Preparation method of novel boiler deoxidant
By reacting isochromic ketone oxime compounds with other components, an environmentally friendly and low-toxicity boiler deoxygenator was prepared, which solved the oxygen corrosion problem in the boiler system, achieved a highly efficient and environmentally friendly deoxygenation effect, and prevented boiler corrosion.
Patent Information
- Application Number
- CN202511308148.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-15
- Publication Date
- 2025-11-11
AI Technical Summary
Oxygen corrosion is a serious problem in existing boiler systems, especially when water quality control fails, operating parameters are out of balance, structural design is flawed, and maintenance is insufficient. Electrochemical reactions caused by dissolved oxygen trigger the corrosion process, and traditional deoxygenating agents are inefficient and highly toxic, making it difficult to effectively prevent boiler corrosion.
Using heterochromatic ketone oxime compounds as raw materials, an environmentally friendly, low-toxicity, and high-efficiency boiler deoxygenator was prepared by reacting it with acetone oxime, acetaldehyde oxime, carbazine, dispersant, pH adjuster, and catalyst in specific proportions and under specific conditions. This deoxygenation agent is used to adjust the deoxygenation performance of boilers.
It effectively reduces the amount of ketoxime in deoxygenators, has low toxicity and high efficiency reducing properties, can passivate boiler pipelines, prevent corrosion damage, maintain good deoxygenation effect and stability in medium and high temperature environments, and prevent corrosion caused by metal deposits.
Abstract
Description
Technical Field
[0001] This invention relates to the fields of chemical synthesis technology and boiler water treatment technology, and to a method for preparing a heterochromatic oxime compound and making it into an environmentally friendly, low-toxicity, and high-efficiency boiler deaerator. Background Technology
[0002] With the surge in the number of industrial boilers, oxygen corrosion in thermal systems has become a key factor restricting the safe operation of equipment. Case studies have revealed that the causes of oxygen corrosion in boiler systems are multi-faceted, mainly manifested as: 1) Failure to control water quality, with the dissolved oxygen concentration in feedwater and the pH value of boiler water consistently exceeding the limits specified in GB / T 12145; 2) Malfunctioning operating parameters, including prolonged low-load operation and frequent start-ups and shutdowns, resulting in unsteady-state conditions; 3) Structural design defects, including excessively high economizer tube bundle density leading to localized oxygen concentration polarization; and 4) Lack of a maintenance system, with no dry / wet protection measures implemented during boiler shutdowns.
[0003] From the perspective of corrosion mechanism, dissolved oxygen, acting as a depolarizer, triggers electrochemical reactions at the metal-water interface, which is the core driving force of the corrosion process. Its main penetration pathways include: ① decreased efficiency of the deaerator in the makeup water system; ② secondary dissolved oxygen caused by the failure of the airtightness of the condensate recovery network; ③ air infiltration caused by the failure of the seals in the negative pressure section of the thermal system (condenser, condensate pump). It is worth noting that dissolved oxygen not only causes continuous corrosion during operation but also accelerates pitting corrosion of the metal matrix during shutdown maintenance due to the oxygen concentration cell effect.
[0004] Organic compounds containing isochorone (six-membered ring lactone) structural units are important components of many natural products and pharmaceutical active molecules. With the development of modern organic synthesis methods, isochorones can now be synthesized through various methods. However, there are currently few reports on the application of isochorone oximeization as an oxygen scavenger.
[0005] Therefore, it is necessary to provide a method for preparing isochromic ketone oxime and a method for adjusting the performance of boiler deaerators. Summary of the Invention
[0006] The purpose of this invention is to overcome the shortcomings of the prior art by providing a method for preparing heterochromatic oxime compounds and using them to prepare an environmentally friendly, low-toxicity, and high-efficiency boiler deaerator.
[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0008] Using isochorium oxime as a raw material, it reacts with hydroxylamine sulfate in a solvent (water, ethanol, or methanol) under acidic conditions (pH = 2-5) to generate isochorium oxime. The obtained isochorium oxime is then mixed with acetone oxime, acetaldehyde oxime, carbazide, dispersant, pH adjuster, catalyst, and water in a certain proportion to prepare a boiler deaerator. The boiler deaerator is made from the following raw materials in parts by weight: isochorium oxime (3-5 parts), acetone oxime (12-16 parts), acetaldehyde oxime (12-14 parts), carbazide (8-12 parts), dispersant (4-7 parts), pH adjuster (5-10 parts), catalyst (5-10 parts), and water (40-50 parts).
[0009] Furthermore, in the method for preparing the novel boiler deaerator, the molar ratio of isocyanate and hydroxylamine sulfate is 1:1.05-1.25.
[0010] Furthermore, the method for preparing a novel boiler deaerator is characterized in that the pH value during the reaction is 2-5, the temperature is 30℃-60℃, and the reaction time is 100-200 min.
[0011] Furthermore, in the method for preparing the novel boiler deoxygenator, the solvent is one of water, ethanol, and methanol.
[0012] Furthermore, in the preparation method of the novel boiler deoxygenator, the weight ratio of the deoxygenator is: isocyanate oxime: acetone oxime: acetaldehyde oxime: carbazide: dispersant: pH adjuster: catalyst: water = 3:15:12:8:5:6:6:45
[0013] Furthermore, in the method for preparing a novel boiler deaerator, the dispersant is any one of polyethylene glycol 200, polyethylene glycol 400, and citric acid.
[0014] Furthermore, in the method for preparing a novel boiler deaerator, the pH adjuster is any one or two of triethylamine, ethanolamine, and cyclohexylamine.
[0015] Furthermore, in the method for preparing a novel boiler deaerator, the catalyst is hydroquinone, resorcinol, or catechol.
[0016] Furthermore, the preparation method of the novel boiler deaerator is carried out by the following method:
[0017] Step 1: Add deionized water (40-50 parts) to the preparation container and heat to 40°C.
[0018] Step 2: Add 3-5 parts of isochorium oxime, 12-16 parts of acetone oxime, 12-14 parts of acetaldehyde oxime, and 8-12 parts of carbazide to the deionized water from Step 1 in sequence, and stir thoroughly to dissolve.
[0019] Step 3: Add 4-7 parts of dispersant, 5-10 parts of pH adjuster, and 5-10 parts of catalyst to the solution obtained in Step 2, continue stirring for 30 minutes, and then let it stand for 1-3 hours to obtain an environmentally friendly, low-toxicity, high-efficiency boiler deaerator.
[0020] Compared with the prior art, the present invention has the following beneficial effects:
[0021] This invention utilizes isochromic ketone oxime to prepare isochromic ketone oxime and uses a small amount of isochromic ketone oxime to adjust the proportion of each component in the boiler deoxygenator. This effectively reduces the amount of ketone oxime used in the deoxygenator and has the advantages of low toxicity and high efficiency in deoxygenation. It can maintain good reducing properties at medium and high temperatures. It can passivate boiler pipelines and equipment and prevent corrosion damage to the boiler caused by metal deposits. Detailed Implementation
[0022] The present invention will now be described in further detail with reference to the embodiments.
[0023] Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be construed as limiting the scope of the invention. Where specific techniques or conditions are not specified in the embodiments, they are performed in accordance with the techniques or conditions described in the literature in the field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased.
[0024] In Example 1, 15g of isochorone and 17g of hydroxylamine sulfate were added to a reaction flask, followed by 100ml of ethanol. The pH was adjusted to 2-3 with 10% (mass fraction) dilute sulfuric acid. The reaction was carried out at 40°C for 3 hours. The ethanol was evaporated to dryness, and the solid was recrystallized from acetone to obtain pure isochorone oxime with a yield of 84.7%.
[0025] In Example 2, 15g of isochorone and 17g of hydroxylamine sulfate were added to a reaction flask, followed by 100ml of ethanol. The pH was adjusted to 2-3 with 10% (mass fraction) dilute sulfuric acid. The reaction was carried out at 30°C for 3 hours. The ethanol was evaporated to dryness, and the solid was recrystallized from acetone to obtain pure isochorone oxime with a yield of 77.6%.
[0026] In Example 3, 15g of isochorone and 17g of hydroxylamine sulfate were added to a reaction flask, followed by 100ml of ethanol. The pH was adjusted to 4-5 with 10% (mass fraction) dilute sulfuric acid. The reaction was carried out at 40°C for 3 hours. The ethanol was evaporated to dryness, and the solid was recrystallized from acetone to obtain pure isochorone oxime with a yield of 65.2%.
[0027] In Example 4, 15g of isochorone and 17g of hydroxylamine sulfate were added to a reaction flask, followed by 100ml of methanol. The pH was adjusted to 2-3 with 10% (mass fraction) dilute sulfuric acid. The reaction was carried out at 40°C for 3 hours. The ethanol was evaporated to dryness, and the solid was recrystallized from acetone to obtain pure isochorone oxime with a yield of 87.8%.
[0028] In Example 5, 15g of isochorone and 17g of hydroxylamine sulfate were added to a reaction flask, followed by 100ml of methanol. The pH was adjusted to 2-3 with 10% (mass fraction) dilute sulfuric acid. The reaction was carried out at 40°C for 4 hours. The ethanol was evaporated to dryness, and the solid was recrystallized from acetone to obtain pure isochorone oxime with a yield of 89.6%.
[0029] In Example 6, 15g of isochorone and 17g of hydroxylamine sulfate were added to a reaction flask, followed by 100ml of methanol. The pH was adjusted to 2-3 with 10% (mass fraction) dilute sulfuric acid. The reaction was carried out at 40°C for 2 hours. The ethanol was evaporated to dryness, and the solid was recrystallized from acetone to obtain pure isochorone oxime with a yield of 73.1%.
[0030] Example 7: An environmentally friendly, low-toxicity, high-efficiency boiler deaerator, made from the following raw materials in parts by weight: isocyanate oxime: acetone oxime: acetaldehyde oxime: carbazide: dispersant: pH adjuster: catalyst: water = 3:15:12:8:5:6:6:45
[0031] The dispersant is polyethylene glycol 200. The pH adjuster is triethylamine. The catalyst is hydroquinone, resorcinol, or catechol.
[0032] An environmentally friendly, low-toxicity, and high-efficiency boiler deaerator is prepared by the following method:
[0033] Step 1: Add 45 parts of deionized water to the preparation container and heat to 40°C.
[0034] Step 2: Add 3 parts of isochorium oxime, 15 parts of acetone oxime, 12 parts of acetaldehyde oxime, and 8 parts of carbazine to the deionized water from Step 1 in sequence, and stir thoroughly to dissolve.
[0035] Step 3: Add 5 parts of dispersant, 6 parts of pH adjuster, and 6 parts of catalyst to the solution obtained in Step 2, continue stirring for 30 minutes, and then let it stand for 1 hour to obtain an environmentally friendly, low-toxicity, high-efficiency boiler deaerator.
[0036] Example 8: An environmentally friendly, low-toxicity, high-efficiency boiler deaerator, made from the following raw materials in parts by weight: isocyanate oxime: acetone oxime: acetaldehyde oxime: carbazide: dispersant: pH adjuster: catalyst: water = 3:15:12:8:4:7:6:45
[0037] The dispersant is citric acid. The pH adjuster is triethylamine. The catalyst is hydroquinone, resorcinol, or catechol.
[0038] An environmentally friendly, low-toxicity, and high-efficiency boiler deaerator is prepared by the following method:
[0039] Step 1: Add 45 parts of deionized water to the preparation container and heat to 40°C.
[0040] Step 2: Add 3 parts of isochorium oxime, 15 parts of acetone oxime, 12 parts of acetaldehyde oxime, and 8 parts of carbazine to the deionized water from Step 1 in sequence, and stir thoroughly to dissolve.
[0041] Step 3: Add 4 parts of dispersant, 7 parts of pH adjuster, and 6 parts of catalyst to the solution obtained in Step 2, continue stirring for 30 minutes, and then let it stand for 1 hour to obtain an environmentally friendly, low-toxicity, high-efficiency boiler deoxygenator.
[0042] Example 9: An environmentally friendly, low-toxicity, high-efficiency boiler deaerator, made from the following raw materials in parts by weight: isocyanate oxime: acetone oxime: acetaldehyde oxime: carbazide: dispersant: pH adjuster: catalyst: water = 3:15:12:8:4:6:6:46
[0043] The dispersant is polyethylene glycol 200. The pH adjuster is ethanolamine. The catalyst is hydroquinone, resorcinol, or catechol.
[0044] An environmentally friendly, low-toxicity, and high-efficiency boiler deaerator is prepared by the following method:
[0045] Step 1: Add 46 parts of deionized water to the preparation container and heat to 40°C.
[0046] Step 2: Add 3 parts of isochorium oxime, 15 parts of acetone oxime, 12 parts of acetaldehyde oxime, and 8 parts of carbazide to the deionized water in Step 1 in sequence, and stir thoroughly to dissolve.
[0047] Step 3: Add 4 parts of dispersant, 6 parts of pH adjuster, and 6 parts of catalyst to the solution obtained in Step 2, continue stirring for 30 minutes, and then let it stand for 1 hour to obtain an environmentally friendly, low-toxicity, high-efficiency boiler deaerator.
[0048] The following experiments illustrate the deoxygenation effect of the environmentally friendly, low-toxicity, high-efficiency boiler deoxygenants prepared in Examples 7-9.
[0049] Under the water quality conditions shown in Table 1 below, equal mass ratios of the environmentally friendly, low-toxicity, high-efficiency boiler deoxygenating agents prepared in Examples 7-9 were added. The deoxygenation time and total residual oxygen of water quality 1 and water quality 2 were statistically analyzed and calculated within the same treatment time. In Table 1, water quality 1 is pure water, and water quality 2 is softened water.
[0050] Water quality 1 Water quality 2 <![CDATA[Ca 2+ (mg / L)]]> 5.0 6.4 <![CDATA[Mg 2+ (mg / L)]]> 0.037 0.045 Dissolved oxygen (mg / L) 5.8 6.4
[0051] Table 1
[0052] The processing results are shown in Table 2.
[0053] Example 7 Example 8 Example 9 Deoxygenation time (h) 1 1 1 Water quality 1: Residual oxygen (mg / L) 0.51 0.46 0.53 Water quality 2: Residual oxygen (mg / L) 0.49 0.51 0.45
[0054] Table 2
[0055] As shown in Table 2, the oxygen scavengers prepared in Examples 7-9 exhibit good oxygen removal effects in a relatively short time. The oxime raw materials used in this invention—isochromone oxime, butanone oxime, and acetaldehyde oxime—have strong reducing properties and are characterized by low toxicity, high efficiency, and rapid oxygen removal, providing passivation protection for the boiler surface. They also exhibit high stability and good oxygen removal function over a wide range of temperature and pressure. Mixing these three substances with carbazine, which also has oxygen removal properties, enhances the oxygen removal capacity. Furthermore, dispersants, catalysts, and pH adjusters are added to ensure a smooth and safe reaction, reduce the formation of derivatives, improve material stability, and accelerate the preparation rate.
[0056] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing comparative examples, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A method for preparing a novel boiler deaerator, characterized in that, Using isochorone as a raw material, it reacts with hydroxylamine sulfate in a solvent under acidic conditions to generate isochorone oxime; the oxygen scavenger is made from the following raw materials in parts by weight: 3-5 parts of isochorone oxime, 12-16 parts of acetone oxime, 12-14 parts of acetaldehyde oxime, 8-12 parts of carbazide, 4-7 parts of dispersant, 5-10 parts of pH adjuster, 5-10 parts of catalyst, and 40-50 parts of water.
2. The method for preparing a novel boiler deaerator according to claim 1, characterized in that, The molar ratio of isochromone and hydroxylamine sulfate is 1:1.05~1.
25.
3. The method for preparing a novel boiler deaerator according to claim 1, characterized in that, The solvent is one of water, ethanol, and methanol.
4. The method for preparing a novel boiler deaerator according to claim 1, characterized in that, The reaction is carried out at a pH of 2-5, a temperature of 30℃-60℃, and a reaction time of 100-200 min.
5. The method for preparing a novel boiler deaerator according to claim 1, characterized in that, The weight ratio of the prepared oxygen scavenger is: isochromic ketone oxime: acetone oxime: acetaldehyde oxime: carbazide: dispersant: pH adjuster: catalyst: water = 3:15:12:8:5:6:6:
45.
6. The method for preparing a novel boiler deaerator according to claim 1, characterized in that, The dispersant is any one of polyethylene glycol 200, polyethylene glycol 400, and citric acid.
7. The method for preparing a novel boiler deaerator according to claim 1, characterized in that, The pH adjuster is any one or two of triethylamine, ethanolamine, and cyclohexylamine.
8. The method for preparing a novel boiler deaerator according to claim 1, characterized in that, The catalyst is hydroquinone, resorcinol, or catechol.
9. A method for preparing a novel boiler deaerator according to claim 1, characterized in that, The preparation method is as follows: Step 1: Add deionized water (40-50 parts) to a preparation container and heat to 40℃. Step 2: Add 3-5 parts of isochorium oxime, 12-16 parts of acetone oxime, 12-14 parts of acetaldehyde oxime, and 8-12 parts of carbazide to the deionized water in Step 1, and stir thoroughly to dissolve. Step 3: Add 4-7 parts of dispersant, 5-10 parts of pH adjuster, and 5-10 parts of catalyst to the solution obtained in Step 2, continue stirring for 30 minutes, and then let stand for 1-3 hours to obtain an environmentally friendly, low-toxicity, high-efficiency boiler deaerator.