CN110882630A - Descaling agent of ceramic ultrafiltration membrane system for treating oily sewage in oil field and preparation method thereof - Google Patents
Descaling agent of ceramic ultrafiltration membrane system for treating oily sewage in oil field and preparation method thereof Download PDFInfo
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- CN110882630A CN110882630A CN201911212656.9A CN201911212656A CN110882630A CN 110882630 A CN110882630 A CN 110882630A CN 201911212656 A CN201911212656 A CN 201911212656A CN 110882630 A CN110882630 A CN 110882630A
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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
- B01D2321/162—Use of acids
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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
Abstract
The invention discloses a descaling agent of a ceramic ultrafiltration membrane system for treating oily sewage of an oil field and a preparation method thereof. The scale remover comprises the following components in percentage by mass: 3-5% of formic acid, 0.5-1% of surfactant, 0.5-1% of solubilizer, 0.5-1% of auxiliary agent and the balance of deionized water. The invention also discloses a preparation method thereof: sequentially adding formic acid, a surfactant, a solubilizer and an auxiliary agent into deionized water according to a ratio, stirring for 1-4 hours at normal temperature, and uniformly stirring to obtain a finished product. The ceramic ultrafiltration membrane system scale remover has good and thorough cleaning effect, ensures that the recovery rate of membrane flux is more than 99 percent, prolongs the membrane pollution period and reduces the cleaning frequency; and the cleaning mode is simpler, and the cleaning time is shorter.
Description
Technical Field
The invention belongs to the technical field of water treatment agents, relates to a scale remover suitable for a ceramic ultrafiltration membrane system, and particularly relates to a scale remover for a ceramic ultrafiltration membrane system for treating oily sewage in an oil field and a preparation method thereof.
Background
China has wide oil field distribution and spreads all over northeast, northeast China, southwest, China and southeast coastal areas. At present, most oil fields enter the middle stage and the later stage of oil exploitation, the water content of the extracted crude oil reaches 70% -80%, the water content of some oil fields reaches even 90%, and a large amount of oily sewage is generated after oil-water separation. If the oily sewage is directly discharged without being treated, not only can the soil and water source be polluted, but also sometimes even the burning accident of the dirty oil can be caused, the life safety of people is threatened, the national economic loss is caused, and the benefits of the oil field can be damaged. Therefore, how to develop the oil field oily sewage treatment and recycling technology which is suitable for the actual conditions of the oil field in China and is efficient and economical to achieve the purposes of saving energy, reducing consumption, protecting the environment and recycling water resources becomes an important problem for the reconstruction and establishment of the oil field water treatment station.
The membrane technology is a new separation technology which rises rapidly after the 60 th century in 20 th, has formed a new industry since the past, is widely applied to the fields of domestic daily chemicals, food, medicine and biochemistry, and is also a research hotspot in the aspect of water treatment in the field of petroleum in recent years. The membrane separation method is to separate substances by using a specially manufactured film with selective permeability under the push of external force, and comprises the methods of reverse osmosis, ultrafiltration, nanofiltration and the like. The operation main body of the membrane separation technology is a membrane for separation, and the driving force of the separation process is the pressure difference, the potential difference, the concentration difference and the temperature difference of two sides of the membrane. The ceramic ultrafiltration membrane has uniform and small-sized pore diameter and can filter and retain pollutants with small particle size. The separation can be carried out at normal temperature, the energy consumption of the operation is low, and the utilization rate of water is high; meanwhile, the composite material also has the advantages of high temperature resistance, high pressure resistance, strong chemical agent resistance, high mechanical strength, pollution resistance, long service life and the like. The ceramic ultrafiltration membrane is more and more widely applied to the treatment of oil extraction sewage in the oil field.
Because most of the prior oil fields enter the middle and later stages of oil exploitation, the long-term exploitation causes the aging of equipment and pipelines, and a large amount of iron rust and iron ions enter the oil-containing sewage. During the treatment of the ceramic ultrafiltration membrane, iron scale is formed on the membrane layer. Most of the iron scale can be removed by using common acidic washing agents (including hydrochloric acid, nitric acid, citric acid and the like), but a small amount of the iron scale cannot be removed. The indissolvable iron scale is accumulated for a long time, finally, the flux of the membrane is reduced, and the treatment effect of the membrane system is seriously influenced. Through detection and analysis, the indissoluble scale is mainly ferroferric oxide and hydroxyl ferric oxide. At present, the following methods are used for treating the indissolvable rust: 1. oxalic acid is selected as a main acid agent, the acidity of the oxalic acid is 10000 times stronger than that of acetic acid, the oxalic acid is strong organic acid and has strong reducibility. The oxalic acid can reduce ferric iron in the indissolvable iron scale into ferrous iron, so that the indissolvable iron scale is more soluble; on the other hand, oxalic acid can form a soluble complex with the iron scale to promote the dissolution of the iron scale. The oxalic acid treatment of iron scale also has obvious disadvantages, such as the formation of calcium oxalate precipitate by oxalic acid and calcium element in sewage or on the surface of the membrane, and the strong toxicity of oxalic acid itself. 2. Hydrofluoric acid is selected as the main acid agent. Hydrofluoric acid can form an easily soluble coordination compound with iron in the indissolvable iron scale, so that the indissolvable iron scale can be almost completely dissolved, and silicon scale on the surface of the film can be removed. The disadvantage of this method is that the excess hydrofluoric acid cannot be handled and can cause severe corrosion of the equipment. 3. Organic phosphonic acid is selected as a main acid agent. Research shows that hydroxyethylidene diphosphonic acid (HEDP) and 2-hydroxyphosphonoacetic acid have good dissolving and descaling effects on indissolvable iron scale. The organic phosphonic acid has good chemical stability, is not easy to hydrolyze and is not easy to be damaged by acid and alkali. However, the medicament is expensive, and long-term use of the medicament can cause serious consequences of water eutrophication. Therefore, aiming at the characteristics of oily sewage, the development of a high-efficiency cleaning agent for a ceramic ultrafiltration membrane system is urgent.
Disclosure of Invention
In order to solve the problem that scale on the surface of a ceramic membrane system for treating oil-containing sewage of an oil field is difficult to remove, the invention provides a scale remover of a ceramic ultrafiltration membrane system for treating the oil-containing sewage of the oil field and a preparation method thereof.
The scale remover composition provided by the invention comprises the following components in percentage by mass:
3-5% of formic acid, 0.5-1% of surfactant, 0.5-1% of solubilizer, 0.5-1% of auxiliary agent and the balance of deionized water;
in the detergent composition, the surfactant is at least one selected from sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
The solubilizer is at least one selected from disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate and sodium citrate.
The auxiliary agent is at least one of sodium silicate, sodium sulfate and sodium chloride.
The mass percentage of the formic acid in the scale remover composition is 4-5%.
The scale remover composition is specifically any one of scale remover compositions a-d;
the scale remover composition a comprises the following components in percentage by mass:
formic acid: 5 percent;
surfactant sodium dodecyl sulfate: 1 percent;
solubilizer disodium ethylene diamine tetraacetate: 1 percent;
auxiliary agent sodium chloride: 1 percent;
deionized water: 92 percent; (ii) a
The scale remover composition b comprises the following components in percentage by mass:
formic acid: 4.5 percent;
surfactant sodium dodecyl benzene sulfonate: 1 percent;
solubilizer ethylenediaminetetraacetic acid tetrasodium salt: 1 percent;
auxiliary agent sodium chloride: 0.5 percent;
deionized water: 93 percent;
the scale remover composition c comprises the following components in percentage by mass:
formic acid: 4.5 percent;
surfactant sodium dodecyl benzene sulfonate: 0.5 percent;
solubilizer sodium citrate: 0.5 percent;
auxiliary agent sodium silicate: 0.5 percent;
deionized water: 94 percent;
the scale remover composition d comprises the following components in percentage by mass:
formic acid: 4 percent;
surfactant sodium lauryl sulfate: 1 percent;
solubilizer sodium citrate: 1 percent;
auxiliary agent sodium sulfate: 0.5 percent;
deionized water: 93.5 percent.
The invention provides a method for preparing the scale remover composition, which comprises the following steps:
and sequentially adding formic acid, a surfactant, a solubilizer and an auxiliary agent into the deionized water according to the proportion, stirring for 1-4 h at normal temperature, and uniformly stirring to obtain the water-based paint.
In addition, the application of the scale remover composition provided by the invention in the scale removal of oily sewage in an oil field also belongs to the protection scope of the invention.
Specifically, the descaling object is the ceramic membrane system of the oily sewage of the oil field.
More specifically, the ceramic membrane is a ceramic ultrafiltration membrane.
Compared with the prior art, the cleaning agent has the following advantages:
1. aiming at the pollution condition of oily sewage in an oil field to the ceramic ultrafiltration membrane, after alkaline washing, a scale layer on the surface of the ceramic membrane can be effectively removed, the phenomenon of surface concentration polarization is reduced, and indissolvable iron scale attached to the surface of the membrane and the inside of a pore channel is completely removed, so that the regeneration of the ceramic ultrafiltration membrane is basically realized, and the recovery rate of membrane flux is more than 99%.
2. The cleaning of the surface and the inner pore channels of the membrane is thorough, the period of membrane pollution is prolonged, the cleaning frequency is reduced, and the service life of the membrane and the whole system is prolonged.
3. The cleaning mode is simple, the cleaning can be carried out without using a back flushing mode, the cleaning time is short, and a large amount of energy consumption is saved.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Examples 1,
The scale remover for the ceramic ultrafiltration membrane system comprises the following components in percentage by mass:
formic acid: 5 percent of
Surfactant (b): 1 percent of
Solubilizer: 1 percent of
Auxiliary agent: 1 percent of
Deionized water: 92 percent of
Wherein the surfactant is sodium dodecyl sulfate, the solubilizer is disodium ethylene diamine tetraacetate, and the auxiliary agent is sodium chloride. The preparation method comprises the following steps: and (3) adding deionized water into a reactor with stirring, then sequentially adding formic acid, a surfactant, a solubilizer and an auxiliary agent, stirring for 3 hours at normal temperature, and uniformly stirring to obtain the scale remover composition provided by the invention.
Example 2
The scale remover for the ceramic ultrafiltration membrane system comprises the following components in percentage by mass:
formic acid: 4.5 percent
Surfactant (b): 1 percent of
Solubilizer: 1 percent of
Auxiliary agent: 0.5 percent
Deionized water: 93 percent
Wherein the surfactant is sodium dodecyl benzene sulfonate, the solubilizer is tetrasodium ethylene diamine tetraacetate, and the auxiliary agent is sodium chloride. The preparation method comprises the following steps: and (2) adding deionized water into a reactor with stirring, then sequentially adding formic acid, a surfactant, a solubilizer and an auxiliary agent, stirring for 2.5 hours at normal temperature, and uniformly stirring to obtain the scale remover composition.
Example 3
The scale remover for the ceramic ultrafiltration membrane system comprises the following components in percentage by mass:
formic acid: 4.5 percent
Surfactant (b): 0.5 percent
Solubilizer: 0.5 percent
Auxiliary agent: 0.5 percent
Deionized water: 94 percent of
Wherein the surfactant is sodium dodecyl benzene sulfonate, the solubilizer is sodium citrate, and the auxiliary agent is sodium silicate. The preparation method comprises the following steps: and (2) adding deionized water into a reactor with stirring, then sequentially adding formic acid, a surfactant, a solubilizer and an auxiliary agent, stirring for 2 hours at normal temperature, and uniformly stirring to obtain the scale remover composition.
Example 4
The scale remover for the ceramic ultrafiltration membrane system comprises the following components in percentage by mass:
formic acid: 4 percent of
Surfactant (b): 1 percent of
Solubilizer: 1 percent of
Auxiliary agent: 0.5 percent
Deionized water: 93.5 percent
Wherein the surfactant is sodium dodecyl sulfate, the solubilizer is sodium citrate, and the auxiliary agent is sodium sulfate. The preparation method comprises the following steps: and (3) adding deionized water into a reactor with stirring, then sequentially adding formic acid, a surfactant, a solubilizer and an auxiliary agent, stirring for 4 hours at normal temperature, and uniformly stirring to obtain the scale remover composition.
Application and Performance testing
The application method of the cleaning agent comprises the following steps:
1. and (3) emptying the sewage in the system, circulating for 5min by using warm water or hot water (30-80 ℃), and then emptying.
2. The system was charged with 1% sodium hydroxide solution, circulated for 1h, and then emptied.
3. Warm water or hot water (30-80 ℃) is injected into the system for circulation for 5min, and then the system is emptied.
4. The system was charged with 1% detergent for 2h of circulation and then emptied.
5. And (3) injecting warm water or hot water (30-80 ℃) into the system, circulating for 5min, then emptying, and finishing cleaning.
The detergent compositions obtained in examples 1 to 4, according to the above-mentioned washing procedure, showed that: the recovery rate of the membrane flux of example 1 is 99.6%, the recovery rate of the membrane flux of example 2 is 99.4%, the recovery rate of the membrane flux of example 3 is 99.3%, and the recovery rate of the membrane flux of example 4 is 99.5%. The ceramic ultrafiltration membrane basically realizes regeneration, and the recovery rate of membrane flux is more than 99%.
Claims (10)
1. A scale remover composition comprises the following components in percentage by mass:
3-5% of formic acid, 0.5-1% of surfactant, 0.5-1% of solubilizer, 0.5-1% of auxiliary agent and the balance of deionized water.
2. The detergent composition of claim 1, wherein: the surfactant is at least one selected from sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
3. The detergent composition according to claim 1 or 2, characterized in that: the solubilizer is at least one selected from disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate and sodium citrate.
4. A detergent composition according to any one of claims 1 to 3, characterized in that: the auxiliary agent is at least one of sodium silicate, sodium sulfate and sodium chloride.
5. The detergent composition according to any one of claims 1 to 4, wherein: the mass percentage of the formic acid in the scale remover composition is 4-5%.
6. The detergent composition according to any one of claims 1 to 5, wherein: the scale remover composition is any one of the scale remover compositions a-d;
the scale remover composition a comprises the following components in percentage by mass:
formic acid: 5 percent;
surfactant sodium dodecyl sulfate: 1 percent;
solubilizer disodium ethylene diamine tetraacetate: 1 percent;
auxiliary agent sodium chloride: 1 percent;
deionized water: 92 percent; (ii) a
The scale remover composition b comprises the following components in percentage by mass:
formic acid: 4.5 percent;
surfactant sodium dodecyl benzene sulfonate: 1 percent;
solubilizer ethylenediaminetetraacetic acid tetrasodium salt: 1 percent;
auxiliary agent sodium chloride: 0.5 percent;
deionized water: 93 percent;
the scale remover composition c comprises the following components in percentage by mass:
formic acid: 4.5 percent;
surfactant sodium dodecyl benzene sulfonate: 0.5 percent;
solubilizer sodium citrate: 0.5 percent;
auxiliary agent sodium silicate: 0.5 percent;
deionized water: 94 percent;
the scale remover composition d comprises the following components in percentage by mass:
formic acid: 4 percent;
surfactant sodium lauryl sulfate: 1 percent;
solubilizer sodium citrate: 1 percent;
auxiliary agent sodium sulfate: 0.5 percent;
deionized water: 93.5 percent.
7. A process for preparing a detergent composition according to any one of claims 1 to 6, comprising:
and sequentially adding formic acid, a surfactant, a solubilizer and an auxiliary agent into the deionized water according to the proportion, stirring for 1-4 h at normal temperature, and uniformly stirring to obtain the water-based paint.
8. Use of the detergent composition according to any one of claims 1-6 for the descaling of oily sewage from oil fields.
9. Use according to claim 8, characterized in that: the descaling object is a ceramic membrane system of the oily sewage of the oil field.
10. Use according to claim 9, characterized in that: the ceramic membrane is a ceramic ultrafiltration membrane.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911212656.9A CN110882630A (en) | 2019-12-02 | 2019-12-02 | Descaling agent of ceramic ultrafiltration membrane system for treating oily sewage in oil field and preparation method thereof |
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| CN201911212656.9A CN110882630A (en) | 2019-12-02 | 2019-12-02 | Descaling agent of ceramic ultrafiltration membrane system for treating oily sewage in oil field and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113684101A (en) * | 2020-05-19 | 2021-11-23 | 中国石油天然气股份有限公司 | Cleaning agent and preparation method and application thereof |
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| CN110241430A (en) * | 2019-06-27 | 2019-09-17 | 湖南省湘电试验研究院有限公司 | A kind of composite organic acid contaminant removing cleaning agent and its application |
| CN110354687A (en) * | 2019-07-23 | 2019-10-22 | 威海翔泽新材料科技有限公司 | A kind of dedicated remover of reverse osmosis membrane iron contaminants and preparation method thereof |
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2019
- 2019-12-02 CN CN201911212656.9A patent/CN110882630A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6239092B1 (en) * | 1997-09-30 | 2001-05-29 | Reckitt Benckiser Inc. | Thickened acidic, hard surface cleaning and disinfecting compositions particularly useful for ceramic surfaces |
| CN1754843A (en) * | 2004-09-29 | 2006-04-05 | 上海万森水处理有限公司 | Descaling agent for industrial cooling circulating water system surface cleaning |
| CN101760352A (en) * | 2009-11-17 | 2010-06-30 | 上海丰信环保科技有限公司 | Composite cleaning agent for cleaning membrane system containing inorganic substance contaminants |
| CN109988679A (en) * | 2017-12-29 | 2019-07-09 | 南京源泉环保科技股份有限公司 | A kind of ceramic membrane dirt detergent and the preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113684101A (en) * | 2020-05-19 | 2021-11-23 | 中国石油天然气股份有限公司 | Cleaning agent and preparation method and application thereof |
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