CN109749877B - Composition for passivating and cleaning ferrous sulfide and application thereof - Google Patents
Composition for passivating and cleaning ferrous sulfide and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of petrochemical industry, and discloses a composition for passivating and cleaning ferrous sulfide and application thereof. The composition contains hydroxyalkyl pyrone, beta-cyclodextrin, organic phosphonic acid type cleaning agent, glycol monoalkyl ether, polyoxyethylene ether type nonionic surfactant and sulfonic acid group-containing acrylic acid type dispersing agent, wherein the weight ratio of the hydroxyalkyl pyrone, the beta-cyclodextrin, the organic phosphonic acid type cleaning agent, the glycol monoalkyl ether, the polyoxyethylene ether type nonionic surfactant and the sulfonic acid group-containing acrylic acid type dispersing agent is 100:10-250:10-500:30-500:2-100: 0.1-6. The invention also discloses application of the composition in cleaning ferrous sulfide. The invention further discloses a method for cleaning ferrous sulfide, which comprises the following steps: contacting the above composition with equipment to be cleaned. The composition of the invention does not generate hydrogen sulfide gas when cleaning ferrous sulfide dirt.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a ferrous sulfide passivation cleaning composition for preventing spontaneous combustion of ferrous sulfide in petrochemical equipment and application thereof.
Background
As the proportion of high sulfur crude oil processed by refineries increases, the corrosion of equipment by sulfur also becomes more severe. The corrosion products are mostly in the form of ferrous sulfide, which refers to FeS and FeS2、Fe2S3And mixtures of several chemicals. Ferrous sulfide is rapidly oxidized at normal temperature and spontaneously combusts, flame does not occur during spontaneous combustion, only the ferrous sulfide is heated to a glowing state, and other substances can be combusted when the ferrous sulfide reaches a certain temperature, so that the material of equipment is damaged. In recent years, domestic multiple sets of chemical devicesThe spontaneous ignition of ferrous sulfide damages the equipment. The harm of spontaneous combustion of the ferrous sulfide is not only to damage equipment, but also to the generation of toxic gases such as sulfur dioxide and the like when the ferrous sulfide detonates and spontaneously combusts in the equipment, and the harm is serious to the health of equipment maintainers. The elimination of ferrous sulfide is the first safety procedure that must be performed in the shutdown and overhaul of modern high sulfur crude oil refineries.
The main influencing factors of the spontaneous combustion of ferrous sulfide are the temperature and the nature of the sulfide. Ferrous sulfide in humid air, Fe2+Is oxidized into Fe3+，S2-Is oxidized to higher sulfur, and this process produces two effects: one is due to S2-Oxidized into high-valence sulfur, so that the acidity of a reaction area is increased, and the dissolution of ferrous sulfide solids is accelerated; secondly, in the oxidation process, a large amount of heat is released, so that the local temperature is raised, the reaction is accelerated, and the oxidation of the surrounding ferrous sulfide is accelerated. The two reactions promote each other, forming a vicious circle. Meanwhile, carbon powder and oil exist in the scale, and after the scale is ignited by ferrous sulfide, the scale is rapidly combusted to emit more heat, so that a large amount of heat is accumulated in a short time, and equipment is possibly damaged.
At present, there are three industrial methods for preventing spontaneous combustion of ferrous sulfide: 1) isolation method-that is, the contact between ferrous sulfide and oxygen in the air is prevented, such as protection by nitrogen, water seal protection, etc.; 2) cleaning method-ferrous sulfide is removed from the equipment, such as mechanical cleaning, chemical cleaning and the like; 3) passivation method-the equipment is treated by passivating agent to convert the ferrous sulfide which is easy to self-ignite into more stable compound, thus preventing the self-ignition of the ferrous sulfide.
The isolation method is suitable for online protection, but the spontaneous combustion of ferrous sulfide is difficult to effectively prevent in the process of maintenance. Passivation methods are costly and do not remove ferrous sulfide from the equipment. The cleaning method comprises physical cleaning and chemical cleaning, wherein the physical cleaning mainly utilizes special machinery to clean a scale layer on the surface of equipment; the chemical cleaning includes alkali cleaning, acid cleaning, organic solvent cleaning, and cleaning with a mixed chemical cleaning solution composed of a surfactant, alkali, an organic solvent, and the like, which is adopted according to different types of scales. In contrast, the cleaning method is simple and effective, has low cost and is a more common method. The chemical cleaning of petrochemical equipment widely adopted at present is actually the combination of the traditional cleaning method and the passivation method, namely, the components of a passivator are properly added in the chemical cleaning. The main used passivating agent cleaning agent mainly comprises potassium permanganate, chlorine dioxide, sodium hypochlorite and the like. Although the passivation cleaning agent can meet the safety production requirement of petrochemical enterprises in eliminating ferrous sulfide. However, potassium permanganate used in passivation cleaning contains a large amount of manganese ions, so that secondary pollution is easily caused; chlorine dioxide corrodes equipment, and particularly, stainless steel is easy to generate pitting corrosion; the acid liquor has serious corrosion to equipment, and although corrosion inhibitor is added to reduce corrosion, the waste liquor after cleaning still needs to be solved; sodium hypochlorite is prone to produce harmful substances. For example, CN102373122A discloses an inorganic ferrous sulfide passivation cleaning agent, which is characterized by consisting of 5-15% of sodium pyrosulfate, 15-35% of sodium hypochlorite, 0.5-10% of trisodium phosphate, 0.1-5% of sodium bicarbonate and 35-79% of water, and the pH value of the product is controlled between 11 and 12. CN102345136A discloses a chemical cleaning agent for removing impurities such as ferrous sulfide, which comprises 1-15% of acid chelating agent (citric acid, tartaric acid and salicylic acid), 0.05-5% of surfactant, 1-20% of alkaline chelating agent, 5-30% of oxidant (hydrogen peroxide, sodium hypochlorite and potassium permanganate), 0.1-1% of corrosion inhibitor, 0.1-2% of cosolvent and the balance of water. CN103160322A discloses a ferrous sulfide passivator and a preparation method thereof, which is characterized in that the passivator is prepared from 30-40% of Tween 80, 0.4-0.6% of citric acid, 15-25% of sodium lauryl sulfate, 1-2% of potassium permanganate and 40-50% of secondary deionized water. The above patents use strong oxidants such as sodium hypochlorite and potassium permanganate, which are easy to generate secondary pollution.
CN102877079A discloses a method for removing ferrous sulfide in petroleum industry pipelines and equipment, which comprises adding 10-1000mg/L of surfactant, 10-100mg/L of phase transfer catalyst (at least one of citric acid, benzoic acid, sulfamic acid and organic phosphonic acid) and 0.001-1% of soluble copper salt (at least one of copper sulfate, copper nitrate and copper chloride) into cleaning water, wherein the pH value is 5-7.
Disclosure of Invention
The invention aims to provide a novel ferrous sulfide passivation cleaning agent, which has the advantages that ferrous sulfide attached to petrochemical equipment, particularly refining equipment can be quickly and effectively cleaned, no harmful substance is generated, and meanwhile, toxic and harmful gases such as hydrogen sulfide and the like generated in the petrochemical equipment can be greatly reduced, so that the novel ferrous sulfide passivation cleaning agent is efficient, safe, environment-friendly, low in cost and deodorant.
In one aspect, the invention provides a ferrous sulfide passivation cleaning composition, which comprises hydroxyalkyl pyrone, beta-cyclodextrin, organic phosphonic acid type cleaning agent, glycol monoalkyl ether, polyoxyethylene ether type nonionic surfactant and sulfonic acid group-containing acrylic acid type dispersing agent, wherein the weight ratio of the hydroxyalkyl pyrone, the beta-cyclodextrin, the organic phosphonic acid type cleaning agent, the glycol monoalkyl ether, the polyoxyethylene ether type nonionic surfactant and the sulfonic acid group-containing acrylic acid type dispersing agent is 100:10-250:10-500:30-500:2-100: 0.1-6.
In another aspect, the present invention provides the use of the above composition for cleaning ferrous sulfide.
In yet another aspect, the present invention provides a method of cleaning ferrous sulfide, the method comprising: contacting the above composition with equipment to be cleaned.
Through the technical scheme, all components in the composition can cooperatively play a role, the chemical property is stable, strong oxidants (such as sodium hypochlorite, potassium permanganate and the like) and/or copper salts are not used, and the composition meets the requirement of environmental protection; the cleaning process is simple, the effect is obvious, and the method is easy to popularize and apply. The composition of the invention can not generate hydrogen sulfide gas when cleaning ferrous sulfide dirt, and has the characteristics of high dirt removing speed, good safety and convenient use.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The composition for passivating and cleaning ferrous sulfide comprises hydroxyalkyl pyrone, beta-cyclodextrin, organic phosphonic acid type cleaning agent, glycol monoalkyl ether, polyoxyethylene ether type nonionic surfactant and sulfonic acid group-containing acrylic acid type dispersing agent, wherein the weight ratio of the hydroxyalkyl pyrone, the beta-cyclodextrin, the organic phosphonic acid type cleaning agent, the glycol monoalkyl ether, the polyoxyethylene ether type nonionic surfactant and the sulfonic acid group-containing acrylic acid type dispersing agent is 100:10-250:10-500:30-500:2-100:0.1-6, preferably 100:20-200:20-100:40-200:10-20: 0.2-5.
According to the present invention, the hydroxyalkylpyrone may be various common γ -pyrones substituted with hydroxy and alkyl groups, and preferably, the hydroxyalkylpyrone is selected from
At least one of the compounds shown, wherein R1、R2And R3Each independently selected from H or C1-C4Alkyl groups (e.g., methyl, ethyl, etc.). More preferably, the hydroxyalkylpyrone is selected from the group consisting of maltol (2-methyl-3-hydroxy-4-pyrone,
) And/or ethyl maltol (2-ethyl-3-hydroxy-4-pyrone,
)。
according to the invention, the beta-cyclodextrin and the hydroxyalkyl pyrone are important components in the composition, namely the mixture of the hydroxyalkyl pyrone and the beta-cyclodextrinThe weight ratio of (A) to (B) is preferably 100:20 to 200. The hydroxyalkylpyranones are capable of eliminating H in the presence of beta-cyclodextrin2And S is released and chelated with ferrous sulfide, so that the environmental protection performance is improved. Under the condition of low content of beta-cyclodextrin, the reaction of the composition and hydrogen sulfide can be well promoted, and the composition has the effect of adsorbing hydrogen sulfide gas.
According to the invention, the organic phosphonic acid type cleaning agent is an important component in the composition, and is beneficial to improving the cleaning and passivating performances of the composition. The weight ratio of the hydroxyalkyl pyrone to the organic phosphonic acid type cleaning agent is preferably 100: 20-100. The organic phosphonic acid type cleaning agent may be an organic phosphonic acid as is common in the art, e.g., C2-C10Preferably, the organic phosphonic acid type cleaning agent is selected from at least one of hydroxyethylidene diphosphonic acid, ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid and sodium salt, potassium salt and ammonium salt thereof.
According to the present invention, the glycol monoalkyl ether is an important component in the composition, and the composition can have excellent cleaning and deactivating properties in combination with other components. The weight ratio between the hydroxyalkyl pyrone and the glycol monoalkyl ether is preferably 100:40 to 200. The glycol monoalkyl ether may be one conventionally selected in the art, and is preferably selected from
At least one of the compounds shown, wherein R4Is C1-C4Alkyl (especially methyl, ethyl, propyl or butyl), R5is-CH2CH2-or-CH (CH)3)CH2-n 1 is 1 or 2. The method specifically comprises the following steps: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl etherAt least one of (1). More preferably, the glycol monoalkyl ether is ethylene glycol monobutyl ether.
According to the present invention, the polyoxyethylene ether type nonionic surfactant is an important constituent in the composition. The weight ratio between the hydroxyalkyl pyrone and the polyoxyethylene ether type nonionic surfactant is preferably 100: 10-20. The polyoxyethylene nonionic surfactant can be selected conventionally in the field, and is preferably selected from long-chain fatty alcohol polyoxyethylene ether and/or alkylphenol polyoxyethylene ether.
More preferably, the long-chain fatty alcohol polyoxyethylene ether is selected from the group consisting of fatty alcohol ethers having the general formula
At least one of the compounds of (1), wherein R6Is C8-C18M is a natural number of 4 to 15, preferably a natural number of 4 to 6. Specifically, as commercially available: OE-4 (C)8-C10Fatty alcohol polyoxyethylene (4) ether), OE-6 (C)8-C10Fatty alcohol polyoxyethylene (6) ether), MOA-4 (C)12-C18Fatty alcohol polyoxyethylene (4) ether), MOA-5 (C)12-C18Fatty alcohol polyoxyethylene (5) ether), MOA-6 (C)12-C18Fatty alcohol polyoxyethylene (6) ether), MOA-9 (C)12-C18Fatty alcohol polyoxyethylene (9) ether), O-5 (C)12-C18Fatty alcohol polyoxyethylene (5) ether), O-8 (C)12-C18Fatty alcohol polyoxyethylene (8) ether), O-10 (C)12-C18Fatty alcohol polyoxyethylene (10) ether), and the like.
More preferably, the alkylphenol ethoxylates are selected from the group consisting of those having the general formula
At least one compound of (1), wherein R7Is C8-C12Is preferably C8Or C9N is a natural number of 4 to 15, more preferably, the alkylphenol ethoxylate is selected from octylphenol polyoxyethylene ether (n ═ 4 to 10) and/orNonylphenol polyoxyethylene ether (n ═ 4-10). Specifically, as commercially available: TX-4 (nonylphenol polyoxyethylene (4) ether), TX-10 (nonylphenol polyoxyethylene (10) ether), TX-15 (nonylphenol polyoxyethylene (15) ether), OP-4 (octylphenol polyoxyethylene (4) ether), OP-10 (octylphenol polyoxyethylene (10) ether), and the like.
According to the invention, the acrylic acid type dispersing agent containing sulfonic acid group is an important component in the composition for ferrous sulfide cleaning, and the weight ratio of the hydroxyalkyl pyrone to the acrylic acid type dispersing agent containing sulfonic acid group is preferably 100: 0.2-5. The sulfonic acid group-containing acrylic acid type dispersant may be a substance commonly used in the art to disperse oil stains and prevent deposit adhesion, and is preferably selected from a copolymer of acrylic acid and sulfonic acid group-containing olefin. More preferably, the sulfonic acid group-containing olefin is selected from at least one of 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, and allyl polyethylene glycol sulfonic acid. The weight average molecular weight of the copolymer can be 1500-50000, and the preferable range of the weight average molecular weight is 1500-15000. In the copolymer, the molar ratio of the structural units provided by acrylic acid and the olefin containing sulfonic acid groups is 2-6: 1. Specific examples of the sulfonic acid group-containing acrylic acid type dispersants are: at least one of AA/SA (acrylic acid/styrenesulfonic acid copolymer), AA/AMPS (acrylic acid/2-acrylamido-2-methylpropanesulfonic acid copolymer), AA/AHPSE (acrylic acid/3-allyloxy-2-hydroxypropanesulfonic acid copolymer) and AA/APES (acrylic acid/allyl polyethylene glycol sulfonic acid copolymer), and most preferably at least one of AA/AMPS, AA/AHPSE and AA/APES.
According to the invention, the composition may also contain a solvent. The solvent used may be water, methanol, ethanol, or other conventional solvents. The solvent is used in an amount such that the components other than the solvent account for 6 to 20% by weight of the total weight of the components other than the solvent and the solvent.
According to the invention, the composition for passivating and cleaning the ferrous sulfide can be obtained by various conventional methods without special requirements, and only the required compositions are mixed uniformly. The ferrous sulfide passivation cleaning agent can also be obtained by dissolving non-solvent components in a solvent. In practice, the non-solvent components are typically dissolved in a solvent for use in the manner of a ferrous sulfide passivating cleaning agent.
The invention also provides application of the composition in cleaning ferrous sulfide, in particular application in cleaning ferrous sulfide dirt in petrochemical equipment.
In addition, the invention also provides a method for cleaning ferrous sulfide, which is characterized by comprising the following steps: the composition as described hereinbefore is contacted with equipment to be cleaned, such as petrochemical equipment, in particular surfaces having ferrous sulphide scale adhered thereto. The amount of the composition may be conventionally selected, but preferably the composition is used in an amount of 1 to 10g, preferably 2 to 7g, in terms of the non-solvent component, per gram of ferrous sulphide attached to the equipment to be cleaned. The contact time is not particularly limited, and may be, for example, 0.5 to 5 hours. When the concentration of the cleaning agent is high and the ferrous sulfide amount is small, the contact time is short; the concentration of the cleaning agent is low, and the contact time is long when the ferrous sulfide amount is large.
The present invention will be described in detail below by way of examples. The weight of the reagents used is calculated as the effective content (or solids content).
The reagents used in the examples and comparative examples are as follows: alpha-cyclodextrin, beta-cyclodextrin, ethylene glycol monobutyl ether, maltol, ethyl maltol, sodium hypochlorite and potassium permanganate are purchased from national medicine group chemical reagent company Limited; ethylene glycol methyl ether, propylene glycol monopropyl ether, dipropylene glycol butyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and diethylene glycol monobutyl ether are all available from Adamas Reagent; hydroxyethylidenediphosphonic acid (HEDPA), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DETMP), 1# AA/AMPS (molar ratio 6:1, Mw 45000), 2# AA/AMPS (molar ratio 3:1, Mw 5000), 3# AA/AMPS (molar ratio 5:1, Mw 1500), AA/AHPSE (molar ratio 3:1, Mw 6000) from santa and water treatment limited; AA/APES (molar ratio 3:1, Mw 15000) from general electric (tin-free) ltd; AA/SS (molar ratio 5:1, Mw 10000) from jiang hai environmental protection gmbh; TX-4, TX-10, OE-6, MOA-4, MOA-6, O-5 and OP-10 were purchased from Jiangsu Haian petrochemical plant.
Example 1
And sequentially adding 50ml of water, 3g of maltol, 1.5g of beta-cyclodextrin, 3g of HEDPA, 3.5g of ethylene glycol monobutyl ether, 0.5g of TX-4 and 0.025g of 2# AA/AMPS into a 250ml beaker with an electromagnetic stirring bar, stirring for dissolving, continuously adding water to the required amount under stirring, and adjusting to 100g of solution to obtain the ferrous sulfide passivation cleaning agent.
Example 2
And sequentially adding 1g of maltol, 2g of beta-cyclodextrin, 1g of HEDPA, 2g of ethylene glycol monobutyl ether, 0.1g of TX-4 and 0.05g of 1# AA/AMPS into a 250ml beaker with an electromagnetic stirring bar, stirring for dissolving, continuously adding water to the required amount under stirring, and adjusting to 100g of solution to obtain the ferrous sulfide passivation cleaning agent.
Example 3
And (2) sequentially adding 5g of ethyl maltol, 1g of beta-cyclodextrin, 5g of EDTMP, 5g of ethylene glycol monobutyl ether, 1g of MOA-6 and 0.01g of AA/AHPSE into a 250ml beaker provided with an electromagnetic stirring bar, stirring to dissolve, continuously adding water to the required amount under stirring, and adjusting to 100g of solution to obtain the ferrous sulfide passivation cleaning agent.
Example 4
And sequentially adding 2g of maltol, 1g of beta-cyclodextrin, 2g of HEDPA, 4g of ethylene glycol monobutyl ether, 0.3g of MOA-4 and 0.04g of 1# AA/AMPS into a 250ml beaker with an electromagnetic stirring bar, stirring for dissolving, continuously adding water to the required amount under stirring, and adjusting to 100g of solution to obtain the ferrous sulfide passivation cleaning agent.
Example 5
And (2) sequentially adding 4g of maltol, 1.5g of beta-cyclodextrin, 4g of EDTMP, 3g of ethylene glycol monobutyl ether, 0.8g of OE-6 and 0.02g of AA/AHPSE into a 250ml beaker with an electromagnetic stirring bar, stirring for dissolving, continuously adding water to the required amount under stirring, and adjusting to 100g of solution to obtain the ferrous sulfide passivation cleaning agent.
Example 6
And (2) sequentially adding 5g of maltol, 1g of beta-cyclodextrin, 1g of DETMP, 2g of ethylene glycol monobutyl ether, 1g of TX-10 and 0.03g of AA/APES into a 250ml beaker with an electromagnetic stirring bar, stirring to dissolve, continuously adding water to the required amount under stirring, and adjusting to 100g of solution to obtain the ferrous sulfide passivation cleaning agent.
Example 7
And sequentially adding 50ml of water, 3g of maltol, 1.5g of beta-cyclodextrin, 3g of HEDPA, 3.5g of ethylene glycol monobutyl ether, 0.5g of O-5 and 0.025g of AA/SS into a 250ml beaker with an electromagnetic stirring bar, stirring for dissolving, continuously adding water to the required amount under stirring, and preparing into 100g of solution to obtain the ferrous sulfide passivation cleaning agent.
Example 8
50ml of water, 3g of maltol, 1.5g of beta-cyclodextrin, 3g of HEDPA, 1.5g of propylene glycol monobutyl ether, 2g of ethylene glycol monomethyl ether, 0.5g of O-10 and 0.025g of 3# AA/AMPS are sequentially added into a 250ml beaker with an electromagnetic stirring bar, stirred and dissolved, and water is continuously added to the required amount under stirring to prepare 100g of solution, thus obtaining the ferrous sulfide passivation cleaning agent.
Example 9
50ml of water, 3g of maltol, 1.5g of beta-cyclodextrin, 3g of HEDPA, 1.5g of propylene glycol monopropyl ether, 2g of diethylene glycol monobutyl ether, 0.5g of OE-6 and 0.025g of 2# AA/AMPS are sequentially added into a 250ml beaker with an electromagnetic stirring bar, stirred and dissolved, and water is continuously added to the required amount under stirring to prepare 100g of solution, thus obtaining the ferrous sulfide passivation cleaning agent.
Example 10
50ml of water, 3g of maltol, 1.5g of beta-cyclodextrin, 3g of HEDPA, 2g of diethylene glycol monoethyl ether, 1.5g of dipropylene glycol monomethyl ether, 0.5g of MOA-6 and 0.025g of 1# AA/AMPS are sequentially added into a 250ml beaker with an electromagnetic stirring bar, stirred and dissolved, and water is continuously added to the required amount under stirring to prepare 100g of solution, thus obtaining the ferrous sulfide passivation cleaning agent.
Example 11
Adding 50ml of water, 3g of maltol, 1.5g of beta-cyclodextrin, 3g of HEDPA, 2g of dipropylene glycol monobutyl ether, 1.5g of ethylene glycol monobutyl ether, 0.5g of TX-4 and 0.025g of 2# AA/AMPS into a 250ml beaker with an electromagnetic stirring bar in sequence, stirring for dissolving, and continuously adding water to the required amount under stirring to prepare 100g of solution, thus obtaining the ferrous sulfide passivation cleaning agent.
Example 12
And sequentially adding 50ml of water, 3g of maltol, 1.5g of beta-cyclodextrin, 3g of HEDPA, 1.5g of ethylene glycol monomethyl ether, 2g of dipropylene glycol monomethyl ether, 0.5g of TX-4 and 0.025g of 2# AA/AMPS into a 250ml beaker with an electromagnetic stirring bar, stirring for dissolving, continuously adding water to the required amount under stirring, and adjusting to 100g of solution to obtain the ferrous sulfide passivation cleaning agent.
Example 13
And sequentially adding 50ml of water, 3g of maltol, 1.5g of beta-cyclodextrin, 3g of HEDPA, 3.5g of diethylene glycol monoethyl ether, 0.5g of TX-4 and 0.025g of 2# AA/AMPS into a 250ml beaker with an electromagnetic stirring bar, stirring for dissolving, continuously adding water to the required amount under stirring, and adjusting to 100g of solution to obtain the ferrous sulfide passivation cleaning agent.
Example 14
A ferrous sulfide passivating cleaner was formulated in the manner of example 1, except that "propylene glycol monomethyl ether" was used in place of "ethylene glycol monobutyl ether".
Comparative example 1
A ferrous sulfide passivating cleaner was formulated in the manner of example 1, except that no beta-cyclodextrin was used.
Comparative example 2
A ferrous sulfide passivating cleaner was formulated in the manner of example 1, except that maltol was not used.
Comparative example 3
A ferrous sulfide passivating cleaner was formulated in the manner of example 1, except that ethylene glycol monobutyl ether was not used.
Comparative example 4
A ferrous sulfide passivating cleaner was formulated as in example 1, except that TX-4 was not used.
Comparative example 5
The cleaning agent was prepared by the method described in example 1 of CN 102345136A.
Comparative example 6
The cleaning agent was prepared by the method described in example 1 of CN 103160322A.
Comparative example 7
The cleaning agent was prepared by the method described in example 1 of CN 102877079A.
Comparative example 8
A ferrous sulfide passivating cleaner was formulated in the manner of example 1, except that "alpha-cyclodextrin" was used instead of "beta-cyclodextrin".
Comparative example 9
A ferrous sulfide passivating cleaner was formulated in the manner of example 1, except that "sodium dodecylbenzenesulfonate (an anionic surfactant)" was used in place of "TX-4".
Comparative example 10
A ferrous sulfide passivating detergent was formulated in the manner of example 2, except that "Tween 80 and sodium lauryl sulfate in a weight ratio of 1: 1" was used in place of "TX-4".
Comparative example 11
A ferrous sulfide passivating cleaner was formulated as in example 1, except that beta-cyclodextrin was used in an amount of 0.5g and TX-4 was used in an amount of 1.5 g.
Test example 1
GB/T25146-2010 chemical cleaning quality acceptance criterion of industrial equipment, the ferrous sulfide passivation cleaning agent obtained in the examples and the comparative examples is evaluated respectively.
Dissolving ferrous sulfide oil dirt test: in a 200ml beaker, weighing 2g of vacuum wax oil (collected from a raisin petrochemical refinery), 3g of catalytic cracking slurry oil (collected from the raisin petrochemical refinery), 2.5g of ferrous sulfide powder, mixing into oil dirt mud, then adding 100g of ferrous sulfide passivation cleaning agent, reacting under the slow stirring of a magnetic stirrer, testing whether hydrogen sulfide overflows or not by using lead acetate test paper (the test paper becomes black to indicate that hydrogen sulfide overflows), recording the phenomena at 0.5 hour, 1.0 hour and 2.0 hours of reaction, and testing the ferrous sulfide conversion rate in the final solution, wherein the conversion rate is (the weight of ferrous sulfide before the test-the weight of ferrous sulfide after the test)/the weight of ferrous sulfide before the test multiplied by 100%.
Judging the cleaning passivation effect: the higher the ferrous sulfide conversion, the better the hydrogen sulfide breakthrough, and the better the precipitate produced. TABLE 1
The results show that the composition of the invention does not generate hydrogen sulfide gas when cleaning ferrous sulfide dirt, and has the characteristics of high dirt removing speed, good safety and convenient use.
In addition, as can be seen from the results of the tests of examples 1 to 14 and comparative examples 1 to 4 and 8 to 11, the components of the ferrous sulfide passivation cleaning agent of the present invention can be used together to exert high efficiency.
In particular, comparing examples 1 to 6 with examples 7 to 14, it can be seen that better cleaning results can be obtained using the preferred dispersant and glycol monoalkyl ether.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (18)
1. A composition for passivating and cleaning ferrous sulfide is characterized by comprising hydroxyalkyl pyrone, beta-cyclodextrin and C2-C10Wherein the hydroxyalkyl pyrone, beta-cyclodextrin, C are contained in the surfactant, and a sulfonic acid group-containing acrylic acid type dispersant2-C10Organic phosphonic acid, glycol monoalkyl ether, polyoxyethylene ether type nonionic surfactant and sulfonic acid group-containing acrylic acid type dispersantIs 100:10-250:10-500:30-500:10-20:0.1-6, and the hydroxyalkyl pyrone is selected from maltol and/or ethyl maltol.
2. The composition of claim 1, wherein the hydroxyalkyl pyrone, beta-cyclodextrin, C2-C10The weight ratio of the organic phosphonic acid, the glycol monoalkyl ether, the polyoxyethylene ether nonionic surfactant and the acrylic dispersant containing sulfonic group is 100:20-200:20-100:40-200:10-20: 0.2-5.
3. The composition of claim 1 or 2, wherein C is2-C10The organic phosphonic acid is selected from at least one of hydroxyl ethylidene diphosphonic acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine penta methylene phosphonic acid and sodium salt, potassium salt and ammonium salt thereof.
4. The composition of claim 1 or 2, wherein the glycol monoalkyl ether is selected from
At least one of the compounds shown, wherein R4Is C1-C4Alkyl of R5is-CH2CH2-or-CH (CH)3)CH2-n 1 is 1 or 2.
5. The composition of claim 4, wherein the glycol monoalkyl ether is selected from at least one of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether.
6. Composition according to claim 1 or 2, wherein the polyoxyethylene-type nonionic surfactant is selected from long-chain fatty alcohol polyoxyethylene ethers and/or alkylphenol polyoxyethylene ethers.
7. The composition of claim 6, wherein the long chain fatty alcohol polyoxyethylene ether is of a formula selected from
At least one compound of (1), wherein R6Is C8-C18M is a natural number of 4 to 15.
8. The composition of claim 7, wherein m is a natural number from 4 to 6.
9. The composition of claim 6, wherein the alkylphenol ethoxylates are selected from the group consisting of those having the general formula
At least one compound of (1), wherein R7Is C8-C12N is a natural number of 4 to 15.
10. The composition of claim 9, wherein R7Is C8Or C9Alkyl group of (1).
11. The composition of claim 9, wherein the alkylphenol ethoxylate is selected from the group consisting of octylphenol ethoxylate and/or nonylphenol ethoxylate.
12. The composition as claimed in claim 1 or 2, wherein the sulfonic acid group-containing acrylic acid-type dispersant is a copolymer of acrylic acid and a sulfonic acid group-containing olefin selected from at least one of 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, and allylpolyethylene glycol sulfonic acid, the copolymer having a weight average molecular weight of 1500-.
13. The composition according to claim 1 or 2, wherein the sulfonic acid group-containing acrylic acid-based dispersant is selected from at least one of acrylic acid/styrene sulfonic acid copolymer, acrylic acid/2-acrylamido-2-methylpropanesulfonic acid polymer, acrylic acid/3-allyloxy-2-hydroxypropanesulfonic acid copolymer, acrylic acid/allyl polyethylene glycol sulfonic acid copolymer.
14. The composition according to claim 1, wherein the composition further comprises a solvent in an amount such that the components other than the solvent account for 6 to 20% by weight of the total weight of the components other than the solvent and the solvent.
15. Use of a composition according to any one of claims 1 to 14 for cleaning ferrous sulphide.
16. A method of cleaning ferrous sulfide, the method comprising: contacting a composition according to any one of claims 1 to 14 with equipment to be cleaned.
17. The method of claim 16, wherein the composition is present in an amount of 1-10g per gram of ferrous sulfide attached to the equipment to be cleaned, as the non-solvent component.
18. The method of claim 17, wherein the composition is present in an amount of 2 to 7g, based on the non-solvent component.
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| CN201711055835.7A CN109749877B (en) | 2017-11-01 | 2017-11-01 | Composition for passivating and cleaning ferrous sulfide and application thereof |
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| MA24577A1 (en) * | 1997-06-26 | 1998-12-31 | Procter & Gamble | METHODS AND COMPOSITIONS FOR REDUCING MICROORGANISM FOR FOOD PRODUCTS |
| US7407650B2 (en) * | 2000-10-27 | 2008-08-05 | The Procter & Gamble Company | Fragrance compositions |
| AU2001214419A1 (en) * | 2000-10-27 | 2002-06-11 | The Procter And Gamble Company | Fragrance compositions |
| JP4942981B2 (en) * | 2005-10-14 | 2012-05-30 | 花王株式会社 | Hard surface cleaner |
| CN101255383B (en) * | 2008-03-27 | 2010-12-01 | 中国石油化工股份有限公司 | Highly effective ferrous sulfide deactivation cleaning agent |
| CN106929197B (en) * | 2017-03-31 | 2020-05-22 | 赵学法 | Oil-based cleaning agent for cleaning petrochemical equipment |
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