CN115627198A - Cleaning agent for removing sulfate scale and preparation method and application thereof - Google Patents

Cleaning agent for removing sulfate scale and preparation method and application thereof Download PDF

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Publication number
CN115627198A
CN115627198A CN202211117034.XA CN202211117034A CN115627198A CN 115627198 A CN115627198 A CN 115627198A CN 202211117034 A CN202211117034 A CN 202211117034A CN 115627198 A CN115627198 A CN 115627198A
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China
Prior art keywords
cleaning agent
scale
sulfate scale
sulfate
acid
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Pending
Application number
CN202211117034.XA
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Chinese (zh)
Inventor
单素灵
王双田
李海争
黄俊博
张静
张驰
卢洪杰
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Beijing Bluestar Cleaning Co Ltd
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Beijing Bluestar Cleaning Co Ltd
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Priority to CN202211117034.XA priority Critical patent/CN115627198A/en
Publication of CN115627198A publication Critical patent/CN115627198A/en
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/32Organic compounds containing nitrogen
    • C11D7/3245Aminoacids
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/265Carboxylic acids or salts thereof
    • C11D2111/20

Abstract

The invention relates to the field of industrial cleaning, and discloses a cleaning agent for removing sulfate scale, and a preparation method and application thereof. The dissolving type sulfate cleaning agent has the advantages of low corrosivity, environmental protection, no toxicity, no phosphorus and good biodegradability, and can be applied to various purposes of removing sulfate scales.

Description

Cleaning agent for removing sulfate scale and preparation method and application thereof
Technical Field
The invention relates to the field of industrial cleaning, in particular to a cleaning agent for removing sulfate scale, a preparation method and application thereof.
Background
The sulfate scale generally refers to the scale mainly containing calcium sulfate, and once the sulfate scale is formed, the sulfate scale is difficult to remove by a general acid pickling method, so the scale is classified as insoluble scale. Is commonly used in phosphate rock factories, sugar factories, paper mills and other systems which use water containing a large amount of sulfate radicals as circulating cooling water. The pickling process is ineffective for insoluble sulfate scale. And because the scale is in a dense layer shape and exists in a long pipeline, the scale is difficult to remove by a physical method, and the traditional method is high-temperature alkaline boiling, so that the time is wasted and the potential safety hazard is caused.
In recent years, sulfate cleaning agents are available on the market, and the cleaning agents can solve the problem of scaling in a common pipeline when used at normal temperature, but the cleaning agents are in a swelling state after being cleaned, so that mud dirt-containing substances with the volume 2-3 times that of the original dirt sample need to be treated, and inconvenience is brought to subsequent cleaning treatment.
The cleaning agent for sulfate scale provided by CN101913713A is the cleaning agent, and the specific composition is 20.0-40.0% of organic carboxylate; 1.4 to 8.0 percent of organic phosphonate; 0.5 to 2.0 percent of reducing agent; 0.1-3.0% of surfactant and 47.0-78.0% of water, and firstly softening the scale and then washing the scale. CN101705159A discloses a cleaning agent which contains OP-10, JFC and other surfactants, wherein the nonionic polyoxyethylene ether surfactants are not easy to biodegrade, generate a large amount of foams in the cleaning process and are not easy to wash. CN103806009A discloses a "neutral sulfate cleaning agent", which contains organic phosphorus, and can eutrophicate water body and cause environmental pollution.
In addition, sulfate scale is also often generated at the front end of membrane water treatment, once sulfate scale is generated on a reverse osmosis membrane, common acidic and alkaline membrane cleaning agents cannot clean the sulfate scale, and the risk of membrane blocking is increased if swelling sulfate cleaning agents are used. Therefore, for sulfate scale in membrane-process water treatment, a cleaning agent treatment is required which can dissolve the insoluble sulfate scale into a solution during the cleaning process.
Disclosure of Invention
The invention aims to overcome the problems of difficult cleaning, follow-up problems after descaling, environmental pollution caused by phosphorus and the like in the prior art, and provides a cleaning agent for removing sulfate scale, a preparation method and application thereof.
In order to achieve the above object, one aspect of the present invention provides a detergent for removing sulfate scale, comprising the following components in a weight ratio of 0.8-5:4-15:9-25 of trisodium dicarboxymethylalanine, hydroxycarboxylic acid chelating agent and tetrasodium glutamate diacetate
The invention provides the application of the cleaning agent for removing sulfate scales in the removal of the sulfate scales.
In a third aspect, the present invention provides a method for removing sulfate scale, comprising: and (3) putting the cleaning agent for removing the sulfate scales into a system deposited with the sulfate scales for cleaning.
Through the technical scheme, the cleaning agent has the advantages of simple formula and easiness in preparation, and can increase the solubility of components of a strong chelating formula, so that the ratio of dirt to a solvent is 1:9-10, the efficiency of the cleaning agent is improved, and the cost performance is further improved; the scale can be completely removed without post-treatment, particularly, after the insoluble sulfate scale is soaked or circularly cleaned, the scale can be completely dissolved and discharged out of the system in a solution state, so that the corrosion to metals such as carbon steel and the like is avoided, and the sulfate scale can be completely removed in a relatively short time; the components of the formula do not contain phosphorus, the biodegradability is excellent, and the formula has the beneficial effects of no toxicity and no pollution to the environment and human bodies. The components of the detergent provided by the invention play a role in a synergistic manner, and only if the components are not enough, the dissolving type sulfate descaling cleaning agent prepared by the technical scheme of the application can effectively remove insoluble sulfate scale generated under various conditions and environments.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the use of trilon, unless stated to the contrary, generally means that MGDA means trisodium dicarboxymethylalanine. GLDA.4Na is generally referred to as tetrasodium glutamate diacetate. EDTA is typically referred to as ethylenediaminetetraacetic acid. DTPA is commonly referred to as diethyltriaminepentaacetic acid. NTA is commonly referred to as nitrilotriacetic acid.
The invention provides a cleaning agent for removing sulfate scale, which comprises the following components in parts by weight of 0.8-5:4-15:9-25 parts of dicarboxymethylalanine trisodium, hydroxycarboxylic acid chelating agent and glutamic diacetic acid tetrasodium.
According to the invention, in order to make the preparation effect more stable and ensure that hard scale is not formed into a soft mud state and is completely dissolved, the weight percentage of the dicarboxymethylalanine trisodium is 0.8-5%, the weight percentage of the hydroxycarboxylic acid chelating agent is 4-15%, and the weight percentage of the glutamic diacetic acid tetrasodium is 9-25% based on the total weight of the cleaning agent.
According to a more preferred embodiment of the invention, the weight ratio of trisodium dicarboxymethylalanine, hydroxycarboxylic acid chelating agent and tetrasodium glutamate diacetate is 1:2-8:6-10; alternatively, the weight percentage of the dicarboxymethylalanine trisodium is preferably 1-3%, the weight percentage of the hydroxycarboxylic acid chelating agent is preferably 5-10%, and the weight percentage of the glutamic diacetic acid tetrasodium is preferably 10-20%.
According to the invention, the hydroxycarboxylic acid chelating agent is at least one of polyacrylic acid, tartaric acid and maleic acid, preferably at least one of polyacrylic acid and maleic acid.
According to a more preferred embodiment of the invention, the polyacrylic acid has a molecular weight of 1500 to 2000.
According to the invention, the cleaning agent also comprises water, and the weight percentage of the water is 77-86.2%.
According to a more preferred embodiment of the invention, the water is present in an amount of 77-82% by weight.
According to the invention, the cleaning agent for removing sulfate scales is prepared by stirring and mixing dicarboxymethylalanine trisodium, hydroxycarboxylic acid chelating agent, glutamic acid diacetic acid tetrasodium and water into a homogeneous solution.
According to the invention, the conditions of said mixing include: the temperature is 23-28 ℃.
The invention provides the application of the cleaning agent for removing sulfate scales in the removal of the sulfate scales.
In a third aspect, the present invention provides a method for removing sulfate scale, the method comprising: and (3) putting the cleaning agent for removing the sulfate scale into a system deposited with the sulfate scale for cleaning.
According to the method of the invention, the total amount of the dicarboxymethylalanine trisodium, the hydroxycarboxylic acid chelating agent, the glutamic acid diacetic acid tetrasodium and water is 900-1000g relative to 100g of sulfate scale.
According to the method of the present invention, the cleaning conditions include: the temperature is 23-28 deg.C, and the time is 15min-4h.
According to the method, the system deposited with the sulfate scale can be a pipeline with the sulfate scale in a factory or a reverse osmosis membrane with the sulfate scale at the front end of membrane water treatment.
According to a more preferred embodiment of the present invention, the sulfate scale removal by the reverse osmosis membrane of the membrane method water treatment is carried out at a pressure of 0.1 to 0.15 MPa.
The present invention will be described in detail below by way of examples. The descaling rate and the corrosion rate are tested according to GB/T25146-2010.
Examples 1 to 3 and comparative examples 1 to 3
All the components are stirred and mixed at 25 ℃ to obtain a homogeneous solution, and the finished cleaning agent is obtained, wherein the addition and the weight percentage of all the components are shown in table 1.
Test example 1
In a carbon steel pipeline of a sugar refinery, 60 wt% of sulfate insoluble scale (the content of sulfate-containing scale in complex scale) is contained, the thickness of the scale is 10mm, and the total amount is estimated to be 100kg. The other components except the sulfate scale are mainly carbonate scale. Adding the cleaning agents of examples 1-3 and comparative examples 1-3, wherein the total weight of the cleaning agents is 1000kg, and the cleaning agents are circularly cleaned for 48 hours at the temperature of about 25 ℃. See table 2 for the effects.
TABLE 1 weight percent of each component
Figure BDA0003845729370000051
TABLE 2
Figure BDA0003845729370000052
Figure BDA0003845729370000061
As can be seen from the results of Table 1, according to the use of examples 1 to 3 in test example 1 of the present application, it was found that the detergent for removing sulfate scales using the specific formulation of the present invention and the sulfate scale removal using chelating agents EDTA (comparative example 1), DTPA (comparative example 2) and NTA (comparative example 3) commonly used in the prior art as components had significantly better effects of removing and descaling up to 95%. The cleaning agent for removing sulfate scale of the specific formula can completely remove the sulfate scale in a relatively short time; the specific formula can effectively avoid the corrosion to the carbon steel; the scale can not swell with the scale, and the scale can be cleaned in a solution state through dissolution without residue, so that the specific formula does not need subsequent treatment. Furthermore, as can be seen from test example 1, the scale dissolution ratio of the formulation specified in the present application is 10:1, compared with the scale dissolving ratio (13-15.
Test example 2
In a water treatment process of a certain membrane method, a two-stage membrane (the membrane is 40 inches long and 8 inches in diameter, the membrane flux is 0.8 ton per hour) is formed on an acid-insoluble scale layer with the thickness of about 0.5mm, the membrane is analyzed to be mainly insoluble sulfate scale, 1 weight percent of MGDA,5 weight percent of maleic acid, 10 weight percent of GLDA 4Na and 84 weight percent of water are added, the total amount is 200kg, the pressure is 0.1013MPa, and the membrane is soaked and cleaned for 12 hours at the temperature of 25 ℃. The membrane flux increased to 1 ton per hour.
According to the test example 2, the specific formula of the application also has excellent effect on solving sulfate scale in membrane method water treatment, so that the membrane flux is improved.
In conclusion, the specific formula of the application does not contain phosphorus, can be biodegraded, and achieves the effect of environmental protection. Therefore, the cleaning agent for removing sulfate scale with a specific formula is environment-friendly and economical, has a wide application range, and can be applied to the conditions of various sulfate scales.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. The cleaning agent for removing sulfate scale is characterized by comprising the following components in a weight ratio of 0.8-5:4-15:9-25 parts of dicarboxymethylalanine trisodium, hydroxycarboxylic acid chelating agent and glutamic diacetic acid tetrasodium.
2. The cleaning agent according to claim 1, wherein the weight percentage of the trisodium dicarboxymethylalanine, the weight percentage of the hydroxycarboxylic acid chelating agent and the weight percentage of the tetrasodium glutamate diacetate are respectively 0.8-5%, 4-15% and 9-25%, respectively, based on the total weight of the cleaning agent.
3. The cleaning agent according to claim 2, wherein the weight ratio of the dicarboxymethylalanine trisodium hydroxycarboxylic acid chelating agent to the glutamic diacetate tetrasodium is 1:2-8:6-10;
alternatively, the weight percentage of the dicarboxymethylalanine trisodium is preferably 1-3%, the weight percentage of the hydroxycarboxylic acid chelating agent is preferably 5-10%, and the weight percentage of the glutamic diacetic acid tetrasodium is preferably 10-20%.
4. The cleaning agent according to claim 1, wherein the hydroxycarboxylic acid chelating agent is at least one of polyacrylic acid, tartaric acid and maleic acid, preferably at least one of polyacrylic acid and maleic acid.
5. The cleaning agent according to any one of claims 1 to 4, wherein the cleaning agent further comprises water, and the water accounts for 77 to 86.2 weight percent.
6. The cleaning agent according to claim 5, wherein the water is contained in an amount of 77 to 82% by weight.
7. Use of the detergent for sulfate scale removal as set forth in any one of claims 1 to 6 for removing sulfate scale.
8. A method for removing sulfate scale, the method comprising: the sulfate scale removing cleaning agent according to any one of claims 1 to 6 is applied to a system on which sulfate scale is deposited to clean the system.
9. The process of claim 8, wherein the total amount of trisodium dicarboxymethylalanine, hydroxycarboxylic acid chelating agent and tetrasodium glutamate diacetate is 124-230g relative to 100g of sulfate scale.
10. The method of claim 8 or 9, the conditions of the washing comprising: the temperature is 23-28 deg.C, and the time is 15min-4h.
CN202211117034.XA 2022-09-14 2022-09-14 Cleaning agent for removing sulfate scale and preparation method and application thereof Pending CN115627198A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101918510A (en) * 2008-01-09 2010-12-15 阿克佐诺贝尔股份有限公司 Contain acidic aqueous solution of sequestrant and uses thereof
CN102046769A (en) * 2008-05-30 2011-05-04 美国消毒者公司 Biodegradable scale control composition for use in highly concentrated alkaline detergents
CN103562144A (en) * 2011-04-14 2014-02-05 巴斯夫欧洲公司 Method of dissolving and/or inhibiting the deposition of scale on surface of system
CN111518533A (en) * 2020-06-03 2020-08-11 中国石油化工股份有限公司天然气分公司 Green environment-friendly multifunctional salt scale inhibitor for oil and gas development and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101918510A (en) * 2008-01-09 2010-12-15 阿克佐诺贝尔股份有限公司 Contain acidic aqueous solution of sequestrant and uses thereof
CN102046769A (en) * 2008-05-30 2011-05-04 美国消毒者公司 Biodegradable scale control composition for use in highly concentrated alkaline detergents
CN103562144A (en) * 2011-04-14 2014-02-05 巴斯夫欧洲公司 Method of dissolving and/or inhibiting the deposition of scale on surface of system
CN111518533A (en) * 2020-06-03 2020-08-11 中国石油化工股份有限公司天然气分公司 Green environment-friendly multifunctional salt scale inhibitor for oil and gas development and preparation method thereof

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