CN106032577B - Restrainer composition and its application and the method that pickling is carried out to equipment - Google Patents

Restrainer composition and its application and the method that pickling is carried out to equipment Download PDF

Info

Publication number
CN106032577B
CN106032577B CN201510124752.3A CN201510124752A CN106032577B CN 106032577 B CN106032577 B CN 106032577B CN 201510124752 A CN201510124752 A CN 201510124752A CN 106032577 B CN106032577 B CN 106032577B
Authority
CN
China
Prior art keywords
acid
restrainer
pickling
equipment
corrosion inhibiter
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510124752.3A
Other languages
Chinese (zh)
Other versions
CN106032577A (en
Inventor
张建枚
罗俊杰
潘亚男
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201510124752.3A priority Critical patent/CN106032577B/en
Publication of CN106032577A publication Critical patent/CN106032577A/en
Application granted granted Critical
Publication of CN106032577B publication Critical patent/CN106032577B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)

Abstract

The present invention relates to industrial chemistrys to clean field, a kind of method for disclosing restrainer composition and its application and carrying out pickling to equipment.The restrainer composition contains benzheterocycle type corrosion inhibiter, rhodanate, ethoxylated quaternary and urea type corrosion inhibiter, and the weight ratio of each component is 1:0.5-10:0.025-12:0.2-8, shown in the structure such as formula (I) of the ethoxylated quaternary, wherein X is halogen;R1、R2And R3It is each independently selected from C1‑C18Straight chained alkyl ,-(CH2)m‑Ph、‑(CH(CH3)CH2O)nH or-(CH2CH2O)nH;M is 0-5;N is 1-10.The invention also discloses a kind of method carrying out pickling to equipment, this method includes that pickle and equipment are waited for that pickling position contacts, and the pickle contains the restrainer composition and acid.In addition, the application the invention also discloses the corrosion inhibiter composition in the pickling of equipment.The restrainer of the present invention is stablized with composition chemical property, environmentally friendly, wide adaptability, and corrosion inhibition is strong.

Description

Restrainer composition and its application and the method that pickling is carried out to equipment
Technical field
The invention belongs to industrial chemistrys to clean field, be related to a kind of restrainer composition and its pickling in equipment In application and to equipment carry out pickling method.
Background technology
Pickling is widely used in heat transmission equipment in each industrial department (such as electric power, petrochemical industry, metallurgy and electronics), heat transfer The cleaning of the incrustation scales and metal dirt on surfaces such as equipment, the rolling mill scale for cooling down equipment, steel and other metal materials and oxide layer. The pickling of the heat power equipment (such as boiler) and chemical industry equipment of power department is even more important.From the perspective of social economy, pickling The fuel brought by dirt can be reduced to expend;From the perspective of environmental protection, reduce exhaust combustion gases and atmosphere pollution;From peace From the point of view of full angle, the heat power equipments such as boiler and heat exchanger gradually form all kinds of dirts in use, and these dirt heat conduction It is bad that boiler tube local temperature can be caused to increase, the intensity of steel is reduced, so as to cause the generation of pipe explosion accident, boiler is influenced and changes Hot equipment operation, and can guarantee the normal operation of equipment by pickling.
The common acid of pickling has the inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, sulfamic acid and citric acid, EDTA etc. Organic acid.But since acid has corrosiveness to metal equipment, the corrosion of especially inorganic acid is even more serious, while the hydrogen released It can be spread to metal inside, make cleaned equipment that hydrogen embrittlement occur.In addition, a large amount of sour gas that pickling is precipitated can deteriorate labour Condition.Therefore, corrosion inhibiter to be added in pickling, to inhibit burn into of the metal in acid medium to reduce the usage amount of acid, carry High pickling effect, the service life for extending heat power equipment.
First patent application of restrainer be Britain's announcement in 1860 use the mixture of syrup and vegetable oil as Corrosion inhibiter when pickling iron plate.To in the 1920s, metal inhibitor has formaldehyde, anthracene, quinoline, pyridine, thiocarbamide and derivative Object;The forties, nitrogenous fatty amine, aromatic amine, heterocyclic compound, thiocarbamide and mercaptan are generally used as restrainer; The fifties is organic inhibitor to the sixties;It is the corrosion inhibiter of compounding composition after the seventies;There is benzimidazole in the eighties The salt acid inhibitor of stainless steel and carbon steel, copper inhibitor and benzyl quaternary ammonium salt solid are mostly used restrainer etc..The nineties is so far The restrainer developed mainly has imidazolines and Sulphur-containing Imidazole quinoline derivant, such as SM- thiocarbamides condensation product, IS-129 imidazoles The salt acid inhibitors of the copper such as quinoline class, dehydrogenation rosin-base imidazoline corrosion inhibitor, SH-707, IS-156, BH-2 etc..The current country is most Common Lan-826 multipurposes restrainer can be used in a variety of pickles, but product placement is also easy to produce precipitation, chemically Matter is unstable, and properties of product is caused easily to reduce, in addition, being cleaned in cupric device procedures with Lan-826, also will produce copper facing Phenomenon.
CN101634030A discloses a kind of restrainer and its application method for cleaning boiler.This is used for boiler The component and mass percentage content of the restrainer of cleaning be:Acid solution 2.0-10.0%, methenamine 0.08-0.25%, Dimethylbenzene thiocarbamide or thiocarbamide 0.04-0.15%, rhodanate 0.01-0.05%, 12-cetyl Methoxybenzyl chlorides or bromination Object 0.03-0.12%, surfactant 0.05-0.12%, surplus are water.
CN101608313A discloses various metals high-performance solid restrainer.If the solid pickling inhibitor is by Tianjin Crushing, stirring forms together with fourth, methenamine, thiocarbamide, benzotriazole and surfactant compound, weight percentage Respectively:50-80%, 10-20%, 10-20%, 5-10%, 1-5%.It is more carbon steel, stainless steel, copper, zinc, aluminium, titanium etc. to be applicable in Kind metal or alloy.
[corrosion and protection, 2007,28 (10) such as Zhao Liping:536-539] report a kind of multi-purpose solid pickling inhibitor CM-911 can be used in nitric acid, hydrochloric acid, sulfuric acid, sulfamic acid, citric acid, oxalic acid, the acid such as EDTA, hydroxyacetic acid, hydrofluoric acid The materials such as washing lotion and carbon steel, stainless steel, brass, red copper and aluminium.
Most of restrainer used at present is for single acid kind, and the inhibition of single metal, specificity is very strong, effect Fruit difference is big, and some unstable chemcial properties need situ configuration, great work intensity to easily cause operation error so that equipment is rotten The risk that erosion accident occurs is larger.
Invention content
It is an object of the invention to overcome the shortage of prior art, provide that a kind of chemical property is stable, toxicity is low, adaptable Restrainer composition and its application and pickling is carried out to equipment method.
To achieve the goals above, on the one hand, the present invention provides a kind of restrainer composition, the pickling inhibitions It is miscellaneous that agent composition contains benzheterocycle type corrosion inhibiter, rhodanate, ethoxylated quaternary and urea type corrosion inhibiter, the benzo Ring-like corrosion inhibiter, rhodanate, ethoxylated quaternary and urea type corrosion inhibiter weight ratio be 1:0.5-10:0.025-12: 0.2-8, shown in the structure such as following formula (I) of the ethoxylated quaternary:
Wherein, X is halogen;R1、R2And R3It is identical or different and be each independently selected from C1-C18Straight chained alkyl ,- (CH2)m-Ph、-(CH(CH3)CH2O)nH or-(CH2CH2O)nH;M is the natural number of 0-5;N is the natural number of 1-10.
Preferably, the restrainer is grouped as with composition by above each group.
On the one hand, the present invention also provides a kind of methods carrying out pickling to equipment, wherein this method includes by pickle Wait for that pickling position is contacted with equipment, the pickle contains above-mentioned restrainer composition and acid.
On the other hand, the application the present invention provides above-mentioned corrosion inhibiter composition in the pickling of equipment.
Through the above technical solutions, restrainer of the present invention can synergistically be sent out mutually with each component in composition The effect of waving, therefore, restrainer of the invention are stablized with composition chemical property, are environmental-friendly restrainer group Object is closed, environmentally protective requirement is met;The restrainer composition of the present invention can be used in ten several inorganic acids or organic In the acid cleaning process of acid, wide adaptability has excellent corrosion inhibition, and dosage is few, and processing procedure is simple and with obvious effects, is easy to It promotes and applies.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Restrainer composition provided by the invention contains benzheterocycle type corrosion inhibiter, rhodanate, ethoxylation The weight ratio of quaternary ammonium salt and urea type corrosion inhibiter, the benzheterocycle type corrosion inhibiter and rhodanate is 1:0.5-10 (preferably 1:1- 5), the weight ratio of the benzheterocycle type corrosion inhibiter and ethoxylated quaternary is 1:0.025-12 (preferably 1:0.05-4), The weight ratio of the benzheterocycle type corrosion inhibiter and urea type corrosion inhibiter is 1:0.2-8 (preferably 1:0.5-5), the ethoxylation Shown in the structure of quaternary ammonium salt such as following formula (I):
Wherein, X is halogen, preferably Cl or Br;R1、R2And R3It is identical or different and be each independently selected from C1-C18It is straight Alkyl group (including C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17Or C18Straight chain alkane Base) ,-(CH2)m- Ph (Ph indicates phenyl) ,-(CH (CH3)CH2O)nH or-(CH2CH2O)nH;M be 0-5 natural number (such as 0,1, 2,3,4 or 5), the preferably natural number of 0-2;N is the natural number of 1-10, the preferably natural number of 1-6.
It is highly preferred that R1For C8-C18Straight chained alkyl, further preferably positive decyl, dodecyl, myristyl or ten Six alkyl.According to the preferred embodiment of the present invention, R2And R3It is asynchronously-(CH2)m- Ph (such as benzyl).
It is highly preferred that R2And R3It is identical or different and be each independently selected from-(CH2CH2O)nH, benzyl, methyl or ethyl, Further preferably selected from-(CH2CH2O)nH or methyl.
N in structural formula of the present invention is the natural number (such as 1,2,3,4,5,6,7,8,9 or 10) of 1-10, preferably For the natural number of 1-6.
In the present invention, the ethoxylated quaternary can be a certain compound that structure meets formula (I), or Structure meets the mixture of the various compounds of formula (I).According to very particularly preferred embodiment of the invention, the ethoxylated quaternary ammonium Salt is ethoxylation cocoyl alkyl dimethyl ammonium chloride (cocoyl C8-C18Alkyl, typical carbon chain is distributed as C8:4 weights Measure %, C10:6 weight %, C12:48 weight %, C14:20 weight %, C16:10 weight %, C18:12 weight %), ethoxylation ox (tallow typical carbon chain is distributed as C to oleyldimethylammonium chloride18:65 weight %, C16:35 weight %), bis- (ethoxylation) oxen Oleyl methyl ammonium chloride, bis- (ethoxylation) cocoyl methyl ammonium chlorides, ethoxylation C9-10It is alkyl dimethyl ammonium chloride, double (ethoxylation) C9-10Alkyl methyl ammonium chloride, bis- (ethoxylation) cocoyl benzyl ammonium chlorides and bis- (ethoxylation) tallows At least one of benzyl ammonium chloride.The ethoxylated quaternary can be prepared voluntarily, can also be commercially available, for example, can Think in BEROL R648,561 BEROL and the BEROL 563 purchased from Akzo Nobel Surface Chemistry companies It is at least one.
According to the present invention, benzheterocycle type corrosion inhibiter (preferably benzothiazole type corrosion inhibiter and/or the benzotriazole type Corrosion inhibiter) be restrainer composition in important component, can be the existing various benzo thiophenes with corrosion inhibitive function Azoles and/or its derivative, the benzotriazole type corrosion inhibiter can be the existing various benzotriazole with corrosion inhibitive function with/ Or derivatives thereof.In the case of preferred, the benzheterocycle type corrosion inhibiter is selected from 2-mercaptobenzothiazole, three nitrogen of methyl benzo At least one of azoles, normal-butyl benzotriazole, benzotriazole and naphtho- triazole.It was found by the inventors of the present invention that this Inventing preferred ethoxylated quaternary and preferred benzheterocycle type corrosion inhibiter has synergistic effect, can further increase acid The corrosion inhibition of pickling inhibitor composition.
According to the present invention, the rhodanate is the important composition ingredient in restrainer composition, can be existing The various water soluble thiocyanates with corrosion inhibitive function having.Under preferable case, the rhodanate is selected from sodium sulfocyanate, sulphur cyanogen At least one of sour potassium and ammonium thiocyanate.It was found by the inventors of the present invention that currently preferred rhodanate and preferred benzene And heterocyclic type corrosion inhibiter has synergistic effect, can further increase the corrosion inhibition of restrainer composition.
According to the present invention, the urea type corrosion inhibiter is the important component in restrainer composition, can be existing The various water-soluble ureas or derivatives thereof with corrosion inhibitive function, it is preferable that the urea type corrosion inhibiter be selected from urea, aminoguanidine hydrochloride At least one of urea, 1,3- diaminoureas hydrochloride, thiosemicarbazides, 1,3- diamino thiocarbamide, dicyandiamidines and guanyl thiourea.
According to the present invention, the restrainer composition can also contain low-carbon alcohols (preferably C1、C2Or C3Alcohol, such as At least one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, ethylene glycol and propylene glycol).The low-carbon alcohols mainly play the work of solvent With each component of restrainer composition capable of being promoted more uniformly to mix, to preferably playing synergistic slow corrosion Therefore performance does not require the dosage of the low-carbon alcohols particularly, as long as can make each of restrainer composition Component fully dissolves.
According to the present invention, the restrainer composition can be obtained by existing various methods, such as can be with The raw material for forming the restrainer composition is uniformly mixed according to aforementioned ratio and is made, therefore the present invention is to described The step of mixing and condition are without particular/special requirement.For convenience of using and each component being promoted to be uniformly mixed, by each component according to upper After stating ratio mixing, a certain amount of dilution solvent (preferably water) can also be added, restrainer is prepared with composition It is spare at certain density medicament.
The method provided by the invention for carrying out pickling to equipment includes that pickle and equipment are waited for that pickling position connects It touches, the pickle contains the above-mentioned restrainer composition and acid of the present invention.
In the present invention, the content of the restrainer composition can be the amount of this field routine, it is preferable that with institute On the basis of the total weight for stating pickle, the dosage of restrainer composition is 0.05-5 weight ‰.It needs to illustrate It is that, in the case where not doing opposite explanation, the dosage of restrainer composition only relates to remove solvent (low-carbon in the present invention Alcohol and water) outer component (active ingredient) weight.
In the present invention, the dosage of the acid is not required particularly, and those skilled in the art can be directed to and wait for pickling The different dosages to acid of equipment select, for example, on the basis of the total weight of the pickle, the dosage of the acid is usual Can be 2-10 weight %.
In the present invention, the acid can be various inorganic acids and/or organic acid suitable for pickling.It is described under preferable case Acid is hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, sulfamic acid, citric acid, hydroxyacetic acid, formic acid, ethylenediamine tetra-acetic acid, grass Acid, tartaric acid, hydroxy ethylene diphosphonic acid, aminotrimethylenephosphonic acid, 2- phosphinylidyne butane -1,2,4- tricarboxylic acids and ethylenediamine At least one of tetramethylene phosphonic acid.
In the present invention, the equipment can be to need the various equipment of pickling.Under preferable case, the equipment waits for pickling The material at position is at least one of carbon steel, stainless steel, copper and its alloy, aluminium and its alloy.
The present invention also provides application of the above-mentioned restrainer composition in the pickling of equipment.The equipment can be with To need the various equipment of pickling.Under preferable case, the material for waiting for pickling position of the equipment be carbon steel, stainless steel, copper and At least one of its alloy, aluminium and its alloy.
The present invention will be described in detail by way of examples below.In following embodiment, embodiment 1-10 is used for illustrating Restrainer composition and preparation method thereof." effective content " that is used in embodiment refers to the component in addition to solvent Weight accounts for the percentage of total solution weight;The reagent used in embodiment and comparative example is as follows:Hydrochloric acid, sulfuric acid, nitric acid, hydrogen Fluoric acid, phosphoric acid, hydroxyacetic acid, formic acid are that analysis is pure (being purchased from Beijing Chemical Plant);Sodium sulfocyanate, potassium rhodanide, ammonium thiocyanate, 2-mercaptobenzothiazole, methyl benzotriazazole, normal-butyl benzotriazole, benzotriazole, naphtho- triazole, urea, salt Sour semicarbazides, 1,3- diaminoureas hydrochloride, 1,3- diamino thiocarbamide, thiosemicarbazides, dicyandiamidines, guanyl thiourea, sulfamic acid, Citric acid, ethylenediamine tetra-acetic acid, oxalic acid, tartaric acid are that analysis is pure (being purchased from Sinopharm Chemical Reagent Co., Ltd.);Hydroxyl Ethylidene phosphonic acids, aminotrimethylenephosphonic acid, 2- phosphono -1,2,4- tricarboxylic acids, ethylenediamine tetramethylene phosphonic acid, dodecyl Dimethyl benzyl ammonium chloride is technical grade (being purchased from Jianghai Environmental Protection Co., Ltd.);Dodecyl pyridinium chloride is point It analyses pure (being purchased from Aladdin Industrial companies);Ethoxylation cocoyl alkyl dimethyl ammonium chloride (trade mark BEROL R648), Bis- (ethoxylation) cocoyl methyl ammonium chlorides (trade mark BEROL 561), ethoxylation C9-10Alkyl dimethyl ammonium chloride (the trade mark BEROL 563) it is purchased from Akzo Nobel Surface Chemistry companies;Lan-826 is mostly used restrainer purchased from indigo plant Star cleans limited liability company;CM-911 is mostly used solid pickling inhibitor and is purchased from Weihai Yun Qing chemical development institute.
Embodiment 1
Weigh the 2-mercaptobenzothiazole of 1g, 1g sodium sulfocyanates, 1, the 3- diamino thiocarbamides of the BEROL R648,5g of 4g, It stirs evenly.
Embodiment 2
Weigh the 2-mercaptobenzothiazole of 0.3g, 0.7g methyl benzotriazazoles, 5g ammonium thiocyanates, the BEROL of 0.05g 561,0.5g semicarbazide hydrochlorides, stir evenly.
Embodiment 3
Weigh the 2-mercaptobenzothiazole of 0.8g, 0.2g benzotriazole, 2.5g potassium rhodanides, the BEROL of 2.5g 1, the 3- diaminourea hydrochlorides of R648,2g, 1.5g thiosemicarbazides stir evenly.
Embodiment 4
Weigh the 2-mercaptobenzothiazole of 0.1g, 0.5g naphtho- triazoles, 0.4g normal-butyl benzotriazole, 3g thiocyanic acids Sodium, the BEROL 563 of the BEROL R648,0.3g of 0.2g, 1.5g dicyandiamidines stir evenly.
Embodiment 5
Weigh the 2-mercaptobenzothiazole of 0.05g, 0.95g benzotriazole, 0.5g sodium sulfocyanates, the BEROL 563 of 8g, The BEROL 561 of 4g, 0.2g semicarbazide hydrochlorides, it is 20% solution to be finally diluting by water to effective content, is stirred evenly.
Embodiment 6
Weigh the 2-mercaptobenzothiazole of 0.9g, 0.1g methyl benzotriazazoles, 0.75g sodium sulfocyanates, the BEROL of 8g 561,4g semicarbazide hydrochlorides, 1, the 3- diamino thiocarbamides of 2g, 2g urea, it is 20% solution to be finally diluted with water to effective content, It stirs evenly.
Embodiment 7
Weigh the 2-mercaptobenzothiazole of 0.5g, 0.5g normal-butyl benzotriazole, 6g ammonium thiocyanates, the BEROL of 0.35g R648,0.3g thiosemicarbazides, 10g ethyl alcohol, it is 20% solution to be finally diluted with water to effective content, is stirred evenly.
Embodiment 8
Weigh the 2-mercaptobenzothiazole of 0.95g, 0.05g benzotriazole, 10.0g sodium sulfocyanates, the BEROL of 4g 561,2g BEROL 563,3g guanyl thioureas, 1, the 3- diaminourea hydrochlorides of 3g, being finally diluted with water to effective content is 20% solution, stirs evenly.
Embodiment 9
Weigh 1g mercaptobenzothiazolers, 10g sodium sulfocyanates, the BEROL 563 of 0.04g, 5g urea is finally diluted with water to Effective content is 20% solution, is stirred evenly.
Embodiment 10
Weigh 1g mercaptobenzothiazolers, 5g sodium sulfocyanates, the BEROL563 of the BEROL R648,4g of 1g, 4g aminoguanidine hydrochlorides Urea, 4g thiosemicarbazides, stirs evenly.
Comparative example 1
Using Lan-826 as restrainer composition, the product that restrainer is mostly used according to Lan-826 is said Bright, dosage is the 0.25% of pickle quality.
Comparative example 2
Using CM-911 as restrainer composition, the product that solid pickling inhibitor is mostly used according to CM-911 is said Bright, dosage is the 0.1% of pickle quality.
Comparative example 3
Restrainer composition is prepared according to the embodiment 2 of CN101634030A.
Comparative example 4
Restrainer composition is prepared according to the embodiment 1 of CN101608313A.
Comparative example 5
Restrainer composition is prepared according to embodiment 1, unlike, use dodecyl benzyl dimethyl ammonium chloride Instead of BEROL R648.
Comparative example 6
Restrainer composition is prepared according to embodiment 1, unlike, it is replaced with dodecyl pyridinium chloride BEROL R648。
Comparative example 7
Restrainer composition is prepared according to embodiment 1, unlike, it is not added with sodium sulfocyanate.
Comparative example 8
Restrainer composition is prepared according to embodiment 1, unlike, it is not added with BEROL R648.
Comparative example 9
Restrainer composition is prepared according to embodiment 1, unlike, do not use 2-mercaptobenzothiazole.
Comparative example 10
Restrainer composition is prepared according to embodiment 1, unlike, the dosage of sodium sulfocyanate is 0.3g, BEROL R648 dosages are 14g.
Test case 1
According to DL/T 523-2007《Chemical cleaning corrosion inhibiter Performance Properties Evaluation index and experimental method》And GB/ T25146-2010《Industrial equipment chemical cleaning inspection of quality specification》, respectively to obtained by embodiment 1-10 and comparative example 1-10 The corrosion inhibition of multipurpose restrainer is evaluated, wherein corrosion rate is lower, illustrates restrainer composition Corrosion inhibition is higher.In table 1, "-" indicates corrosion rate of the pickling corrosion inhibitor in the pickle made from undetermined.
Table 1
The restrainer composition that can be seen that the present invention from the evaluation experimental result of table 1 has good delay Corrosion energy, adds the pickle after the restrainer composition of the present invention, and corrosion rate is much smaller than DL/T 523-2007 《Chemical cleaning corrosion inhibiter Performance Properties Evaluation index and experimental method》Specified in salt acid inhibitor corrosion rate<1.5g/ (m2H), the corrosion rate of hydrofluoric acid corrosion inhibiter<1.0g/(m2H), the corrosion rate of EDTA corrosion inhibiter<1.5g/(m2H), The corrosion rate of sulfamic acid corrosion inhibiter<1.0g/(m2H), the corrosion rate of lemon acid inhibitor<1.0g/(m2H), copper is slow Lose the corrosion rate of agent<0.3g/(m2H) requirement is respectively less than GB/T25146-2010 to the corrosion rate of unlike material《Work Industry equipment chemical cleaning inspection of quality specification》Specified in corrosion of carbon steel rate≤2.0g/ (m2H), Corrosion of Stainless Steel rate ≤1.0g/(m2H), brass corrosion rate≤1.0g/ (m2H), red copper corrosion rate≤1.0g/ (m2H), aluminium corrosion speed Rate≤1.0g/ (m2·h).Therefore, restrainer composition of the invention can meet the slow of various metals material pickling Erosion requires.
From the above it can also be seen that the use concentration of the restrainer composition of the present invention is low, in processing acid It only needs to add the 0.05-5 weight ‰ relative to pickle total weight when washing down lotion, good corrosion inhibition can be obtained.
In addition, the measurement result of comparing embodiment 1-10 and comparative example 1-4 can be seen that the corrosion inhibiter combination of the present invention Object shows more excellent corrosion mitigating effect than existing corrosion inhibiter with composition.By the measurement knot of embodiment 1 and comparative example 5-6 Fruit is compared as can be seen that the ethoxylated quaternary of the specific structure in the corrosion inhibiter composition of the present invention has significant delay Effect is lost, is irreplaceable, and common quaternary ammonium salt can not obtain corrosion mitigating effect so.By embodiment 1 and comparative example The measurement result of 7-10 compares as can be seen that when each ingredient of the corrosion inhibiter composition of the present invention is used cooperatively with specific quantity The corrosion inhibition of collaboration can be played.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (17)

1. a kind of restrainer composition, which is characterized in that it is slow that the restrainer composition contains benzheterocycle type Lose agent, rhodanate, ethoxylated quaternary and urea type corrosion inhibiter, the benzheterocycle type corrosion inhibiter, rhodanate, ethyoxyl The weight ratio for changing quaternary ammonium salt and urea type corrosion inhibiter is 1:0.5-10:0.025-12:0.2-8, the knot of the ethoxylated quaternary Shown in structure such as following formula (I):
Wherein, X is halogen;R1、R2And R3It is identical or different and be each independently selected from C1-C18Straight chained alkyl ,-(CH2)m- Ph、-(CH(CH3)CH2O)nH or-(CH2CH2O)nH;M is the natural number of 0-5;N is the natural number of 1-10.
2. restrainer composition according to claim 1, wherein the benzheterocycle type corrosion inhibiter, thiocyanic acid The weight ratio of salt, ethoxylated quaternary and urea type corrosion inhibiter is 1:1-5:0.05-4:0.5-5.
3. restrainer composition according to claim 1 or 2, wherein X is Cl or Br.
4. restrainer composition according to claim 1 or 2, wherein m is the natural number of 0-2.
5. restrainer composition according to claim 1 or 2, wherein n is the natural number of 1-6.
6. restrainer composition according to claim 1 or 2, wherein R1For C8-C18Straight chained alkyl;R2And R3 It is identical or different and be each independently selected from-(CH2CH2O)nH, benzyl, methyl or ethyl.
7. restrainer composition according to claim 6, wherein R1For positive decyl, dodecyl, myristyl Or cetyl.
8. restrainer composition according to claim 6, wherein R2And R3It is identical or different and each independently Selected from-(CH2CH2O)nH or methyl.
9. restrainer composition according to claim 1 or 2, wherein the benzheterocycle type corrosion inhibiter is selected from In 2-mercaptobenzothiazole, methyl benzotriazazole, normal-butyl benzotriazole, benzotriazole and naphtho- triazole at least It is a kind of.
10. restrainer composition according to claim 1 or 2, wherein the rhodanate is selected from thiocyanic acid At least one of sodium, potassium rhodanide and ammonium thiocyanate.
11. restrainer composition according to claim 1 or 2, wherein the urea type corrosion inhibiter be selected from urea, In semicarbazide hydrochloride, 1,3- diaminoureas hydrochloride, thiosemicarbazides, 1,3- diamino thiocarbamide, dicyandiamidines and guanyl thiourea extremely Few one kind.
12. a kind of method carrying out pickling to equipment, which is characterized in that this method includes that pickle and equipment are waited for pickling portion Position is contacted, and the pickle contains restrainer composition and acid described in any one of claim 1-11.
13. according to the method for claim 12, wherein on the basis of the total weight of the pickle, the pickling inhibition The dosage of agent composition is 0.05-5 weight ‰.
14. method according to claim 12 or 13, wherein it is described acid be hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, Sulfamic acid, citric acid, hydroxyacetic acid, formic acid, ethylenediamine tetra-acetic acid, oxalic acid, tartaric acid, hydroxy ethylene diphosphonic acid, amino At least one of trimethylene phosphonic, 2- phosphinylidyne butane -1,2,4- tricarboxylic acids and ethylenediamine tetramethylene phosphonic acid.
15. according to the method for claim 12, wherein the material for waiting for pickling position of the equipment be carbon steel, stainless steel, At least one of copper and its alloy, aluminium and its alloy.
16. application of the restrainer composition in the pickling of equipment described in any one of claim 1-11.
17. application according to claim 16, wherein the material for waiting for pickling position of the equipment be carbon steel, stainless steel, At least one of copper and its alloy, aluminium and its alloy.
CN201510124752.3A 2015-03-20 2015-03-20 Restrainer composition and its application and the method that pickling is carried out to equipment Active CN106032577B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510124752.3A CN106032577B (en) 2015-03-20 2015-03-20 Restrainer composition and its application and the method that pickling is carried out to equipment

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510124752.3A CN106032577B (en) 2015-03-20 2015-03-20 Restrainer composition and its application and the method that pickling is carried out to equipment

Publications (2)

Publication Number Publication Date
CN106032577A CN106032577A (en) 2016-10-19
CN106032577B true CN106032577B (en) 2018-11-02

Family

ID=57148904

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510124752.3A Active CN106032577B (en) 2015-03-20 2015-03-20 Restrainer composition and its application and the method that pickling is carried out to equipment

Country Status (1)

Country Link
CN (1) CN106032577B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110541171B (en) * 2019-08-27 2020-07-03 河南大学 Benzene sulfonamide pickling inhibitor containing nitrogen and oxygen heteroatoms as well as preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1075164A (en) * 1993-03-04 1993-08-11 朱几 Efficient and multi-purpose liquid detergent

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1075164A (en) * 1993-03-04 1993-08-11 朱几 Efficient and multi-purpose liquid detergent

Also Published As

Publication number Publication date
CN106032577A (en) 2016-10-19

Similar Documents

Publication Publication Date Title
CN104513998B (en) Corrosion inhibiter is with composition and its application and method that pickling is carried out to equipment
CN103484875B (en) A kind of restrainer composition and application thereof
CN108004554B (en) Corrosion inhibiter composition and its application and the method that pickling is carried out to equipment
US4104303A (en) Acid inhibitor composition and process in hydrofluoric acid chemical cleaning
CN105088251A (en) Corrosion inhibitor composition, applications thereof, and method using same to carry out pickling on equipment
CN106032576B (en) Restrainer composition and its application and the method that pickling is carried out to equipment
CN104277932A (en) Scale cleaning agent and preparation method thereof
CN104513999B (en) Corrosion inhibiter is with composition and its application and method that pickling is carried out to equipment
CN101928075A (en) Closed-type circulating cooling water system inhibiter and preparation method thereof
CN111441058A (en) Descaling rust-removing corrosion-inhibition prefilming agent and preparation method and application thereof
CN105386066A (en) Carbon steel pickling solution and use thereof
CN106032577B (en) Restrainer composition and its application and the method that pickling is carried out to equipment
CN106555190B (en) A kind of modified high-molecular product compound corrosion inhibitor and the preparation method and application thereof
US4370256A (en) Corrosion inhibitor for aluminum in aqueous acids
CN105821421A (en) Composition used for corrosion inhibitor and application thereof and method for pickling equipment
CN110306196A (en) A kind of environmental protection deashing agent
CN108004555B (en) Corrosion inhibiter composition and its application and the method that pickling is carried out to equipment
CN104513992A (en) Corrosion inhibitor composition, applications thereof, and method using same to perform acid-washing on equipment
CN105821423A (en) Composition used for corrosion inhibitor and application thereof and method for pickling equipment
CN110066998A (en) A kind of transient metal complex efficient metal restrainer and its application
CN105821422A (en) Composition used for corrosion inhibitor and application thereof and method for pickling equipment
CN108754517A (en) A kind of rust remover and preparation method thereof for mechanical equipment
CN105018943B (en) A kind of pickling additive and preparation method thereof
GB2059432A (en) Anti-freeze composition
CN101586240B (en) Green benzoic acid heterocyclic carbon steel restrainer and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant