CN1749434A - A kind of natural green pickling corrosion inhibitor and its application - Google Patents
A kind of natural green pickling corrosion inhibitor and its application Download PDFInfo
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- 230000007797 corrosion Effects 0.000 title claims abstract description 49
- 238000005260 corrosion Methods 0.000 title claims abstract description 49
- 239000003112 inhibitor Substances 0.000 title claims abstract description 36
- 238000005554 pickling Methods 0.000 title abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 14
- 239000010959 steel Substances 0.000 claims abstract description 14
- VKJGBAJNNALVAV-UHFFFAOYSA-M Berberine chloride (TN) Chemical compound [Cl-].C1=C2CC[N+]3=CC4=C(OC)C(OC)=CC=C4C=C3C2=CC2=C1OCO2 VKJGBAJNNALVAV-UHFFFAOYSA-M 0.000 claims abstract description 8
- FPJQGFLUORYYPE-UHFFFAOYSA-N epiberberine Chemical compound C1=C2C=C(C3=C(C=C(C(=C3)OC)OC)CC3)[N+]3=CC2=C2OCOC2=C1 FPJQGFLUORYYPE-UHFFFAOYSA-N 0.000 claims abstract description 8
- JKMUUZMCSNHBAX-UHFFFAOYSA-N 2,9,10-trimethoxy-5,6-dihydroisoquinolino[2,1-b]isoquinolin-3-one;hydrochloride Chemical compound [Cl-].COC1=CC=C2C=C3C(C=C(C(=C4)O)OC)=C4CC[N+]3=CC2=C1OC JKMUUZMCSNHBAX-UHFFFAOYSA-N 0.000 claims description 7
- 235000021110 pickles Nutrition 0.000 claims 4
- 239000000837 restrainer Substances 0.000 claims 3
- 239000001117 sulphuric acid Substances 0.000 claims 2
- 235000011149 sulphuric acid Nutrition 0.000 claims 2
- 230000002000 scavenging effect Effects 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000000419 plant extract Substances 0.000 abstract description 2
- 244000184734 Pyrus japonica Species 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 241000037740 Coptis chinensis Species 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000972672 Phellodendron Species 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 102000011759 adducin Human genes 0.000 description 1
- 108010076723 adducin Proteins 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YBHILYKTIRIUTE-UHFFFAOYSA-N berberine Chemical compound C1=C2CC[N+]3=CC4=C(OC)C(OC)=CC=C4C=C3C2=CC2=C1OCO2 YBHILYKTIRIUTE-UHFFFAOYSA-N 0.000 description 1
- 229940093265 berberine Drugs 0.000 description 1
- QISXPYZVZJBNDM-UHFFFAOYSA-N berberine Natural products COc1ccc2C=C3N(Cc2c1OC)C=Cc4cc5OCOc5cc34 QISXPYZVZJBNDM-UHFFFAOYSA-N 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Chemical group 0.000 description 1
- 239000001301 oxygen Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
本发明公开一种绿色酸洗缓蚀剂及其应用，它由以下重量百分比的各组分组成：盐酸小檗碱80％－98％，盐酸表小檗碱0.1％－10％，盐酸药根碱0.1％－10％。其应用是：酸洗液为稀盐酸或稀硫酸，浓度为0.1－2M，加入缓蚀剂0.001kg/m3－5kg/m3，升温至25－50℃，加入待清洗钢材，浸没1－3h；或者将配好的酸液作为清洗液直接加入待清洗设备。本发明产品用于各类钢铁及其产品的工业酸洗，能防止钢铁的全面腐蚀和局部腐蚀，与目前常用的酸洗缓蚀剂比较，具有用量低，缓蚀效率高，持续作用能力强的突出优点。本发明产品为天然植物提取物，对环境和生物无毒无害，符合酸洗缓蚀剂发展的趋势，具有良好的应用前景。The invention discloses a green pickling corrosion inhibitor and its application, which is composed of the following components in percentage by weight: 80%-98% of berberine hydrochloride, 0.1%-10% of epiberberine hydrochloride, and japonica hydrochloride Alkali 0.1%-10%. Its application is: the pickling solution is dilute hydrochloric acid or dilute sulfuric acid, the concentration is 0.1-2M, add corrosion inhibitor 0.001kg/m 3 -5kg/m 3 , raise the temperature to 25-50°C, add the steel to be cleaned, immerse 1- 3h; or add the prepared acid solution directly into the equipment to be cleaned as a cleaning solution. The product of the present invention is used for industrial pickling of various types of steel and its products, and can prevent overall corrosion and local corrosion of steel. Compared with currently commonly used pickling corrosion inhibitors, it has the advantages of low dosage, high corrosion inhibition efficiency and strong continuous action ability. outstanding advantages. The product of the invention is a natural plant extract, non-toxic and harmless to the environment and organisms, conforms to the development trend of pickling corrosion inhibitors, and has good application prospects.
Description
技术领域technical field
本发明涉及一种用以防止钢铁及其制品在酸洗过程中不必要的全面腐蚀和局部腐蚀的天然绿色酸洗缓蚀剂及其应用，属缓蚀剂生产技术领域。The invention relates to a natural green pickling corrosion inhibitor for preventing unnecessary overall corrosion and localized corrosion of steel and its products in the pickling process and application thereof, which belongs to the technical field of corrosion inhibitor production.
背景技术Background technique
以稀硫酸或稀盐酸进行酸洗可以去除钢铁表面的氧化膜，此工艺广泛应用于钢铁的精炼，锅炉除垢，热交换器的清洗等方面。为了避免酸洗过程中金属或酸的过度消耗以及防止局部腐蚀的发生，在酸中加入缓蚀剂是常用有效的手段。Pickling with dilute sulfuric acid or dilute hydrochloric acid can remove the oxide film on the steel surface. This process is widely used in steel refining, boiler descaling, heat exchanger cleaning, etc. In order to avoid excessive consumption of metal or acid during pickling and prevent localized corrosion, adding corrosion inhibitors to acid is a commonly used and effective means.
目前广泛应用的酸洗缓蚀剂中，主要由无机和有机两大类，这些缓蚀剂大都由化学合成得来，其中部分缓蚀剂有一定得毒性和环境危害性，比如含有毒铬酸根的无机缓蚀化合物，一些有机磷缓蚀化合物的排放造成水体的富营养化等。Among the currently widely used pickling corrosion inhibitors, there are mainly two categories: inorganic and organic. Most of these corrosion inhibitors are obtained by chemical synthesis. Some of them have certain toxicity and environmental hazards, such as poisonous chromate. The discharge of inorganic corrosion inhibitor compounds and some organic phosphorus corrosion inhibitor compounds cause eutrophication of water bodies, etc.
从现有公开的缓蚀剂配方专利来看，有些缓蚀剂产品中的一些化合物合成复杂，价格昂贵，提高了使用者的使用成本，经济效益较差，市场竞争能力弱。Judging from the existing published patents of corrosion inhibitor formulas, some compounds in some corrosion inhibitor products are complicated to synthesize and expensive, which increases the user's cost of use, poor economic benefits, and weak market competitiveness.
因此，开发新的环保，廉价，来源广泛，无公害的酸洗缓蚀剂是目前缓蚀剂开发的新方向。Therefore, the development of new environmentally friendly, cheap, wide-source, and pollution-free pickling corrosion inhibitors is a new direction for the development of corrosion inhibitors.
发明内容Contents of the invention
本发明的目的在于提供一种天然绿色酸洗缓蚀剂及其应用，用以防止钢铁及其制品在酸洗过程中不必要的全面腐蚀和局部腐蚀。The object of the present invention is to provide a kind of natural green pickling corrosion inhibitor and application thereof, in order to prevent unnecessary general corrosion and partial corrosion of steel and its products in pickling process.
本发明的技术方案是：一种天然绿色酸洗缓蚀剂，由中国黄连、黄柏或三颗针等植物中提取，其特征在于由以下组分组成：按重量百分比计，盐酸小檗碱80％-98％，盐酸表小檗碱0.1％-10％，盐酸药根碱0.1％-10％。使用浓度范围：酸洗液为稀盐酸或稀硫酸，浓度为0.1-2M，加入黄连提取物(缓蚀剂)0.001kg/m3-5kg/m3，升温至25-50℃，加入待清洗钢材，浸没1-3h；或者，将所得溶液作为清洗液直接加入待清洗设备，浸泡3-12小时。The technical scheme of the present invention is: a kind of natural green pickling corrosion inhibitor, is extracted from plants such as Chinese Coptidis Rhizoma, Phellodendron Phellodendron or Three Needles, and is characterized in that it is composed of the following components: by weight percentage, berberine hydrochloride 80 %-98%, epiberberine hydrochloride 0.1%-10%, jatrorrhizine hydrochloride 0.1%-10%. Concentration range: the pickling liquid is dilute hydrochloric acid or dilute sulfuric acid, the concentration is 0.1-2M, add Coptis chinensis extract (corrosion inhibitor) 0.001kg/m 3 -5kg/m 3 , heat up to 25-50°C, add to be cleaned For steel, immerse for 1-3 hours; or, directly add the obtained solution as a cleaning solution to the equipment to be cleaned, and soak for 3-12 hours.
本发明的原理在于：小檗碱等生物碱具有异喹啉结构，分子内含有杂环、氮、氧等原子或原子团，能有效地吸附于钢铁表面，起到缓蚀作用。The principle of the present invention is that alkaloids such as berberine have an isoquinoline structure and contain atoms or atomic groups such as heterocycles, nitrogen, and oxygen in the molecules, which can be effectively adsorbed on the surface of steel and play a role of corrosion inhibition.
本发明的有益效果是：The beneficial effects of the present invention are:
(1)本发明黄连植物来源广泛，2004年市场报价在60～120元/公斤之间，提取方法简单，按7％收率计算，提取物价格可控制在800-1600元/公斤，成本较低。(1) Coptis chinensis plant of the present invention has a wide range of sources, and the market quotation in 2004 was between 60～120 yuan/kg, and the extraction method was simple, and calculated by 7% yield, the price of the extract could be controlled at 800-1600 yuan/kg, and the cost was relatively low. Low.
(2)本发明缓蚀剂为天然植物提取物，提取物为无毒无害绿色物质，与目前化学合成的缓蚀剂相比，不存在使用后的环境问题，对环境和生物无毒无害，符合酸洗缓蚀剂发展的趋势，具有良好的应用前景。(2) The corrosion inhibitor of the present invention is a natural plant extract, and the extract is a non-toxic and harmless green substance. Compared with the current chemically synthesized corrosion inhibitor, there is no environmental problem after use, and it is non-toxic and harmless to the environment and organisms. Harmful, in line with the development trend of pickling corrosion inhibitors, has a good application prospect.
(3)本发明用于各类钢铁及其产品的工业酸洗，可有效抑制金属基体在酸中的全面腐蚀和局部腐蚀，与目前常用的酸洗缓蚀剂比较，具有用量低，缓蚀效率高，持续作用能力强的突出优点，可反复使用。(3) The present invention is used for industrial pickling of various types of steel and its products, which can effectively inhibit the overall corrosion and local corrosion of metal substrates in acid. The outstanding advantages of high efficiency and strong continuous action ability can be used repeatedly.
具体实施方式Detailed ways
本发明按照GB10124-88《金属材料实验室均匀腐蚀全浸试验方法》进行挂片失重试验，试验酸洗液为盐酸和硫酸，浓度为0.1-2M，试片为Q235碳钢，试验温度25-50℃，实验时间1-3h，试验结果获得的最高缓蚀效率高于98％，显示为高效的缓蚀剂。The present invention carries out the hanging piece weight loss test according to GB10124-88 "Metal Material Laboratory Uniform Corrosion Full Immersion Test Method", the test pickling solution is hydrochloric acid and sulfuric acid, the concentration is 0.1-2M, the test piece is Q235 carbon steel, and the test temperature is 25- 50 ℃, test time 1-3h, the highest corrosion inhibition efficiency obtained in the test results is higher than 98%, showing that it is an efficient corrosion inhibitor.
本发明缓蚀剂可以采用以下提取过程：它由黄连植物采用乙醇法提取，具体步骤如下：将黄连磨碎，加入95％乙醇，回流半小时，冷却静置1h，过滤，滤饼重复上述操作3次；合并3次所得滤液，减压蒸发；加入1％乙酸溶液，加热，滤去杂质，加入37％HCl使之沉淀完全，过滤，滤饼以无水乙醇洗，真空干燥即可。所述黄连植物可以为中国黄连、黄柏或三颗针。The corrosion inhibitor of the present invention can adopt the following extraction process: it is extracted by the ethanol method from the Coptis chinensis plant, and the specific steps are as follows: Grind the Coptis chinensis, add 95% ethanol, reflux for half an hour, cool and stand for 1 hour, filter, and repeat the above operations for the filter cake 3 times; combine the filtrate obtained from 3 times, evaporate under reduced pressure; add 1% acetic acid solution, heat, filter to remove impurities, add 37% HCl to make the precipitation complete, filter, wash the filter cake with absolute ethanol, and vacuum dry. The Coptis chinensis plant can be Chinese Coptis chinensis, Phellodendron phellodendri, or three needles.
本发明缓蚀剂也可以直接取其三个组分混合而成。The corrosion inhibitor of the present invention can also be directly obtained by mixing its three components.
实施例1Example 1
缓蚀剂按重量百分比计，盐酸小檗碱98％，盐酸表小檗碱0.1％，盐酸药根碱1.9％。The corrosion inhibitor is calculated by weight percentage, and the berberine hydrochloride is 98%, the epiberberine hydrochloride is 0.1%, and the jatrorrhizine hydrochloride is 1.9%.
酸洗液为稀盐酸，浓度为0.1M，酸洗液用量100L，加入缓蚀剂30g，升温至40℃，加入待清洗钢材，浸没3h即可。The pickling solution is dilute hydrochloric acid, the concentration is 0.1M, the amount of pickling solution is 100L, add 30g of corrosion inhibitor, raise the temperature to 40°C, add the steel to be cleaned, and immerse for 3 hours.
实施例2Example 2
缓蚀剂按重量百分比计，盐酸小檗碱96％，盐酸表小檗碱1％，盐酸药根碱3％。The corrosion inhibitor is calculated by weight percentage, including 96% of berberine hydrochloride, 1% of epiberberine hydrochloride, and 3% of jatrorrhizine hydrochloride.
酸洗液为稀盐酸，浓度为0.5M，酸洗液用量100L，加入缓蚀剂45g，升温至35℃，加入待清洗钢材，浸没2h即可。The pickling solution is dilute hydrochloric acid, the concentration is 0.5M, the amount of pickling solution is 100L, add 45g of corrosion inhibitor, raise the temperature to 35°C, add the steel to be cleaned, and immerse for 2 hours.
实施例3Example 3
缓蚀剂按重量百分比计，盐酸小檗碱94％，盐酸表小檗碱1％，盐酸药根碱5％。The corrosion inhibitor is calculated by weight percentage, including 94% of berberine hydrochloride, 1% of epiberberine hydrochloride, and 5% of jatrorrhizine hydrochloride.
酸洗液为稀硫酸，浓度为1M，酸洗液用量100L，加入缓蚀剂90g，升温至30℃，加入待清洗钢材，浸没2h即可。The pickling solution is dilute sulfuric acid, the concentration is 1M, the amount of pickling solution is 100L, add 90g of corrosion inhibitor, raise the temperature to 30°C, add the steel to be cleaned, and immerse for 2 hours.
实施例4Example 4
缓蚀剂按重量百分比计，盐酸小檗碱92％，盐酸表小檗碱5％，盐酸药根碱3％。The corrosion inhibitor is calculated by weight percentage, and the berberine hydrochloride is 92%, the epiberberine hydrochloride is 5%, and the jatrorrhizine hydrochloride is 3%.
酸洗液为稀硫酸，浓度为1M，酸洗液用量100L，加入缓蚀剂120g，将所得溶液作为清洗液直接注入待清洗设备或容器内，浸泡6h即可。The pickling solution is dilute sulfuric acid, the concentration is 1M, the amount of pickling solution is 100L, and 120g of corrosion inhibitor is added, and the resulting solution is directly injected into the equipment or container to be cleaned as a cleaning solution, and soaked for 6 hours.
实施例5Example 5
缓蚀剂按重量百分比计，盐酸小檗碱90％，盐酸表小檗碱5％，盐酸药根碱5％。The corrosion inhibitor is calculated by weight percentage, including 90% of berberine hydrochloride, 5% of epiberberine hydrochloride, and 5% of jatrorrhizine hydrochloride.
酸洗液为稀硫酸，浓度为0.5M，酸洗液用量100L，加入缓蚀剂200g，将所得溶液作为清洗液直接注入待清洗设备或容器内，浸泡12h即可。The pickling solution is dilute sulfuric acid with a concentration of 0.5M. The amount of pickling solution is 100L, and 200g of corrosion inhibitor is added. The resulting solution is directly injected into the equipment or container to be cleaned as a cleaning solution and soaked for 12 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100419123C (en) * | 2006-04-07 | 2008-09-17 | 中国科学院海洋研究所 | A kind of carbon steel acid cleaning agent and application thereof |
| CN101787533A (en) * | 2010-03-18 | 2010-07-28 | 重庆大学 | Corrosion inhibitor for engine coolant and preparation method thereof |
| CN103757641A (en) * | 2014-01-21 | 2014-04-30 | 中国石油大学(华东) | Corrosion inhibition cleanser for sea water desalting plant and application thereof |
| CN106400033A (en) * | 2016-11-11 | 2017-02-15 | 中北大学 | Sunflower head corrosion inhibitor extract and method for preparing metal acid-pickling solution using the same |
| CN109023401A (en) * | 2018-09-28 | 2018-12-18 | 深圳市泽成丰新材料有限公司 | A kind of environment-friendly degradable degreasing agent |
| US10988669B2 (en) * | 2014-12-09 | 2021-04-27 | Halliburton Energy Services, Inc. | Use of berberine as corrosion inhibitor in well operations |
| CN113897615A (en) * | 2021-09-30 | 2022-01-07 | 河南省科学院能源研究所有限公司 | A kind of zinc corrosion inhibitor in mixed acid medium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1041118C (en) * | 1994-11-18 | 1998-12-09 | 刘威 | Scaling agent for water tank of automobile |
| CN1206390C (en) * | 2002-10-28 | 2005-06-15 | 启东尤希路化学工业有限公司 | Wet levelling liquid |
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| CN101787533A (en) * | 2010-03-18 | 2010-07-28 | 重庆大学 | Corrosion inhibitor for engine coolant and preparation method thereof |
| CN101787533B (en) * | 2010-03-18 | 2011-06-15 | 重庆大学 | Corrosion inhibitor for engine coolant and preparation method thereof |
| CN103757641A (en) * | 2014-01-21 | 2014-04-30 | 中国石油大学(华东) | Corrosion inhibition cleanser for sea water desalting plant and application thereof |
| US10988669B2 (en) * | 2014-12-09 | 2021-04-27 | Halliburton Energy Services, Inc. | Use of berberine as corrosion inhibitor in well operations |
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| CN106400033A (en) * | 2016-11-11 | 2017-02-15 | 中北大学 | Sunflower head corrosion inhibitor extract and method for preparing metal acid-pickling solution using the same |
| CN106400033B (en) * | 2016-11-11 | 2019-01-25 | 中北大学 | A kind of sunflower disk corrosion inhibitor extract and method for preparing metal pickling solution |
| CN109023401A (en) * | 2018-09-28 | 2018-12-18 | 深圳市泽成丰新材料有限公司 | A kind of environment-friendly degradable degreasing agent |
| CN113897615A (en) * | 2021-09-30 | 2022-01-07 | 河南省科学院能源研究所有限公司 | A kind of zinc corrosion inhibitor in mixed acid medium |
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| CN100348779C (en) | 2007-11-14 |
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