阅读说明：本技术 一种制氧厂专用可示踪无磷缓蚀阻垢剂 (Traceable phosphorus-free corrosion and scale inhibitor special for oxygen plant ) 是由 庞宏磊 王国瑞 周继柱 冯春晖 孙松厚 马凯 金鑫 张志平 石伟杰 于 2019-09-10 设计创作，主要内容包括：本发明公开了一种制氧厂专用可示踪无磷缓蚀阻垢剂,所述缓蚀阻垢剂由以下质量百分比原料组成：羧基烷基硫代丁二酸10％～40％,磺酸盐共聚物5％～20％,铜缓蚀剂1％～6％,锌盐2％～8％,荧光示踪因子0.5％～2％,去离子水余量；本发明缓蚀阻垢剂专用于制氧厂冷却水系统,因其具有无磷、环保、高效、无毒、可生物降解,可精准控制加药等优点,具有广阔的应用前景。(The invention discloses a traceable phosphorus-free corrosion and scale inhibitor special for an oxygen plant, which comprises the following raw materials in percentage by mass: 10-40% of carboxyalkyl thiosuccinic acid, 5-20% of sulfonate copolymer, 1-6% of copper corrosion inhibitor, 2-8% of zinc salt, 0.5-2% of fluorescent tracing factor and the balance of deionized water; the corrosion and scale inhibitor is specially used for a cooling water system of an oxygen plant, has the advantages of no phosphorus, environmental protection, high efficiency, no toxicity, biodegradability, accurate control of dosing and the like, and has wide application prospect.)

1. The phosphorus-free traceable corrosion and scale inhibitor special for the oxygen plant is characterized by comprising the following raw materials in percentage by mass: 10-40% of carboxyalkyl thiosuccinic acid, 5-20% of sulfonate copolymer, 1-6% of copper corrosion inhibitor, 2-8% of zinc salt, 0.5-2% of fluorescent tracing factor and the balance of deionized water; wherein the carboxyalkyl thiosuccinic acid is carboxymethyl thiosuccinic acid or carboxyethylthiosuccinic acid, and the sulfonate copolymer is any one or a mixture of more of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid-hydroxypropyl acrylate terpolymer, acrylic acid-acrylate-sulfonate copolymer, acryloyl-sulfonic acid-amido copolymer and carboxylate-sulfonate-nonionic copolymer; the fluorescent tracing factor is 1,3,6, 8-pyrenetetrasulfonic acid tetrasodium salt.

2. The phosphorus-free traceable corrosion and scale inhibitor special for the oxygen plant as claimed in claim 1, characterized in that the corrosion and scale inhibitor is composed of the following raw materials by mass percent: 20-30% of carboxyalkyl thiosuccinic acid, 10-15% of sulfonate copolymer, 2-5% of copper corrosion inhibitor, 4-6% of zinc salt, 1-1.5% of fluorescent tracing factor and the balance of deionized water.

3. The phosphorus-free traceable corrosion and scale inhibitor special for the oxygen plant according to claim 1 or 2, which is characterized in that: in the corrosion and scale inhibitor, the mass ratio of the carboxyalkyl sulfosuccinate to the sulfonate copolymer is 1-2: 1.

4. The phosphorus-free traceable corrosion and scale inhibitor special for the oxygen plant according to claim 1 or 2, which is characterized in that: the copper corrosion inhibitor is mercaptobenzothiazole or benzotriazole.

5. The phosphorus-free traceable corrosion and scale inhibitor special for the oxygen plant according to claim 1 or 2, which is characterized in that: the zinc salt is any one of zinc sulfate, zinc chloride and zinc nitrate.

Technical Field

The invention belongs to the technical field of industrial water treatment, and particularly relates to a phosphorus-free traceable corrosion and scale inhibitor special for an oxygen plant.

Background

With the large-scale popularization and application of the molecular sieve of the oxygen generator, the development of the oxygen generation industry is greatly promoted.

The adsorption capacity and the temperature of the molecular sieve are in negative correlation, namely the lower the temperature is, the larger the adsorption capacity is; the higher the temperature, the smaller the adsorption capacity. Therefore, the compressed air needs to be cooled to the lowest possible temperature by the low-temperature cooling water and then enters the adsorber, so that reliable guarantee is provided for achieving the maximum adsorption effect, the switching time can be prolonged, and the switching loss can be reduced.

In order to meet the production requirement of the molecular sieve of the oxygen generator, the temperature of the circulating cooling water is generally not more than 10 ℃. Due to the extremely low water temperature, low temperature fouling occurs in the circulation system. Scales are concentrated on the pipe wall, the spray head and the like, the system pressure is increased by light persons, and the heat exchange efficiency is reduced; the heavy equipment stops to cause production accidents.

The scale body component of the medium-high temperature circulating cooling water system is mainly carbonate insoluble substances, and the scale body of the low-temperature scale is mainly phosphate insoluble substances. In order to inhibit corrosion and scale formation at low temperature, a commonly used method is to add a corrosion and scale inhibitor. At present, the special medicament for the oxygen plant under the low temperature condition is very few, wherein the phosphorus-containing corrosion and scale inhibitor accounts for a large proportion. In the operation process of the system, the continuous addition of the phosphorus-containing medicament enables the content of phosphate radicals to be continuously increased, so that phosphate insoluble substances are continuously precipitated and separated out, and carbonate insoluble substances begin to be separated out due to the coprecipitation effect, and finally scales are formed.

The dosage of the corrosion and scale inhibitor also plays an important role in the scale inhibition performance. If the dosage is insufficient, scale adhesion and metal corrosion can occur; if the dosage is excessive, the medicament is wasted. At present, the medicine adding mode of most domestic manufacturers adopts manual medicine adding and metering pump medicine adding, and the medicine adding amount can not be adjusted in real time according to the actual concentration of the medicine in the water body. The phosphorus-free corrosion and scale inhibitor has a plurality of components, but the content of each component in circulating water is only a few ppm, and the content of the component in water is difficult to rapidly analyze by the conventional method, so that the difficulty is brought to monitoring, and the popularization and application of a phosphorus-free formula are hindered to a certain extent. For example: the Chinese patent application with the application number of 201510231310.9 discloses a special phosphorus-free corrosion and scale inhibitor for an oxygen plant and a preparation method thereof, wherein a fluorescent tracing factor is not added, the content of a medicament cannot be accurately monitored, and the medicament can be accurately added.

Disclosure of Invention

The invention aims to provide a special corrosion and scale inhibitor for a circulating cooling system of an oxygen plant, which has the advantages of no phosphorus, environmental protection, effective inhibition of low-temperature scaling, high corrosion inhibition rate, accurate dosing and the like, and can realize full-automatic dosing by matching with a full-automatic fluorescent tracing dosing device.

Aiming at the purposes, the phosphorus-free traceable corrosion and scale inhibitor special for the oxygen plant is composed of the following raw materials in percentage by mass: 10-40% of carboxyalkyl thiosuccinic acid, 5-20% of sulfonate copolymer, 1-6% of copper corrosion inhibitor, 2-8% of zinc salt, 0.5-2% of fluorescent tracing factor and the balance of deionized water; wherein the carboxyalkyl thiosuccinic acid is carboxymethyl thiosuccinic acid or carboxyethylthiosuccinic acid, and the sulfonate copolymer is any one or a mixture of more of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid-hydroxypropyl acrylate terpolymer, acrylic acid-acrylate-sulfonate copolymer, acryloyl-sulfonic acid-amido copolymer and carboxylate-sulfonate-nonionic copolymer; the fluorescent tracing factor is 1,3,6, 8-pyrenetetrasulfonic acid tetrasodium salt.

The corrosion and scale inhibitor of the invention is preferably prepared from the following raw materials in percentage by mass: 20-30% of carboxyalkyl thiosuccinic acid, 10-15% of sulfonate copolymer, 2-5% of copper corrosion inhibitor, 4-6% of zinc salt, 1-1.5% of fluorescent tracing factor and the balance of deionized water.

In the corrosion and scale inhibitor, the mass ratio of the carboxyalkyl sulfosuccinate to the sulfonate copolymer is preferably 1-2: 1.

The copper corrosion inhibitor is mercaptobenzothiazole or benzotriazole.

The zinc salt is any one of zinc sulfate, zinc chloride and zinc nitrate.

The preparation method of the special phosphorus-free traceable corrosion and scale inhibitor for the oxygen plant comprises the following steps: adding deionized water into a stirring kettle, heating to 80-100 ℃, sequentially adding a copper corrosion inhibitor, zinc salt and a fluorescent tracing factor, starting a stirrer to stir for 60-100 r/min until the materials are completely dissolved, cooling to normal temperature, adding carboxyalkyl sulfosuccinate and a sulfonate copolymer, stirring for 30min at normal temperature, and subpackaging to obtain the special corrosion and scale inhibitor product for the oxygen plant.

The corrosion and scale inhibitor is added in an amount of 10-50 mg/L, the pH value application range is 5-9, the temperature application range is 0-100 ℃, the preferable addition amount is 20-30 mg/L, the pH value application range is 6-8, and the temperature application range is 5-80 ℃.

The invention has the following beneficial effects:

1. The corrosion and scale inhibitor is specially used for a cooling circulating water system of an oxygen plant, and can effectively inhibit low-temperature scaling.

2. The corrosion and scale inhibitor does not contain phosphorus, is not limited in discharge and cannot cause water eutrophication. The phosphate radical can not be decomposed into phosphate radical in water, the content of the phosphate radical in the system can not be increased after the phosphate radical is added, and the calcium phosphate can not be precipitated and scaled at low temperature.

3. The corrosion and scale inhibitor takes carboxyalkyl sulfosuccinic acid as a main agent, has particularly excellent biodegradability in similar products, has good chelating and dispersing effects on various metal ions due to a plurality of carboxyl groups in the molecules, and can effectively prevent dirt from depositing. Meanwhile, the molecules of the carboxyalkyl thiosuccinic acid contain sulfur and oxygen atoms, which can provide lone pair electrons, so that the carboxyalkyl thiosuccinic acid can be tightly adsorbed on the surface of metal, and the metal corrosion is effectively prevented. In addition, the excellent corrosion inhibition performance reduces the addition of zinc salt and reduces the pollution to the water quality of the system caused by the introduction of heavy metal ions.

4. The corrosion and scale inhibitor takes the sulfonate copolymer as an auxiliary scale inhibitor component, and the sulfonic group is an effective group for inhibiting calcium phosphate scale, and has good effects on stabilizing zinc salt and dispersing ferric oxide. In addition, the sulfonate copolymer is not influenced by metal ions in water, has strong inhibiting effect on calcium carbonate, calcium sulfate, magnesium carbonate and other scales, especially calcium phosphate scales, is compounded with the carboxyalkyl thiosuccinic acid for use, has good compatibility, and can greatly reduce the dosage of the medicament.

5. The fluorescent tracing factor added in the corrosion and scale inhibitor has a special molecular structure, has the advantages of high fluorescence efficiency, good compatibility with medicaments, good stability and the like, can detect the fluorescence value of water in a system through a fluorescent tracer, detect the concentration of the corrosion and scale inhibitor, and further control the medicament content in the water through manual regulation and dosing pump; also can connect the automatic reagent feeding system, carry out the PID operation with the medicament concentration that detects with the settlement concentration to carry out flow control to the dosing pump through control system with operation result real-time output to control system, thereby accomplish automatic analysis, automatic reagent feeding, accurate medicine feeding.

Detailed Description

The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.

The acrylic acid-2-acrylamido-2-methylpropanesulfonic acid (AA/AMPS) copolymer used in the following examples was supplied by Shandong Tai and Water treatment science and technology Co., Ltd and has the following structural formula:

Acrylic acid-2-acrylamide-2-methylpropanesulfonic acid-hydroxypropyl acrylate (AA/AMPS/HPA) terpolymer is provided by Shandongtai and Water treatment science and technology Co., Ltd and has the following structural formula:

Both the acrylic acid-acrylate-sulfonate copolymer TH-613 and the carboxylate-sulfonate-nonionic terpolymer TH-3100 are available from Shandong Tai and Water treatment science, Inc.