Organic steam cleaning stabilizer for boiler water treatment and its preparation method and apparatus

Abstract

This invention discloses an organic steam cleaning stabilizer for boiler water treatment, characterized by comprising the following components by weight percentage: chelated organic matter 0.5%–5.0%, passivating reducing agent 0.5%–5.0%, surfactant 0.0%–1.0%, short-chain and long-chain film-forming adsorbents totaling 0.5%–5.0%, volatile steam pH stabilizer 5.0%–25.0%, high-molecular-weight organophosphorus salts 0.5%–5.0%, with the remainder being deionized water. This invention also discloses a method and apparatus for preparing the organic steam cleaning stabilizer for boiler water treatment. The advantages of this organic steam cleaning stabilizer for boiler water treatment are: it can significantly reduce the conductivity of boiler water, resulting in higher protection performance of thermal equipment; it can significantly reduce boiler blowdown, reduce heat loss and water waste, and help improve boiler thermal energy utilization.

Description

Technical Field

[0001] This invention belongs to the field of boiler water treatment agents, specifically relating to an organic steam cleaning stabilizer for boiler water treatment and its preparation method and apparatus. Background Technology

[0002] Boiler systems, as the core power source and thermal equipment for industrial production, are crucial for the safe and stable operation of enterprises. Boiler malfunctions can lead to a complete shutdown of the enterprise, causing safety accidents, significant economic losses, and severely impacting production stability. For a long time, many enterprises have lacked effective protection for the internal components of boiler steam pipes, and have lacked effective measures for corrosion prevention and scale removal. This has resulted in frequent corrosion and scaling problems in boiler systems, including water-cooled walls, superheaters, and reheaters, and even frequent tube ruptures.

[0003] Traditional boilers employ simple in-boiler treatment processes such as adding ammonia to feedwater and phosphate to boiler water. These methods offer limited steam protection and fail to effectively protect steam pipes. Furthermore, the introduced trisodium phosphate easily causes crystallization in the steam pipes, and the introduced ammonia tends to accumulate locally, leading to pipe corrosion. Moreover, traditional boiler water treatment processes require inspection of steam pipes during boiler shutdown and maintenance periods. Chemical cleaning is used for scaled steam pipes, and pipe replacement is necessary for severely corroded pipes. These traditional methods are reactive and fail to provide timely and effective protection for steam pipes.

[0004] The prior art, document CN118908428A, discloses a tank cleaning agent with anti-scaling and steam purification functions and its preparation method. This technical solution comprises the following components by weight: 20-40 parts of a self-made scale inhibitor, 3-5 parts of a penetrant, 20-30 parts of a dispersant, 1-5 parts of an oxygen scavenger, 0.003-0.017 parts of a catalyst, and 100-150 parts of water. The shortcomings of this technical solution are:

[0005] The technical solution utilizes the benzene ring structure in the scale inhibitor to enhance the molecular structure stability through synergistic hydrogen bonding. However, such molecular structure stability is only applicable to low and medium pressure boilers (below 5.3 MPa). Under high pressure (5.3–13.7 MPa), it is prone to decomposition reaction, so it is difficult to use in high pressure boilers and its application range is relatively limited.

[0006] Based on this, the applicant considers designing an organic steam cleaning stabilizer for boiler water treatment with better applicability under multiple pressure environments, as well as its preparation method and apparatus. Summary of the Invention

[0007] In view of the shortcomings of the prior art, the technical problem to be solved by the present invention is: how to provide an organic steam cleaning stabilizer for boiler water treatment with better applicability under multiple pressure environments, as well as its preparation method and apparatus.

[0008] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0009] An organic steam cleaning stabilizer for boiler water treatment is characterized by comprising the following components in the indicated weight percentages: chelated organic matter 0.5%–5.0%, passivating reducing agent 0.5%–5.0%, surfactant 0.0%–1.0%, short-chain film-forming adsorbent and long-chain film-forming adsorbent together accounting for 0.5%–5.0%, volatile steam pH stabilizer 5.0%–25.0%, high molecular weight organophosphorus salts 0.5%–5.0%, with the remainder being deionized water.

[0010] Compared with the prior art, the advantages of the organic steam cleaning stabilizer for boiler water treatment of the present invention are:

[0011] This invention provides an organic steam cleaning stabilizer for boiler water treatment that remains stable under pressures ranging from atmospheric to subcritical (the agent does not decompose or undergo side reactions under any pressure). Therefore, it is suitable for medium-pressure (2.5–5.3 MPa), high-pressure (5.3–13.7 MPa), ultra-high-pressure (13.7–16.7 MPa), and subcritical (16.7–22.1 MPa) boiler systems. This organic steam cleaning stabilizer for boiler water treatment can more effectively protect boiler steam piping systems, reduce scaling and corrosion, clean various types of scale, prevent corrosion and scaling problems, significantly reduce the risk of boiler tube rupture, and improve the operational safety and stability of the boiler system, as well as the timeliness and effectiveness of boiler system protection.

[0012] The mechanism by which the organic steam cleaning stabilizer for boiler water treatment of this invention achieves the above functions is as follows:

[0013] Chelated organic matter: It chelates hard scale such as calcium, magnesium, iron, copper, and silicon in steam pipes, causing the scale layer in the steam pipes to gradually decrease and fall off. The dissolved hard scale is then discharged from the steam pipes through steam flushing.

[0014] Passivating reducing agent: This agent promotes metal passivation and reduces metal oxides. It can be at least one of N-isopropylhydroxylamine (C3H9ON) (which does not easily decompose under various pressure conditions) or ethylidene hydroxylamine (C2H5NO) (which remains effective under high temperature and pressure). It can promptly remove various rust and copper rust from steam pipes (it has a certain complexing effect on corrosion products such as iron and copper ions), promote the formation of a passivation film (passivating the metal surface and inhibiting corrosion), and provide long-lasting and effective protection for steam pipes. The chemical formula for the reaction is:

[0015] 2CH3-CH=N-OH+O2→2CH3-CH=O+N2O+H2O (Dissolved oxygen in water intensifies the electrochemical corrosion reaction; here, a chemical deoxygenation treatment effect can be achieved, slowing down or preventing the occurrence of the electrochemical corrosion reaction.)

[0016] 2CH3-CH=N-OH + 3Fe2O3 → CH3-CH=O + N2 + 2Fe3O4 (Forms a durable metal passivation film: Fe3O4 crystals have high hardness, and their microscopic state (observed at the 100nm level by scanning electron microscopy (SEM)) has sharp protrusions that can better abrade and break down hard scale; at the same time, Fe3O4 crystals are easily magnetized and become magnetic, which can better adsorb onto the pipe wall, forming a stable and durable protective film)

[0017] Surfactants are amphiphilic: one end is a hydrophilic polar group (hydrophilic group), also known as an oleophobic group, such as -COOH, -SO3H, -NH2, etc. The other end is a lipophilic nonpolar group, simply called a lipophilic group, also known as a hydrophobic group, such as R- (alkyl) and Ar- (aryl). These two types of molecular groups with diametrically opposed structures and properties are located at opposite ends of the same molecule and connected by chemical bonds, forming an asymmetric, polar structure. This endows such special molecules with the property of being both hydrophilic and lipophilic, but not entirely hydrophilic or lipophilic. This technical solution utilizes the dual properties of surfactants to disrupt the surface tension of soft organic scale, dissolving and removing soft organic scale from steam pipes. The organic scale gradually dissolves and detaches, and the dissolved soft organic scale is then discharged from the steam pipes through steam flushing. The surfactant may be at least one of the following: polyvinyl alcohol (e.g., octadecylamine polyoxyethylene ether), fatty alcohol polyoxyethylene ether (e.g., dodecyl polyoxyethylene ether), polyether amine (e.g., polyethylene glycol diamine), sodium alkylbenzene sulfonate (e.g., sodium dodecylbenzene sulfonate), fatty acid salt (e.g., sodium stearate), quaternary ammonium salt (e.g., hexadecyltrimethylammonium chloride), or acetylhydroxylamine (e.g., acetylhydroxamic acid).

[0018] Short-chain and long-chain film-forming adsorbents work together in two ways: Short-chain amines adsorb first, quickly occupying sites on the metal surface and providing initial rapid protection (forming a basic protective film within 10-30 minutes). Long-chain amines then align under the guidance of the short-chain amines, forming a denser and more durable bilayer film (long-chain molecules have stronger van der Waals forces at the interface, making them less susceptible to water erosion or dissolution by the medium, extending the film lifespan from 1-3 days for a single short-chain amine to 7-15 days). The small size of short-chain amine molecules allows them to fill the "gaps" (microscopic gaps (width <100nm) or narrow channels (such as the gaps between heat exchanger tubes) in the long-chain amine film. The hydrophobic tails of the long-chain amines are arranged on the outer layer, enhancing the overall hydrophobicity and barrier properties of the film. The better dispersibility of short-chain amines improves the dispersibility and uniformity of long-chain amines, ensuring uniform film formation. Short-chain amines are highly volatile and can enter the steam condensation system to protect the piping network; long-chain amines mainly remain on the boiler water and heated surfaces, providing stable corrosion protection at high temperatures. The combined use of short-chain and long-chain film-forming adsorbents with chelating agents (for scale prevention) can reduce secondary deposition of metal ions and synergistically enhance scale prevention. Simultaneously, the proportions can be easily adjusted (e.g., 60%-70% short-chain film-forming adsorbent for low-temperature (below 50℃) scenarios, and 60%-70% long-chain film-forming adsorbent for high-temperature (80-150℃) scenarios), allowing for wide-range application from 0-150℃, covering all scenarios from ambient temperature circulating water to medium- and high-temperature boiler water. This eliminates the need for frequent reagent changes based on temperature, enabling more flexible and customized production, better meeting actual user needs while reducing operation and maintenance costs. As shown above, short-chain adsorbents can act as "gap fillers," while long-chain adsorbents can act as "surface reinforcers." When the two are combined in a 3:7-5:5 ratio, the total dosage can be reduced by 20%-30% (compared to single-agent formulations) while achieving better results. Simultaneously, the strong hydrophobicity of long-chain molecules reduces the amount of subsequent scale inhibitors and corrosion inhibitors required, and the biodegradability of amine derivatives (especially long-chain aliphatic amines) is superior to traditional chemical corrosion inhibitors, reducing environmental emissions. Therefore, the combined formulation of short-chain and long-chain film-forming adsorbents demonstrates significant effectiveness, ensuring uniform distribution of the adsorbent throughout the boiler steam system. The film-forming adsorbent produces a dense adsorption film on the metal surface. This film effectively isolates dissolved oxygen, CO2, and other gases in the steam, preventing reactions between the metal and oxides and significantly reducing the corrosion rate of steam pipelines. The film-forming adsorbent adheres to the inner wall of the steam pipe, and the scale-forming groups do not easily adhere to the metal surface and gradually fall off, effectively preventing scale from accumulating in the steam pipe and improving the heating efficiency of the steam pipeline (ensuring that the heat exchange zone in the boiler system can exchange heat for a long time and efficiently, and reducing energy consumption).

[0019] Volatile steam pH stabilizer: This agent is weakly alkaline, which can make the medium-term steam pipeline and steam condensate slightly alkaline. In a slightly alkaline environment, the metal corrosion rate is significantly reduced, thus effectively reducing the risk of steam pipeline corrosion and protecting the steam pipeline and steam condensate system.

[0020] High-molecular-weight organophosphonic salts mainly contain functional groups such as phosphonite esters RP(=O)(OH)2, phosphonite esters RP(=O)(OH)R, phosphate esters ROP(=O)(OH)2, and phosphate diesters HOPO(OR)2 (e.g., polyamino-polyether methylenephosphonic acid, hydroxyethylidene diphosphonic acid, etc.). These high-molecular-weight organophosphonic salts can form stable complexes with various metal ions such as iron, copper, and zinc, and can dissolve oxides on metal surfaces. They also exhibit excellent scale inhibition, dispersion, and corrosion inhibition properties, effectively protecting boiler economizers, water-cooled walls, and other boiler water systems, maintaining the stability of boiler water parameters. Furthermore, these high-molecular-weight organophosphonic salts can chelate with multiple metal ions to form multiple monomeric macromolecular network complexes, loosely dispersed in water, thus disrupting the normal crystallization of calcium and magnesium scale, significantly reducing boiler blowdown volume, minimizing blowdown, and improving boiler thermal efficiency.

[0021] Furthermore, the chelated organic matter contains at least one of the chelated chemical functional groups R-COOH or R-COONa.

[0022] R-COOH (carboxyl group) is a weak acidic group that can ionize to release H+ to form -COO. - (Carboxyl anion); R-COONa (sodium carboxylate) is the sodium salt of the carboxyl group, which directly dissociates into -COO in water or polar environments. - and Na + -COO - The oxygen atom in it has a lone pair of electrons, which can react with metal ions (such as Ca). 2+ Mg 2+ Fe 3+ Zn 2+ Cu 2+ (e.g., citric acid, EDTA, humic acid, etc.) form coordinate bonds; if an organic molecule contains multiple carboxyl groups (e.g., citric acid, EDTA, humic acid, etc.), multiple -COO groups form coordinate bonds. - It can form a "ring structure" (chelate ring) around metal ions. The "ring structure" (chelate ring) is more stable than ordinary ionic bonds and forms soluble chelates, avoiding its reaction with carbonate and bicarbonate ions in hard water to form scale. Therefore, the scale removal effect is more significant.

[0023] In addition to chelating metal ions, these organic substances can also act as dispersants: -COO -Carboxyl anions carry a negative charge. When they adsorb onto the surface of tiny impurity particles (such as iron oxide and silicates) in water, they cause these particles to acquire a negative charge. Because like charges repel each other, these small particles do not aggregate to form large precipitates, but are instead evenly dispersed in the water. Through this dispersion, suspended solids that might otherwise precipitate are stably dispersed in the boiler water and can be effectively removed through blowdown, preventing them from depositing on the pipe walls to form new deposits or scale.

[0024] In addition, carboxylate groups can sometimes react with metal surfaces (such as iron) to form a dense passivation film. This film is more stable than ordinary rust and can effectively prevent further corrosion.

[0025] The R–COOH and R–COONa functional groups in organic matter are mostly biodegradable structures (such as sodium polyacrylate or polyaspartic acid), which are more environmentally friendly than phosphonates or chromium salts.

[0026] In summary, chelating organic matter containing -COOH or -COONa groups plays a role in boiler water treatment by controlling scale-forming ions and suspended solids in the water through chelation and dispersion, thereby achieving the goals of preventing scaling, cleaning old scale, maintaining heat transfer efficiency, and stabilizing water quality.

[0027] Furthermore, the chelating organic matter is one or more of the following: sodium diacetate (NTA), ethylenediaminetetraacetic acid (EDTA), aminocarboxylic acid, 1,3-dione, hydroxycarboxylic acid, diethylenetriaminepentaacetic acid (DTPA), sodium polyacrylate, or polyaspartic acid.

[0028] The above chelated organic matter is classified according to its function as follows:

[0029] Strong chelation and descaling agents: EDTA, DTPA, tetrasodium amino acid diacetate (NTA), aminocarboxylic acid, 1,3-dione, hydroxycarboxylic acid;

[0030] Dispersion and scale inhibition framework: Sodium polyacrylate (PAA-Na), polyaspartic acid (PASP);

[0031] Gentle cleansing: hydroxycarboxylic acids (such as citric acid), 1,3-diones (targeting transition metals), and some aminocarboxylic acids.

[0032] The following combination of components is preferred:

[0033] 1. Mix (EDTA or DTPA) and (hydroxycarboxylic acid or NTA) in a weight ratio of 1:(1.5-3). In this way, when used, hydroxycarboxylic acid or NTA will "pry" the metal ions in the scale or deposit into a migratory complex, so that cleaning can be completed with a low conductivity increase. Then, EDTA or DTPA will firmly chelate and remove them, avoiding secondary deposition.

[0034] 2. 1,3-Diketone is mixed with (EDTA or DTPA) at a weight ratio of (0.5-1):(0.5-3). This ensures that, during use, 1,3-Diketone preferentially coordinates with Fe. 3+ or Cu 2+ Transition metals are introduced to inhibit their catalytic oxidation; then, EDTA or DTPA is used for long-term stabilization to prevent them from entering the steam system. This significantly reduces the corrosion rate of brass and carbon steel systems in the condenser; lowers the copper or iron content in the steam, and improves steam quality.

[0035] 3. DTPA is mixed with 1,3-diones and hydroxycarboxylic acids in a weight ratio of (0.5-1):(0.5-1):(2-4). This results in a broad-spectrum chelating effect during use, utilizing DTPA's ability to chelate Fe... 3+ Al 3+ and Mn 2+ ; utilizing the preferential coordination of 1,3-diketone with Fe 3+ or Cu 2+ Transition metals are inhibited from catalytic oxidation, preventing them from forming copper scale or catalytic corrosion with other ions. Hydroxycarboxylic acids assist in dispersion and corrosion inhibition, effectively preventing DTPA from failing due to decreased adsorption capacity after chelating multiple metal ions, thus ensuring a long-lasting chelation effect. Therefore, this formulation achieves "multiple metal ion control," effectively preventing the formation of manganese dioxide and copper scale, and slowing down copper-carbon steel galvanic corrosion, reducing the risk of boiler pipe blockage by more than 60% and effectively extending the service life of the pipes.

[0036] Furthermore, the short-chain film-forming adsorbent is a short-chain aliphatic alkylamine derivative having at least one amine group and composed of C3 to C6.

[0037] Chelated organic matter is used to prevent scaling; short-chain film-forming adsorbents can form a protective film on the metal surface, blocking oxygen and corrosion ions from contacting the metal; the combination of the two can achieve an integrated boiler water treatment effect of "cleaning + scale prevention + corrosion inhibition".

[0038] C3-C6 short-chain amines (such as propylamine, butylamine, and hexylamine derivatives) have small molecules and short chains, are inexpensive to produce, and have simple synthetic routes. They are easier to dissolve and disperse than long-chain organic amines, have less steric hindrance, and can quickly penetrate into tiny gaps on metal surfaces (such as pipe scratches), effectively preventing crevice corrosion. The protective film formed can be repeatedly repaired (when part of the film is damaged, amine molecules in the solution can be adsorbed and covered again).

[0039] At the same time, short-chain film-forming adsorbents are also highly volatile, and can flow with the steam in the boiler and effectively protect the entire system (including steam pipelines and condensate return water pipelines), better achieving corrosion protection of the entire boiler system, especially effectively preventing acid corrosion of condensate water pipelines.

[0040] Furthermore, the short-chain film-forming adsorbent is n-butylamine (CH3—CH2—CH2—NH 2） Or at least one of diethylhydroxylamine (DEHA,(C2H5)2NOH).

[0041] n-Butylamine, a weak base, has a polar hydrophilic amine group at one end of its molecule, allowing it to firmly adsorb onto metal surfaces. The butyl group at the other end is a hydrophobic organic long chain. This structure enables it to align directionally at the metal interface, forming a monomolecular hydrophobic protective film. Simultaneously, n-Butylamine neutralizes acidic substances such as dissolved CO2 and CO3 in the boiler water, maintaining a slightly alkaline environment that protects the metal and stabilizes the boiler water quality. Furthermore, its small molecular size and good solubility allow it to penetrate the micropores or oxide layer gaps on the metal surface, forming a denser protective film and preventing crevice corrosion (a high-frequency risk of boiler water corrosion).

[0042] At boiler operating temperatures, diethylhydroxylamine (DEHA) rapidly reacts with dissolved oxygen in the water, reducing it back to water and thus completely removing dissolved oxygen from boiler feedwater and boiler water, fundamentally preventing oxygen corrosion. It also forms a magnetic iron oxide protective film (Fe3O4) on the metal surface. This protective film has high density and stability, effectively passivating the metal surface and providing a long-term physical barrier for boiler pipes, preventing corrosion. Furthermore, the hydroxylamine group (-NOH) of diethylhydroxylamine is more polar, resulting in slightly better film adhesion than n-butylamine, and the film is more stable at high temperatures (100-300℃ boiler operating conditions) and less prone to erosion by water flow.

[0043] Furthermore, the long-chain film-forming adsorbent has at least one amine group and is composed of C 16 ~C 24 Composed of long-chain fatty alkylamine derivatives.

[0044] Compared to short-chain amines, long-chain film-forming adsorbents are characterized by a molecular structure with one end being hydrophilic / reactive (amine group) and the other end being strongly hydrophobic (C). 16 ~C 24 Because of its long carbon chain, a tough and durable monomolecular superhydrophobic protective film will form on the metal surface (the metal surface of the boiler body (economizer, boiler tube, steam drum)). This film can significantly reduce the contact between the metal surface and boiler water, oxygen or impurities, effectively preventing corrosion and scale.

[0045] Long-chain film-forming adsorbents possess significant adsorption and hydrophobic properties due to their long-chain alkyl groups. They form an extremely dense, durable, and superhydrophobic monomolecular physical barrier on the metal surface, thereby absolutely isolating water vapor and corrosive media from contact with the metal and achieving long-term corrosion protection.

[0046] Furthermore, the long-chain film-forming adsorbent is N-oleo-1,3-propanediamine (C 21 H 44 N2), bis(2-hydroxyethoxy)oleamide (C 22 H 45 At least one of NO2).

[0047] N-Oleyl-1,3-Propylene Diamine (C 21 H 44 The N2 molecule contains two amine groups, which have strong interactions with metal surfaces. It can be firmly adsorbed through electrostatic and coordination interactions, and can form a uniform hydrophobic layer on the metal surface, effectively isolating dissolved oxygen and corrosive ions (chloride ions and sulfate ions). The adsorption rate is relatively fast, the film-forming ability is strong, and it is resistant to high temperature and high pressure erosion.

[0048] Bis(2-hydroxyethoxy)oleamide contains hydroxyethoxy groups, and its molecules have a better balance between hydrophilicity and hydrophobicity. It has better dispersion performance in water than pure amines, and it is easier to distribute evenly and cover metal surfaces. The film layer has both hydrogen bond stabilization and hydrophobic protection, which enhances the passivation film.

[0049] Furthermore, the volatile vapor pH stabilizer is cyclohexylamine (C6H4O2). 13 N) or diethylamine (C4H) 11 At least one of N).

[0050] The following combination of components is preferred:

[0051] 1. Diethylamine ring and hexylamine are mixed in a weight ratio of (6-8):(2-4) to achieve rapid adsorption and film formation.

[0052] 2. The weight ratio of diethylamine ring to hexylamine is (2-4):(6-8) to achieve more stable adsorption, denser film, and better high temperature and erosion resistance.

[0053] A method for preparing an organic steam cleaning stabilizer for boiler water treatment, characterized by comprising the following steps:

[0054] Step 1: Preparation of deionized water: Deoxygenate the deionized water and keep the temperature of the deoxygenated deionized water between 50℃ and 80℃.

[0055] Step 2: Preparation of mixed emulsion A1: Short-chain film-forming adsorbent and long-chain film-forming adsorbent are emulsified in a high-temperature and high-pressure emulsification reactor at 200℃~250℃ and 0.5–1.0MPa by adding 7 to 10 times the total weight of deionized water of the short-chain film-forming adsorbent and long-chain film-forming adsorbent to ensure that the short-chain film-forming adsorbent and long-chain film-forming adsorbent are fully mixed and emulsified into a uniform small-particle gel liquid, and mixed emulsion A1 is obtained.

[0056] Step 3: Preparation of Mixture B2: Mix the passivating reducing agent, surfactant, chelating organic matter and high molecular weight organophosphorus salt, and add 10 to 15 times the weight of the mixture of deionized water for thorough mixing to obtain Mixture B2.

[0057] Step 4: Mixing A1 and B2: In a rotary reactor, turn on the stirrer, then pour the mixed emulsion A1 into the rotary reactor in a clockwise direction around the outer ring and the mixed solution B2 into the rotary reactor in a counterclockwise direction around the inner ring to carry out the mixing reaction; maintain the temperature at 50°C to 80°C and continue the reaction for at least 60 minutes.

[0058] Step 5: Cooling and stirring: After the above reaction is complete, cool the solution in the rotary reactor to below 30°C, then start injecting the volatile vapor pH stabilizer and the remaining deionized water, and then turn on the stirrer to stir evenly.

[0059] During implementation, regarding the first step, preparation of deionized water: Deionized water is prepared through a two-stage reverse osmosis system to ensure that the quality of the deionized water meets the requirements for boiler feedwater regulation; high-temperature and high-pressure steam (2.5MPa / 250℃ or higher quality) is used to thermally heat and deoxygenate the deionized water.

[0060] When implementing this procedure, in step five, turn on the mixer and stir for at least 15 minutes.

[0061] The advantages of the preparation method of the organic steam cleaning stabilizer for boiler water treatment of the present invention are:

[0062] The first and second steps (preparation of emulsion A1) involve emulsification in a high-temperature, high-pressure emulsification reactor. This ensures that the short-chain and long-chain film-forming adsorbents are fully mixed and form a uniform small-particle gel liquid, thereby improving its dispersibility and stability in water. This helps to form a uniform film layer in water, effectively protecting the internal surfaces of the boiler.

[0063] In the third step (preparation of mixture B2), the passivating reducing agent, surfactant, and chelating agent are thoroughly mixed and then efficiently mixed with deionized water.

[0064] In the fourth step, the rotary reactor uses counter-current stirring between the inner and outer rings to inject the mixed emulsion A1 and mixture B2 into the reactor in a specific sequence for mixing and reaction. The counter-current injection design serves two main purposes: 1. Improving reaction uniformity and efficiency: Counter-current stirring between the outer and inner rings ensures sufficient contact and mixing of the emulsion and mixture, maximizing reaction efficiency and preventing component aggregation or uneven reaction. 2. Controlling the reaction sequence and rate: Injecting emulsion A1 first ensures uniform dispersion of the film-forming adsorbent. Then, mixing B2 (containing passivating agents, surfactants, chelating agents, etc.) is added, ensuring sufficient reaction time between these active ingredients and the uniformly dispersed film-forming adsorbent, thereby achieving a synergistic effect of multiple functions.

[0065] The fifth step involves cooling the mixture to below 30°C after the reaction is complete, adding a volatile vapor pH stabilizer, and then further stirring to ensure the stability and effectiveness of the final product. At this point, the addition of the volatile vapor pH stabilizer neutralizes acidic substances and stabilizes the pH of the reaction solution, providing better stability for boiler water treatment.

[0066] In summary, the organic steam cleaning stabilizer for boiler water treatment prepared by the above methods has reliable and stable quality, can effectively improve the scaling problem of steam pipelines, clean various types of scale inside steam pipelines, and achieves good corrosion inhibition through the synergistic effect of multiple components, thus establishing a more comprehensive safety protection system inside steam pipelines.

[0067] An apparatus for preparing an organic steam cleaning stabilizer for boiler water treatment includes three reactors fixedly arranged at close intervals. One reactor is an emulsification reactor for preparing mixed emulsion A1, another reactor is a second reactor for preparing mixed emulsion B2, and the last reactor is a rotary reactor for completing the fourth and fifth steps.

[0068] The purpose of the three reaction vessels in the preparation apparatus for the organic steam cleaning stabilizer for boiler water treatment in this invention is as follows:

[0069] 1. Emulsification reactor (for preparing mixed emulsion A1): Used to emulsify short-chain and long-chain film-forming adsorbents with deionized water under high temperature and pressure; this allows the film-forming agent to form a stable small-particle colloidal dispersion system, improving its dispersibility and adsorption in water. Direct emulsification with other components will cause mutual interference, leading to incomplete emulsification or unstable colloids.

[0070] 2. Second Reactor (Preparation of Mixture B2): Used for dissolving and uniformly mixing passivating reducing agents, chelating agents, surfactants, and organophosphorus salts; forming a chemically uniform cleaning-passivation functional liquid. If directly mixed with emulsion A1, the film-forming effect may be affected due to interference from chelating agents and surfactants on the colloid.

[0071] 3. Rotary Reactor (Final Synthesis Reaction): Responsible for injecting mixed emulsion A1 and mixed emulsion B2 sequentially and through different flow fields (inner and outer rings), and controlling temperature, stirring, and cooling; completing the synergistic combination of the film-forming system and the cleaning-passivation system, and then uniformly adjusting the pH value for stability after cooling. This avoids the side reactions and instabilities that occurred during the previous separate processing, ensuring the multifunctionality and long-term stability of the final product.

[0072] The advantages of the apparatus for preparing the organic steam cleaning stabilizer for boiler water treatment according to the present invention are:

[0073] 1. Modularization of functions to complete each step: The mixed emulsion A1 is processed in a separate reactor, which can fully form nano- and micron-sized dispersed particles; this ensures a more uniform and denser protective film on the boiler metal surface, enhancing the stability of the formulation components. Chelating agents, surfactants, and phosphonates, if in contact with the film-forming agent in advance, may alter the structure of the emulsion colloid; by separately preparing the pre-mixed solution B2, premature failure or precipitation can be avoided, improving the emulsification effect and film formation quality.

[0074] 2. High flexibility and controllability: After the three reactors are divided into three parts, the temperature, pressure and stirring method can be adjusted separately for different formula requirements; the process parameters are easier to optimize and adjust, and the formula can be adjusted according to the actual needs of different users, which can also improve the consistency and reproducibility (formula stability) of the initial product.

[0075] 3. Improve the overall performance of the final product: Mixed emulsion A1 is responsible for film formation and protection, while mixed emulsion B2 is responsible for cleaning, passivation and chelation. The rotary reactor achieves synergistic fusion. The final stabilizer has multiple effects such as cleaning, scale prevention, corrosion inhibition, film formation and protection and pH stabilization.

[0076] 4. Industrial-scale safety and scalable production capacity: Three reactors can operate in parallel, increasing output; separating processes reduces the complexity of a single reactor and facilitates monitoring and safety management. It avoids interference between processing steps (film-forming agent emulsification, chelating agent dissolution, and the final reaction are three different mechanisms; if carried out together, they will affect the efficacy of the final product; separate reactors ensure that each step is carried out under optimal process conditions, avoiding mutual interference), while also improving the synchronicity of the second and third steps and better ensuring the timely implementation of the fourth and fifth steps.

[0077] During implementation, the stirring blades inside the rotary reactor are arranged in at least two sets at intervals in the height direction. Each blade is a long strip-shaped plate structure that extends radially and is inclined along the rotary reactor, which is used to generate a composite flow field of radial and axial directions to achieve a uniform stirring effect.

[0078] The rotary reactor is fixedly provided with a conveying pipe for conveying mixed emulsion A1 and equipped with a control valve. The conveying pipe for A1 is tangentially connected to the rotary reactor, and the liquid output through the conveying pipe for A1 can be injected into the reactor from the outer periphery of the rotary reactor in a clockwise direction.

[0079] The rotary reactor is also fixedly provided with a B2 delivery pipe for conveying the mixture B2 and equipped with a control valve. The B2 delivery pipe is located in the space between two adjacent sets of stirring blades in the height direction. The end of the pipe section inside the rotary reactor is an arc-shaped nozzle near the blade axis, so that the mixture B2 output from the end of the B2 delivery pipe can be injected into the reactor counterclockwise from the inner circumferential area near the blade axis.

[0080] The advantages of the above structure are:

[0081] 1. The stirring blades are arranged in layers at intervals along the height of the rotary reactor, ensuring thorough mixing of liquids at different heights, preventing stratification, guaranteeing consistent reaction throughout the large-volume reactor, and improving mixing uniformity. The outer and inner circumferences of the rotary reactor are separately injected with mixed emulsion A1 and mixed liquid B2, allowing them to gradually mix in the stirring area, avoiding instantaneous reaction at the pipe inlet, thus preventing localized high-concentration reactions, reducing side reactions and particle agglomeration, and effectively improving the stability and performance of the final product.

[0082] 2. The structure of the B2 delivery pipe inside the rotary reactor can enhance the reverse injection effect of the mixed liquid B2 in the inner circumferential space of the rotary reactor, while reducing the resistance to blade rotation, reducing stirring energy consumption, and better ensuring the efficiency of uniform stirring.

[0083] 3. The two fluids, emulsion A1 and emulsion B2, generate opposite tangential flows at different radial positions, which can form strong turbulence and shearing action, accelerate the mixing between emulsion A1 and emulsion B2, and effectively avoid stratification caused by density or viscosity differences. Attached Figure Description

[0084] Figure 1 This is a flowchart of the preparation method of the organic steam cleaning stabilizer for boiler water treatment according to the present invention;

[0085] Figure 2aThis is a three-dimensional structural schematic diagram of the apparatus for preparing the organic steam cleaning stabilizer for boiler water treatment according to the present invention;

[0086] Figure 2b This is a front view of the apparatus for preparing the organic steam cleaning stabilizer for boiler water treatment according to the present invention.

[0087] Figure 3a This is a front view of the rotary reactor of the apparatus for preparing the organic steam cleaning stabilizer for boiler water treatment according to the present invention.

[0088] Figure 3b for Figure 3a Section II in the middle;

[0089] Figure 4 Comparison chart of iron ion detection in steam of boiler #1 (unit: micrograms / liter);

[0090] Figure 5 Comparison chart of sodium ion detection in steam of boiler #1 (unit: micrograms / liter);

[0091] Figure 6 Comparison chart of silica detection in steam from boiler #1 (unit: micrograms / liter);

[0092] Figure 7 Comparison chart of sodium ion detection in steam of boiler #2 (unit: micrograms / liter);

[0093] Figure 8 Comparison chart of silica detection in steam from boiler #2 (unit: micrograms / liter);

[0094] Figure 9a Photographs of condensate collected after the boiler system was equipped with a process that combined trisodium phosphate and sodium hydroxide (the condensate exhibits a red rust-like appearance).

[0095] Figure 9b Photographs of condensate collected after using the organic steam cleaning stabilizer for boiler water treatment of this invention on the boiler system (the condensate is colorless, transparent, clear, and free of impurities).

[0096] Figure 10a Photos of the inside of some steam pipes after the boiler system was equipped with a trisodium phosphate and sodium hydroxide co-process (scale and corrosion were observed inside the pipes).

[0097] Figure 10b Photographs of the inside of steam pipes after using the organic steam cleaning stabilizer for boiler water treatment of this invention in the boiler system (the inside of the pipes is covered with a gray passivation film, with no scaling or corrosion).

[0098] Figure 11aPhotos of the inside of some steam pipes after the boiler system was equipped with a trisodium phosphate and sodium hydroxide co-process (scale and corrosion were observed inside the pipes).

[0099] Figure 11b These are partial photographs of the inside of steam pipes after the application of the organic steam cleaning stabilizer for boiler water treatment of this invention to the boiler system (the inside of the pipes is covered with a gray passivation film, with no scaling or corrosion).

[0100] The diagram is marked as follows:

[0101] 1. Emulsification reactor;

[0102] 2. Second Reactor;

[0103] 3 Rotary Reactor: 31 A1 conveying pipe, 32 B2 conveying pipe, 33 heating coil. Detailed Implementation

[0104] The present invention will now be described in further detail with reference to the accompanying drawings.

[0105] An organic steam cleaning stabilizer for boiler water treatment comprises the following components by weight percentage: chelated organic matter 0.5%–5.0%, passivating reducing agent 0.5%–5.0%, surfactant 0.0%–1.0%, short-chain film-forming adsorbent and long-chain film-forming adsorbent together accounting for 0.5%–5.0%, volatile steam pH stabilizer 5.0%–25.0%, high molecular weight organophosphorus salts 0.5%–5.0%, and the balance being deionized water.

[0106] Examples of various component ratios are shown in Table 1.

[0107] Table 1 shows the mixing ratio of organic steam cleaning stabilizers for boiler water treatment.

[0108]

[0109] See Figure 1 As shown, the preparation method of the organic steam cleaning stabilizer for boiler water treatment includes the following steps:

[0110] Step 1: Preparation of deionized water: Deoxygenate the deionized water and keep the temperature of the deoxygenated deionized water between 50℃ and 80℃.

[0111] Step 2: Preparation of mixed emulsion A1: Short-chain film-forming adsorbent and long-chain film-forming adsorbent are emulsified in a high-temperature and high-pressure emulsification reactor at 200℃~250℃ and 0.5–1.0MPa by adding 7 to 10 times the total weight of deionized water of the short-chain film-forming adsorbent and long-chain film-forming adsorbent to ensure that the short-chain film-forming adsorbent and long-chain film-forming adsorbent are fully mixed and emulsified into a uniform small-particle gel liquid, and mixed emulsion A1 is obtained.

[0112] Step 3: Preparation of Mixture B2: Mix the passivating reducing agent, surfactant, chelating organic matter and high molecular weight organophosphorus salt, and add 10 to 15 times the weight of the mixture of deionized water for thorough mixing to obtain Mixture B2.

[0113] Step 4: Mixing A1 and B2: In a rotary reactor, turn on the stirrer, then pour the mixed emulsion A1 into the rotary reactor in a clockwise direction around the outer ring and the mixed solution B2 into the rotary reactor in a counterclockwise direction around the inner ring to carry out the mixing reaction; maintain the temperature at 50°C to 80°C and continue the reaction for at least 60 minutes.

[0114] Step 5: Cooling and stirring: After the above reaction is completed, cool the solution in the rotary reactor to below 30°C, then start injecting the volatile vapor pH stabilizer and the remaining deionized water, and then turn on the stirrer to stir evenly.

[0115] See Figure 2a and 2b As shown, the apparatus for preparing organic steam cleaning stabilizer for boiler water treatment includes three reactors fixedly arranged at close intervals. One reactor is an emulsification reactor 1 for preparing mixed emulsion A1, another reactor 2 is a second reactor for preparing mixed emulsion B2, and the last reactor is a rotary reactor 3 for completing the fourth and fifth steps.

[0116] See Figure 3a and Figure 3b As shown, a conveying pipe 31 for conveying mixed emulsion A1 and equipped with a control valve is fixedly installed on the outside of the rotary reactor 3. The conveying pipe 31 for A1 is tangentially connected to the rotary reactor 3, and the liquid output through the conveying pipe 31 for A1 can be injected into the reactor from the outer periphery of the rotary reactor 3 in a clockwise direction.

[0117] See Figure 3b As shown, a B2 delivery pipe 32 for conveying the mixture B2 and equipped with a control valve is also fixedly installed on the outside of the rotary reactor 3. The B2 delivery pipe 32 is located in the space between two adjacent sets of stirring blades in the height direction, and the end of the pipe section of the B2 delivery pipe 32 inside the rotary reactor 3 is an arc-shaped nozzle near the blade rotation axis, so that the mixture B2 output through the end of the B2 delivery pipe 32 can be injected into the reactor counterclockwise from the inner circumferential area near the blade rotation axis.

[0118] See Figure 3b As shown, a heating coil 33 is also fixedly installed inside the rotary reactor 3 near the side wall.

[0119] Application examples:

[0120] I. Operating conditions when using a coordinated process of trisodium phosphate and sodium hydroxide to treat boiler water:

[0121] Two ultra-high pressure boilers, boiler model Q258 / 980-260-13.7 / 545. The boilers are designed to have an evaporation capacity of 260 t / h and a design steam pressure of 13.7 MPa. The generated steam is first used for power generation by a steam turbine. The low-quality steam after power generation is then used in coal chemical processes such as coking, methanol, coal tar, synthetic ammonia, crude benzene, and ammonium sulfate production. The original boiler water treatment used a coordinated process of trisodium phosphate and sodium hydroxide, and the following problems existed during operation:

[0122] (1) The boiler feedwater is affected by the coal chemical production process, and the recovered condensate fluctuates. During some periods, the recovered condensate is contaminated by the process, resulting in unstable feedwater. During some periods, there are unqualified parameters. During the maintenance period, the economizer has some red rust and a small amount of black pitted oxygen corrosion.

[0123] (2) During normal periods, only trisodium phosphate is added as an in-furnace chemical addition process, and the phosphate concentration is controlled to be ≤3.0 mg / L. When the pH value of the boiler water is lower than 9.0, sodium hydroxide is added to raise the pH value of the boiler water.

[0124] (3) The pH value of the boiler water is required to be controlled between 9.0 and 9.7, and the conductivity of the boiler water is required to be <20μs / cm. During operation, there are large fluctuations and some periods of exceeding the standard.

[0125] (4) The sodium ion content of the saturated steam and superheated steam of the boiler is required to be <5μg / L and the silica content is required to be <15μg / L. However, there are instances of exceeding the standards during certain periods.

[0126] (5) During the annual maintenance of steam pipelines in coal chemical processes such as coking, methanol, coal tar, synthetic ammonia, crude benzene, and ammonium sulfate, a large amount of scaling and corrosion were found. This resulted in serious exceedances of iron ions in the recovered condensate. The excessive iron ions exacerbated the corrosion of the pipelines, and the corrosion of the steam pipelines would again cause the iron ions to exceed the standard, thus exacerbating the deterioration.

[0127] (6) In the past five years, the company has experienced a few sporadic steam pipe bursts. At the burst sites, varying degrees of thinning of the pipe wall, scaling, and oxygen corrosion were found, causing the company to shut down. This has seriously affected the company's safe production stability and caused significant economic losses.

[0128] (7) The total amount of boiler blowdown is large. Based on the amount of fresh demineralized water replenishment, the boiler blowdown rate is more than 2.5%, resulting in a large amount of waste of demineralized water and heat loss.

[0129] (8) The boiler steam quality is difficult to meet the requirements of the relevant standards and specifications for ultra-high pressure boilers in GB / T12145-2016 Steam Quality Standard for Thermal Power Generating Units and Steam Power Equipment.

[0130] II. Organic steam cleaning stabilizer for boiler water treatment using this solution and its operating conditions after use:

[0131] (1) Dosing situation

[0132] When using organic steam cleaning stabilizer for boiler water treatment, the average evaporation rate of the two boilers is about 2×248.3t / h, the average monthly dosage is about 1725kg (69 barrels, 25kg / barrel), and the average dosage concentration is about 4.82g / t•evaporation rate.

[0133] (2) Stability of boiler steam quality

[0134] Table 2 Comparison of Steam and Water Quality in Boiler #1 (260t / h)

[0135]

[0136] The comparison chart of iron ion detection in the steam of boiler #1 (unit: micrograms / liter) is shown below. Figure 4 As shown; Comparison chart of sodium ion detection in steam of boiler #1 (unit: micrograms / liter) Figure 5 As shown; Comparison chart of silica detection in steam from boiler #1 (unit: micrograms / liter) Figure 6 As shown.

[0137] Table 3 Comparison of Steam and Water Quality in Boiler #2 (260t / h)

[0138]

[0139] The comparison chart of sodium ion detection in the steam of boiler #2 (unit: micrograms / liter) is shown below. Figure 7 As shown; Comparison chart of silica detection in boiler #2 steam (unit: micrograms / liter) Figure 8 As shown.

[0140] Remark:

[0141] (1) The condensate water from boiler #1 and boiler #2 is mixed, and the iron ion data of the condensate water are the same.

[0142] (2) As can be seen from the steam quality, the steam cleanliness is higher and the impurities are lower after using the organic steam cleaning stabilizer for boiler water treatment of the present invention.

[0143] (3) Maintenance status of steam pipelines

[0144] When using a combined process of trisodium phosphate and sodium hydroxide: various types of scale exist in the steam pipeline, and corrosion occurs inside the pipe wall (see...). Figure 10a As shown), there is red and black rust on the thinned pipe wall (see...). Figure 10a As shown), the condensate appears reddish-rusty at certain times (see...). Figure 9a As shown in the image, the condensate contained excessive levels of iron ions. Several sporadic pipe bursts occurred at the chemical plant during the use of trisodium phosphate and sodium hydroxide in a coordinated process, all resulting in some degree of production stoppage.

[0145] When using the organic steam cleaning stabilizer for boiler water treatment of this invention: there is basically no scale inside the pipes during maintenance (see...). Figure 10b As shown), the pipe wall has a layer of gray passivation protective film (see...). Figure 11b As shown), the pipe wall showed no signs of thinning or corrosion (see...). Figure 10b and 11b As shown), the condensate no longer exhibits red rust corrosion (see...). Figure 9b As shown), the iron ion content in condensate is significantly reduced (see figure). Figure 4 As shown in the image, the pipe bursting phenomenon will no longer occur after use.

[0146] In summary, after using the organic steam cleaning stabilizer for boiler water treatment of this invention, the corrosion and scaling of steam pipelines are significantly improved, achieving a better pipeline protection effect.

[0147] (4) Boiler blowdown and energy saving

[0148] Continuous discharge status: When using the trisodium phosphate and sodium hydroxide coordinated process, the opening degrees of the electric continuous discharge valves of the company's No. 1 260t / h and No. 2 260t / h were 50% and 60%, respectively. After using organic steam cleaning stabilizer, the opening degrees of the electric continuous discharge valves of the company's No. 1 260t / h and No. 2 260t / h were both adjusted to 2.0%, and the number of continuous discharge valves was significantly reduced.

[0149] Scheduled exhaust: When using a coordinated process of trisodium phosphate and sodium hydroxide, the company required scheduled exhaust once per shift for each boiler, with each exhaust pipe lasting approximately 30 seconds. After adopting the organic steam cleaning stabilizer for boiler water treatment of this invention, the company now performs scheduled exhaust once every 7 days on average, with each exhaust pipe lasting approximately 20 seconds.

[0150] Energy Saving: When using a coordinated process of trisodium phosphate and sodium hydroxide, the company's average demineralized water consumption for its 2×260t / h boilers was approximately 2.51%, resulting in significant demineralized water consumption and substantial heat loss due to wastewater discharge. After adopting the organic steam cleaning stabilizer for boiler water treatment of this invention, the company's average demineralized water consumption for its 2×260t / h boilers decreased to approximately 0.63%, saving approximately 1.88% in wastewater discharge and reducing demineralized water consumption by approximately 9.35t / h. Based on the company's annual operation of 8000 hours, this translates to a saving of approximately 74,800t / year of demineralized water and approximately 897,600 RMB / year in water treatment costs. Simultaneously, it saves approximately 4,151,200 RMB / year in heat consumption costs, resulting in a comprehensive benefit of 5,048,800 RMB / year (water saving + energy saving), creating significant energy-saving benefits.

[0151] III. Effect Description of the Organic Steam Cleaning Stabilizer for Boiler Water Treatment of the Invention

[0152] The organic steam cleaning stabilizer for boiler water treatment of this invention can better inhibit the corrosion and scaling of boiler steam pipes, improve the heat exchange efficiency of boiler system, and at the same time have the functions of cleaning scale, film adsorption, corrosion and scale inhibition, passivation and reduction. It can better stabilize the quality of boiler water and steam, better ensure the operational stability of boiler system, extend equipment life, and make boiler system operation and management safer, more convenient and efficient.

[0153] The above are merely preferred embodiments of the present invention. It should be noted that any modifications and improvements made by those skilled in the art without departing from the present technical solution should also be considered to fall within the scope of protection claimed in this claim.

Claims

1. An organic steam cleaning stabilizer for boiler water treatment, characterized in that: It contains the following components by weight percentage: chelated organic matter 0.5%–5.0%, passivating and reducing agent 0.5%–5.0%, surfactant 0.0%–1.0%, short-chain film-forming adsorbent and long-chain film-forming adsorbent together 0.5%–5.0%, volatile vapor pH stabilizer 5.0%–25.0%, high molecular weight organophosphorus salts 0.5%–5.0%, and the remainder is deionized water; The short-chain film-forming adsorbent is n-butylamine (C4H4H4O2). 11 At least one of N) or diethylhydroxylamine (DEHA, (C2H5)2NOH); The long-chain film-forming adsorbent has at least one amine group and is composed of C 16 ~C 24 Composed of long-chain fatty alkylamine derivatives.

2. The organic vapor cleaning stabilizer according to claim 1, characterized in that: The chelated organic matter contains at least one of the chelated chemical functional groups R-COOH or R-COONa.

3. The organic vapor cleaning stabilizer according to claim 1 or 2, characterized in that: The chelating organic matter is one or more of the following: sodium diacetate (NTA), ethylenediaminetetraacetic acid (EDTA), aminocarboxylic acid, 1,3-dione, hydroxycarboxylic acid, diethylenetriaminepentaacetic acid (DTPA), sodium polyacrylate, or polyaspartic acid.

4. The organic vapor cleaning stabilizer according to claim 1 or 2, characterized in that: The long-chain film-forming adsorbent is N-oleo-1,3-propylene diamine (C 21 H 44 N2), bis(2-hydroxyethoxy)oleamide (C 22 H 45 At least one of NO2).

5. The organic steam cleaning stabilizer according to claim 1, characterized in that: The volatile vapor pH stabilizer is cyclohexane (C6H4O). 13 N) or diethylamine (C4H) 11 At least one of N).

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