CN111437728A - Reverse osmosis special-purpose pickling cleaning agent and preparation method thereof - Google Patents

Reverse osmosis special-purpose pickling cleaning agent and preparation method thereof Download PDF

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Publication number
CN111437728A
CN111437728A CN202010440523.3A CN202010440523A CN111437728A CN 111437728 A CN111437728 A CN 111437728A CN 202010440523 A CN202010440523 A CN 202010440523A CN 111437728 A CN111437728 A CN 111437728A
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parts
acid
reverse osmosis
cleaning agent
special
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余莉
宋勇
李红丽
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Xinjiang Water Treatment Engineering Technology Research Center Co ltd
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Xinjiang Water Treatment Engineering Technology Research Center Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D65/00Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02Membrane cleaning or sterilisation ; Membrane regeneration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025Reverse osmosis; Hyperfiltration
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2321/00Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/16Use of chemical agents
    • B01D2321/162Use of acids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2321/00Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/16Use of chemical agents
    • B01D2321/168Use of other chemical agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/14Maintenance of water treatment installations

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention provides a reverse osmosis special pickling cleaning agent and a preparation method thereof, wherein the reverse osmosis special pickling cleaning agent is mainly prepared from the following raw materials: 30-50 parts of organic acid, 3-5 parts of bactericide, 3-6 parts of complexing agent, 5-12 parts of inorganic salt, 1-4 parts of surfactant and a proper amount of water. The reverse osmosis special acid cleaning agent ensures that carbonate dirt possibly existing on the surface of a membrane element and dirt blockage caused by most metal oxides are cleaned through chemical reaction under the condition of pH value of 2-3, water flows through a membrane to physically wash the dirt on the surface of the membrane to play a role in stripping, and after the cleaning agent is used for cleaning, the running flux and the pressure difference of the reverse osmosis membrane can be basically recovered to the level before pollution, the stability is good, and the long-time running of the membrane element can be ensured not to be polluted after the cleaning.

Description

Reverse osmosis special-purpose pickling cleaning agent and preparation method thereof
Technical Field
The invention relates to the field of membrane module cleaning, in particular to a reverse osmosis special acid-washing cleaning agent and a preparation method thereof.
Background
In recent years, reverse osmosis membrane technology has been rapidly developed in water treatment, during the operation of reverse osmosis systems, the surface of reverse osmosis membranes can be deposited due to the existence of jelly, organic matters, microorganisms, mud and other substances in raw water and the concentration of insoluble substances during membrane separation, so that the reverse osmosis membranes can be polluted, the pollution of reverse osmosis membranes comprises the adsorption of colloid particles, inorganic scaling and the breeding of microorganisms, after the reverse osmosis membranes are polluted, the decline of membrane performances such as the reduction of water yield of the system, the increase of salt permeability and the like can occur, and if the reverse osmosis systems which are polluted to a certain extent are not cleaned in time, it is very difficult to thoroughly remove pollutants attached to the surface of the membranes for a long time. Therefore, the biggest problem encountered in the application of reverse osmosis systems is membrane fouling.
At present, the membrane component acidic cleaning agent used in the market is easily available and common chemicals (citric acid and hydrochloric acid), slightly pollutes the membrane and can meet the cleaning requirement. After cleaning, the operation condition of the system can be temporarily improved, but because cleaning and decontamination are not thorough, the operation maintaining time is not long, the membrane is polluted again, the operation parameters of the system do not reach ideal parameters, and the system is often required to be cleaned again.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a reverse osmosis special pickling cleaning agent, which ensures that carbonate dirt possibly existing on the surface of a membrane element and dirt blockage caused by most metal oxides are cleaned by chemical reaction under the condition of pH value of 2-3.
The second purpose of the invention is to provide the preparation method of the reverse osmosis special acid pickling cleaning agent, which has the advantages of simple operation, mild operation conditions, no pollution, no discharge of three wastes, safety and environmental protection.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a reverse osmosis special acid washing cleaning agent which is mainly prepared from the following raw materials: 30-50 parts of organic acid, 3-5 parts of bactericide, 3-6 parts of complexing agent, 5-12 parts of inorganic salt, 1-4 parts of surfactant and a proper amount of water.
Preferably, as a further implementable scheme, by mass, 32-45 parts of organic acid, 3.5-4.5 parts of bactericide, 3.5-5.5 parts of complexing agent, 6-11 parts of inorganic salt, 2-3.5 parts of surfactant and 40-50 parts of water.
Preferably, as a further implementable scheme, by mass parts, 36 parts of organic acid, 4 parts of bactericide, 5 parts of complexing agent, 10 parts of inorganic salt, 3 parts of surfactant and 42 parts of water.
In the formula of the reverse osmosis special acid washing cleaning agent, the inorganic salt mainly has the effect of adjusting the osmotic pressure of the cleaning agent, the salt concentration of the cleaning agent side is far greater than that of the water production side in the cleaning process, and if sufficient purified water is supplied to the water production side of the cleaned reverse osmosis membrane, at the same time, under proper cleaning pressure, the purified water on the water production side of the membrane can permeate the membrane, so that the purified water permeates into the cleaning agent and flows into the cleaning agent in an osmotic mode, so that the cleaning agent is different from the original reverse osmosis, namely forward osmosis. By forward osmosis, water flows through the membrane to physically flush the fouling on the membrane surface, which acts as a stripping action.
The organic acid mainly has the function of adjusting pH, the complexing agent mainly has the functions of softening scale and preventing scale, and the added surfactant can improve the dispersibility, reduce the interfacial tension and enable the cleaning agent to penetrate into the membrane for deeper cleaning.
In the formula, the added organic acid has a relatively large dosage compared with other raw material components, the cleaning capacity of the other components on dirt can be obviously improved by increasing the dosage of the organic acid, and particularly the dispersibility and the solubilization of metal ions are improved, so the dosage proportion is determined by a large amount of practice and grope. The usage amount of the bactericide and the complexing agent is equivalent, and the purpose is to improve the effect of removing organic fouling and inorganic scaling, reduce the pressure difference of membrane operation and practically prolong the service life of the reverse osmosis membrane.
Preferably, the organic acid is at least one of carboxylic acid, sulfonic acid, sulfinic acid, thiocarboxylic acid, sulfamic acid, hydrofluoric acid, glycolic acid, oxalic acid and ethylenediamine tetraacetic acid.
More preferably, 2-3 kinds of organic acid are preferably selected for compounding, and compared with single organic acid, the cleaning agent has better effect of improving the decontamination capability of the cleaning agent.
Preferably, the complexing agent is at least one of aminocarboxylate, hydroxycarboxylic acid salt and polyacrylic acid.
Preferably, the bactericide is a non-oxidizing bactericide which is an isothiazolinone or formaldehyde solution.
Preferably, the surfactant is a nonionic surfactant, and the nonionic surfactant is at least one of polyoxyethylene type and polyhydric alcohol type. More preferably one or more of polyoxyethylene ether, polyoxyethylene and polypropylene glycol compounds.
Preferably, the inorganic salt is at least one of sodium chloride, sodium nitrate, potassium chloride and potassium nitrate.
Preferably, the water for preparing the cleaning agent can be selected from water produced by a reverse osmosis system, so that the effects of saving water and reducing energy consumption can be achieved.
The invention provides a formula of a reverse osmosis special acid cleaning agent and a preparation method thereof, and the preparation method comprises the following steps:
mixing organic acid, complexing agent, bactericide and inorganic salt, stirring, adding surfactant, and stirring.
Preferably, the mixing and stirring temperature of the organic acid, the complexing agent, the bactericide and the inorganic salt is 20-60 ℃, and the stirring time is 10-20 min.
Preferably, the temperature for continuously stirring the mixture after adding the surfactant is 20-55 ℃, and the time for continuously stirring the mixture is 10-30 min.
The quality of the prepared reverse osmosis special acid cleaning agent is improved by limiting each operation parameter in the preparation method.
In a word, the reverse osmosis special acid washing cleaning agent prepared by the preparation method is environment-friendly, good in cleaning effect and excellent in stability.
Before cleaning with the cleaning agent, the polluted membrane element can be soaked in the cleaning agent for 8-48h according to the pollution degree of the reverse osmosis membrane, and then cleaning is carried out, so that the cleaning effect is more excellent.
Compared with the prior art, the invention has the beneficial effects that:
(1) the reverse osmosis special acid cleaning agent adopts a compound formula, and a plurality of components are matched for use, so that the synergistic effect is obviously increased, and the removal effect on carbonate and silicate inorganic dirt is obvious.
(2) By adopting the special pickling cleaning agent for reverse osmosis, water flows through the membrane to physically wash dirt on the surface of the membrane, so that a stripping effect is achieved, and the running flux and the differential pressure of the reverse osmosis membrane can be basically recovered to the level before the pollution after the cleaning agent is used for cleaning
(3) The special reverse osmosis acid pickling cleaning agent has good stability, and can ensure that the membrane component can not be polluted after being cleaned for a long time, so that the cleaning agent is worthy of wide popularization and application.
(4) The preparation method of the reverse osmosis special pickling cleaning agent is simple to operate, the whole preparation method is mild in operation condition, free of pollution, free of three-waste discharge, safe and environment-friendly.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The specific preparation process of the reverse osmosis special acid cleaning agent comprises the following steps:
1. the raw materials are mixed according to the following parts by mass:
30 parts of organic acid (10 parts of thiocarboxylic acid, 10 parts of hydrofluoric acid and 10 parts of ethylene diamine tetraacetic acid), 3 parts of ethylene diamine tetraacetic acid salt, 3 parts of isothiazolinone, 5 parts of sodium chloride, 1 part of polyoxyethylene ether and 58 parts of water;
2. mixing organic acid, edetate, isothiazolinone and sodium chloride, adding into a variable speed stirrer, and stirring at 20 deg.C for 20min to obtain mixture A;
3. dissolving the mixture A and polyoxyethylene ether, mixing, adding into a variable speed type stirrer, and continuously stirring for 30min at the temperature of 20 ℃ to obtain the reverse osmosis special acid cleaning agent;
4. and packaging, detecting and forming a product for sale.
Example 2
The specific preparation process of the reverse osmosis special acid cleaning agent comprises the following steps:
1. the raw materials are mixed according to the following parts by mass:
50 parts of an organic acid (20 parts of sulfamic acid, 20 parts of glycolic acid, 10 parts of sulfinic acid), 6 parts of diethylenetriamine pentacarboxylate, 5 parts of isothiazolinone, 12 parts of sodium nitrate, 4 parts of polyoxyethylene and 23 parts of water;
2. mixing organic acid, ethylene triamine pentacarboxylate, isothiazolinone and sodium nitrate, adding into a variable speed stirrer, and stirring at 60 ℃ for 10min to obtain a mixture A;
3. dissolving the mixture A and polyoxyethylene, mixing, adding into a variable speed type stirrer, and continuously stirring for 10min at the temperature of 55 ℃ to obtain the reverse osmosis special acid cleaning agent;
4. and packaging, detecting and forming a product for sale.
Example 3
The specific preparation process of the reverse osmosis special acid cleaning agent comprises the following steps:
1. the raw materials are mixed according to the following parts by mass:
36 parts of organic acid (15 parts of carboxylic acid, 11 parts of sulfonic acid and 10 parts of oxalic acid), 5 parts of polyacrylic acid, 4 parts of formaldehyde solution (the concentration of the formaldehyde solution is 30 wt%), 10 parts of potassium chloride, 3 parts of polyoxyethylene ether and 42 parts of water;
2. mixing organic acid, polyacrylic acid, formaldehyde solution and potassium chloride, adding into a variable speed stirrer, and stirring at 40 deg.C for 15min to obtain mixture A;
3. dissolving the mixture A and polyoxyethylene, mixing, adding into a variable speed type stirrer, and continuously stirring for 20min at the temperature of 40 ℃ to obtain the reverse osmosis special acid cleaning agent;
4. and packaging, detecting and forming a product for sale.
Example 4
The specific preparation process of the reverse osmosis special acid cleaning agent comprises the following steps:
1. the raw materials are mixed according to the following parts by mass:
32 parts of organic acid (12 parts of carboxylic acid, 11 parts of sulfonic acid and 10 parts of oxalic acid), 5.5 parts of polyacrylic acid, 3.5 parts of formaldehyde solution (the concentration of the formaldehyde solution is 40 wt%), 6 parts of potassium chloride, 3.5 parts of polyoxyethylene ether and 50 parts of water;
2. mixing organic acid, polyacrylic acid, formaldehyde solution and potassium chloride, adding into a variable speed stirrer, and stirring at 40 deg.C for 15min to obtain mixture A;
3. dissolving the mixture A and polyoxyethylene, mixing, adding into a variable speed type stirrer, and continuously stirring for 20min at the temperature of 40 ℃ to obtain the reverse osmosis special acid cleaning agent;
4. and packaging, detecting and forming a product for sale.
Example 5
The specific preparation process of the reverse osmosis special acid cleaning agent comprises the following steps:
1. the raw materials are mixed according to the following parts by mass:
45 parts of organic acid (15 parts of carboxylic acid, 15 parts of sulfonic acid and 15 parts of sulfamic acid), 3.5 parts of polyacrylic acid, 4.5 parts of formaldehyde solution (the concentration of the formaldehyde solution is 40 wt%), 11 parts of potassium chloride, 2 parts of polyoxyethylene ether and 40 parts of water;
2. mixing organic acid, polyacrylic acid, formaldehyde solution and potassium chloride, adding into a variable speed stirrer, and stirring at 30 deg.C for 18min to obtain mixture A;
3. dissolving the mixture A and polyoxyethylene, mixing, adding into a variable speed type stirrer, and continuously stirring for 25min at the temperature of 35 ℃ to obtain the reverse osmosis special acid cleaning agent;
4. and packaging, detecting and forming a product for sale.
Example 6
The procedure was as in example 3 except that the organic acid was 36 parts carboxylic acid.
Comparative example 1
The specific procedure was identical to example 3, except that the organic acid was 20 parts (10 parts sulfonic acid, 5 parts oxalic acid, 5 parts carboxylic acid).
Comparative example 2
The specific procedure is identical to that of example 3, except that no biocide is added.
Comparative example 3
The procedure was as in example 3, except that 2 parts of polyacrylic acid and 7 parts of a formaldehyde solution (concentration of the formaldehyde solution: 30% by weight) were used.
Experimental example 1
The specific treatment effects of the pickling cleaning agent for reverse osmosis of examples 1 to 6 and comparative examples 1 to 3 were evaluated, and the specific results are shown in table 1 below:
TABLE 1 results of treatment
Figure BDA0002503898390000081
Figure BDA0002503898390000091
As can be seen from table 1 above, the reverse osmosis special acid cleaning agent of the present invention requires the combination of the components in the raw materials to achieve a better cleaning effect, but if a component is absent from the raw materials or is not added within a proper range, the cleaning effect of the penetrant is affected, and therefore, the components in the raw materials need to be controlled within a proper range.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (10)

1. The special reverse osmosis acid pickling cleaning agent is characterized by being mainly prepared from the following raw materials: 30-50 parts of organic acid, 3-5 parts of bactericide, 3-6 parts of complexing agent, 5-12 parts of inorganic salt, 1-4 parts of surfactant and a proper amount of water.
2. A reverse osmosis special acid cleaning detergent as claimed in claim 1, wherein the detergent comprises, by mass, 32-45 parts of organic acid, 3.5-4.5 parts of bactericide, 3.5-5.5 parts of complexing agent, 6-11 parts of inorganic salt, 2-3.5 parts of surfactant and 40-50 parts of water.
3. The special reverse osmosis acid cleaning agent as claimed in claim 1, wherein the special reverse osmosis acid cleaning agent comprises 36 parts by mass of organic acid, 4 parts by mass of bactericide, 5 parts by mass of complexing agent, 10 parts by mass of inorganic salt, 3 parts by mass of surfactant and 42 parts by mass of water.
4. A reverse osmosis dedicated acid cleaning agent according to any one of claims 1-3, wherein the organic acid is at least one of carboxylic acid, sulfonic acid, sulfinic acid, thiocarboxylic acid, sulfamic acid, hydrofluoric acid, glycolic acid, oxalic acid, and ethylenediaminetetraacetic acid.
5. A reverse osmosis dedicated acid washing cleaning agent according to any one of claims 1-3, wherein the complexing agent is at least one of aminocarboxylate, hydroxycarboxylic acid salt and polyacrylic acid.
6. A reverse osmosis dedicated acid washing detergent according to any one of claims 1-3, wherein the bactericide is a non-oxidizing bactericide which is an isothiazolinone or formaldehyde solution.
7. The special pickling cleaning agent for reverse osmosis according to any one of claims 1 to 3, wherein the surfactant is a nonionic surfactant, and the nonionic surfactant is at least one of polyoxyethylene type and polyhydric alcohol type;
preferably, the inorganic salt is at least one of sodium chloride, sodium nitrate, potassium chloride and potassium nitrate.
8. The preparation method of the reverse osmosis special acid cleaning detergent as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
mixing organic acid, complexing agent, bactericide and inorganic salt, stirring, adding surfactant, and stirring.
9. The preparation method according to claim 8, wherein the mixing and stirring temperature of the organic acid, the complexing agent, the bactericide and the inorganic salt is 20-60 ℃, and the stirring time is 10-20 min.
10. The method according to claim 8, wherein the temperature of the surfactant is 20-55 ℃ and the stirring is continued for 10-30 min.
CN202010440523.3A 2020-05-22 2020-05-22 Reverse osmosis special-purpose pickling cleaning agent and preparation method thereof Pending CN111437728A (en)

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN113150882A (en) * 2021-03-09 2021-07-23 上海三邦水处理技术有限公司 Reverse osmosis membrane acidic cleaning agent and use method thereof
CN114100376A (en) * 2021-11-29 2022-03-01 胡翠华 Cleaning agent and preparation method and application thereof
CN114504948A (en) * 2022-02-17 2022-05-17 厦门嘉戎技术股份有限公司 Reverse osmosis membrane silica scale cleaning agent and preparation method thereof
CN114749028A (en) * 2022-05-20 2022-07-15 山东天庆科技发展有限公司 Reverse osmosis cleaning agent and preparation method thereof
CN114854499A (en) * 2022-05-12 2022-08-05 山东天庆科技发展有限公司 Efficient cleaning agent for double-membrane method and preparation method thereof
CN115161125A (en) * 2022-06-30 2022-10-11 金瓷科技实业发展有限公司 Biological sterilization cleaning composition and application thereof, composite biological sterilization cleaning agent and preparation method and application thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113150882A (en) * 2021-03-09 2021-07-23 上海三邦水处理技术有限公司 Reverse osmosis membrane acidic cleaning agent and use method thereof
CN114100376A (en) * 2021-11-29 2022-03-01 胡翠华 Cleaning agent and preparation method and application thereof
CN114504948A (en) * 2022-02-17 2022-05-17 厦门嘉戎技术股份有限公司 Reverse osmosis membrane silica scale cleaning agent and preparation method thereof
CN114854499A (en) * 2022-05-12 2022-08-05 山东天庆科技发展有限公司 Efficient cleaning agent for double-membrane method and preparation method thereof
CN114749028A (en) * 2022-05-20 2022-07-15 山东天庆科技发展有限公司 Reverse osmosis cleaning agent and preparation method thereof
CN115161125A (en) * 2022-06-30 2022-10-11 金瓷科技实业发展有限公司 Biological sterilization cleaning composition and application thereof, composite biological sterilization cleaning agent and preparation method and application thereof

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Application publication date: 20200724