Efficient ceramic membrane cleaning agent, preparation method and application thereof

Abstract

The application discloses a kind of efficient ceramic membrane cleaning agent and its preparation method and application, belong to ceramic membrane cleaning technical field.The ceramic membrane cleaning agent is by the following components by mass percentage: sodium carboxymethyl cellulose 0.05-3%, methyl cellulose ether 1-3%, triethanolamine 0.1-1%, polyphosphate 0.5-3%, hydroxymethyl cellulose 1-3%, cocamide propyl hydroxyl sulfobetaine 4-8%, corrosion inhibitor 0.01-1%, xanthan gum 0.5-5%, methyl sulfonic acid 5-15%, tannic acid 5-15%, dipotassium hydrogen phosphate 3-8%, modified alkyl glycoside 5-10%, alkylphenol polyoxyethylene ether 5-10%, and the balance is water.The ceramic membrane cleaning agent prepared by the application is mild in formula, can achieve the purpose of removing dirt without damaging the surface of ceramic membrane at recommended concentration, can replace nitric acid cleaning agent, and the working fluid after use can be directly discharged.

Description

Technical Field

[0001] This invention belongs to the field of ceramic membrane cleaning technology, specifically relating to a highly efficient ceramic membrane cleaning agent, its preparation method, and its application. Background Technology

[0002] While certain measures can be taken to prevent and control membrane fouling during filtration, it is impossible to completely avoid it. With prolonged operation, the permeate flux of ceramic membranes decreases rapidly, failing to meet industrial design requirements. Furthermore, long-term adsorption of pollutants on the membrane surface and within the pores can chemically react with the membrane, shortening its lifespan. Therefore, to restore membrane performance parameters as much as possible, minimize the rate of decline over time, extend membrane lifespan, and reduce replacement costs, regular cleaning of ceramic membranes is essential.

[0003] Ceramic membrane cleaning can be divided into physical cleaning and chemical cleaning. Physical cleaning methods mainly involve mechanical cleaning, including water rinsing, backwashing, gas-liquid pulse flushing and scraping, and ultrasonic vibration. Physical cleaning methods are characterized by not introducing new contaminants, simple cleaning steps, and the ability to perform online cleaning. However, this method is only effective in the early stages of ceramic membrane fouling, and the cleaning effect decreases rapidly over time. Physical cleaning lacks specificity and can generally remove multiple pollutants, but the removal is not thorough. Chemical cleaning methods involve adding specific chemical agents to the water. This method can remove complex deposits and quickly restore membrane flux. Chemical cleaning methods use chemical reagents to remove deposits and fouling on the membrane surface. Commonly used chemical cleaning agents include acids, alkalis, oxidants, and chelating agents. However, chemical cleaning carries the possibility of introducing new contaminants into the membrane system, and the possibility of chemical reactions between contaminants and the membrane cannot be ruled out. Nitric acid is a commonly used chemical cleaning agent. However, the dilution process of nitric acid is difficult and requires careful and slow handling. The leakage of nitrogen dioxide gas poses a hazard to the occupational health of workers. At the same time, nitric acid is highly corrosive, and the waste liquid after cleaning causes great environmental pollution and easily corrodes structures. Summary of the Invention

[0004] The purpose of this invention is to provide a highly efficient ceramic membrane cleaning agent, its preparation method, and its application, so as to solve the problems of incomplete cleaning effect and significant damage to the ceramic membrane surface caused by existing ceramic membrane cleaning agents during the cleaning process.

[0005] The objective of this invention can be achieved through the following technical solutions: In a first aspect, the present invention provides a highly efficient ceramic membrane cleaning agent, comprising the following components by mass percentage: sodium carboxymethyl cellulose 0.05-3%, methyl cellulose ether 1%-3%, triethanolamine 0.1-1%, polyphosphate 0.5-3%, hydroxymethyl cellulose 1-3%, cocamidopropyl hydroxysulfonate betaine 4-8%, corrosion inhibitor 0.01-1%, xanthan gum 0.5-5%, methanesulfonic acid 5-15%, tannic acid 5%-15%, dipotassium hydrogen phosphate 3-8%, modified alkyl glycoside 5-10%, alkylphenol polyoxyethylene ether 5-10%, with the balance being water.

[0006] Furthermore, the polyphosphate is any one or any two of sodium dipolyphosphate, sodium tripolyphosphate, hexasodium pyrophosphate, and sodium hexametaphosphate mixed in a mass ratio of 1:1.

[0007] Furthermore, the corrosion inhibitor is any one of benzotriazole and hexadecylpyridine chloride, or a mixture of benzotriazole and hexadecylpyridine chloride in a mass ratio of 1:1.

[0008] Secondly, the present invention provides a method for preparing a highly efficient ceramic membrane cleaning agent, comprising the following steps: S1. Weigh each component according to the above mass percentages; S2. At room temperature (25-30℃), methanesulfonic acid and tannic acid are added to water and stirred at 1000 r / min for 1 h. Then, sodium carboxymethyl cellulose, polyphosphate, methyl cellulose ether and corrosion inhibitor are added sequentially, and stirring is continued for 1-1.5 h to obtain a uniformly dispersed solution A. S3. Under normal temperature conditions, triethanolamine, hydroxymethyl cellulose, cocamidopropyl hydroxysulfonate betaine, xanthan gum, dipotassium hydrogen phosphate, modified alkyl glycoside, and alkylphenol polyoxyethylene ether were added to water sequentially, and stirred at a stirring rate of 1000 r / min for 1.5 h to obtain a uniformly dispersed solution B; S4. Add solution A to solution B and mix thoroughly to obtain ceramic membrane cleaning agent.

[0009] Furthermore, the mass ratio of water used in S2 and S3 is 1:1.

[0010] Thirdly, the present invention also provides a method for applying a highly efficient ceramic membrane cleaning agent, comprising the following steps: Step 1: Dilute the ceramic membrane cleaning agent prepared above to a working concentration of 1‰-5%; Step 2: The coking wastewater in the feed tank 1 is pumped to the ceramic membrane module 3 for circulation filtration through the circulation pump 2. After the membrane flux of the ceramic membrane module 3 reaches a stable level, the coking wastewater in the feed tank 1 is discharged, and then diluted ceramic membrane cleaning agent is discharged into the feed tank 1 for circulation cleaning for 30 minutes. After cleaning, pure water is circulated and rinsed until neutral.

[0011] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention provides a ceramic membrane cleaning agent that effectively removes contaminants deposited on the surface of ceramic membranes, restoring the membrane's filtration function and achieving a membrane flux recovery rate of over 95%. It can be widely used in ceramic membrane filtration devices in industries such as petroleum, steel, mineral processing, and metal processing. The working fluid after use can be directly discharged.

[0012] 2. This invention selects modified alkyl glycosides, sodium carboxymethyl cellulose, and cocamidopropyl hydroxysulfonate betaine, all of which can improve the cleaning effect. This is because the combination of modified alkyl glycosides and alkylphenol polyoxyethylene ethers, two surfactants, can improve wetting, penetration, emulsification, dispersion, and solubilization; the combination of sodium carboxymethyl cellulose, polyphosphate, and hydroxymethyl cellulose has a chelating effect on metal ions, thus dispersing and preventing the redeposition of metal and other pollutant ions; the combination of triethanolamine and cocamidopropyl hydroxysulfonate can improve its penetration, softening of pollutants, and solubilization capabilities.

[0013] 3. Compared with traditional cleaning agents (nitric acid), the present invention selects xanthan gum, which can remove dirt from the surface of the ceramic membrane without damaging the surface of the ceramic membrane.

[0014] 4. The preparation process of this invention is simple, the manufacturing cost is low, and the product is mild; it can overcome the safety hazards of existing nitric acid cleaning agents during use. Attached Figure Description

[0015] The invention will now be further described with reference to the accompanying drawings.

[0016] Figure 1 These are cleaning flowcharts for Embodiments 4-6 and Comparative Example 2 of the present invention; In the diagram: 1. Feed tank; 2. Circulation pump; 3. Ceramic membrane module; 4. Flow meter. Detailed Implementation

[0017] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0018] Example 1 A method for preparing a highly efficient ceramic membrane cleaning agent includes the following steps: S1. Weigh each component by mass percentage: sodium carboxymethyl cellulose 2.8%, methyl cellulose ether 3%, triethanolamine 1%, polyphosphate (hexasodium pyrophosphate and sodium tripolyphosphate mixed in a mass ratio of 1:1) 3%, hydroxymethyl cellulose 2.5%, cocamidopropyl hydroxysulfonate betaine 8%, corrosion inhibitor (benzotriazole and hexadecylpyridine chloride mixed in a mass ratio of 1:1) 0.1%, xanthan gum 5%, methanesulfonic acid 10%, tannic acid 12%, dipotassium hydrogen phosphate 8%, modified alkyl glycoside (APG0811) 10%, alkylphenol polyoxyethylene ether 10%, and the balance is water.

[0019] S2. At room temperature, methanesulfonic acid and tannic acid are added to 1 / 2 the mass of water and stirred at 1000 r / min for 1 h. Then, sodium carboxymethyl cellulose, polyphosphate, methyl cellulose ether and corrosion inhibitor are added in sequence, and stirring is continued for 1 h to obtain a uniformly dispersed solution A. S3. Under normal temperature conditions, triethanolamine, hydroxymethyl cellulose, cocamidopropyl hydroxysulfonate betaine, xanthan gum, dipotassium hydrogen phosphate, modified alkyl glycoside, and alkylphenol polyoxyethylene ether were sequentially added to the remaining 1 / 2 mass of water, and stirred at a stirring rate of 1000 r / min for 1.5 h to obtain a uniformly dispersed solution B; S4. Add solution A to solution B and mix thoroughly to obtain ceramic membrane cleaning agent.

[0020] Example 2 A method for preparing a highly efficient ceramic membrane cleaning agent includes the following steps: S1. Weigh each component by mass percentage: sodium carboxymethyl cellulose 1.5%, methyl cellulose ether 2%, triethanolamine 0.1%, sodium dipolyphosphate 0.5%, hydroxymethyl cellulose 1.5%, cocamidopropyl hydroxysulfonate betaine 6%, benzotriazole 0.05%, xanthan gum 0.6%, methanesulfonic acid 15%, tannic acid 9%, dipotassium hydrogen phosphate 5.5%, modified alkyl glycoside (APG0811) 5%, alkylphenol polyoxyethylene ether 7.5%, with the balance being water.

[0021] S2. At room temperature, methanesulfonic acid and tannic acid are added to 1 / 2 the mass of water and stirred at 1000 r / min for 1 h. Then, sodium carboxymethyl cellulose, sodium dipolyphosphate, methyl cellulose ether and benzotriazole are added in sequence, and stirring is continued for 1.2 h to obtain a uniformly dispersed solution A. S3. Under normal temperature conditions, triethanolamine, hydroxymethyl cellulose, cocamidopropyl hydroxysulfonate betaine, xanthan gum, dipotassium hydrogen phosphate, modified alkyl glycoside, and alkylphenol polyoxyethylene ether were sequentially added to the remaining 1 / 2 mass of water, and stirred at a stirring rate of 1000 r / min for 1.5 h to obtain a uniformly dispersed solution B; S4. Add solution A to solution B and mix thoroughly to obtain ceramic membrane cleaning agent.

[0022] Example 3 A method for preparing a highly efficient ceramic membrane cleaning agent includes the following steps: S1. Weigh each component by mass percentage: sodium carboxymethyl cellulose 0.2%, methyl cellulose ether 1.1%, triethanolamine 0.55%, sodium hexametaphosphate 1.6%, hydroxymethyl cellulose 1%, cocamidopropyl hydroxysulfonate betaine 4%, hexadecyl pyridine chloride 0.012%, xanthan gum 2.6%, methanesulfonic acid 5.5%, tannic acid 5.5%, dipotassium hydrogen phosphate 3.2%, modified alkyl glycoside (APG0811) 7.8%, alkylphenol polyoxyethylene ether 5.6%, with the balance being water.

[0023] S2. At room temperature, methanesulfonic acid and tannic acid are added to 1 / 2 the mass of water and stirred at 1000 r / min for 1 h. Then, sodium carboxymethyl cellulose, sodium hexametaphosphate, methyl cellulose ether and hexadecyl pyridine chloride are added in sequence, and stirring is continued for 1.5 h to obtain a uniformly dispersed solution A. S3. Under normal temperature conditions, triethanolamine, hydroxymethyl cellulose, cocamidopropyl hydroxysulfonate betaine, xanthan gum, dipotassium hydrogen phosphate, modified alkyl glycoside, and alkylphenol polyoxyethylene ether were sequentially added to the remaining 1 / 2 mass of water, and stirred at a stirring rate of 1000 r / min for 1.5 h to obtain a uniformly dispersed solution B; S4. Add solution A to solution B and mix thoroughly to obtain ceramic membrane cleaning agent.

[0024] Comparative Example 1 Dilute concentrated nitric acid to a 5% (w / w) nitric acid solution.

[0025] Comparative Example 2 A method for preparing a ceramic membrane cleaning agent is described, with the specific preparation method being the same as in Example 1, except that the ceramic membrane cleaning agent does not contain 2.8% sodium carboxymethyl cellulose by mass.

[0026] Comparative Example 3 A method for preparing a ceramic membrane cleaning agent, the specific preparation method is the same as in Example 1, the difference being that the ceramic membrane cleaning agent does not contain 8% by mass of cocamidopropyl hydroxysulfonate betaine.

[0027] Comparative Example 4 A method for preparing a ceramic membrane cleaning agent, the specific preparation method is the same as in Example 1, the difference being that the ceramic membrane cleaning agent does not contain 10% by mass of modified alkyl glycoside (APG0811).

[0028] Comparative Example 5 A method for preparing a ceramic membrane cleaning agent, the specific preparation method is the same as in Example 1, the difference being that the ceramic membrane cleaning agent does not contain 5% by mass of yellow collagen.

[0029] Example 4 An application method for a highly efficient ceramic membrane cleaning agent, such as... Figure 1 As shown in the diagram, 1 is the feed tank, 2 is the circulating pump, 3 is the ceramic membrane module, 4 is the flow meter, K1-K4 are valves, T is the thermometer, P1 is the inlet pressure gauge, and P2 is the outlet pressure gauge; the process includes the following steps: Step 1: Dilute the ceramic membrane cleaning agent prepared in Example 1 to a working concentration of 2.8%; Step 2: The coking wastewater in the feed tank 1 is pumped to the ceramic membrane module 3 for circulation filtration through the circulation pump 2. After the membrane flux of the ceramic membrane module 3 reaches a stable level, the coking wastewater in the feed tank 1 is discharged, and then diluted ceramic membrane cleaning agent is discharged into the feed tank 1 for circulation cleaning for 30 minutes. After cleaning, pure water is circulated and rinsed until neutral.

[0030] Example 5 An application method for a highly efficient ceramic membrane cleaning agent, such as... Figure 1 As shown in the diagram, 1 is the feed tank, 2 is the circulating pump, 3 is the ceramic membrane module, 4 is the flow meter, K1-K4 are valves, T is the thermometer, P1 is the inlet pressure gauge, and P2 is the outlet pressure gauge; the process includes the following steps: Step 1: Dilute the ceramic membrane cleaning agent prepared in Example 2 to a working concentration of 5‰; Step 2: The coking wastewater in the feed tank 1 is pumped to the ceramic membrane module 3 for circulation filtration through the circulation pump 2. After the membrane flux of the ceramic membrane module 3 reaches a stable level, the coking wastewater in the feed tank 1 is discharged, and then diluted ceramic membrane cleaning agent is discharged into the feed tank 1 for circulation cleaning for 30 minutes. After cleaning, pure water is circulated and rinsed until neutral.

[0031] Example 6 An application method for a highly efficient ceramic membrane cleaning agent, such as... Figure 1 As shown in the diagram, 1 is the feed tank, 2 is the circulating pump, 3 is the ceramic membrane module, 4 is the flow meter, K1-K4 are valves, T is the thermometer, P1 is the inlet pressure gauge, and P2 is the outlet pressure gauge; the process includes the following steps: Step 1: Dilute the ceramic membrane cleaning agent prepared in Example 3 to a working concentration of 4.8%; Step 2: The coking wastewater in the feed tank 1 is pumped to the ceramic membrane module 3 for circulation filtration through the circulation pump 2. After the membrane flux of the ceramic membrane module 3 reaches a stable level, the coking wastewater in the feed tank 1 is discharged, and then diluted ceramic membrane cleaning agent is discharged into the feed tank 1 for circulation cleaning for 30 minutes. After cleaning, pure water is circulated and rinsed until neutral.

[0032] Comparative Example 6 An application method for a nitric acid cleaning agent, such as Figure 1 As shown in the diagram, 1 is the feed tank, 2 is the circulating pump, 3 is the ceramic membrane module, 4 is the flow meter, K1-K4 are valves, T is the thermometer, P1 is the inlet pressure gauge, and P2 is the outlet pressure gauge; the process includes the following steps: The coking wastewater in the feed tank 1 is pumped to the ceramic membrane module 3 for circulation filtration by the circulation pump 2. After the membrane flux of the ceramic membrane module 3 reaches a stable level, the coking wastewater in the feed tank 1 is discharged, and then a 5% nitric acid solution obtained by dilution of Comparative Example 1 is discharged into the feed tank 1 for circulation cleaning for 30 minutes. After cleaning, pure water is circulated and rinsed until neutral.

[0033] Comparative Example 7 A method for applying a ceramic membrane cleaning agent is described, with the specific application method being the same as in Example 4, except that the ceramic membrane cleaning agent is prepared from Comparative Example 2.

[0034] Comparative Example 8 A method for applying a ceramic membrane cleaning agent is described, with the specific application method being the same as in Example 4, except that the ceramic membrane cleaning agent is prepared from Comparative Example 3.

[0035] Comparative Example 9 A method for applying a ceramic membrane cleaning agent, the specific application method is the same as in Example 4, the difference being that the ceramic membrane cleaning agent is prepared from Comparative Example 4.

[0036] Performance testing: Ceramic membrane surface protection test: Dilute the ceramic membrane cleaning agent prepared in Example 1 to 5%, take 1000 mL, and record it as E1; dilute the ceramic membrane cleaning agent prepared in Comparative Example 5 to 5%, take 1000 mL, and record it as E2; take 1000 mL of Comparative Example 1, and record it as E3.

[0037] After immersing the ceramic membrane module in the above three solutions at room temperature for one month, remove it, rinse it with deionized water, and visually inspect the appearance of the ceramic membrane module.

[0038] Visual inspection results: The ceramic membrane modules treated with E2 and E3 solutions all showed discoloration, while the ceramic membrane modules treated with E1 showed no obvious changes. The discoloration was more pronounced with E3 compared to E2.

[0039] Membrane flux recovery rate To characterize the cleaning effect of Examples 4-6 and Comparative Examples 6-9 on the ceramic membrane:

[0040] in: The stable flux of the ceramic membrane module for filtering coking wastewater after cleaning with ceramic membrane cleaning agent; The values ​​represent the stable flux of the ceramic membrane module filtering coking wastewater before cleaning; the test results are shown in Table 1. Table 1

[0041] As shown in Table 1, the ceramic membrane cleaning agent prepared by this invention has a good effect on removing pollutants deposited on the surface of ceramic membranes, restoring the membrane's filtration function, and achieving a membrane flux recovery rate of over 95%. The modified alkyl glycoside, sodium carboxymethyl cellulose, and cocamidopropyl hydroxysulfonate selected by this invention can all improve its cleaning effect.

[0042] Compared to traditional cleaning agents (nitric acid), the formula of this invention is mild and achieves the effect of removing dirt without damaging the surface of the ceramic film at the working concentration.

[0043] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0044] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A highly efficient ceramic membrane cleaning agent, characterized in that, The composition by mass percentage is as follows: sodium carboxymethyl cellulose 0.05-3%, methyl cellulose ether 1%-3%, triethanolamine 0.1-1%, polyphosphate 0.5-3%, hydroxymethyl cellulose 1-3%, cocamidopropyl hydroxysulfonate betaine 4-8%, corrosion inhibitor 0.01-1%, xanthan gum 2-5%, methanesulfonic acid 5-15%, tannic acid 5%-15%, dipotassium hydrogen phosphate 3-8%, modified alkyl glycoside 5-10%, alkylphenol polyoxyethylene ether 5-10%, and the balance being water; The polyphosphate is any one or any two of sodium dipolyphosphate, sodium tripolyphosphate, hexasodium pyrophosphate and sodium hexametaphosphate mixed in a mass ratio of 1:

1. The corrosion inhibitor is either benzotriazole or hexadecylpyridine chloride, or a mixture of benzotriazole and hexadecylpyridine chloride in a mass ratio of 1:

1.

2. A method for preparing the high-efficiency ceramic membrane cleaning agent as described in claim 1, characterized in that, The steps include the following: S1. Weigh each component according to its mass percentage; S2. At room temperature, add methanesulfonic acid and tannic acid to water and stir at a stirring rate of 1000 r / min for 1 h. Then add sodium carboxymethyl cellulose, polyphosphate, methyl cellulose ether and corrosion inhibitor in sequence, and continue stirring for 1-1.5 h to obtain a uniformly dispersed solution A. S3. Under normal temperature conditions, triethanolamine, hydroxymethyl cellulose, cocamidopropyl hydroxysulfonate betaine, xanthan gum, dipotassium hydrogen phosphate, modified alkyl glycoside and alkylphenol polyoxyethylene ether were added to water in sequence and stirred at a stirring rate of 1000 r / min for 1.5 h to obtain a uniformly dispersed solution B. S4. Add solution A to solution B and mix thoroughly to obtain ceramic membrane cleaning agent.

3. The method for preparing the high-efficiency ceramic membrane cleaning agent according to claim 2, characterized in that, The mass ratio of water used in S2 and S3 is 1:

1.

4. A method for applying the highly efficient ceramic membrane cleaning agent as described in claim 1, characterized in that, The steps include the following: Step 1: Dilute the ceramic membrane cleaning agent to a working concentration of 1‰-5%; Step 2: The coking wastewater is circulated and filtered through the ceramic membrane module. After the membrane flux reaches a stable level, the coking wastewater is discharged, and then diluted ceramic membrane cleaning agent is introduced for circulation cleaning for 30 minutes. After cleaning, pure water is circulated and rinsed until neutral.

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