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Environmental protection oilfield corrosion and scale inhibitors

2016-11-23 22:40:24

    In order to prevent the use of pipelines and equipment corrosion and fouling serious, we must add corrosion inhibitors, to ensure the safe operation of equipment. And these water treatment chemicals will eventually be discharged into the environment as waste. With the increasing awareness of environmental protection, various types of water treatment chemicals have also put forward higher and higher requirements, environmental regulations become increasingly stringent, chromium corrosion inhibitor for environmental reasons its use is limited, phosphorus system formula Phosphorus-containing compounds and easy to nourish bacteria and algae, the water eutrophication, has been limited emissions, "green water treatment agent" concept came into being. Therefore, non-phosphorus non-chromium, the environment-friendly with scale-inhibiting performance of all organic polymers, copolymers and other series of "green" products will become an important direction of water treatment research at home and abroad.

    1 containing phosphine corrosion and scale inhibitors
    1.1 Organophosphonic acid carboxylic acid Organophosphonic acid is a group of molecules containing both carboxyl and phosphonic acid groups of a class of compounds. 2-phosphonic acid butane 1,2,4-tricarboxylic acid (PETCA), developed in the late 1970s, shows excellent corrosion inhibition and scale inhibition properties in all-organic formulations. In recent years, relevant research has been active again. The compound has good chemical stability, good thermal stability and low toxicity (P0i-l1.5%), has good scale inhibition effect on c ~ co3, Ca3 (PO4) 2, CaSO4, Mssio3, etc., Of the organic phosphonate sediment, and zinc salts and other dispersant components synergistic effect, the dosage of 5-15mg · L-1, is a highly efficient corrosion inhibitor [2]. Beijing New Dayu Fine Chemical Company [3] developed BC-605 corrosion and scale inhibitor, the experiment is an excellent performance of water quality stabilizer, its performance has reached the Japanese company KURIZET S-112 and KURIZT S-113 standard, widely used in petrochemical, metallurgical and other circulating water treatment plant.
    1.2 macromolecular amino phosphonic acid 20th century, 90's Calgon pioneered the development of polyaminopolyether methylene phosphonic acid (PAPEMP) (relative average molecular weight of about 600), the introduction of ether bonds in the molecule, more hydrophilic, can at the same time Prevent CaCO3, Ca3 (PO4) 2 scale, with a high calcium tolerance, scale inhibition is better than organic phosphonic acid and polymers, the silicon scale is also very effective, and can well stabilize iron, zinc, manganese Oxide, good corrosion inhibition performance, especially for high concentration multiple run. China has also made breakthrough progress, is embarking on industrialization. ZHANG Jun et al synthesized glycine dimethyldiphosphonic acid (GDMP). The scale inhibition performance of calcium carbonate scale was better than that of ATMP, the corrosion inhibition performance was good, and the synergistic effect was obvious. In addition, research on ethanolamine methylene phosphonic acid, alkanolamide methylene phosphonic acid is also carried out.
    1.3 low-phosphorus polymer Low-phosphorus polymer refers to the molecular structure containing phosphono, carboxyl, sulfonic acid groups and other high-molecular polymer. (PO43- less than 5%), which is a kind of organic phosphonic acid, which has the advantages of strong chelating action of organic phosphonic acid and high dispersibility of polymer, good performance of scale inhibition and corrosion inhibition, stable structure, Toxicity, compatibility with other agents is good. If the amount of 5mg · L-1, the phosphorus content of the system is less than 0.25mg.L-1, may be composed of micro-phosphorus or phosphorus-free water treatment formulations, it has become a hot research and development in recent years at home and abroad.
    1.3.1 Phosphine-based polycarboxylic acid (PCA) is generally divided into two categories: namely phosphine-based polyacrylic acid (phosphine-based PAA) and phosphine-based polymaleic acid (phosphine-based PMA), respectively, Maleic acid (MA) as the basic monomer, with peroxide and sodium hypophosphite (0Z can be regarded as monomer) as initiator, and other monomer copolymer. Nalco company in the late 1970s study found that phosphine PAA with HEDP, zinc salt and a variety of water-soluble polymer composition of the various formulations of the corrosion and scale inhibition effect, there is a clear synergistic effect of phosphine-based PMA in the low Dosage has good scale inhibition and certain corrosion inhibition performance, high tolerance to calcium, high temperature and high pressure stability, inhibition of BaSO4 is better than the former. 80 years of the 20th century, Betz company found that PCA and from a Ⅲ, A (hydroxypropyl acrylate) after the compound to inhibit CaCO Ca3 (1O4) 2 scale and dispersion of iron oxide and slime have synergistic effect. In the 1990s, Mogul found that the phosphine-based PAA had a certain solubility in MgSiO3 scale, making the study re-active. At present, the main products are A-phosphoric acid, AA / HPA / hypophosphorous acid, MA / hypophosphorous acid, MA / AA / hypophosphorous acid, AA / AMPS / AM / hypophosphorous acid, .
    1.3.2 phosphocarboxylic acid polymer (PoCA) is the late 20th century, 90, developed by the FMC macromolecular organophosphorus compounds in the cooling water system can both scale and corrosion inhibition, and chlorine almost no Work, has a high calcium tolerance, is considered a true multi-functional agent, has the following structure: R can be sodium propylene sulfonate, acrylic, ATMS and other monomers. Domestic research on phosphorus-containing polymers began in the late 1980s, Diao Yue-min and other water as the solvent, under the action of the catalyst from the hydrolysis of polymaleic acid, acrylic acid and hypophosphorous acid copolymerization, one-step synthesis of phosphonate MA / AA copolymer (IPPA) AA / HPA terpolymers were synthesized, which had the double effect of scale inhibition and corrosion inhibition. Because the copolymer of sulfonic acid has good inhibition on Ca3 (PO4) 2 scale and organic phosphonic acid scale and can stabilize the metal ions and disperse the particles effectively, it is difficult to gel under the condition of high calcium. Therefore, the recent studies focused on phosphine Sulfonic acid-based multi-functional polymer synthesis. Zhang Yingxiong, etc.] developed a containing sulfonic acid, carboxyl, phosphonic acid and a non-ionic group of multi-copolymer, which can effectively inhibit CaCO3, MgSi03, dispersed iron oxide and zinc salt, alkaline water cycle system; Xiao-ming and other prepared phosphoric acid AMPS copolymer, inhibition of Ca3 (PO4) 2 scale, stable zinc salt and dispersed iron oxide performance is better than HEDP and A AMPS Senru Petroleum.
    1.4 new phosphorus-free corrosion inhibitor 15 mg · L), the presence of a number of sulfonic acid groups to ensure its dispersion performance, greatly improving the organic phosphonic acid deficiencies.
    1.4.1 alkyl epoxy carboxylate (AEC) is Betz developed a new phosphorus-free, nitrogen-resistant corrosion inhibitor, has a high calcium tolerance, high temperature, good resistance to chlorine, Can replace the organic phosphonate corrosion inhibitor. When combined with a small amount of phosphate or zinc salt, the carbon steel has a good corrosion inhibition, which can form a low phosphorus (zinc) formula for high pH, ​​high alkalinity, high hardness and high concentration of cooling Water system, and accepted by the environment. Although these compounds have high activity, toxicity, but not yet have biodegradable properties.
    1.4.2 tungsten stabilizer is developed in recent years, a new non-chromium non-phosphorus corrosion inhibitor, mainly by our research and development, using sodium tungstate and other tungstate inhibitor. Is an anodic passivation inhibitor, it can adsorbed on the metal surface and the formation of non-protective complex of ferrous iron ions. Ferrous iron is dissolved oxidation into ferric iron, so that iron-tungstate complex into ferric tungstate, the formation of passivation on the metal protective film. This membrane is formed on the premise that the presence of dissolved oxygen. Is characterized by pollution-free, corrosion inhibition performance is better than molybdenum and phosphorus, can be run in alkaline, easy to operate. Of carbon steel, copper, copper alloy, aluminum, zinc corrosion inhibition. To prevent chloride corrosion of carbon steel and stainless steel stress corrosion have a better role. East China University of Science and Technology anti-corrosion center Tan Weigang, etc. According to China's rich tungsten resources, reserves, production and export volume of the world's first, from the environmental protection, sustainable development of highly tungsten water treatment agent phosphate, Zinc sulfate, benzotriazole (BTA), polyaspartic acid (PASP), and sodium tungstate complex as a normal operating agent. This is of great significance to reduce corrosion hazard, save water, promote the use of green chemistry technology. 1.4.3 polyaspartic acid J (PASP) is a non-phosphorus, biodegradable good green corrosion inhibitor, it is an amino acid polymer, naturally occurring in mollusks and snails Is a kind of environmentally friendly water treatment agent, is recognized as a green polymer and water treatment agent replacement products. It is a kind of environmentally friendly water treatment agent, is a water-soluble carboxylic acid, Polyaspartic acid is aspartic acid or maleic anhydride as raw materials and synthesis, with biodegradable, high scale and other characteristics. Huo Yu-Ning and other successful synthesis of the relative molecular weight of 40,000 polyaspartic acid, and its performance were studied. It was found that the scale inhibition rate reached 100% when the concentration of the agent was 2.0 mg · L. Polyaspartic acid in the carboxylic acid functional group is the resistance Caco3, CaSO4 scale the main functional groups, and amide on Ca3 (PO4) 2 scale beneficial, so the polyaspartic acid has a good scale and corrosion inhibition. The scale inhibition performance of polyaspartic acid with different molecular weights was different. Liu Guohuan for the first time the combination of tungstate and polyaspartic acid practical formula formulation research and development, treatment formula mainly contains: tungstate, polyaspartic acid (PASP), zinc sulfate, sodium benzoate, sodium gluconate. The results show that the corrosive rate is 0.0124mm · a-1, the corrosion rate is 98.71%, and the corrosion resistance is 98.71%. The fouling rate was 91.67%.
    1.4.4 polyepoxysuccinic acid (PESA) is a non-phosphorus, non-nitrogen, has a good biodegradable activity of green water treatment agent, not only scale dispersion performance, but also has a certain corrosion performance, and Other agents can be combined with better performance of low phosphorus or phosphorus-free formula, suitable for high-alkali high water system. Maleic anhydride as raw material to make alkaline hydrolysis of maleic acid salt, and then sodium tungstate as catalyst in the hydrogen peroxide maleate salt epoxidized into oxygen succinate, and then epoxidized into oxygen Succinic acid methyl esterification or ethyl esterification, in the absence of solvent system or inert system in ring-opening polymerization, and then the hydrolysis of the polymer obtained, that is, polyepoxysuccinic acid. It is also possible to convert a portion of the carboxyl groups of the polyepoxysuccinic acid into a salt form with monovalent or divalent cations or organic amine cations. Epoxy succinic acid on the performance of the experimental study, the results show that the scale inhibition performance of polyepoxysuccinic acid is superior to sodium polyacrylate, polymaleic acid and tartaric acid, and has corrosion inhibition performance. Domestic Xiong Rongchun led the research team led the research work in this area, and made gratifying progress, the synthesis of ideas is very worth learning.
Green is undoubtedly the 21st century development direction of water treatment agent.
    Therefore, the future work should focus on the performance, economic and environmental goals. On the basis of further improving the existing products and improving the quality, we should strengthen the mechanism research and compound research, reduce the cost and reduce the pollution. Accelerate the development of our country's resource advantages. Molybdenum, tungsten water treatment agent in the research and application; in the synthesis of new products, we must break through existing ideas, and actively use green chemistry technology, the first target molecules green, the use of clean technology, synthesis of non-phosphorus, non-nitrogen , Non-toxic substances, easy to biodegradable, the real environment-friendly efficient corrosion inhibitor to completely replace the phosphorus formulations.




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