CN114032534A - Passivating agent for hydrogen peroxide device before driving and preparation and application methods thereof - Google Patents

Passivating agent for hydrogen peroxide device before driving and preparation and application methods thereof Download PDF

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Publication number
CN114032534A
CN114032534A CN202111287351.1A CN202111287351A CN114032534A CN 114032534 A CN114032534 A CN 114032534A CN 202111287351 A CN202111287351 A CN 202111287351A CN 114032534 A CN114032534 A CN 114032534A
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China
Prior art keywords
passivating agent
hydrogen peroxide
passivating
acid
30min
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CN202111287351.1A
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Inventor
范昌海
杨卫东
陈鸿飞
李明英
李祥艳
胡宪正
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Jiangsu Jiahong New Material Co ltd
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Jiangsu Jiahong New Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides

Abstract

The invention provides a passivating agent for a hydrogen peroxide device before driving and a preparation and use method thereof, and relates to the field of pickling and passivating of a hydrogen peroxide complete set device. The passivating agent is mainly prepared by dissolving and stirring hydrofluoric acid, sulfamic acid, sodium citrate, disodium ethylene diamine tetraacetate, peroxide, a corrosion inhibitor, an auxiliary agent and the balance of water, and is diluted to be 3-5% of low concentration when in use, and then circulated or soaked. The invention overcomes the defects of the prior art, and the prepared passivating agent does not contain nitric acid and other nitrogen oxides, does not contain heavy metal ions, has good relative stability in a device, can be used at a low concentration and has good economical efficiency.

Description

Passivating agent for hydrogen peroxide device before driving and preparation and application methods thereof
Technical Field
The invention relates to the field of pickling and passivation of hydrogen peroxide complete equipment, in particular to a passivating agent for a hydrogen peroxide device before driving and a preparation and use method thereof.
Background
The hydrogen peroxide solution is commonly called as hydrogen peroxide, before the complete set of equipment is put into production, welding slag, organic matters (such as protective grease), oxide skin, metal ions and the like can be remained in the processes of transportation, installation and welding, and if the complete set of equipment is directly put into use, the hydrogen peroxide with strong oxidizing property can generate strong exothermic reaction with the substances, so that the accident of equipment driving explosion can be possibly caused.
The equipment, storage tanks and pipelines in the current domestic hydrogen peroxide complete set are all made of stainless steel, and are usually 304L or 316L. The equipment, storage tank and pipeline need to be degreased, pickled and passivated before driving to achieve the aim of smooth driving. After passivation is finished, a hydrogen peroxide stability test is required, and the test is qualified when the relative stability is more than 90%. The prior hydrogen peroxide device passivation processes comprise two processes, wherein after acid cleaning is finished, a nitric acid solution with the concentration of 33% is used for passivation for 2 hours at normal temperature, or an acidic potassium dichromate solution with a certain concentration is used for passivation.
In the two processes, the high-concentration nitric acid used in the former process releases a large amount of nitrogen oxide NOXMoreover, the wastewater contains high-concentration nitrate, which causes serious environmental pollution and wastewater treatment cost; the latter potassium dichromate is a strong carcinogen, can cause serious injury to human bodies, generates waste liquid containing heavy metal chromium, has serious ecological hazard, and is difficult to treat.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a passivating agent before the driving of a hydrogen peroxide device and a preparation and use method thereof, wherein the obtained passivating agent does not contain nitric acid and other nitrogen oxides, does not contain heavy metal ions, can be used at a lower concentration and has good economy.
In order to achieve the above purpose, the technical scheme of the invention is realized by the following technical scheme:
the passivating agent for the hydrogen peroxide device before the start of the vehicle is composed of the following substances in percentage by mass: 2-8% of hydrofluoric acid, 2-8% of sulfamic acid, 1-10% of sodium citrate, 1-10% of disodium ethylene diamine tetraacetate, 1-5% of peroxide, 1-3% of corrosion inhibitor, 1-5% of assistant and the balance of deionized water for making up 100%.
Preferably, the peroxide is any one or more of hydrogen peroxide, sodium percarbonate, persulfuric acid, perphosphoric acid, peroxyacetic acid and salts thereof.
Further preferably, the peroxide is peroxyacetic acid.
Preferably, the corrosion inhibitor is one or more of thiourea, urotropin or Lan-826.
Further preferably, the corrosion inhibitor is urotropin.
Preferably, the coagent is at least one polyol containing more than two hydroxyl groups and having greater than or equal to 2 and less than or equal to 8 carbon atoms.
Further preferably, the auxiliary agent is sorbitol.
Preferably, the pH value of the passivating agent is between 2.5 and 5.5.
The preparation process of the passivator comprises the following steps:
(1) preparing materials: weighing and preparing each raw material for later use according to the mass percentage of each component;
(2) preliminary mixing: dissolving sodium citrate and disodium ethylene diamine tetraacetate in deionized water, slowly adding peroxide, and stirring at a rotation speed of 120r/min for 30min to obtain a primary mixture for later use;
(3) and (3) secondary mixing: and slowly adding the initial mixture into hydrofluoric acid and sulfamic acid, stirring for 30min at the rotating speed of 120r/min, finally adding the corrosion inhibitor and the auxiliary agent, and continuously stirring for 30min at the rotating speed of 120r/min to obtain the passivating agent.
Preferably, the using method comprises the steps of diluting the passivating agent to 3-5% of the total concentration of each component, and circularly or soaking and passivating the device for more than 2 hours by adopting the diluted passivating agent at normal temperature.
The invention provides a passivating agent for a hydrogen peroxide device before driving and a preparation and use method thereof, and compared with the prior art, the passivating agent has the advantages that:
(1) the passivating agent does not contain nitric acid and other nitric oxides, and does not release toxic and harmful gases in the using process;
(2) the passivating agent does not contain heavy metal elements, and the waste liquid treatment is relatively simple;
(3) the passivator prepared by the application can be used at low concentration when in use, and has higher economy;
(4) after the passivator prepared by the application is used for processing equipment, the passivator can meet the requirement of a hydrogen peroxide stability test, the relative stability is more than 95%, and the quality of a passivation film formed on the equipment by the passivator meets the requirement of HG/T2387 + 2007 industrial equipment chemical cleaning quality standard on a stainless steel passivation film.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all 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.
Example 1:
preparation of a passivating agent: 4kg of sodium citrate and 3kg of disodium ethylene diamine tetraacetate are dissolved in 80kg of deionized water, then the mixture is placed in a stirrer, the rotating speed is adjusted to 120r/min, 2kg of sodium peroxide is slowly added and stirred for 30min, 5kg of hydrofluoric acid and 3kg of sulfamic acid are slowly added and stirred for 30min, and finally 1kg of sorbitol and 2kg of urotropine are added and stirred for 30min to obtain the passivator.
Example 2:
preparation of a passivating agent: 5kg of sodium citrate and 3kg of disodium ethylene diamine tetraacetate are dissolved in 83kg of deionized water, then the mixture is placed in a stirrer, the rotating speed is adjusted to 120r/min, 3kg of persulfuric acid is slowly added and stirred for 30min, then 1kg of hydrofluoric acid and 2kg of sulfamic acid are slowly added and stirred for 30min, and finally 2kg of sorbitol and 1kg of Lan-826 are added and stirred for 30min to obtain the passivator.
Example 3:
preparation of a passivating agent: 3kg of sodium citrate and 2kg of disodium ethylene diamine tetraacetate are dissolved in 81kg of deionized water, then the mixture is placed in a stirrer, the rotating speed is adjusted to 120r/min, 3kg of sodium percarbonate is slowly added and stirred for 30min, then 1kg of hydrofluoric acid and 7kg of sulfamic acid are slowly added and stirred for 30min, and finally 1kg of sorbitol and 2kg of thiourea are added and stirred for 30min to obtain the passivator.
Example 4:
preparation of a passivating agent: 1kg of sodium citrate and 7kg of disodium ethylene diamine tetraacetate are dissolved in 73kg of deionized water, then the mixture is placed in a stirrer, the rotating speed is adjusted to 120r/min, 3kg of peroxyacetic acid is slowly added and stirred for 30min, 5kg of hydrofluoric acid and 5kg of sulfamic acid are slowly added and stirred for 30min, and finally 2kg of xylitol, 1kg of sorbitol and 3kg of Lan-826 are added and stirred for 30min to obtain the passivator.
Example 5:
preparation of a passivating agent: dissolving 7kg of sodium citrate and 1kg of disodium ethylene diamine tetraacetate in 76kg of deionized water, then placing the mixture in a stirrer, adjusting the rotating speed to 120r/min, slowly adding 3kg of sodium persulfate, stirring for 30min, slowly adding 4kg of hydrofluoric acid and 4kg of sulfamic acid, continuously stirring for 30min, finally adding 3kg of glycerol, 1kg of urotropine and 1kg of Lan-826, and stirring for 30min to obtain the passivator.
Comparative example 1:
preparation of a passivating agent: dissolving 7kg of sodium citrate in 80kg of deionized water, placing the mixture in a stirrer, adjusting the rotating speed to 120r/min, slowly adding 2kg of sodium peroxide, stirring for 30min, slowly adding 5kg of hydrofluoric acid and 3kg of sulfamic acid, continuously stirring for 30min, finally adding 1kg of sorbitol and 2kg of urotropine, and stirring for 30min to obtain the passivator.
Comparative example 2:
preparation of a passivating agent: dissolving 7kg of disodium ethylene diamine tetraacetate in 80kg of deionized water, placing the mixture in a stirrer, adjusting the rotating speed to 120r/min, slowly adding 2kg of sodium peroxide, stirring for 30min, slowly adding 5kg of hydrofluoric acid and 3kg of sulfamic acid, continuously stirring for 30min, finally adding 1kg of sorbitol and 2kg of urotropine, and stirring for 30min to obtain the passivator.
Comparative example 3:
preparation of a passivating agent: dissolving 7kg of sodium citrate in 80kg of deionized water, placing the mixture in a stirrer, adjusting the rotating speed to 120r/min, slowly adding 2kg of sodium peroxide, stirring for 30min, slowly adding 8kg of sulfamic acid, continuously stirring for 30min, and finally adding 1kg of sorbitol and 2kg of urotropine, and stirring for 30min to obtain the passivator.
And (3) detection:
1. selecting the passivating agents obtained in the above examples 1-5, respectively adding deionized water to dilute the passivating agents to 3%, 4% and 5% of the original concentration, soaking the surface of the stainless steel with the diluted passivating solution at normal temperature for 2h, drying, and detecting according to the requirements of HG/T2387-:
TABLE 1
Figure BDA0003333386390000051
2. Selecting the passivators obtained in the comparative examples 1-3 as control groups 1-3 respectively, selecting a nitric acid solution with the concentration of 33% as a control group 4, setting the passivators prepared in the examples 1-5 as experiment groups 1-5, adding deionized water into the passivators in the experiment groups 1-5 and the control groups 1-3 to dilute the passivators to 4% of the original concentration, then respectively adopting the solutions in the control groups and the experiment groups to carry out circulating or soaking passivation treatment on the equipment and the pipeline for 2 hours at normal temperature, then drying, selecting hydrogen peroxide with the concentration of 27.5% and the stability of more than 97% to carry out circulating spray soaking on the equipment and the pipeline for more than 4 hours, soaking for more than 6 hours, and measuring the relative stability of the hydrogen peroxide in each group after 10 hours, wherein the results are shown in the following table 2:
TABLE 2
Figure BDA0003333386390000061
The above table shows that the passivating agent prepared by the invention can passivate a device at low concentration, and effectively ensures that hydrogen peroxide maintains higher relative stability in the processing and storing processes.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (8)

1. The passivating agent for the hydrogen peroxide device before the start of the vehicle is characterized by comprising the following substances in percentage by mass: 2-8% of hydrofluoric acid, 2-8% of sulfamic acid, 1-10% of sodium citrate, 1-10% of disodium ethylene diamine tetraacetate, 1-5% of peroxide, 1-3% of corrosion inhibitor, 1-5% of assistant and the balance of deionized water for making up 100%.
2. A passivating agent before a hydrogen peroxide device is driven according to claim 1, which is characterized in that: the peroxide is any one or more of hydrogen peroxide, sodium percarbonate, persulfuric acid, perphosphoric acid, peroxyacetic acid and salts thereof.
3. A passivating agent before a hydrogen peroxide device is driven according to claim 1, which is characterized in that: the corrosion inhibitor is any one or more of thiourea, urotropine or Lan-826.
4. A passivating agent before a hydrogen peroxide device is driven according to claim 1, which is characterized in that: the auxiliary agent is at least one polyol containing more than two hydroxyl groups and having 2 or more and 8 or less carbon atoms.
5. A passivating agent before a hydrogen peroxide device is driven according to claim 1, which is characterized in that: the pH value of the passivating agent is between 2.5 and 5.5.
6. The preparation method of the passivating agent before the start-up of the hydrogen peroxide device according to claim 1, wherein the preparation process of the passivating agent comprises the following steps:
(1) preparing materials: weighing and preparing each raw material for later use according to the mass percentage of each component;
(2) preliminary mixing: dissolving sodium citrate and disodium ethylene diamine tetraacetate in deionized water, slowly adding peroxide and stirring for 30min to obtain a primary mixture for later use;
(3) and (3) secondary mixing: and slowly adding hydrofluoric acid and sulfamic acid into the primary mixture, stirring for 30min, finally adding the corrosion inhibitor and the auxiliary agent, and continuously stirring for 30min to obtain the passivating agent.
7. The method for preparing the passivating agent before the start-up of the hydrogen peroxide device according to claim 6, wherein the rotation speed of the stirring in the steps (2) and (3) is 120 r/min.
8. A method of using a passivating agent before a hydrogen peroxide plant is driven according to claim 1, characterized in that: the using method comprises the steps of diluting the passivating agent to 3-5% of the total concentration of each component, and circularly or soaking and passivating the device for more than 2 hours at normal temperature by adopting the diluted passivating agent.
CN202111287351.1A 2021-11-02 2021-11-02 Passivating agent for hydrogen peroxide device before driving and preparation and application methods thereof Pending CN114032534A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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JPH09228082A (en) * 1996-02-20 1997-09-02 Mitsubishi Gas Chem Co Inc Pickling solution for stainless steel
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CN102162105A (en) * 2011-03-31 2011-08-24 河南省科学院能源研究所有限公司 Boiler pipeline descaling agent and preparation method thereof
CN103820796A (en) * 2014-03-26 2014-05-28 东莞市凯盟表面处理技术开发有限公司 Environment-friendly stainless steel pickling agent free of nitrogen and phosphorus elements and application method thereof
CN105331989A (en) * 2015-11-24 2016-02-17 苏州盖德精细材料有限公司 Novel stainless steel pickling-passivating solution and pickling-passivating process thereof
CN106086848A (en) * 2016-07-19 2016-11-09 东莞市凯盟表面处理技术开发有限公司 A kind of acid-washing stainless steel passivating solution and preparation method thereof and using method
CN106702396A (en) * 2015-11-17 2017-05-24 上海蓝浦清洗技术有限公司 Cleaning passivator and preparation method
CN111690941A (en) * 2020-06-18 2020-09-22 中国科学院过程工程研究所 Sulfamic acid rust removing liquid and rust removing method using same
CN112725813A (en) * 2020-12-25 2021-04-30 德蓝水技术股份有限公司 Acidic cleaning agent and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1101950A (en) * 1993-10-18 1995-04-26 北京柯力动力化学防腐技术开发公司 Detergent for steel, aluminium and copper materials
JPH09228082A (en) * 1996-02-20 1997-09-02 Mitsubishi Gas Chem Co Inc Pickling solution for stainless steel
JP2000064069A (en) * 1998-08-13 2000-02-29 A & K Kk Scale removing agent
CN102162105A (en) * 2011-03-31 2011-08-24 河南省科学院能源研究所有限公司 Boiler pipeline descaling agent and preparation method thereof
CN103820796A (en) * 2014-03-26 2014-05-28 东莞市凯盟表面处理技术开发有限公司 Environment-friendly stainless steel pickling agent free of nitrogen and phosphorus elements and application method thereof
CN106702396A (en) * 2015-11-17 2017-05-24 上海蓝浦清洗技术有限公司 Cleaning passivator and preparation method
CN105331989A (en) * 2015-11-24 2016-02-17 苏州盖德精细材料有限公司 Novel stainless steel pickling-passivating solution and pickling-passivating process thereof
CN106086848A (en) * 2016-07-19 2016-11-09 东莞市凯盟表面处理技术开发有限公司 A kind of acid-washing stainless steel passivating solution and preparation method thereof and using method
CN111690941A (en) * 2020-06-18 2020-09-22 中国科学院过程工程研究所 Sulfamic acid rust removing liquid and rust removing method using same
CN112725813A (en) * 2020-12-25 2021-04-30 德蓝水技术股份有限公司 Acidic cleaning agent and preparation method thereof

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