CN115478268B - Production process of large-caliber stainless steel seamless steel pipe - Google Patents
Production process of large-caliber stainless steel seamless steel pipe Download PDFInfo
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- CN115478268B CN115478268B CN202210932026.4A CN202210932026A CN115478268B CN 115478268 B CN115478268 B CN 115478268B CN 202210932026 A CN202210932026 A CN 202210932026A CN 115478268 B CN115478268 B CN 115478268B
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- steel seamless
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- 239000010935 stainless steel Substances 0.000 title claims abstract description 60
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 60
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 31
- 239000010959 steel Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims description 82
- 238000006243 chemical reaction Methods 0.000 claims description 67
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 54
- 239000007795 chemical reaction product Substances 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000013556 antirust agent Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 239000003995 emulsifying agent Substances 0.000 claims description 20
- 239000012065 filter cake Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- LJTFFORYSFGNCT-UHFFFAOYSA-N Thiocarbohydrazide Chemical compound NNC(=S)NN LJTFFORYSFGNCT-UHFFFAOYSA-N 0.000 claims description 11
- 229940074391 gallic acid Drugs 0.000 claims description 11
- 235000004515 gallic acid Nutrition 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- WFELVFKXQJYPSL-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutanoyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Cl)=O WFELVFKXQJYPSL-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 7
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 238000005422 blasting Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- SGNZYJXNUURYCH-UHFFFAOYSA-N 5,6-dihydroxyindole Chemical compound C1=C(O)C(O)=CC2=C1NC=C2 SGNZYJXNUURYCH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 19
- 230000007797 corrosion Effects 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000012423 maintenance Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- -1 iron ions Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- C23C22/68—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 solutions with pH between 6 and 8
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/09—Heterocyclic compounds containing no sulfur, selenium or tellurium compounds in the ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
Abstract
The invention relates to the technical field of steel pipe production, which is used for solving the problems that the conventional large-caliber stainless steel seamless steel pipe is easy to generate punctiform corrosion when being in corrosion contact with chemical products, the performance is reduced after corrosion, and the application requirement of large-scale equipment is not met; in the production process, rust-proof liquid is sprayed on the inner wall and the outer wall of the large-caliber stainless steel seamless pipe blank, so that good corrosion resistance of the large-caliber stainless steel seamless pipe is provided, long-term safe use of the large-caliber stainless steel seamless pipe is ensured, and maintenance and replacement times of the large-caliber stainless steel seamless pipe are reduced.
Description
Technical Field
The invention relates to the technical field of steel pipe production, in particular to a production process of a large-caliber stainless steel seamless steel pipe.
Background
Stainless steel pipe is widely used in various industries due to excellent mechanical property, machining property and corrosion resistance, corrosion resistance of stainless steel pipe comes from chromium and nickel in self alloy, so that a layer of compact oxide film, namely passivation layer, can be generated after the stainless steel is oxidized, further, the corrosion speed of the stainless steel pipe in an oxidizing medium is reduced, and the large-caliber stainless steel seamless steel pipe is large in caliber and is made of stainless steel and widely applied to the fields of large boilers, petrochemical industry, coal-to-oil hydrocracking, large pressurized containers, large hydraulic equipment and the like.
However, stainless steel is not absolutely stainless, punctiform corrosion is easy to generate when the stainless steel contacts certain chemical products, the performance is reduced after corrosion, the application requirements of large-scale equipment are not met, in addition, the large-caliber composite pipe is very laborious to install due to the large size of the large-caliber composite pipe, and the difficulty in the assembly and welding processes is large.
How to improve the corrosion resistance of the existing large-caliber stainless steel seamless steel pipe is not good, so that a production process of the large-caliber stainless steel seamless steel pipe is needed to solve the problems.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a production process of a large-caliber stainless steel seamless steel pipe, which comprises the following steps: the method comprises the steps of adding methyl methacrylate, an antirust agent, butyl acrylate, an emulsifier, an initiator and water into a reaction kettle for stirring reaction, cooling a reaction product to room temperature after the reaction is finished to obtain an antirust liquid, performing shot blasting cleaning on the inner wall and the outer wall of a large-caliber stainless steel seamless steel pipe blank, spraying the antirust liquid on the inner wall and the outer wall of the large-caliber stainless steel seamless pipe blank, and curing the antirust liquid to obtain the large-caliber stainless steel seamless pipe.
The aim of the invention can be achieved by the following technical scheme:
a production process of a large-caliber stainless steel seamless steel pipe comprises the following steps:
step one: weighing 35-45 parts of methyl methacrylate, 5-25 parts of antirust agent, 30-35 parts of butyl acrylate, 1.6-2.3 parts of emulsifier, 1.2-1.5 parts of initiator and 35-55 parts of water according to parts by weight for standby;
step two: adding methyl methacrylate, an antirust agent, butyl acrylate, an emulsifier, an initiator and water into a reaction kettle, stirring and reacting for 20-30min under the conditions of 30-40 ℃ and stirring speed of 800-1000r/min, heating to 85-95 ℃ and continuing stirring and reacting for 4-5h, and cooling the reaction product to room temperature after the reaction is finished to obtain an antirust liquid;
step three: and performing shot blasting cleaning on the inner and outer walls of the large-caliber stainless steel seamless pipe blank, spraying antirust liquid on the inner and outer walls of the large-caliber stainless steel seamless pipe blank, and curing the antirust liquid to obtain the large-caliber stainless steel seamless pipe.
As a further scheme of the invention: the emulsifier is one of an emulsifier OP-7 and an emulsifier OP-10, and the initiator is ammonium persulfate.
As a further scheme of the invention: the antirust agent is prepared by the following steps:
a1: adding gallic acid, isobutyric anhydride, 4-dimethylaminopyridine, triethylamine and N, N-dimethylformamide into a three-neck flask with a stirrer and a thermometer, stirring and reacting for 1.5-2 hours under the condition that the temperature is 25-30 ℃ and the stirring speed is 300-400r/min, adding a reaction product into a hydrochloric acid solution after the reaction is finished, standing for precipitation, vacuum filtering, washing a filter cake with distilled water for 2-3 times, and then placing the filter cake in a vacuum drying oven, and drying for 3-5 hours under the condition that the temperature is 60-70 ℃ to obtain an intermediate 1;
the reaction principle is as follows:
a2: adding the intermediate 1, 3-diaminothiourea into a three-neck flask provided with a stirrer and a thermometer, stirring at 160-170 ℃ and stirring speed of 300-400r/min until the intermediate 1, 3-diaminothiourea is molten, continuing stirring for 3-4h, cooling the reaction product to room temperature after the reaction is finished, adding the reaction product into distilled water at 80-90 ℃, vacuum-filtering, recrystallizing a filter cake with absolute ethyl alcohol, and then placing the filter cake in a vacuum drying oven, and drying at 60-70 ℃ for 3-5h to obtain an intermediate 2;
the reaction principle is as follows:
a3: adding the intermediate 2, triethylamine and methylene dichloride into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, gradually adding a heptafluorobutyryl chloride solution dropwise while stirring at a temperature of-5-0 ℃ and a stirring rate of 300-400r/min, controlling the dropping rate to be 1-2 drops/s, continuing stirring for reaction for 0.5-1h after the dripping is finished, heating to 45-50 ℃ and continuing stirring for reaction for 5-6h, cooling a reaction product to room temperature after the reaction is finished, performing reduced pressure distillation to remove a solvent, washing with distilled water for 2-3 times, recrystallizing with acetone, placing in a vacuum drying oven, and drying for 3-5h at a temperature of 60-70 ℃ to obtain the intermediate 2;
the reaction principle is as follows:
a4: adding the intermediate 2, triethylamine and tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, gradually adding acryloyl chloride dropwise while stirring under the conditions of the temperature of-5-0 ℃ and the stirring rate of 300-400r/min, controlling the dropping rate to be 1-2 drops/s, continuing stirring for reaction for 1-2h after the dripping is finished, then heating to 42-46 ℃ and continuing stirring for reaction for 5-6h, adding a reaction product into ice water after the reaction is finished, standing for precipitation, vacuum filtering, recrystallizing a filter cake with absolute ethyl alcohol, and then placing in a vacuum drying box, and drying for 3-5h under the conditions of the temperature of 60-70 ℃ to obtain an intermediate 4;
the reaction principle is as follows:
a5: adding the intermediate 4 and absolute ethyl alcohol into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, dropwise adding a hydrazine hydrate solution while stirring at the temperature of 25-30 ℃ and the stirring rate of 300-400r/min, controlling the dropping rate to be 1-2 drops/s, continuing stirring for reaction for 1-2h after the dropping, dropwise adding a hydrochloric acid solution while stirring to adjust the pH to 7, controlling the dropping rate to be 1-2 drops/s, continuing stirring for reaction for 10-15min, extracting the reaction product with ethyl acetate for 2-3 times after the reaction is finished, drying the extract with absolute magnesium sulfate, vacuum filtering, and rotationally evaporating the filtrate to remove the solvent to obtain the antirust agent.
The reaction principle is as follows:
as a further scheme of the invention: the dosage ratio of the gallic acid, the isobutyric anhydride, the 4-dimethylaminopyridine, the triethylamine and the N, N-dimethylformamide in the step A1 is 0.1mol:0.35-0.4mol:0.1mol:0.35-0.4mol:50-60mL, wherein the molar concentration of the hydrochloric acid solution is 1-1.5mol/L.
As a further scheme of the invention: the dosage ratio of the intermediate 1, 3-diaminothiourea in the step A2 is 0.1mol:0.1mol.
As a further scheme of the invention: the dosage ratio of the intermediate 2, triethylamine, methylene chloride and perfluorobutyryl chloride solution in the step A3 is 0.1mol:0.1mol:40-50mL:10-15mL of the perfluorobutyryl chloride solution is perfluorobutyryl chloride according to the ratio of 0.08-0.12mol:10mL of the solution was dissolved in methylene chloride.
As a further scheme of the invention: the dosage ratio of the intermediate 2, triethylamine, tetrahydrofuran and acryloyl chloride in the step A4 is 0.1mol:0.11-0.13mol:50-60mL:0.11-0.13mol.
As a further scheme of the invention: the dosage ratio of the intermediate 4, the absolute ethyl alcohol and the hydrazine hydrate solution in the step A5 is 0.1mol:60-80mL:6.5-7g, wherein the mass fraction of the hydrazine hydrate solution is 80%, and the mass fraction of the hydrochloric acid solution is 15-20%.
The invention has the beneficial effects that:
according to the production process of the large-caliber stainless steel seamless steel pipe, methyl methacrylate, an antirust agent, butyl acrylate, an emulsifier, an initiator and water are added into a reaction kettle to perform stirring reaction, a reaction product is cooled to room temperature after the reaction is finished, so that an antirust liquid is obtained, the inner wall and the outer wall of the large-caliber stainless steel seamless steel pipe blank are subjected to shot blasting cleaning, then the inner wall and the outer wall of the large-caliber stainless steel seamless steel pipe blank are sprayed with the antirust liquid, and the large-caliber stainless steel seamless steel pipe is obtained after the antirust liquid is solidified; in the production process, rust-proof liquid is sprayed on the inner wall and the outer wall of the large-caliber stainless steel seamless pipe blank, so that good corrosion resistance of the large-caliber stainless steel seamless pipe is provided, long-term safe use of the large-caliber stainless steel seamless pipe is ensured, and maintenance and replacement times of the large-caliber stainless steel seamless pipe are reduced;
firstly preparing an antirust agent in the process of producing the large-caliber stainless steel seamless steel pipe, firstly utilizing gallic acid and isobutyric anhydride to react, introducing isobutyl into the gallic acid, successfully protecting phenolic hydroxyl groups of the gallic acid to obtain an intermediate 1, then utilizing intermediate 1, 3-diaminothiourea to react, introducing amino groups and secondary amine groups into the intermediate 1 to obtain an intermediate 2, utilizing heptafluorobutyryl chloride to react with the amino groups on the intermediate 2 in a nucleophilic substitution way, introducing a large number of C-F bonds to obtain an intermediate 3, utilizing acryloyl chloride to react with the secondary amine groups on the intermediate 3 in a nucleophilic substitution way, introducing alkenyl groups to obtain an intermediate 4, and then utilizing hydrazine hydrate solution to carry out deprotection reaction on the phenolic hydroxyl groups on the intermediate 4 to obtain the antirust agent; the molecular structure of the rust inhibitor contains a large number of C-F bonds, so that the good chemical resistance of the large-caliber stainless steel seamless steel pipe is endowed, the corrosion resistance of the stainless steel seamless steel pipe is greatly improved, the molecular structure of the rust inhibitor contains a large number of phenolic hydroxyl groups, the active type of the phenolic hydroxyl groups is high, and the rust inhibitor can be matched with Fe 2+ And Fe (Fe) 3+ After the reaction, the iron rust exists in an ionic state after the large-caliber stainless steel seamless steel pipe is corroded and rusted, and phenolic hydroxyl groups and Fe 2+ And Fe (Fe) 3+ Well chelate together and can form stable complex with iron ions, thereby inhibiting the continuous rusting of the iron ions and further improving the corrosion resistance of the iron ions.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
the embodiment is a preparation method of an antirust agent, which comprises the following steps:
a1: adding 0.1mol of gallic acid, 0.35mol of isobutyric anhydride, 0.1mol of 4-dimethylaminopyridine, 0.35mol of triethylamine and 50mLN, N-dimethylformamide into a three-neck flask provided with a stirrer and a thermometer, stirring at a temperature of 25 ℃ and a stirring rate of 300r/min for reaction for 1.5 hours, adding a reaction product into a hydrochloric acid solution with a molar concentration of 1mol/L after the reaction is finished, standing for precipitation, vacuum filtering, washing a filter cake with distilled water for 2 times, and then placing in a vacuum drying oven, and drying for 3 hours at a temperature of 60 ℃ to obtain an intermediate 1;
a2: adding 0.1mol of intermediate 1 and 0.1mol of 1, 3-diaminothiourea into a three-neck flask provided with a stirrer and a thermometer, stirring at 160 ℃ and a stirring rate of 300r/min until the intermediate 1 and 1, 3-diaminothiourea are molten, continuing stirring for 3 hours, cooling a reaction product to room temperature after the reaction is finished, adding the reaction product into distilled water at 80 ℃, vacuum-filtering, recrystallizing a filter cake with absolute ethyl alcohol, and then placing the filter cake in a vacuum drying oven, and drying for 3 hours at 60 ℃ to obtain an intermediate 2;
a3: 0.1mol of intermediate 2, 0.1mol of triethylamine and 40mL of methylene chloride were charged into a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, and 10mL of perfluorobutyryl chloride was added dropwise with stirring at a temperature of-5℃and a stirring rate of 300r/min in accordance with 0.08mol:10mL of heptafluorobutyryl chloride solution formed by dissolving in dichloromethane, controlling the dropping rate to be 1 drop/s, continuously stirring for reaction for 0.5h after the dropping is finished, continuously stirring for reaction for 5h under the condition of heating to 45 ℃, cooling a reaction product to room temperature after the reaction is finished, removing a solvent by reduced pressure distillation, washing with distilled water for 2 times, recrystallizing with acetone, and drying for 3h under the condition of 60 ℃ to obtain an intermediate 2;
a4: adding 0.1mol of intermediate 2, 0.11mol of triethylamine and 50mL of tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, gradually adding 0.11mol of acryloyl chloride while stirring at a temperature of-5 ℃ and a stirring rate of 300r/min, controlling the dropping rate to be 1 drop/s, continuing stirring for reaction for 1h after the dripping is finished, heating to 42 ℃ and continuing stirring for reaction for 5h, adding a reaction product into ice water after the reaction is finished, standing for precipitation, vacuum filtering, recrystallizing a filter cake with absolute ethyl alcohol, and then placing in a vacuum drying oven, and drying for 3h at a temperature of 60 ℃ to obtain an intermediate 4;
a5: adding 0.1mol of intermediate 4 and 60mL of absolute ethyl alcohol into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, gradually adding 6.5g of hydrazine hydrate solution with the mass fraction of 80% under the condition of the temperature of 25 ℃ and the stirring rate of 300r/min, controlling the dropping rate to be 1 drop/s, continuously stirring for reaction for 1h after the completion of the dropping, gradually adding hydrochloric acid solution with the mass fraction of 15% under the condition of stirring for regulating the pH value to be 7, controlling the dropping rate to be 1 drop/s, continuously stirring for reaction for 10min, extracting the reaction product with ethyl acetate for 2 times after the completion of the reaction, drying the extract with anhydrous magnesium sulfate, vacuum suction filtering, and rotationally evaporating the filtrate to remove the solvent to obtain the antirust agent.
Example 2:
the embodiment is a preparation method of an antirust agent, which comprises the following steps:
a1: adding 0.1mol of gallic acid, 0.4mol of isobutyric anhydride, 0.1mol of 4-dimethylaminopyridine, 0.4mol of triethylamine and 60mLN, N-dimethylformamide into a three-neck flask provided with a stirrer and a thermometer, stirring at a temperature of 30 ℃ and a stirring rate of 400r/min for reaction for 2 hours, adding a reaction product into a hydrochloric acid solution with a molar concentration of 1.5mol/L after the reaction is finished, standing for precipitation, vacuum filtering, washing a filter cake with distilled water for 3 times, and then placing in a vacuum drying oven, and drying for 5 hours at a temperature of 70 ℃ to obtain an intermediate 1;
a2: adding 0.1mol of intermediate 1 and 0.1mol of 1, 3-diaminothiourea into a three-neck flask provided with a stirrer and a thermometer, stirring at 170 ℃ and stirring speed of 400r/min until the intermediate 1 and 1, 3-diaminothiourea are molten, continuing stirring reaction for 4 hours, cooling a reaction product to room temperature after the reaction is finished, adding the reaction product into distilled water at 90 ℃, vacuum-filtering, recrystallizing a filter cake with absolute ethyl alcohol, and then placing the filter cake in a vacuum drying oven, and drying for 5 hours at 70 ℃ to obtain an intermediate 2;
a3: 0.1mol of intermediate 2, 0.1mol of triethylamine and 50mL of methylene chloride were charged into a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, and 15mL of perfluorobutyryl chloride was added dropwise with stirring at a temperature of 0℃and a stirring rate of 400r/min in an amount of 0.12mol:10mL of heptafluorobutyryl chloride solution formed by dissolving in dichloromethane, controlling the dropping rate to be 2 drops/s, continuing to stir for reaction for 1h after the dropping is finished, then heating to 50 ℃ for continuous stirring for reaction for 6h, cooling a reaction product to room temperature after the reaction is finished, then distilling under reduced pressure to remove a solvent, washing with distilled water for 3 times, recrystallizing with acetone, and then placing in a vacuum drying oven for drying for 5h at the temperature of 70 ℃ to obtain an intermediate 2;
a4: adding 0.1mol of intermediate 2, 0.13mol of triethylamine and 60mL of tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, dropwise adding 0.13mol of acryloyl chloride under the condition of 0 ℃ and stirring speed of 400r/min, controlling the dropping speed to be 2 drops/s, continuing stirring for reaction for 2 hours after the dripping is finished, heating to 46 ℃ and continuing stirring for reaction for 6 hours, adding a reaction product into ice water after the reaction is finished, standing for precipitation, vacuum filtering, recrystallizing a filter cake with absolute ethyl alcohol, and then placing in a vacuum drying oven, and drying for 5 hours under the condition of 70 ℃ to obtain an intermediate 4;
a5: adding 0.1mol of intermediate 4 and 80mL of absolute ethyl alcohol into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, dropwise adding 7g of hydrazine hydrate solution with the mass fraction of 80% under the condition of the temperature of 30 ℃ and the stirring rate of 400r/min, controlling the dripping rate to be 2 drops/s, continuing stirring for reaction for 2 hours after the dripping is finished, dropwise adding hydrochloric acid solution with the mass fraction of 20% to adjust the pH to be 7, controlling the dripping rate to be 2 drops/s, continuing stirring for reaction for 15 minutes, extracting a reaction product with ethyl acetate for 3 times after the reaction is finished, drying an extract with anhydrous magnesium sulfate, vacuum filtering, and rotationally evaporating filtrate to remove the solvent to obtain the antirust agent.
Example 3:
the embodiment is a production process of a large-caliber stainless steel seamless steel pipe, comprising the following steps of:
step one: 35 parts of methyl methacrylate, 5 parts of an antirust agent from example 1, 30 parts of butyl acrylate, 1.6 parts of an emulsifier, 1.2 parts of an initiator and 35 parts of water are weighed according to parts by weight for standby; the emulsifier is emulsifier OP-7, and the initiator is ammonium persulfate;
step two: adding methyl methacrylate, an antirust agent, butyl acrylate, an emulsifier, an initiator and water into a reaction kettle, stirring and reacting for 20min under the condition that the temperature is 30 ℃ and the stirring speed is 800r/min, then continuously stirring and reacting for 4h under the condition that the temperature is raised to 85 ℃, and cooling the reaction product to room temperature after the reaction is finished to obtain an antirust liquid;
step three: and performing shot blasting cleaning on the inner and outer walls of the large-caliber stainless steel seamless pipe blank, spraying antirust liquid on the inner and outer walls of the large-caliber stainless steel seamless pipe blank, and curing the antirust liquid to obtain the large-caliber stainless steel seamless pipe.
Example 4:
the embodiment is a production process of a large-caliber stainless steel seamless steel pipe, comprising the following steps of:
step one: 45 parts of methyl methacrylate, 25 parts of an antirust agent from example 2, 35 parts of butyl acrylate, 2.3 parts of an emulsifier, 1.5 parts of an initiator and 55 parts of water are weighed according to parts by weight for standby; the emulsifier is emulsifier OP-10, and the initiator is ammonium persulfate;
step two: adding methyl methacrylate, an antirust agent, butyl acrylate, an emulsifier, an initiator and water into a reaction kettle, stirring and reacting for 30min under the condition that the temperature is 40 ℃ and the stirring speed is 1000r/min, then continuously stirring and reacting for 5h under the condition that the temperature is raised to 95 ℃, and cooling the reaction product to room temperature after the reaction is finished to obtain an antirust liquid;
step three: and performing shot blasting cleaning on the inner and outer walls of the large-caliber stainless steel seamless pipe blank, spraying antirust liquid on the inner and outer walls of the large-caliber stainless steel seamless pipe blank, and curing the antirust liquid to obtain the large-caliber stainless steel seamless pipe.
Comparative example 1:
comparative example 1 differs from example 4 in that no rust inhibitor was added.
Comparative example 2:
comparative example 2 differs from example 4 in that gallic acid was used instead of the rust inhibitor.
The performances of the large-caliber stainless steel seamless steel pipes of the examples 3-4 and the comparative examples 1-2 are detected, the neutral salt spray resistance performance of the stainless steel pipes is tested according to the method described in the national industry standard GB/T6461-2002, the corrosion area ratio after 24H is recorded, the corrosion resistance performance of the stainless steel pipes against ferric trichloride points is tested according to the method described in the national industry standard GB/T17897-1999, the corrosion rate is calculated, and the detection results are shown in the following table:
referring to the data in the table above, according to the comparison between the example 4 and the comparative examples 1-2, it can be known that the addition of gallic acid and the rust inhibitor can significantly improve the corrosion resistance of the large-caliber stainless steel seamless steel pipe, wherein the rust inhibitor has better improving effect, can control the corrosion area to be less than 1%, and has the corrosion efficiency to be less than 1.2 mg/(cm) 2 ·h -1 )。
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (7)
1. The production process of the large-caliber stainless steel seamless steel pipe is characterized by comprising the following steps of:
step one: weighing 35-45 parts of methyl methacrylate, 5-25 parts of antirust agent, 30-35 parts of butyl acrylate, 1.6-2.3 parts of emulsifier, 1.2-1.5 parts of initiator and 35-55 parts of water according to parts by weight for standby;
step two: adding methyl methacrylate, an antirust agent, butyl acrylate, an emulsifier, an initiator and water into a reaction kettle, stirring and reacting for 20-30min under the conditions of 30-40 ℃ and stirring speed of 800-1000r/min, heating to 85-95 ℃ and continuing stirring and reacting for 4-5h, and cooling the reaction product to room temperature after the reaction is finished to obtain an antirust liquid;
step three: performing shot blasting cleaning on the inner and outer walls of the large-caliber stainless steel seamless pipe blank, spraying antirust liquid on the inner and outer walls of the large-caliber stainless steel seamless pipe blank, and curing the antirust liquid to obtain the large-caliber stainless steel seamless pipe;
the antirust agent is prepared by the following steps:
a1: adding gallic acid, isobutyric anhydride, 4-dimethylaminopyridine, triethylamine and N, N-dimethylformamide into a three-neck flask with a stirrer and a thermometer, stirring and reacting for 1.5-2 hours under the condition that the temperature is 25-30 ℃ and the stirring speed is 300-400r/min, adding a reaction product into a hydrochloric acid solution after the reaction is finished, standing for precipitation, vacuum filtering, washing a filter cake with distilled water for 2-3 times, and then placing the filter cake in a vacuum drying oven, and drying for 3-5 hours under the condition that the temperature is 60-70 ℃ to obtain an intermediate 1;
a2: adding the intermediate 1, 3-diaminothiourea into a three-neck flask provided with a stirrer and a thermometer, stirring at 160-170 ℃ and stirring speed of 300-400r/min until the intermediate 1, 3-diaminothiourea is molten, continuing stirring for 3-4h, cooling the reaction product to room temperature after the reaction is finished, adding the reaction product into distilled water at 80-90 ℃, vacuum-filtering, recrystallizing a filter cake with absolute ethyl alcohol, and then placing the filter cake in a vacuum drying oven, and drying at 60-70 ℃ for 3-5h to obtain an intermediate 2;
a3: adding the intermediate 2, triethylamine and methylene dichloride into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, gradually adding a heptafluorobutyryl chloride solution dropwise while stirring at a temperature of-5-0 ℃ and a stirring rate of 300-400r/min, controlling the dropping rate to be 1-2 drops/s, continuing stirring for reaction for 0.5-1h after the dripping is finished, heating to 45-50 ℃ and continuing stirring for reaction for 5-6h, cooling a reaction product to room temperature after the reaction is finished, performing reduced pressure distillation to remove a solvent, washing with distilled water for 2-3 times, recrystallizing with acetone, placing in a vacuum drying oven, and drying for 3-5h at a temperature of 60-70 ℃ to obtain the intermediate 2;
a4: adding the intermediate 2, triethylamine and tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, gradually adding acryloyl chloride dropwise while stirring under the conditions of the temperature of-5-0 ℃ and the stirring rate of 300-400r/min, controlling the dropping rate to be 1-2 drops/s, continuing stirring for reaction for 1-2h after the dripping is finished, then heating to 42-46 ℃ and continuing stirring for reaction for 5-6h, adding a reaction product into ice water after the reaction is finished, standing for precipitation, vacuum filtering, recrystallizing a filter cake with absolute ethyl alcohol, and then placing in a vacuum drying box, and drying for 3-5h under the conditions of the temperature of 60-70 ℃ to obtain an intermediate 4;
a5: adding the intermediate 4 and absolute ethyl alcohol into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, dropwise adding a hydrazine hydrate solution while stirring at the temperature of 25-30 ℃ and the stirring rate of 300-400r/min, controlling the dropping rate to be 1-2 drops/s, continuing stirring for reaction for 1-2h after the dropping, dropwise adding a hydrochloric acid solution while stirring to adjust the pH to 7, controlling the dropping rate to be 1-2 drops/s, continuing stirring for reaction for 10-15min, extracting the reaction product with ethyl acetate for 2-3 times after the reaction is finished, drying the extract with absolute magnesium sulfate, vacuum filtering, and rotationally evaporating the filtrate to remove the solvent to obtain the antirust agent.
2. The process for producing the large-caliber stainless steel seamless steel tube according to claim 1, wherein the emulsifier is one of an emulsifier OP-7 and an emulsifier OP-10, and the initiator is ammonium persulfate.
3. The process for producing a large-caliber stainless steel seamless steel pipe according to claim 1, wherein the dosage ratio of gallic acid, isobutyric anhydride, 4-dimethylaminopyridine, triethylamine and N, N-dimethylformamide in the step A1 is 0.1mol:0.35-0.4mol:0.1mol:0.35-0.4mol:50-60mL, wherein the molar concentration of the hydrochloric acid solution is 1-1.5mol/L.
4. The process for producing the large-caliber stainless steel seamless steel tube according to claim 1, wherein the dosage ratio of the intermediate 1, 3-diaminothiourea in the step A2 is 0.1mol:0.1mol.
5. The process for producing a large-caliber stainless steel seamless steel tube according to claim 1, wherein the dosage ratio of the intermediate 2, triethylamine, methylene dichloride and perfluorobutyryl chloride solution in the step A3 is 0.1mol:0.1mol:40-50mL:10-15mL of the perfluorobutyryl chloride solution is perfluorobutyryl chloride according to the ratio of 0.08-0.12mol:10mL of the solution was dissolved in methylene chloride.
6. The process for producing a large-caliber stainless steel seamless steel pipe according to claim 1, wherein the dosage ratio of the intermediate 2, triethylamine, tetrahydrofuran and acryloyl chloride in the step A4 is 0.1mol:0.11-0.13mol:50-60mL:0.11-0.13mol.
7. A process for producing a large-caliber stainless steel seamless steel pipe according to claim 3, wherein the dosage ratio of the intermediate 4, the absolute ethyl alcohol and the hydrazine hydrate solution in the step A5 is 0.1mol:60-80mL:6.5-7g, wherein the mass fraction of the hydrazine hydrate solution is 80%, and the mass fraction of the hydrochloric acid solution is 15-20%.
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