CN108546953B - Heating furnace tube outer wall cleaning passivator - Google Patents
Heating furnace tube outer wall cleaning passivator Download PDFInfo
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- CN108546953B CN108546953B CN201810437338.1A CN201810437338A CN108546953B CN 108546953 B CN108546953 B CN 108546953B CN 201810437338 A CN201810437338 A CN 201810437338A CN 108546953 B CN108546953 B CN 108546953B
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C22/00—Chemical 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
- C23C22/05—Chemical 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
- C23C22/06—Chemical 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
- C23C22/48—Chemical 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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention discloses a passivating agent for cleaning the outer wall of a furnace tube of a heating furnace, which comprises the following components: the method comprises the following steps: 0.3-0.6 wt% of corrosion inhibitor, 10-15 wt% of organic acid, 5-10 wt% of inorganic acid, 8-12 wt% of surfactant, 10-18 wt% of inorganic salt, 5-10 wt% of assistant and the balance of water. The cleaning passivator integrates the effects of removing dust and scale, removing rust and passivating, has good cleaning effect, high dirt removal rate and no damage to equipment, and can obviously reduce the smoke exhaust temperature of the heating furnace and improve the heat efficiency of the heating furnace after the heating furnace is cleaned by using the cleaning passivator.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a passivating agent for cleaning the outer wall of a heating furnace tube.
Background
The surface of the furnace tube of the heating furnace of the oil refinery deposits ash scales with different shapes in the combustion process, and the formation of the ash scales not only reduces the efficiency of the heating furnace, but also increases the energy consumption. More importantly, the ash scale on the surface of the furnace tube has stronger adsorption force, the ash scale can adsorb gases such as disulfide trioxide, sulfur dioxide, water vapor and the like in smoke, the gases are continuously diffused into the scale layer after being adsorbed, and meanwhile, the disulfide trioxide and the carbon dioxide respectively react with water on the ash scale to generate sulfate scale, sulfite scale and carbonate scale, so that the under-scale corrosion of the furnace tube is accelerated, and the service life of the furnace tube is shortened. Meanwhile, oil and other media in the furnace tube form oil dirt in the furnace tube due to long-term operation of the equipment, and generate a plurality of impurity dirt, thereby reducing the use effect of the heating furnace. Therefore, timely removing the dirt on the inner wall of the furnace tube, removing the deposited dirt on the outer wall of the furnace tube, and keeping the surface of the furnace tube clean is an important measure for saving energy, prolonging the service life of the furnace tube and improving economic benefit.
The cleaning mode of the heating furnace tube comprises disassembly cleaning and on-line chemical cleaning. The disassembly and cleaning are realized by disassembling the furnace tube of the heating furnace one by one and cleaning one by one, the method can clean the outer wall of the furnace tube, but takes time and labor, needs disassembly and assembly, is easy to damage equipment, needs to clean each tube in the cleaning process, is long in use, and is not beneficial to the time arrangement of the maintenance period. The on-line chemical cleaning adopts a spray circulation mode to carry out the passivation treatment of removing rust and dust on the outer wall of the furnace tube and preventing the surface of the furnace tube from being oxidized to generate corrosion. Cleaning agents flow into the gap between the outer wall pipes of the furnace pipe and react with dirt on the pipe wall, and no dead angle is left in the cleaning process. On-line chemical cleaning uses the furnace tube cleaning agent integrating rust removal, ash scale removal, passivation and the like, has short cleaning time and thorough cleaning, and can guarantee the overall requirement of the construction period of maintenance. Therefore, the heating furnace tube is descaled by adopting a chemical cleaning mode, and the method is a good cleaning mode. However, the currently commonly used cleaning agent for the furnace tube of the heating furnace has the problems of equipment corrosion of the cleaning solution, low cleaning efficiency, unsatisfactory cleaning effect and the like.
Disclosure of Invention
In order to overcome the defects of the existing heating furnace tube cleaning passivator, the invention provides a heating furnace tube passivator which is efficient, time-saving and corrosion-free in cleaning.
The passivating agent for cleaning the outer wall of the furnace tube of the heating furnace comprises the following components or consists of the following components: 0.3-0.6 wt% of corrosion inhibitor, 10-15 wt% of organic acid, 5-10 wt% of inorganic acid, 8-12 wt% of surfactant, 10-18 wt% of inorganic salt, 5-10 wt% of assistant and the balance of water.
According to a preferred embodiment of the invention, the cleaning passivator comprises or consists of the following components: 0.3-0.6 wt% of Lan-826, 10-15 wt% of citric acid, 5-10 wt% of inorganic acid, 8-12 wt% of sodium dodecyl benzene sulfonate, 10-18 wt% of inorganic salt, 5-10 wt% of auxiliary agent and the balance of water.
According to a preferred embodiment of the invention, the mineral acid is hydrochloric acid and/or sulfamic acid. In a preferred embodiment, the mineral acids are hydrochloric acid and sulfamic acid.
According to a preferred embodiment of the invention, the inorganic salts are sodium carbonate, sodium bicarbonate and sodium nitrite, preferably the mass ratio of sodium carbonate and sodium bicarbonate is 1 (1-1.5), preferably 1 (1-1.2), for example the mass ratio of sodium carbonate and sodium bicarbonate may be 1:1, 1:1.15, 1:1.18, 1: 1.2. In a preferred embodiment, the sum of the amounts of sodium carbonate and sodium bicarbonate is greater than the amount of sodium nitrite.
According to a preferred embodiment of the invention, the adjuvant is selected from one or more of sodium benzoate, sodium salicylate, niacinamide and acetamide. The purpose of the additive added in the invention is to increase the solubility of various components in the cleaning passivator and enable the various components to form a uniform mixed solution after being mixed.
According to a preferred embodiment of the invention, the cleaning passivator comprises or consists of the following components: 0.3-0.6 wt% of Lan-826, 10-15 wt% of citric acid, 4-8 wt% of hydrochloric acid, 1-2 wt% of sulfamic acid, 8-12 wt% of sodium dodecyl benzene sulfonate, 3-6 wt% of sodium carbonate, 3-6 wt% of sodium bicarbonate, 4-8 wt% of sodium nitrite, 5-10 wt% of auxiliary agent and the balance of water.
According to a preferred embodiment of the invention, Lan-826 may be used in the cleaning passivator in an amount of 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt% and any value in between.
According to a preferred embodiment of the invention, the amount of citric acid in the cleaning passivator may be 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt% and any value in between.
According to a preferred embodiment of the invention, the amount of hydrochloric acid in the cleaning passivator may be 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt% and any value in between.
According to a preferred embodiment of the invention, the amount of sulfamic acid used in the cleaning passivator may be 1 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, 2 wt% and any value in between.
According to a preferred embodiment of the present invention, the amount of sodium dodecylbenzenesulfonate in the cleaning passivator may be 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt% and any value in between.
According to a preferred embodiment of the invention, the amount of sodium carbonate in the cleaning passivator may be 3 wt%, 4 wt%, 5 wt%, 6 wt% and any value in between.
According to a preferred embodiment of the invention, the amount of sodium bicarbonate in the cleaning deactivant may be 3 wt%, 4 wt%, 5 wt%, 6 wt% and any value in between.
According to a preferred embodiment of the present invention, the amount of sodium nitrite used in the cleaning passivation agent may be 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt% and any value therebetween.
According to a preferred embodiment of the invention, the amount of the auxiliary agent in the cleaning passivator may be 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt% and any value in between.
In a preferred embodiment of the invention, the cleaning passivator comprises or consists of: 0.5 wt% Lan-826, 13 wt% citric acid, 5.6 wt% hydrochloric acid, 1.4 wt% sulfamic acid, 10 wt% sodium dodecyl benzene sulfonate, 3 wt% sodium carbonate, 3 wt% sodium bicarbonate, 5 wt% sodium nitrite, 5-7 wt% auxiliary agent and the balance of water.
In the invention, Lan-826 is an excellent pickling corrosion inhibitor, is suitable for chemical cleaning of various organic acids and inorganic acids, and has excellent capability of inhibiting steel from absorbing hydrogen and Fe in pickling3+Accelerated corrosion capability, outstanding corrosion inhibition performance, small smell and more durable stability.
According to a preferred embodiment of the invention, the amount of organic acid used in the cleaning passivator needs to be larger than the amount of inorganic acid used, preferably the ratio of the amount of organic acid to the amount of inorganic acid used is (1.5-2.2):1, preferably (1.7-2):1, such as the ratio of the amount of organic acid to the amount of inorganic acid may be 1.7:1, 1.8:1, 1.85:1, 1.9:1, 2:1, etc.
According to a preferred embodiment of the invention, a better cleaning effect of the cleaning deactivant is obtained when the amount of hydrochloric acid and sulfamic acid in the mineral acid is from 2:1 to 5:1, such as 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, preferably from 3.5 to 4: 1. The dosage of the organic acid and the inorganic acid and the dosage ratio of the hydrochloric acid to the sulfamic acid in the inorganic acid are controlled, the various acids show synergistic action and coact with Lan-826 to show excellent cleaning and passivating effects, the cleaning rate of the cleaning passivator can be obviously improved, and the cleaning time is shortened.
The invention also provides application of the passivating agent for cleaning the outer wall of the heating furnace tube in cleaning the heating furnace tube.
According to a preferred embodiment of the present invention, the heating furnace is a heating furnace using heavy oil or natural gas as fuel.
According to the preferred embodiment of the invention, the cleaning passivator is diluted by 10-20 times to prepare the cleaning solution, and the cleaning solution is used for cleaning petrochemical equipment.
According to a preferred embodiment of the invention, the cleaning deactivant has a density of 0.90 to 1.30g/cm at 20 ℃3。
The furnace lining of the heating furnace is made of casting materials or refractory bricks, and the equipment cannot be cleaned by a method of soaking or filling the equipment with cleaning liquid by a low inlet and a high outlet, but only can be cleaned by spraying. In order to ensure the cleaning effect, a cleaning mode combining pre-cleaning, cleaning and flushing is adopted, and the cleaning residual liquid is discharged after being settled so as to prevent the sewer from being blocked by dirt.
The cleaning agent is sprayed on the surface of the outer wall of the furnace tube by a cleaning distributor in the pre-cleaning process, so that the cleaning agent gradually wets the surface of dirt and permeates into the dirt, the dirt is loosened and easily dissolved, and floating dust and loose dirt on the surface of the outer wall of the tube are removed by the pre-cleaning process. The pre-cleaning process is generally carried out in an up-down counter flushing cleaning mode, and the cleaning distributor is used for cleaning an upper row of furnace tubes (operation outside a manhole) and a lower row of furnace tubes (operation inside a furnace), wherein when the upper row of furnace tubes are cleaned, a plurality of manholes can be opened simultaneously, and the cleaning distributor is inserted into the furnace for cleaning at various angles so as to achieve the comprehensiveness of the cleaning operation.
And after the pre-cleaning is finished, the heating furnace tube cleaning passivating agent is used for circularly spraying and cleaning the outer wall of the heating furnace tube, so that the cleaning passivating agent fully permeates the dirt on the outer wall, and the dirt is dispersed and dissolved in the cleaning liquid and flows out along with the cleaning passivating agent by utilizing the dispersing, dissolving and stripping properties of the cleaning passivating agent, so that the hard ash dirt and the oxidation layer on the outer wall of the furnace tube are cleaned, and an anti-corrosion passivating film is formed on the outer wall of the tube.
And after the cleaning is finished, washing the furnace tube by using water, and washing the cleaning passivator on the surface of the furnace tube.
The cleaning passivator provided by the invention has the following advantages:
the cleaning passivator integrates the effects of removing dust and scale, removing rust and passivating, can effectively reduce the discharge amount of sewage, and can shorten the cleaning time, wherein the cleaning time of the outer wall of the furnace tube of a single heating furnace is about 8-12 h. The cleaning passivator has good effects of removing dust and scale, and can remove 98% of dust, scale and rust. In addition, the cleaning temperature is between 20 and 30 ℃, and the cleaning condition is mild.
The cleaning passivator is weakly acidic, has little corrosion to equipment and human bodies, and can be used for various gold such as carbon steel, stainless steel, copper, aluminum and the likeCorrosion of the metal is about 1-2g/m2H, less than the requirements specified in the industrial equipment chemical cleaning quality standard HG/T2387-.
After the passivating agent for cleaning provided by the invention is used for attacking the outer wall of the furnace tube of the heating furnace, the exhaust gas temperature of the heating furnace can be reduced by 10-40 ℃ compared with that before cleaning, the heat efficiency of the heating furnace is improved by more than 2%, and the use amount of fuel oil and fuel gas can be reduced.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Example 1
A passivating agent for cleaning the outer wall of a furnace tube of a heating furnace comprises, by mass, 0.5% of LAN-826, 13% of citric acid, 5.6% of hydrochloric acid, 1.4% of sulfamic acid, 10% of sodium dodecyl benzene sulfonate, 3% of sodium carbonate, 3% of sodium bicarbonate, 5% of sodium nitrite, 6% of sodium benzoate and the balance of water. The components are mixed according to the proportion to obtain the passivating agent for cleaning the outer wall of the furnace tube of the heating furnace.
The cleaning passivator is used for cleaning the waste heating furnace tube outer wall fragments of a certain chemical plant, black and tan dirt is fully distributed on the outer wall of the furnace tube, and the dirt is determined to be carbonate, sulfate, ferric oxide and a small amount of ash dirt by collecting dirt sample analysis. The results are shown in Table 2.
Examples 2 to 14
Examples 2-14 were the same as example 1 except that the amounts of citric acid, hydrochloric acid, sulfamic acid, sodium dodecylbenzenesulfonate, sodium carbonate and sodium bicarbonate were varied and the amounts of the components used in examples 2-14 are shown in table 1. The configured cleaning passivator is used for cleaning the furnace tube outer wall scraps of the heating furnace, and the results are shown in table 2.
Comparative example 1
The difference from example 1 is that sulfuric acid of equal mass is used instead of hydrochloric acid.
Comparative examples 2 and 3
The same as example 1, except that oxalic acid and tartaric acid of equal mass were used instead of citric acid, respectively.
Comparative example 4
The same as example 1, except that sodium bicarbonate was replaced by equal mass of disodium bicarbonate.
TABLE 1
TABLE 2
Example 15
20 tons of cleaning passivates were formulated according to the formulation of example 1.
Mixing the ferrous sulfide cleaning passivator and water according to a mass ratio of 10:90, uniformly stirring to form a cleaning solution, and performing convection on a convection section (heat exchange area is 390 m) of an atmospheric and vacuum workshop F-01 atmospheric furnace of a chemical plant by using the cleaning solution2) F-01 atmospheric furnace preheater (heat exchange area 1500 m)2) F-02 vacuum furnace convection section (heat exchange area 284 m)2) And F-02 vacuum furnace water heating medium (heat exchange area 684 m)2) And (3) ash removal is carried out on the outer wall of the furnace tube, descaling chemical cleaning and passivation are carried out, and the cleaning and passivation time of a single set of device is 8 hours. After the cleaning construction is finished, the equipment is opened for inspection, the surface of the furnace tube is very clean, the natural color of metal is exposed, the light transmittance reaches 98 percent, the cleaning requirement is met, the descaling rate reaches more than 98 percent, the cleaning rate reaches more than 98 percent, and the cleaned equipment is not damaged in the cleaning and passivating process. After the cleaned device is started, the normal pressure exhaust temperature is reduced to 120 ℃ from 150 ℃ before cleaning, and the exhaust temperature of the pressure reducing furnace is reduced to about 120 ℃ from 160 ℃ before cleaning, so that the energy can be effectively saved.
Example 16
6 tons of cleaning passivates were formulated according to the formulation of example 1.
The ferrous sulfide cleaning passivator and water are mixed according to the mass ratio of 10:90, the mixture is uniformly stirred to form cleaning liquid, the cleaning liquid is used for cleaning the outer wall of a No. 2 furnace air preheater pipe of Guangxi petrochemical company of China, and before cleaning, the pipe wall of the preheater is fully covered with dirt for 6 hours.
The surface of the preheater tube is clean after cleaning, bright metal natural color is exposed, no ash residue is left on the surface, a good passivation protective film is formed on the surface of the preheater tube, no pitting corrosion is generated on the metal surface, the cleaned equipment is not damaged, the exhaust gas temperature of the 2# furnace after cleaning is reduced by 15-20 ℃, and the energy is effectively saved.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (6)
1. The passivating agent for cleaning the outer wall of the furnace tube of the heating furnace comprises the following components: 0.3-0.6 wt% of Lan-826, 10-15 wt% of citric acid, 4-8 wt% of hydrochloric acid, 1-2 wt% of sulfamic acid, 8-12 wt% of sodium dodecyl benzene sulfonate, 3-6 wt% of sodium carbonate, 3-6 wt% of sodium bicarbonate, 4-8 wt% of sodium nitrite, 5-10 wt% of auxiliary agent and the balance of water.
2. The cleaning passivator of claim 1 wherein the cleaning passivator comprises the following components: 0.5 wt% Lan-826, 13 wt% citric acid, 5.6 wt% hydrochloric acid, 1.4 wt% sulfamic acid, 10 wt% sodium dodecyl benzene sulfonate, 3 wt% sodium carbonate, 3 wt% sodium bicarbonate, 5 wt% sodium nitrite, 5-7 wt% auxiliary agent and the balance of water.
3. The cleaning deactivant of claim 1, wherein the adjuvant is selected from one or more of sodium benzoate, sodium salicylate, niacinamide and acetamide.
4. The use of the passivator for cleaning the outer wall of a furnace tube of a heating furnace according to any one of claims 1 to 3 for cleaning furnace tubes.
5. The use of claim 4, wherein the furnace is a heavy oil, natural gas fueled furnace.
6. The application of claim 4 or 5, wherein the cleaning passivator is diluted by 10-20 times to prepare a cleaning solution, and the cleaning solution is used for cleaning petrochemical equipment.
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| CN111519193A (en) * | 2020-06-03 | 2020-08-11 | 江苏久茂精密电子科技有限公司 | Pickling agent for producing electronic product shell and preparation method thereof |
| CN111690941B (en) * | 2020-06-18 | 2022-07-01 | 中国科学院过程工程研究所 | Sulfamic acid rust removing liquid and rust removing method using sulfamic acid rust removing liquid |
| CN111979063A (en) * | 2020-08-03 | 2020-11-24 | 瑞派尔(宜昌)科技集团股份有限公司 | Preparation method of concrete crack cleaning agent |
| CN113564609A (en) * | 2021-06-09 | 2021-10-29 | 湖北中油优艺环保科技集团有限公司 | Efficient scale remover for incineration system and preparation method thereof |
| CN115386434A (en) * | 2022-07-14 | 2022-11-25 | 广州市人和清洗有限公司 | Bi-component cleaning agent for cleaning pipeline and preparation method thereof |
| CN115584496A (en) * | 2022-10-25 | 2023-01-10 | 福建省长汀金龙稀土有限公司 | Surface treatment method for permanent magnet, permanent magnet and protective film thereof |
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| CN101864575B (en) * | 2010-06-27 | 2012-02-29 | 金宏 | Special cleaning agent for stainless steel equipment and use method thereof |
| JP2013010987A (en) * | 2011-06-29 | 2013-01-17 | Yushiro Chemical Industry Co Ltd | Aqueous solution of rust-removing agent |
| CN103468420A (en) * | 2013-08-20 | 2013-12-25 | 李从波 | Weak acid cleaner and application thereof to removal of GGH (gas-gas heater) hard scale |
| CN104726881B (en) * | 2015-02-12 | 2017-11-28 | 国家电网公司 | A kind of chemical cleaning method of high-efficiency environment friendly |
| CN106222675A (en) * | 2016-08-18 | 2016-12-14 | 广州斯特福材料科技有限公司 | A kind of citric acid cleaning passivator and passivating method |
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