CN114733358A - Reverse osmosis membrane calcium sulfate scale cleaning agent and cleaning method - Google Patents
Reverse osmosis membrane calcium sulfate scale cleaning agent and cleaning method Download PDFInfo
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- CN114733358A CN114733358A CN202210484712.XA CN202210484712A CN114733358A CN 114733358 A CN114733358 A CN 114733358A CN 202210484712 A CN202210484712 A CN 202210484712A CN 114733358 A CN114733358 A CN 114733358A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/164—Use of bases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/168—Use of other chemical agents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a reverse osmosis membrane calcium sulfate scale cleaning agent and a cleaning method, wherein the cleaning agent is prepared from the following raw materials in parts by mass of solutes: 5% -30% of chelating agent, 5% -15% of dispersing agent, 1% -3% of penetrating agent, 0.2% -0.4% of pH regulator and the balance of pure water, and the invention has the advantages that: the method has the advantages of normal-temperature operation, environmental friendliness, simple and convenient operation, short cleaning time, high calcium sulfate scale removal rate of over 90 percent, pulverization, falling and separation from the membrane surface in the form of original solid calcium sulfate, thorough scale cleaning and removal, energy consumption reduction, yield improvement, equipment service life prolongation, production cost saving, acid-base neutralization discharge of cleaning waste liquid, small environmental pollution and wide application to cleaning of various reverse osmosis membrane calcium sulfate scales, especially cleaning of zero-discharge waste water treatment flat membrane reverse osmosis calcium sulfate scales.
Description
Technical Field
The invention relates to a cleaning agent, in particular to a reverse osmosis membrane calcium sulfate scale cleaning agent and a cleaning method, and belongs to the technical field of water treatment.
Background
The reverse osmosis technology is a technology for separating substances to obtain pure water by using pressure as a driving force and utilizing selective permeability of a membrane, and is used for desalting RO and NF membranes (roll type/flat plate) to treat high-calcium and high-sulfate raw water such as mine water, and the problems of calcium sulfate scaling and fouling on the membrane surface are faced, so that the pressure difference is increased, and the water production flux is reduced. The scale of the reverse osmosis membrane is mainly carbonate scale, sulfate scale and silicate scale, and a small amount of iron-aluminum-silicon compounds, wherein the sulfate scale is very difficult to remove. And because of the crystal form characteristics of the calcium sulfate scale, the calcium sulfate scale is deposited and blocked, the water flow resistance is increased, the water yield is reduced, the transmembrane pressure difference is increased, the membrane surface is expanded and pierced, and the water production quality is reduced. The selection of the reverse osmosis cleaning agent and the cleaning method has important influence on the performance recovery of the reverse osmosis membrane after pollution and the condition that the expected service life can be reached.
The two-step method of carbonate scale type conversion and hydrochloric acid dissolution and removal is used for cleaning calcium sulfate scale, the calcium sulfate scale is converted into calcium carbonate scale in situ by means of diffusion and permeation of carbonate, sulfate radical becomes ions which are dissolved in water and is discharged, after scale type conversion is sufficient, the calcium carbonate scale is dissolved into calcium ions, chloride ions and carbon dioxide (bicarbonate radical) by using hydrochloric acid, and cleaning wastewater is discharged. Has cleaning effect on common, slight and new calcium sulfate scale. The mechanism of ion diffusion scale type conversion determines that cleaning is time-consuming and labor-consuming, and one set of membrane system usually requires three to five days. The system has high operation rate and shutdown loss. The dosage of the medicament is large, a large amount of sodium ions and chloride ions are introduced into the system, and zero discharge salt separation actually forms 'dead circulation'.
Chelating dissolving method, the chelating agent such as EDTA mole ratio chemical reaction is completely dissolved, and the calcium sulfate scale is changed into calcium ion and sulfate ion dissolved in water. The cleaning effect is good and the speed is moderate for common, slight and new calcium sulfate scale, the effect is not good for long-time, fully developed and complete dihydrate gypsum CaSO4.2H2O scale, the operation rate and shutdown loss of the system are still considerable, the dosage of the medicament is large, the cost is high, the introduction system of TDS is large, and a large amount of water-soluble organic chelating agents are not environment-friendly and are difficult to treat.
Disclosure of Invention
The invention aims to provide a reverse osmosis membrane calcium sulfate scale cleaning agent and a cleaning method, aims to clean scale of a reverse osmosis system, particularly the scale blockage situation of calcium sulfate scale, and aims to recover the flux and the desalination rate of a reverse osmosis membrane and reduce the pressure difference, thereby reducing the production cost and prolonging the service life of the membrane.
In order to achieve the purpose, the invention provides the following technical scheme: a reverse osmosis membrane calcium sulfate scale cleaning agent is prepared from the following raw materials in parts by mass: 5 to 30 percent of chelating agent, 5 to 15 percent of dispersant, 1 to 3 percent of penetrating agent, 0.2 to 0.4 percent of pH regulator and the balance of pure water.
As a preferred technical solution of the present invention, the pH adjuster is NaOH: na (Na)3PO4Premix 3: 1.
As a preferable technical scheme of the invention, the dispersant is one or more of polyacrylic acid, polymaleic acid, polyepoxysuccinic acid, polyaspartic acid, AA, AMPS and terpolymer.
As a preferable technical scheme of the invention, the chelating agent is one or more of EDTA, EGTA, NTA, MGDA and ATMP.
As a preferable technical scheme of the invention, the penetrating agent is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, medium-low carbon fatty alcohol polyoxyethylene ether, medium-low isomeric alcohol polyoxyethylene ether and low-carbon alcohol ether ester.
As a preferable technical scheme of the invention, the pH value of the cleaning agent is 9-10.
As a preferred technical scheme of the invention, the cleaning method of the reverse osmosis membrane calcium sulfate scale cleaning agent comprises the following steps:
preparing an alkaline washing cleaning solution, fully dissolving and diluting a cleaning agent stock solution by using reverse osmosis produced water, adjusting the pH value of the diluted cleaning solution by using a small amount of sodium hydroxide, and placing the diluted cleaning solution in an alkaline washing cleaning box;
step two, starting a cleaning pump, injecting an alkali cleaning solution into the reverse osmosis membrane system, controlling the flow rate of the cleaning solution to be 2-3m/s, stopping the pump for soaking for 1h after circularly cleaning for 1h, and repeating circularly cleaning and soaking for 2-4 times; during the period, the pH value, the conductivity and the dirty pressure difference of the filter of the cleaning solution are monitored, and the stock solution of the cleaning agent is supplemented according to the system reaction;
and step three, after the alkaline cleaning is finished, flushing the system by using reverse osmosis produced water until the pH value is close to the pH value of the reverse osmosis produced water.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention relates to a reverse osmosis membrane calcium sulfate scale cleaning agent and a cleaning method, and the cleaning agent has the characteristics that: the method has the advantages of compatibility of membrane materials, normal-temperature cleaning, simplicity and convenience in operation, quick cleaning time, environmental friendliness, high calcium sulfate scale removal rate of over 90% to 100%, wherein over 70% of the calcium sulfate scale removal rate is realized by using calcium sulfate as an original ecological solid state to pulverize, fall and separate from a membrane surface, the scale is thoroughly cleaned and removed, the energy consumption is reduced, the yield is improved, the service life of the membrane is prolonged, the production cost is saved, meanwhile, cleaning waste liquid can be discharged after acid and alkali neutralization, the environmental pollution is small, and the method can be widely applied to cleaning of various reverse osmosis (nanofiltration) membrane calcium sulfate scales, and particularly cleaning of zero-discharge waste water treatment flat membrane reverse osmosis (nanofiltration) calcium sulfate scales.
Drawings
Fig. 1 is a table diagram according to a first embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the invention provides a technical scheme of a reverse osmosis membrane calcium sulfate scale cleaning agent and a cleaning method:
a reverse osmosis membrane calcium sulfate scale cleaning agent is prepared from the following raw materials in parts by mass: 5 to 30 percent of chelating agent, 5 to 15 percent of dispersant, 1 to 3 percent of penetrating agent, 0.2 to 0.4 percent of pH regulator and the balance of pure water.
The pH regulator is NaOH: na (Na)3PO41: 1, dispersing agent is one or more of polyacrylic acid, polymaleic acid, polyepoxysuccinic acid, polyaspartic acid, AA, AMPS and terpolymer, chelating agent is one or more of EDTA, EGTA, NTA, MGDA and ATMP, and penetrating agent is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, medium-low carbon fatty alcohol polyoxyethylene ether, medium-low carbon isomeric alcohol polyoxyethylene ether and low-carbon alcohol ether esterThe pH value of the cleaning agent is 9-10.
A cleaning method of a reverse osmosis membrane calcium sulfate scale cleaning agent comprises the following steps:
preparing an alkaline cleaning solution, wherein the concentration of the cleaning solution is 30%, the circulating flow rate (membrane surface flow rate) of the cleaning solution is 2-3m/s, fully dissolving and diluting a stock solution of the cleaning solution by using reverse osmosis produced water, adjusting the pH value of the diluted cleaning solution by using a small amount of sodium hydroxide, and placing the diluted cleaning solution in an alkaline cleaning tank;
step two, starting a cleaning pump, injecting an alkali cleaning solution into the reverse osmosis membrane system, controlling the flow rate of the cleaning solution to be 2-3m/s, stopping the pump for soaking for 1h after circularly cleaning for 1h, and repeating circularly cleaning and soaking for 2-4 times; during the period, the pH value, the conductivity and the dirty pressure difference of the filter of the cleaning solution are monitored, and the stock solution of the cleaning agent is supplemented according to the system reaction;
and step three, after the alkaline cleaning is finished, flushing the system by using reverse osmosis produced water until the pH value is close to the pH value of the reverse osmosis produced water.
Example one
A method for cleaning reverse osmosis calcium sulfate scale comprises the following steps of proportioning raw materials according to mass fraction of solute:
preparing an alkaline washing cleaning solution, fully dissolving a stock solution by using reverse osmosis produced water, adjusting the pH value of the diluted cleaning solution to 9.5 by using a small amount of sodium hydroxide, and placing the diluted cleaning solution in an alkaline washing cleaning box;
step two, starting a cleaning pump, injecting an alkali cleaning solution into the reverse osmosis membrane system, controlling the flow rate of the cleaning solution (membrane surface flow rate) to be 3m/s, circularly cleaning for 1h, stopping the pump, soaking for 1h, and repeatedly cleaning and soaking for 3 times; during the period, the pH value, the conductivity and the dirty pressure difference of the filter of the cleaning solution are monitored, and the stock solution of the cleaning agent is supplemented according to the system reaction;
and step three, after the alkaline cleaning is finished, flushing the system by using reverse osmosis produced water until the pH value is close to the pH value of the reverse osmosis produced water.
The cleaning effect of the first embodiment is shown in fig. 1.
A chelating dissolution, permeation, peeling, pulverization and dispersion method is characterized in that calcium sulfate scale is not completely dissolved and changed into calcium ions and sulfate ions dissolved in water, but calcium sulfate crystal scale shape characteristics are combined, and the method is characterized by permeation, diffusion, chelating dissolution, cracking, pulverization and dispersion, wherein most of the calcium sulfate scale is separated from a membrane surface in a pulverized and fine powdery calcium sulfate original solid suspended substance form and then is washed away in water, and is subsequently intercepted by a cleaning filter, the original solid form leaves a water body, and a specific combination mixture of a penetrating agent, a chelating agent and a dispersing agent has good cleaning effect and high speed on common, slight and new calcium sulfate scale; the method has good effect and high speed on long-time, fully developed and complete dihydrate gypsum CaSO4.2H2O scale and even massive dihydrate gypsum CaSO4.2H2O scale in pipeline equipment, the cleaning is usually completed within 6-12h, the operation efficiency and shutdown loss of a system are low, the dosage of a medicament is small, the amount of waste liquid, waste water and waste residues discharged to the outside is small, and the TDS introduction system is very small.
In the description of the present invention, it is to be understood that the indicated orientations or positional relationships are based on the orientations or positional relationships shown in the drawings and are only for convenience in describing the present invention and simplifying the description, but are not intended to indicate or imply that the indicated devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are not to be construed as limiting the present invention.
In the present invention, unless otherwise explicitly specified or limited, for example, it may be fixedly attached, detachably attached, or integrated; can be mechanically or electrically connected; the terms may be directly connected or indirectly connected through an intermediate, and may be communication between two elements or interaction relationship between two elements, unless otherwise specifically limited, and the specific meaning of the terms in the present invention will be understood by those skilled in the art according to specific situations.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A reverse osmosis membrane calcium sulfate scale cleaning agent is characterized by being prepared from the following raw materials in percentage by mass: 5 to 30 percent of chelating agent, 5 to 15 percent of dispersant, 1 to 3 percent of penetrating agent, 0.2 to 0.4 percent of pH regulator and the balance of pure water.
2. A reverse osmosis membrane calcium sulfate scale cleaning agent according to claim 1, which is characterized in that: the pH regulator is NaOH: na (Na)3PO4Premix 3: 1.
3. A reverse osmosis membrane calcium sulfate scale cleaning agent according to claim 1, which is characterized in that: the dispersant is one or more of polyacrylic acid, polymaleic acid, polyepoxysuccinic acid, polyaspartic acid, AA, AMPS and terpolymer.
4. A reverse osmosis membrane calcium sulfate scale cleaning agent according to claim 1, which is characterized in that: the chelating agent is one or more of EDTA, EGTA, NTA, MGDA and ATMP.
5. A reverse osmosis membrane calcium sulfate scale cleaning agent according to claim 1, which is characterized in that: the penetrating agent is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, medium-low carbon fatty alcohol polyoxyethylene ether, medium-low carbon isomeric alcohol polyoxyethylene ether and low-carbon alcohol ether ester.
6. A reverse osmosis membrane calcium sulfate scale cleaning agent according to claim 1, which is characterized in that: the pH value of the cleaning agent is 9-10.
7. A cleaning method of a reverse osmosis membrane calcium sulfate scale cleaning agent is characterized by comprising the following steps:
preparing an alkaline washing cleaning solution, fully dissolving and diluting a cleaning agent stock solution by using reverse osmosis produced water, adjusting the pH value of the diluted cleaning solution by using a small amount of sodium hydroxide, and placing the diluted cleaning solution in an alkaline washing cleaning box;
step two, starting a cleaning pump, injecting an alkali cleaning solution into the reverse osmosis membrane system, controlling the flow rate of the cleaning solution to be 2-3m/s, stopping the pump for soaking for 1h after circularly cleaning for 1h, and repeating circularly cleaning and soaking for 2-4 times; during the period, the pH value, the conductivity and the dirty pressure difference of the filter of the cleaning solution are monitored, and the stock solution of the cleaning agent is supplemented according to the system reaction;
and step three, after the alkaline cleaning is finished, flushing the system by using reverse osmosis produced water until the pH value is close to the pH value of the reverse osmosis produced water.
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| CN202210484712.XA CN114733358A (en) | 2022-05-06 | 2022-05-06 | Reverse osmosis membrane calcium sulfate scale cleaning agent and cleaning method |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977711A (en) * | 2014-05-16 | 2014-08-13 | 威海翔宇环保科技有限公司 | Compound cleaner for cleaning reverse osmosis membrane and preparation method of compound cleaner |
| CN205627663U (en) * | 2015-12-25 | 2016-10-12 | 广州小众环保科技有限公司 | Novel reverse osmosis membrane washs device |
| CN110898675A (en) * | 2019-12-09 | 2020-03-24 | 吉林省电力科学研究院有限公司 | Calcium sulfate scale cleaning agent for reverse osmosis membrane and cleaning method |
| CN111440679A (en) * | 2020-04-03 | 2020-07-24 | 山东鲁东环保科技有限公司 | Cleaning agent for cleaning high sulfate scale and preparation method and application thereof |
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- 2022-05-06 CN CN202210484712.XA patent/CN114733358A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977711A (en) * | 2014-05-16 | 2014-08-13 | 威海翔宇环保科技有限公司 | Compound cleaner for cleaning reverse osmosis membrane and preparation method of compound cleaner |
| CN205627663U (en) * | 2015-12-25 | 2016-10-12 | 广州小众环保科技有限公司 | Novel reverse osmosis membrane washs device |
| CN110898675A (en) * | 2019-12-09 | 2020-03-24 | 吉林省电力科学研究院有限公司 | Calcium sulfate scale cleaning agent for reverse osmosis membrane and cleaning method |
| CN111440679A (en) * | 2020-04-03 | 2020-07-24 | 山东鲁东环保科技有限公司 | Cleaning agent for cleaning high sulfate scale and preparation method and application thereof |
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