Antifoams and their use in aqueous organic amine desulfurization decarbonization solutions

Abstract

The present application relates to the field of gas purification, and discloses a defoaming agent and application thereof in organic amine desulfurization and decarburization aqueous solution. The composition contains 67-90 wt% of main agent, 8-30 wt% of auxiliary agent I and 1-3 wt% of auxiliary agent II, based on the total weight of the defoaming agent; wherein the main agent is selected from at least two of polyamide-amine, polyoxyethylene fatty alcohol ether and silicone oil; the auxiliary agent I includes alkyl phenol surfactant and polyol surfactant, and the auxiliary agent II includes adhesive and silicon-based waterproof agent; the weight average molecular weight of the polyoxyethylene fatty alcohol ether is 3000-4000. The defoaming agent has the characteristics of strong defoaming capacity, small addition amount and strong wear resistance.

Description

Technical Field

[0001] This invention relates to the field of gas purification, specifically to an antifoaming agent and its application in aqueous solutions for desulfurization and decarbonization of organic amines. Background Technology

[0002] In industries such as petrochemicals, natural gas processing, coking, and steel, there is a need to remove acidic components such as hydrogen sulfide and carbon dioxide from process gases or waste gases. Research on the removal of these acidic components has been ongoing for nearly a century, resulting in hundreds of process technologies. Among these technologies, the organic amine method has become the dominant gas purification process in many industries due to its mature technology, adjustable precision in removing acidic components, and wide applicability. While the organic amine method for desulfurization and decarbonization has been widely applied, its operation is susceptible to foaming in the absorption tower and / or regeneration tower if not properly maintained. This can be caused by secondary factors such as impurities introduced into the process gas or waste gas, and by deterioration products generated during the organic amine's operation. If foaming occurs in the organic amine desulfurization and decarbonization system and is not controlled, it can lead to deviations from stable operation of the absorption tower and regeneration tower, resulting in liquid clogging in the absorption tower and regeneration tower. Furthermore, the organic amine desulfurization and decarbonization solution can be carried from the gas phase into the product gas and exhaust gas, ultimately causing substandard product gas, loss of organic amine solvent, and in severe cases, abnormal shutdowns of downstream production. In production, foaming is detected by monitoring the operating pressure difference of the absorption tower and regeneration tower. If the pressure difference suddenly shows a rapid increasing trend, defoamer is added to defoam and prevent production from being affected. Commonly used defoamers include silicone oil, higher alcohols, polyethers, and polyether-modified silicone. These defoamers are very effective in defoaming organic amine desulfurization and decarbonization solutions, especially polyether defoamers.

[0003] To maintain the cleanliness of the organic amine desulfurization and decarbonization solution, activated carbon filtration systems are installed in all organic amine desulfurization and decarbonization systems to remove some organic matter introduced into the system by the raw gas and deterioration products generated during the operation of the organic amine desulfurization and decarbonization solution itself. Therefore, the activated carbon filtration device, while removing organic impurities, also retains some of the active components of the defoamer. Over time, the defoamer content in the organic amine decreases to the point of being ineffective. Consequently, organic amine desulfurization and decarbonization systems operating in harsh environments require frequent addition of defoamer, thus increasing the annual consumption of defoamer. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of weak defoaming ability and poor wear resistance of defoamers due to use in the prior art, and to provide a defoamer and its application in organic amine desulfurization and decarbonization aqueous solution. This defoamer has the characteristics of strong defoaming ability, low addition amount and high wear resistance.

[0005] To achieve the above objectives, the first aspect of the present invention provides an antifoaming agent, characterized in that, based on the total weight of the antifoaming agent, the antifoaming agent contains 67-90 wt% of a main agent, 8-30 wt% of auxiliary agent I and 1-3 wt% of auxiliary agent II;

[0006] The main agent is selected from at least two of polyamide-amine, polyoxyethylene fatty alcohol ether, and silicone oil;

[0007] The auxiliary agent I includes alkylphenol surfactants and polyol surfactants, and the auxiliary agent II includes adhesives and silicone-based waterproofing agents;

[0008] The weight-average molecular weight of the polyoxyethylene fatty alcohol ether is 3000-4000.

[0009] The second aspect of the present invention provides an application of an antifoaming agent in an aqueous solution for desulfurization and decarbonization of organic amines, characterized in that the antifoaming agent is the antifoaming agent provided in the first aspect of the present invention;

[0010] The amount of defoamer added is 0.01-0.1 wt%, based on the total weight of the organic amine desulfurization and decarbonization aqueous solution.

[0011] Through the above technical solution, the defoamer provided by the present invention and its application in organic amine desulfurization and decarbonization aqueous solution achieve the following beneficial effects: the defoamer is formulated by using specific components and specific ratios. When used in organic amine desulfurization and decarbonization aqueous solution, it can enhance the stability of the desulfurization and decarbonization process of organic amine aqueous solution, significantly improve its defoaming ability during use, reduce the amount of loss during use, and reduce the annual amount of defoamer used. Detailed Implementation

[0012] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0013] The first aspect of the present invention provides an antifoaming agent, characterized in that, based on the total weight of the antifoaming agent, the antifoaming agent contains 67-90 wt% of a main agent, 8-30 wt% of auxiliary agent I and 1-3 wt% of auxiliary agent II;

[0014] The main agent is selected from at least two of polyamide-amine, polyoxyethylene fatty alcohol ether, and silicone oil;

[0015] The auxiliary agent I includes alkylphenol surfactants and polyol surfactants, and the auxiliary agent II includes adhesives and silicone-based waterproofing agents;

[0016] The weight-average molecular weight of the polyoxyethylene fatty alcohol ether is 3000-4000.

[0017] In this invention, the defoamer is formulated by compounding specific components in specific proportions, with each component working synergistically to improve its defoaming ability and durability.

[0018] Furthermore, the weight-average molecular weight of the polyoxyethylene fatty alcohol ether meets the above-mentioned range, which can further improve the dispersibility of the defoamer during application and further improve the defoaming efficiency.

[0019] Furthermore, based on the total weight of the defoamer, the composition contains 75-90 wt% of the main agent, 8-23.5 wt% of auxiliary agent I and 1.5-2.5 wt% of auxiliary agent II.

[0020] According to the present invention, the terminal groups of the polyamide-amine are amine groups and / or hydroxyl groups.

[0021] In this invention, the defoamer has an acid value of 0.01-0.05 mg KOH / g and a hydroxyl value of 80-150 KOH / g.

[0022] In this invention, the polyamide-amine is a dendritic macromolecular polymer prepared from ethylenediamine and methyl acrylate as initial raw materials through Michael addition and amidation.

[0023] In this invention, the inventors discovered that when the polyamide-amine is a second- to sixth-generation dendritic macromolecular polymer prepared from ethylenediamine and methyl acrylate as initial raw materials through Markel addition and amidation, better technical effects can be obtained, namely, improved defoaming ability.

[0024] Furthermore, when the polyamide-amine is a third- or fourth-generation dendritic macromolecular polymer prepared from ethylenediamine and methyl acrylate as initial raw materials via Markel addition and amidation, the defoaming ability of the defoamer can be further improved.

[0025] According to the present invention, the silicone oil is selected from at least one of polymethylsiloxane, polydimethylsiloxane, polyether silicone oil and methyl silicone oil.

[0026] According to the present invention, the main agent comprises polyamide-amine, polyoxyethylene fatty alcohol ether and silicone oil, and the mass ratio of the sum of the mass of the polyamide-amine and the polyoxyethylene fatty alcohol ether to the mass ratio of the silicone oil is (5-10):1, and the mass ratio of the polyamide-amine to the polyoxyethylene fatty alcohol ether is (0.35-1.5):1.

[0027] In this invention, the mass ratio of the sum of the mass of the polyamide-amine and the polyoxyethylene fatty alcohol ether to the mass ratio of the silicone oil satisfies the above-mentioned range, and the mass ratio of the polyamide-amine to the polyoxyethylene fatty alcohol ether satisfies the above-mentioned range, which can improve the defoaming ability of the defoamer and further improve the stability of the defoamer in use.

[0028] Furthermore, the mass ratio of the sum of the polyamide-amine and the polyoxyethylene fatty alcohol ether to the mass of the silicone oil is (6-10):1, and the mass ratio of the polyamide-amine to the polyoxyethylene fatty alcohol ether is (1-1.5):1.

[0029] Alternatively, the main agent comprises polyamide-amine and polyoxyethylene fatty alcohol ether, wherein the mass ratio of polyamide-amine to polyoxyethylene fatty alcohol ether is (0.35-1.5):1, and the mass ratio of polyamide-amine to polyoxyethylene fatty alcohol ether is (1-1.5):1.

[0030] According to the present invention, the alkylphenol surfactant is selected from at least one of nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, and heptaphenol polyoxyethylene ether.

[0031] Furthermore, the alkylphenol surfactant is selected from nonylphenol polyoxyethylene ether and / or octylphenol polyoxyethylene ether.

[0032] According to the present invention, the polyol surfactant is selected from dehydrated sorbitan fatty acid esters and / or polysorbates.

[0033] In this invention, in order to further improve the defoaming ability and durability of the defoamer, the dehydrated sorbitan fatty acid ester is preferably Span-80, and the polysorbate is Tween-80.

[0034] According to the present invention, the mass ratio of the alkylphenol surfactant to the polyol surfactant is 0.8:1 to 1:0.8.

[0035] In this invention, when the type of additive I meets the above-mentioned range, it can improve the defoaming ability of the defoamer and reduce the defoaming time.

[0036] According to the present invention, the binder is selected from sodium carboxymethyl cellulose and / or methyl cellulose.

[0037] According to the present invention, the silicone-based waterproofing agent is selected from organosilicon waterproofing agents or inorganic silicone waterproofing agents.

[0038] Furthermore, the silicon-based waterproofing agent is selected from hydrophobic silicon dioxide.

[0039] According to the present invention, the mass ratio of the adhesive to the silicone-based waterproofing agent is (1-3):1.

[0040] In this invention, the adhesive and the silicone-based waterproofing agent meet the above-mentioned requirements, which can improve the wear resistance of the defoamer, increase its service life, and reduce the frequency of addition.

[0041] Furthermore, the mass ratio of the adhesive to the silicone-based waterproofing agent is (2-3):1.

[0042] According to the present invention, the content of the silicone-based waterproofing agent is not less than 0.5 wt%, based on the total mass of the defoamer.

[0043] In this invention, there are no special requirements for the preparation method of the defoamer; it is sufficient to mix the components of the defoamer in proportion and make them uniform.

[0044] The second aspect of the present invention provides an application of an antifoaming agent in an aqueous solution for desulfurization and decarbonization of organic amines, characterized in that the antifoaming agent is the antifoaming agent provided in the first aspect of the present invention;

[0045] The amount of defoamer added is 0.01-0.15 wt%, based on the total weight of the organic amine desulfurization and decarbonization aqueous solution.

[0046] In this invention, the application can achieve defoaming of organic amine desulfurization and decarbonization aqueous solution with a relatively small amount of defoamer added, and has strong durability.

[0047] In this invention, the inventors discovered that, based on the total weight of the organic amine desulfurization and decarbonization aqueous solution, when the amount of defoamer added is 0.01-0.1 wt%, excellent results can be achieved while saving the amount of defoamer used.

[0048] In this invention, there are no particular limitations on the source and type of organic amines in the organic amine desulfurization and decarbonization aqueous solution. For example, it can be N-methyldiethanolamine (MDEA), N-methylmonoethanolamine (MMEA), diethanolamine (DEA), monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), piperazine (PZ), hydroxyethylpiperazine (HPZ), etc.

[0049] In this invention, the organic amine desulfurization and decarbonization aqueous solution contains 20-55 wt% of the above-mentioned organic amines.

[0050] According to the present invention, the defoamer is used at a temperature of 20-140°C.

[0051] Furthermore, the defoamer is used at a temperature of 40-130℃.

[0052] In this invention, the defoamer is first diluted with a small amount of organic amine desulfurization and decarbonization aqueous solution (not less than 10-20 times the amount of defoamer used) before being added to the inlet solution pipeline of the absorption tower or regeneration tower.

[0053] The present invention will be described in detail below through embodiments.

[0054] In the following examples, the organic amine desulfurization and decarbonization aqueous solution contains 40 wt% MDEA and 5 wt% DEA.

[0055] The defoaming performance test was conducted in accordance with the petroleum and natural gas industry standard SY / T 6538-2002 "Formulated Selective Desulfurization Solvents".

[0056] The following examples illustrate the preparation of defoamers.

[0057] Example 1

[0058] 21.5g of polyamide-amine 3rd generation, 43g of polyoxyethylene fatty alcohol ether (weight average molecular weight of 3497), 10.7g of polydimethylsiloxane, 11.8g of nonylphenol polyoxyethylene ether, 11.8g of Span 80, 1g of sodium carboxymethyl cellulose, and 0.5g of hydrophobic silica were mixed evenly to obtain defoamer A1.

[0059] The mass ratio of polyamide-amine 3rd generation and polyoxyethylene fatty alcohol ether is 0.5:1, and the mass ratio of the sum of the above two to polydimethylsiloxane is 6:1. In additive I, nonylphenol polyoxyethylene ether and Span 80 are in a mass ratio of 1:1.

[0060] In defoamer A1, the main component has a mass fraction of 75%, and the auxiliary component I has a mass fraction of 23.5%; the auxiliary component II has a mass fraction of 1.5%, of which sodium carboxymethyl cellulose and hydrophobic silica account for 1% and 0.5% of the mass fraction of defoamer A1, respectively; the defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 93 KOH / g.

[0061] Example 2

[0062] The preparation method is the same as in Example 1, except that the amount of polyamide-amine 3-substituted product is 32.2g and the amount of polyoxyethylene fatty alcohol ether is 32.2g, thus obtaining defoamer A2;

[0063] The mass ratio of polyamide-amine 3rd generation and polyoxyethylene fatty alcohol ether is 1:1, and the mass ratio of the sum of the above two to polydimethylsiloxane is 6:1. In additive I, nonylphenol polyoxyethylene ether and Span 80 are in a mass ratio of 1:1.

[0064] In A2, the main agent has a mass fraction of 75%, and the auxiliary agent I has a mass fraction of 23.5%; the auxiliary agent II has a mass fraction of 1.5%, of which sodium carboxymethyl cellulose and hydrophobic silica account for 1% and 0.5% of the mass fraction of defoamer A2, respectively; the defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 101 KOH / g.

[0065] Example 3

[0066] The preparation method is the same as in Example 1, except that the amount of polyamide-amine 3-substituted is 36.8g and the amount of polyoxyethylene fatty alcohol ether is 25.7g, thus obtaining defoamer A3;

[0067] The mass ratio of polyamide-amine 3rd generation and polyoxyethylene fatty alcohol ether is 1.5:1, and the mass ratio of the sum of the above two to polydimethylsiloxane is 6:1. In additive I, nonylphenol polyoxyethylene ether and Span 80 are in a mass ratio of 1:1.

[0068] In A3, the main agent has a mass fraction of 75%, and the auxiliary agent I has a mass fraction of 23.5%; the auxiliary agent II has a mass fraction of 1.5%, of which sodium carboxymethyl cellulose and hydrophobic silica account for 1% and 0.5% of the mass fraction of defoamer A3, respectively; the defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 116 KOH / g.

[0069] Example 4

[0070] The preparation method is the same as in Example 1, except that the amount of polyamide-amine 3-substituted is 42.9g and the amount of polyoxyethylene fatty alcohol ether is 21.5g, thus obtaining defoamer A4;

[0071] The mass ratio of polyamide-amine 3rd generation and polyoxyethylene fatty alcohol ether is 2:1; the mass ratio of the sum of the above two to polydimethylsiloxane is 6:1; and the mass ratio of nonylphenol polyoxyethylene ether and Span 80 in additive I is 1:1.

[0072] In A4, the main agent has a mass fraction of 75%, auxiliary agent I has a mass fraction of 23.5%, and auxiliary agent II has a mass fraction of 1.5%. Among them, sodium carboxymethyl cellulose and hydrophobic silica account for 1% and 0.5% of the mass fraction of defoamer A4, respectively. The defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 123 KOH / g.

[0073] Example 5

[0074] The preparation method is the same as in Example 1, except that the amount of polydimethylsiloxane used is 7.5g, resulting in defoamer A5;

[0075] The mass ratio of polyamide-amine 3rd generation to polyoxyethylene fatty alcohol ether is 0.5:1, the mass ratio of the sum of the masses of polyamide-amine 3rd generation and polyoxyethylene fatty alcohol ether to the mass ratio of polydimethylsiloxane is 9:1, and the mass ratio of nonylphenol polyoxyethylene ether and Span 80 in additive I is 1:1.

[0076] In A5, the main agent has a mass fraction of 75%, auxiliary agent I has a mass fraction of 23.5%, and auxiliary agent II has a mass fraction of 1.5%. Among them, sodium carboxymethyl cellulose and hydrophobic silica account for 1% and 0.5% of the mass fraction of defoamer A5, respectively. The defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 115 KOH / g.

[0077] Example 6

[0078] The preparation method is the same as in Example 1, except that the amount of polydimethylsiloxane used is 5.8g, resulting in defoamer A6;

[0079] The mass ratio of polyamide-amine 3rd generation to polyoxyethylene fatty alcohol ether is 0.5:1, and the mass ratio of nonylphenol polyoxyethylene ether and Span 80 in additive I is 1:1.

[0080] In A6, the main agent has a mass fraction of 75%, auxiliary agent I has a mass fraction of 23.5%, and auxiliary agent II has a mass fraction of 1.5%. Among them, sodium carboxymethyl cellulose and hydrophobic silica account for 1% and 0.5% of the mass fraction of defoamer A6, respectively.

[0081] The mass ratio of the sum of the third-generation polyamide-amine and the polyoxyethylene fatty alcohol ether to the mass of polydimethylsiloxane is 12:1; the defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 127 KOH / g.

[0082] Example 7

[0083] The preparation method is the same as in Example 1, except that the amount of polyamide-amine 3-generation is 40.6g, the amount of polyoxyethylene fatty alcohol ether is 81.2g, and the amount of polydimethylsiloxane is 20.3g, to obtain defoamer A7;

[0084] The mass ratio of polyamide-amine 3rd generation and polyoxyethylene fatty alcohol ether is 0.5:1, and the mass ratio of the sum of the above two to polydimethylsiloxane is 6:1. In additive I, nonylphenol polyoxyethylene ether and Span 80 are in a mass ratio of 1:1.

[0085] In A7, the mass fraction of the main agent is 85%, the mass fraction of auxiliary agent I is 14.9%, and the mass fraction of auxiliary agent II is 0.9%. The defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 105 KOH / g.

[0086] Example 8

[0087] The preparation method is the same as in Example 1, except that the amount of polyamide-amine 3-generation is 64.5g, the amount of polyoxyethylene fatty alcohol ether is 129g, and the amount of polydimethylsiloxane is 32.3g, to obtain defoamer A8;

[0088] The mass ratio of polyamide-amine 3rd generation and polyoxyethylene fatty alcohol ether is 0.5:1, and the mass ratio of the sum of the above two to polydimethylsiloxane is 6:1. In additive I, nonylphenol polyoxyethylene ether and Span 80 are in a mass ratio of 1:1.

[0089] In defoamer A8, the mass fraction of the main agent is 90%, the mass fraction of auxiliary agent I is 9.4%, and the mass fraction of auxiliary agent II is 0.6%. The defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 118 KOH / g.

[0090] Example 9

[0091] The preparation method is consistent with that in Example 1, except that Span 80 is replaced with an equal amount of Tween 80; defoamer A9 is obtained; wherein the mass fraction of the main agent is 75%, the mass fraction of auxiliary agent I is 23.5%, and the mass fraction of auxiliary agent II is 1.5%; the defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 96 KOH / g.

[0092] Example 10

[0093] The preparation method is consistent with that in Example 1, except that nonylphenol polyoxyethylene ether is replaced with an equal amount of octylphenol polyoxyethylene ether, and Span 80 is replaced with an equal amount of Tween 80; defoamer A10 is obtained; wherein the mass fraction of the main agent is 75%, the mass fraction of auxiliary agent I is 23.5%, and the mass fraction of auxiliary agent II is 1.5%; the defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 95 KOH / g.

[0094] Example 11

[0095] The preparation method is the same as in Example 1, except that nonylphenol polyoxyethylene ether is replaced with an equal amount of octylphenol polyoxyethylene ether to obtain defoamer A11; wherein, the mass fraction of the main agent is 75%, the mass fraction of auxiliary agent I is 23.5%, and the mass fraction of auxiliary agent II is 1.5%; the defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 97 KOH / g.

[0096] Example 12

[0097] The preparation method is the same as in Example 1, except that the amount of sodium carboxymethyl cellulose is 1.7g and the amount of hydrophobic silica is 0.8g, resulting in defoamer A12. The main agent has a mass fraction of 74.2%, auxiliary agent I has a mass fraction of 23.3%, and auxiliary agent II has a mass fraction of 2.5%. In auxiliary agent II, sodium carboxymethyl cellulose and hydrophobic silica account for 1.7% and 0.8% of the mass fraction of defoamer A12, respectively. The defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 100 KOH / g.

[0098] Example 13

[0099] The method is consistent with that in Example 1, except that polyoxyethylene fatty alcohol ether is replaced with methyl silicone oil to obtain defoamer A13, wherein the mass fraction of the main agent is 75%, the mass fraction of auxiliary agent I is 23.5%, and the mass fraction of auxiliary agent II is 1.5%. The defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 102 KOH / g.

[0100] Example 14

[0101] The method is consistent with that in Example 1, except that polyamide-amine 3 is replaced with methyl silicone oil to obtain defoamer A14, wherein the mass fraction of the main agent is 75%, the mass fraction of auxiliary agent I is 23.5%, and the mass fraction of auxiliary agent II is 1.5%. The defoamer has an acid value of 0.04 mg KOH / g and a hydroxyl value of 87 KOH / g.

[0102] Example 15

[0103] The method is consistent with that in Example 1, except that polyamide-amine 3rd generation is replaced with polyamide-amine 4th generation to obtain defoamer A15, wherein the mass fraction of the main agent is 75%, the mass fraction of auxiliary agent I is 23.5%, and the mass fraction of auxiliary agent II is 1.5%. The defoamer has an acid value of 0.04 mg KOH / g and a hydroxyl value of 105 KOH / g.

[0104] Example 16

[0105] The method is consistent with that in Example 1, except that polyamide-amine 3rd generation is replaced with polyamide-amine 5th generation to obtain defoamer A16, wherein the mass fraction of the main agent is 75%, the mass fraction of auxiliary agent I is 23.5%, and the mass fraction of auxiliary agent II is 1.5%. The defoamer has an acid value of 0.02 mg KOH / g and a hydroxyl value of 110 KOH / g.

[0106] Example 17

[0107] The method is consistent with that in Example 1, except that polyamide-amine 3rd generation is replaced with polyamide-amine 1st generation to obtain defoamer A17, wherein the mass fraction of the main agent is 75%, the mass fraction of auxiliary agent I is 23.5%, and the mass fraction of auxiliary agent II is 1.5%. The defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 87 KOH / g.

[0108] Comparative Example 1

[0109] The method is consistent with that in Example 1, except that polyoxyethylene fatty alcohol ether (weight average molecular weight of 2032) is used to obtain defoamer D1, which has an acid value of 0.03 mg KOH / g and a hydroxyl value of 79 KOH / g.

[0110] Comparative Example 2

[0111] The method is consistent with that in Example 1, except that polyoxyethylene fatty alcohol ether (weight average molecular weight of 5024) is used to obtain defoamer D2, which has an acid value of 0.06 mg KOH / g and a hydroxyl value of 98 KOH / g.

[0112] Comparative Example 3

[0113] The method is consistent with that in Example 1, except that Span 80 is not included and the total amount of additive I remains unchanged to obtain defoamer D3, wherein the mass fraction of the main agent is 75%, the mass fraction of additive I is 23.5%, and the mass fraction of additive II is 1.5%. The defoamer has an acid value of 0.03 mg KOH / g and a hydroxyl value of 70 KOH / g.

[0114] Comparative Example 4

[0115] The method is consistent with that in Example 1, except that it does not contain nonylphenol polyoxyethylene ether and the total amount of additive I remains unchanged, to obtain defoamer D4, wherein the mass fraction of the main agent is 75%, the mass fraction of additive I is 23.5%, and the mass fraction of additive II is 1.5%. The defoamer has an acid value of 0.02 mg KOH / g and a hydroxyl value of 77 KOH / g.

[0116] Comparative Example 5

[0117] The commercially available GPE polyether alcohol defoamer D5 is used, with the following parameters: acid value 0.03 mg KOH / g and hydroxyl value 53 mg KOH / g.

[0118] Comparative Example 6

[0119] The preparation method is the same as in Example 1, except that the amount of polyamide-amine 3rd generation is 13.3g, the amount of polyoxyethylene fatty alcohol ether is 26.6g, the amount of polydimethylsiloxane is 6.7g, and the mass ratio of polyamide-amine 3rd generation to polyoxyethylene fatty alcohol ether is 0.5:1, to obtain defoamer D6; in defoamer D6, the mass fraction of the main agent is 65%, the mass fraction of auxiliary agent I is 33%, and the mass fraction of auxiliary agent II is 2%; the acid value of this defoamer is 0.03mgKOH / g, and the hydroxyl value is 71KOH / g.

[0120] Blank example

[0121] The blank examples show the foam height and defoaming time of organic amine desulfurization and decarbonization aqueous solutions without the addition of any defoamer, as detailed in Table 1. Unless otherwise specified, all temperatures in Table 1 are 40℃.

[0122] Application Example 1

[0123] The defoamer A1 prepared in Example 1 was added to the organic amine desulfurization and decarbonization aqueous solution of the blank example, wherein the amount of defoamer added accounted for 0.03 wt% of the total weight of the organic amine desulfurization and decarbonization aqueous solution, and the defoamer was used at a temperature of 40°C.

[0124] Application Example 2-17

[0125] The method is the same as in Application Example 1, except that defoamer A1 is replaced with defoamers A2-A17.

[0126] Application Example 18

[0127] The method is consistent with that in Application Example 1, except that the amount of defoamer A1 added is 0.08 wt% of the total weight of the organic amine desulfurization and decarbonization aqueous solution.

[0128] Application Example 19

[0129] The method is consistent with that in Application Example 1, except that the amount of defoamer A1 added is 0.15 wt% of the total weight of the organic amine desulfurization and decarbonization aqueous solution.

[0130] Application Example 20

[0131] The method is the same as in Application Example 1, except that the operating temperature is 25°C.

[0132] Application Example 21

[0133] The method is the same as in Application Example 1, except that the operating temperature is 140°C.

[0134] Comparative Application Examples 1-6

[0135] The method is the same as in Application Example 1, except that defoamer A1 is replaced with defoamers D1-D6.

[0136] Compare and contrast with examples 7-8

[0137] The method is consistent with that in Application Example 1, except that defoamer A1 is replaced with defoamer D5, and the amount of D5 added accounts for 0.08 wt% and 0.15 wt% of the total weight of the organic amine desulfurization and decarbonization aqueous solution, respectively.

[0138] Comparative Application Example 9

[0139] The method is consistent with that in Application Example 1, except that defoamer A1 is replaced with defoamer D1, and the amount of D1 added is 0.007 wt% of the total weight of the organic amine desulfurization and decarbonization aqueous solution.

[0140] Test case

[0141] The application examples and comparative application examples were subjected to foam height, defoaming time and consumption resistance tests, and the results are shown in Table 1.

[0142] The wear-resistance treatment method is as follows:

[0143] The desulfurization and decarbonization aqueous solution containing an organic amine containing defoamer was mixed with coconut shell activated carbon at a volume ratio of 1:5. After shaking in a shaker for half an hour, the mixture was allowed to stand, filtered through a 600-mesh filter, and the filtrate was used for defoaming performance testing. This process was repeated, and the results were recorded on the 5th test. The activated carbon used had an iodine value >1000mg / g and a mesh size of 2-8.

[0144] Table 1

[0145]

[0146]

[0147] As can be seen from Table 1, Application Examples 1-21 have a good defoaming effect, with foam height not exceeding 65mm and defoaming time not less than 14s.

[0148] Among them, application examples 1-3, 5, 7-16, and 18-19 showed better results, with foam height not exceeding 45 mm and defoaming time not exceeding 10 seconds. It can be seen that the defoamers A1-A3, A5, A7, and A10-17 in application examples 1-3, 5, 7, and 10-17 have good defoaming ability.

[0149] Application examples 18-19 show that the defoamer described in this application can produce good defoaming effects within the preferred addition range.

[0150] In Application Examples 4 and 6, the components in the main agent are not within the range and therefore do not achieve the expected effect. Similarly, if the amount of main agent used is too large, the effect will not be significantly enhanced (Application Example 8), but if the amount used is insufficient, the expected effect will not be achieved (Compare Application Example 9).

[0151] Application examples 20-21 also show that good results can be obtained within the temperature range described in this application, but the preferred range is not met, and its defoaming ability is slightly inferior to that of Example 1.

[0152] Furthermore, the wear resistance of Application Example 1 is relatively strong. After the wear resistance test, the bubble height is 47 mm and the defoaming time is 8 seconds. In contrast, although the defoamer D5 in Application Example 5 has a decent defoaming effect, its defoaming ability significantly decreases after the wear resistance treatment. The bubble height increases from 75 mm before the wear resistance treatment to 127 mm, and the defoaming time increases from 17 seconds to 26 seconds.

[0153] The defoamer provided by this invention has high defoaming ability and strong wear resistance, thereby reducing annual wear during actual use.

[0154] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A defoamer, characterized in that, Based on the total weight of the defoamer, the defoamer contains 67-90 wt% of the main agent, 8-30 wt% of auxiliary agent I and 1-3 wt% of auxiliary agent II; The main agent is selected from at least two of polyamide-amine, polyoxyethylene fatty alcohol ether, and silicone oil; The auxiliary agent I includes alkylphenol surfactants and polyol surfactants, and the auxiliary agent II includes adhesives and silicone-based waterproofing agents; The weight-average molecular weight of the polyoxyethylene fatty alcohol ether is 3000-4000.

2. The defoamer according to claim 1, wherein, The terminal groups of the polyamide-amine are amine groups and / or hydroxyl groups.

3. The defoamer according to claim 1 or 2, wherein, The silicone oil is selected from at least one of polymethylsiloxane, polydimethylsiloxane, polyether silicone oil, and methyl silicone oil.

4. The defoamer according to claim 1 or 2, wherein, The main agent includes polyamide-amine, polyoxyethylene fatty alcohol ether and silicone oil, and the mass ratio of the sum of the mass of the polyamide-amine and the polyoxyethylene fatty alcohol ether to the mass of the silicone oil is (5-10):1; the mass ratio of the polyamide-amine to the polyoxyethylene fatty alcohol ether is (0.35-1.5):1; Alternatively, the main agent may include polyamide-amine and polyoxyethylene fatty alcohol ether, and the mass ratio of polyamide-amine to polyoxyethylene fatty alcohol ether is (0.35-1.5):

1.

5. The defoamer according to claim 1 or 2, wherein, The alkylphenol surfactant is selected from at least one of nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether and heptylphenol polyoxyethylene ether; And / or, the polyol surfactant is selected from dehydrated sorbitan fatty acid esters and / or polysorbates.

6. The defoamer according to claim 1 or 2, wherein, The mass ratio of the alkylphenol surfactant to the polyol surfactant is 0.8:1 to 1:0.

8.

7. The defoamer according to claim 1 or 2, wherein, The binder is selected from sodium carboxymethyl cellulose and / or methyl cellulose; And / or, the silicone-based waterproofing agent is selected from organosilicon waterproofing agents and / or inorganic silicone waterproofing agents.

8. The defoamer according to claim 7, wherein, The silicon-based waterproofing agent is hydrophobic silicon dioxide.

9. The defoamer according to claim 1 or 2, wherein, The mass ratio of the adhesive to the silicone-based waterproofing agent is (1-3):

1.

10. The defoamer according to claim 1 or 2, wherein, Based on the total mass of the defoamer, the content of the silicone-based waterproofing agent is not less than 0.5 wt%.

11. The application of an antifoaming agent in an aqueous solution for desulfurization and decarbonization of organic amines, characterized in that, The defoamer is the defoamer according to any one of claims 1-10; The amount of defoamer added is 0.01-0.1 wt%, based on the total weight of the organic amine desulfurization and decarbonization aqueous solution.

12. The application according to claim 11, wherein, The defoamer is used at a temperature of 20-140℃ for organic amine desulfurization and decarbonization aqueous solutions.

13. The application according to claim 12, wherein, The defoamer is used at a temperature of 40-130℃ for organic amine desulfurization and decarbonization aqueous solutions.

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