CN103243337A - Anti-depositing citric acid chemical cleaning fluid - Google Patents
Anti-depositing citric acid chemical cleaning fluid Download PDFInfo
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 238000004140 cleaning Methods 0.000 title abstract description 39
- 239000000126 substance Substances 0.000 title abstract description 30
- 238000000151 deposition Methods 0.000 title 1
- 239000012530 fluid Substances 0.000 title 1
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical group OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims abstract description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims abstract description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 3
- 229940120146 EDTMP Drugs 0.000 claims abstract description 3
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000174 gluconic acid Substances 0.000 claims abstract description 3
- 235000012208 gluconic acid Nutrition 0.000 claims abstract description 3
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 3
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims abstract description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 230000002000 scavenging effect Effects 0.000 claims 14
- 230000001376 precipitating effect Effects 0.000 claims 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- 230000002829 reductive effect Effects 0.000 claims 3
- 239000013543 active substance Substances 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 229940095064 tartrate Drugs 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 30
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- ONBWNNUYXGJKKD-UHFFFAOYSA-N 1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonic acid;sodium Chemical compound [Na].CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC ONBWNNUYXGJKKD-UHFFFAOYSA-N 0.000 abstract description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011538 cleaning material Substances 0.000 abstract description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 abstract description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011975 tartaric acid Substances 0.000 abstract description 2
- 235000002906 tartaric acid Nutrition 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010040844 Skin exfoliation Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Detergent Compositions (AREA)
Abstract
一种防止沉淀的柠檬酸化学清洗液，为在柠檬酸化学清洗液配方中，加入防沉淀剂PPA，加入的防沉淀剂PPA占防止沉淀的柠檬酸化学清洗液总质量的0.3%～2%；所述防沉淀剂PPA为有机混合物，由10%～30%的络合剂、5%～10%的表面活性剂以及余量水组成；所述络合剂为葡萄糖酸、酒石酸、聚丙烯酸、羟乙基乙二胺三乙酸、亚胺基二乙酸和乙二胺四甲叉膦酸中的一种或多种，为多种时，为任意比混合；所述表面活性剂为酯肪醇聚氧乙烯醚、磺化琥珀酸二辛酯钠盐和琥珀酸二仲辛酯磺酸钠中的一种或多种，为多种时，为任意比混合；本发明清洗液在防止沉淀的同时，并未增加对清洗材质的腐蚀性，且能够大幅度提高柠檬酸的使用浓度，保证高垢量、低容积热力设备如过热器的柠檬酸化学清洗的顺利进行。A citric acid chemical cleaning solution for preventing precipitation, comprising adding an anti-precipitation agent PPA to the formula of the citric acid chemical cleaning solution, and the added anti-precipitation agent PPA accounts for 0.3% to 2% of the total mass of the citric acid chemical cleaning solution for preventing precipitation ; The anti-precipitation agent PPA is an organic mixture, composed of 10% to 30% complexing agent, 5% to 10% surfactant and the remainder of water; the complexing agent is gluconic acid, tartaric acid, polyacrylic acid , hydroxyethylethylenediaminetriacetic acid, iminodiacetic acid and ethylenediaminetetramethylenephosphonic acid, one or more, when there are more than one, mix in any ratio; the surfactant is fatty One or more of alcohol polyoxyethylene ether, dioctyl sulfosuccinate sodium salt and dioctyl sulfosuccinate sodium sulfonate, when multiple, mix in any ratio; cleaning solution of the present invention prevents precipitation At the same time, it does not increase the corrosiveness to cleaning materials, and can greatly increase the concentration of citric acid used to ensure the smooth progress of citric acid chemical cleaning of high-scale, low-volume thermal equipment such as superheaters.
Description
技术领域technical field
本发明涉及高垢量低系统水容积的电力、石化和核电设备化学清洗技术领域，具体涉及一种防止沉淀的柠檬酸化学清洗液。The invention relates to the technical field of chemical cleaning of electric power, petrochemical and nuclear power equipment with high scale amount and low system water volume, in particular to a citric acid chemical cleaning solution for preventing precipitation.
背景技术Background technique
大容量火电机组锅炉过热器和再热器氧化皮的脱落、堵塞导致的爆管问题日益突出，严重影响火力发电厂的安全稳定运行，柠檬酸是常用的络合性化学清洗剂具有溶垢效率高、不含氯离子、腐蚀性小、对奥氏体钢材质没有晶间腐蚀和应力腐蚀、价格低廉、对人体无害、废液易于处理等优点，适用于过热器和再热器的化学清洗。但柠檬酸的化学清洗容易出现沉淀，特别是使用高浓度柠檬酸清洗高垢量、低系统水容积热力设备时容易出现因沉淀导致的化学清洗事故。本发明专为防止柠檬酸化学清洗沉淀而开发。Large-capacity thermal power unit boiler superheater and reheater oxide skin peeling off, blockage caused by bursting problems have become increasingly prominent, seriously affecting the safe and stable operation of thermal power plants, citric acid is a commonly used complexing chemical cleaning agent with scale dissolution efficiency High, no chloride ion, low corrosion, no intergranular corrosion and stress corrosion to austenitic steel materials, low price, harmless to human body, easy to handle waste liquid, etc., suitable for superheater and reheater chemical cleaning. However, chemical cleaning with citric acid is prone to precipitation, especially when high-concentration citric acid is used to clean thermal equipment with high scale and low system water volume, chemical cleaning accidents caused by precipitation are prone to occur. This invention was developed specifically to prevent citric acid chemical cleaning deposits.
发明内容Contents of the invention
为了解决上述现有技术存在的问题，本发明的目的在于提供一种防止沉淀的柠檬酸化学清洗液，本发明清洗液在防止沉淀的同时，并未增加对清洗材质的腐蚀性，且能够大幅度提高柠檬酸的使用浓度，保证高垢量、低容积热力设备如过热器的柠檬酸化学清洗的顺利进行。In order to solve the problems in the above-mentioned prior art, the object of the present invention is to provide a citric acid chemical cleaning solution that prevents precipitation. The cleaning solution of the present invention prevents precipitation, does not increase the corrosiveness to cleaning materials, and can greatly Significantly increase the concentration of citric acid used to ensure the smooth progress of citric acid chemical cleaning of high-scale, low-volume thermal equipment such as superheaters.
为达到以上目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种防止沉淀的柠檬酸化学清洗液，所述防止沉淀的柠檬酸化学清洗液为在柠檬酸化学清洗液配方中，加入防沉淀剂PPA，所述加入的防沉淀剂PPA占防止沉淀的柠檬酸化学清洗液总质量的0.3%～2.0%。A kind of citric acid chemical cleaning liquid that prevents precipitation, the citric acid chemical cleaning liquid that prevents precipitation is in the citric acid chemical cleaning liquid formula, adds anti-precipitation agent PPA, and the anti-precipitation agent PPA of described adding accounts for the citric acid chemical cleaning liquid that prevents precipitation 0.3% to 2.0% of the total mass of acid chemical cleaning solution.
所述防沉淀剂PPA为有机混合物，由10%～30%的络合剂、5%～10%的表面活性剂以及余量水组成。The anti-precipitation agent PPA is an organic mixture consisting of 10% to 30% of complexing agent, 5% to 10% of surfactant and the balance of water.
所述络合剂为葡萄糖酸、酒石酸、聚丙烯酸、羟乙基乙二胺三乙酸、亚胺基二乙酸和乙二胺四甲叉膦酸中的一种或多种，为多种时，为任意比混合。The complexing agent is one or more of gluconic acid, tartaric acid, polyacrylic acid, hydroxyethylethylenediaminetriacetic acid, iminodiacetic acid and ethylenediaminetetramethylenephosphonic acid, and when it is multiple, Mix in any ratio.
所述表面活性剂为酯肪醇聚氧乙烯醚、磺化琥珀酸二辛酯钠盐和琥珀酸二仲辛酯磺酸钠中的一种或多种，为多种时，为任意比混合。The surfactant is one or more of fatty alcohol polyoxyethylene ether, dioctyl sulfosuccinate sodium salt and dioctyl sulfosuccinate sodium sulfonate. .
所述柠檬酸化学清洗液配方为：柠檬酸化学清洗液中柠檬酸的质量百分比为3.0%～15.0%，氨水调节pH=3.5～4.5后，加入占柠檬酸化学清洗液质量百分比为0.3%～0.5%的缓蚀剂和0.1%～0.3%的还原剂。The formula of the citric acid chemical cleaning solution is as follows: the mass percentage of citric acid in the citric acid chemical cleaning solution is 3.0% to 15.0%, and after the ammonia water is adjusted to pH=3.5 to 4.5, 0.3% to 0.3% of the mass percentage of the citric acid chemical cleaning solution is added. 0.5% corrosion inhibitor and 0.1% to 0.3% reducing agent.
所述还原剂为异VCNa、联氨中的一种或多种，为多种时，为任意比混合。The reducing agent is one or more of iso-VCNa and hydrazine, and when there are multiple, it is mixed in any ratio.
所述柠檬酸化学清洗液中加入所述缓蚀剂、还原剂和防沉淀剂PPA后，其pH值如果不在3.5～4.5范围内，则向其中加入柠檬酸或氨水进行调整。After adding the corrosion inhibitor, reducing agent and anti-precipitation agent PPA to the citric acid chemical cleaning solution, if the pH value is not within the range of 3.5-4.5, then add citric acid or ammonia water for adjustment.
本发明和现有技术相比，优点如下：Compared with the prior art, the present invention has the following advantages:
本发明清洗液在防止沉淀的同时，采用配套柠檬酸缓蚀剂配方就能确保清洗过程中材质的腐蚀速度控制在标准要求范围，且能够大幅度提高柠檬酸的使用浓度，保证高垢量、低容积热力设备（如过热器）的柠檬酸化学清洗的顺利进行；由于，通常柠檬酸浓度超6%后，或清洗液中铁含量超过10000mg/L后，清洗过程出现沉淀的风险加大。因而限制了柠檬酸在高垢量、低容积热力设备清洗中的应用效果。通过在清洗液中添加络合剂和表面活性剂，增加柠檬酸清洗液中铁的稳定性，从而确保在柠檬酸浓度更高的条件下，溶解更多的铁垢而不出现沉淀。While preventing precipitation, the cleaning liquid of the present invention can ensure that the corrosion rate of the material in the cleaning process is controlled within the standard requirement range by adopting a matching citric acid corrosion inhibitor formula, and can greatly increase the concentration of citric acid used to ensure high scale volume, The citric acid chemical cleaning of low-volume thermal equipment (such as superheater) is carried out smoothly; because, usually, when the concentration of citric acid exceeds 6%, or the iron content in the cleaning solution exceeds 10000mg/L, the risk of precipitation in the cleaning process increases. Therefore, the application effect of citric acid in the cleaning of high-scale, low-volume thermal equipment is limited. By adding a complexing agent and a surfactant in the cleaning solution, the stability of iron in the citric acid cleaning solution is increased, thereby ensuring that under the condition of a higher concentration of citric acid, more iron scale is dissolved without precipitation.
具体实施方式Detailed ways
以下结合具体实施例，对本发明作进一步的详细描述。The present invention will be described in further detail below in conjunction with specific embodiments.
实施例1Example 1
本实施例一种防止沉淀的柠檬酸化学清洗液500mL中各组分的含量为：含6.0%wt柠檬酸、0.3%wt缓蚀剂、0.1%wt还原剂、1.0%wtPPA，余量为盐水，上述%wt均为占防止沉淀的柠檬酸化学清洗液的总质量百分比；氨水调节pH=3.6，升温至90℃，清洗实际运行过热器管，总铁浓度大到15600mg/L，没有出现沉淀现象。The content of each component in a 500mL citric acid chemical cleaning solution to prevent precipitation in this embodiment is: containing 6.0%wt citric acid, 0.3%wt corrosion inhibitor, 0.1%wt reducing agent, 1.0%wtPPA, and the balance is salt water , the above %wt is the total mass percentage of the citric acid chemical cleaning solution to prevent precipitation; adjust the pH to 3.6 with ammonia water, raise the temperature to 90°C, and clean the superheater tube in actual operation. The total iron concentration is as high as 15600mg/L, and no precipitation occurs Phenomenon.
实施例2Example 2
本实施例一种防止沉淀的柠檬酸化学清洗液500mL中各组分的含量为：含8.0%wt柠檬酸、0.3%wt缓蚀剂、0.1%wt还原剂、1.2%wtPPA，，余量为盐水，上述%wt均为占防止沉淀的柠檬酸化学清洗液的总质量百分比；氨水调节pH=3.6，升温至90℃，清洗实际运行过热器管，总铁浓度大到20400mg/L，没有出现沉淀现象。The content of each component in a kind of citric acid chemical cleaning solution 500mL that prevents precipitation in this embodiment is: containing 8.0%wt citric acid, 0.3%wt corrosion inhibitor, 0.1%wt reducing agent, 1.2%wtPPA, and the balance is For salt water, the %wt above is the total mass percentage of the citric acid chemical cleaning solution to prevent precipitation; ammonia water adjusts the pH=3.6, raises the temperature to 90°C, and cleans the superheater tube in actual operation. The total iron concentration is as large as 20400mg/L, and no occurrence precipitation phenomenon.
实施例3Example 3
本实施例一种防止沉淀的柠檬酸化学清洗液500mL中各组分的含量为：含12.0%wt柠檬酸、0.5%wt缓蚀剂、0.2%wt还原剂、1.5%wtPPA，余量为盐水，上述%wt均为占防止沉淀的柠檬酸化学清洗液的总质量百分比；氨水调节pH=3.8，升温至90℃，清洗实际运行过热器管，总铁浓度大到32000mg/L，没有出现沉淀现象。The content of each component in a 500mL citric acid chemical cleaning solution to prevent precipitation in this embodiment is: containing 12.0%wt citric acid, 0.5%wt corrosion inhibitor, 0.2%wt reducing agent, 1.5%wtPPA, and the balance is salt water , the above %wt is the total mass percentage of the citric acid chemical cleaning solution to prevent precipitation; adjust the pH to 3.8 with ammonia water, raise the temperature to 90°C, and clean the superheater tube in actual operation. The total iron concentration is as high as 32000mg/L, and no precipitation occurs Phenomenon.
本发明适用于高垢量低系统水容积热力设备（如：过热器）采用高浓度柠檬酸进行化学清洗。The invention is suitable for chemically cleaning high-concentration citric acid for thermal equipment with high scale and low system water volume (such as superheaters).
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施方式仅限于此，对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单的推演或替换，都应当视为属于本发明由所提交的权利要求书确定专利保护范围。The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments. It cannot be determined that the specific embodiments of the present invention are limited thereto. Under the circumstances, some simple deduction or replacement can also be made, all of which should be regarded as belonging to the scope of patent protection determined by the submitted claims of the present invention.
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Cited By (5)
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| CN105603446A (en) * | 2016-02-24 | 2016-05-25 | 苏州龙腾万里化工科技有限公司 | Deposition prevention water-based cleaning agent |
| CN107190532A (en) * | 2017-06-28 | 2017-09-22 | 常州武城服饰有限公司 | A kind of antisettling agent |
| CN108251851A (en) * | 2018-01-12 | 2018-07-06 | 海宁汉得隆科技有限公司 | A kind of stainless steel surface environment-friendly cleaning agent |
| CN109402648A (en) * | 2018-11-27 | 2019-03-01 | 广东科林化学清洗有限公司 | A kind of station boiler cleaning citric acid hydrotropy cleaning agent and its application |
| CN113174296A (en) * | 2021-05-10 | 2021-07-27 | 广东环凯生物技术有限公司 | Low-temperature foam cleaning agent for meat processing place and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105603446A (en) * | 2016-02-24 | 2016-05-25 | 苏州龙腾万里化工科技有限公司 | Deposition prevention water-based cleaning agent |
| CN107190532A (en) * | 2017-06-28 | 2017-09-22 | 常州武城服饰有限公司 | A kind of antisettling agent |
| CN108251851A (en) * | 2018-01-12 | 2018-07-06 | 海宁汉得隆科技有限公司 | A kind of stainless steel surface environment-friendly cleaning agent |
| CN109402648A (en) * | 2018-11-27 | 2019-03-01 | 广东科林化学清洗有限公司 | A kind of station boiler cleaning citric acid hydrotropy cleaning agent and its application |
| CN113174296A (en) * | 2021-05-10 | 2021-07-27 | 广东环凯生物技术有限公司 | Low-temperature foam cleaning agent for meat processing place and preparation method thereof |
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