiometric titration. The end point was determined by the potential jump of the potentiometric titration curve.
Back titration method: The sample was dissolved in the titration solvent, and excessive perchlorate glacial acetic acid standard titration solution was added. After the reaction was completed, the sodium acetate glacial acetic acid standard titration solution was titrated, and the end point was determined by the potential jump of the potentiometric titration curve.
当试样正滴定曲线电位突跃不明显时,再用返滴定方法.
When the positive titration curve potential jump of the sample is not obvious, the back titration method is used
意义/meaning：
当石油产品加有添加剂时,石油产品就可能有碱性组分,用酸滴定的方法可以测定这些组分的相对含量.
When additives are added to petroleum products, petroleum products may have alkaline components, and the relative content of these components can be determined by acid titration
仪器/instrument：
电位滴定仪(或酸度计)：自动或手工滴定均可.
Potentiometric titrator (or acidity meter) : Automatic or manual titration can be done
玻璃电极;231型.
Glass electrode; Type 231
甘汞电极：232型或271型,或银 氯化银电圾.电板内电解液需改用非水溶液作盐桥.
Calomel electrode: Type 232 or 271, or silver chloride. Non-aqueous solution should be used as the salt bridge for the electrolyte in the electric plate
磁力搅拌器：可调速和有良好的接地.
Magnetic stirrer: Adjustable speed and good grounding
滴定管：10或20mL,分度为0.05mL.
Burette: 10 or 20mL, division is 0.05mL
实验步骤/Experimental procedure
正滴定方法/Positive titration method
试样量X:(g)按式(4)计算：
X:=28/BN,
式中：BN,--预估的碱值,mgKOH/g.
往：如果预估的碱值不知道,则可以用一个简单的相略地估计,称取0.2~0.3g试样570mV为终点,计算试样碱值,该值作为试样的预估值
Sample size X:(g) Calculated according to formula (4) :
X:=28/BN,
Where: BN, -- estimated base value, mgKOH/g.
If the estimated base value is not known, you can use a simple phase estimate, weighing the 0.2-0.3g sample 570mV as the end point, calculate the sample base value, which is used as the sample estimate
在称有试样的烧杯中加入120mL滴定溶剂,将旋杯放在演定台上,搅拌直至试样全部溶解.将已准备好的玻璃-甘汞电极对插人试样溶液中,其浸入位置尽可能的低,至少应浸入试样溶液10mm以下,开始搅拌,搅拌速度要控制在没有溶液飞展和产生气泡的情况下尽可能的大.
Add 120mL of titration solvent to the beaker weighing the sample, place the rotating cup on the stage, and stir until the sample is completely dissolved. The prepared glass-calomel electrode is inserted into the human sample solution, and the immersion position is as low as possible, at least 10mm below the sample solution, and the mixing speed should be controlled in the case of no solution flying and producing bubbles as large as possible
滴定/titration：
手工滴定.用高氯酸冰乙靓标准滴定溶液滴定,演定管尖端应浸入烧杯内溶液的液面以下.滴定之前和滴定过程中,应间断的记录滴定剂体积和电位滴定仅的读数,滴定速度一般控制在0.1mL/min,滴定过程中可根据溶液的电位值变化大小改变滴定速度.当加入0.ImL/min滴定剂,溶液电位值变化大于30mV或相当于0.5个pH时,演定曲线可能出现拐点,这时,可以减小滴定速度为0.05mL/min.
Titration by hand. Titrating with the standard titration solution of perchlorate, the tip of the determined tube should be immersed below the liquid level of the solution in the beaker. Before and during titration, the volume of titrant and the reading of potentiometric titration should be continuously recorded, and the titration speed is generally controlled at 0.1mL/min, and the titration speed can be changed according to the change in the potential value of the solution during the titration process. When 0.ImL/min titrant is added and the change of solution potential value is greater than 30mV or equivalent to 0.5 pH, the inflection point may appear in the deduced curve, and the titration speed can be reduced to 0.05mL/min
滴定到最后阶段,当加入0.1mL滴定剂,试样溶液电位变化小于5mV或相当于0.1个pH时,可结束滴定.
At the final stage of titration, titration can be ended when 0.1mL of titrant is added and the potential change of the sample solution is less than 5mV or equivalent to 0.1 pH
碱值的计算/Calculation of base value：
根据高氯酸液使用的体积和浓度以及氢氧化钾的分子量折合计算具体的碱值.
The specific base value is calculated according to the volume and concentration of the high chloric acid solution used and the molecular weight of potassium hydroxide