EP3591091B1 - Method for zero-discharge phosphatization and saponification based on high-pressure closed circulation system - Google Patents

Method for zero-discharge phosphatization and saponification based on high-pressure closed circulation system Download PDF

Info

Publication number
EP3591091B1
EP3591091B1 EP18187806.7A EP18187806A EP3591091B1 EP 3591091 B1 EP3591091 B1 EP 3591091B1 EP 18187806 A EP18187806 A EP 18187806A EP 3591091 B1 EP3591091 B1 EP 3591091B1
Authority
EP
European Patent Office
Prior art keywords
autoclave
kettle
hydraulic pump
workpiece
separation
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
EP18187806.7A
Other languages
German (de)
French (fr)
Other versions
EP3591091A1 (en
Inventor
Jingfeng Yang
Weirong Yu
Peng Shen
Haibin Wang
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of EP3591091A1 publication Critical patent/EP3591091A1/en
Application granted granted Critical
Publication of EP3591091B1 publication Critical patent/EP3591091B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • 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
    • C23C22/73—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 characterised by the process
    • 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
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents

Definitions

  • the invention relates to the field of phosphatization and saponification pretreatment in the metal cold-working industry, and particularly to a method for zero-discharge phosphatization and saponification based on a high-pressure closed circulation system.
  • the specific phosphatization process flow is as follows: firstly, the surface of a metal workpiece is degreased and derusted by an acid and a base, and the surface of the treated metal workpiece is washed with water; secondly, zinc-series phosphorization is performed, and the surface of the treated metal workpiece is washed with water; and thirdly, the surface of the metal workpiece is saponified with sodium stearate and then dried.
  • the reasons for zinc-series phosphatization are as follows: firstly, a zinc-series phosphatized film is saponified to form a zinc stearate layer with excellent lubricity; and secondly, zinc-series phosphatization is carried out at a relatively low operating temperature and can be performed at 40, 60 or 90°C.
  • EP1314799A1 relates to a novel electrochemical reaction method and an electrochemical reaction apparatus thereof with small or zero in amount of generation of liquid waste such as electrolytic solution, using matter shifted into a supercritical or subcritical state and an electrolytic solution.
  • CN1283710C relates to a process for phosphonating iron and steel includes pickling, water washing, phosphonating, drying in air, saponifying and natural drying and CN105018920A discloses a phosphorus saponification production process to improve the production efficiency, the safety, the reliability, the heating efficiency, the quality, to save energy and reduce the production cost. These processes are not in a closed circulation system, causing the problem of pollution and waste.
  • the invention provides a high-pressure closed circulation system and a method for zero-discharge phosphatization and saponification using the system.
  • a method for zero-discharge phosphatization and saponification based on a high-pressure closed circulation system comprises an autoclave, a separation kettle, a buffer kettle, a hydraulic pump and a recovery vat.
  • the method comprises the following steps:
  • a further improvement is that the carbon dioxide separated from the separation kettle in the step 5 and the step 7 is refrigerated, pressurized and then introduced to the autoclave for cyclic washing.
  • the invention has the following beneficial effects: after the technical solution of the present application is employed, the solubility of oil stains, phosphoric acid, phosphate and sodium stearate can be changed by adjusting the temperature and pressure changes to achieve the purpose of cyclic separation and collection, the amount of acids, bases and industrial water used is greatly reduced, the chemical solution flows in a closed pipeline without volatilization and leakage, no sewage and waste liquid are discharged to the environment, good working conditions are provided, and production residues can be conveniently collected and treated without environmental pollution.
  • a method for zero-discharge phosphatization and saponification based on a high-pressure closed circulation system comprises an autoclave, a separation kettle, a buffer kettle, a hydraulic pump and a recovery vat. The method comprises the following steps:

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Processing Of Solid Wastes (AREA)

Description

    FIELD OF THE INVENTION
  • The invention relates to the field of phosphatization and saponification pretreatment in the metal cold-working industry, and particularly to a method for zero-discharge phosphatization and saponification based on a high-pressure closed circulation system.
    • BACKGROUND OF THE INVENTION
  • In the metal cold-working industry, when procedures such as wire drawing, extrusion, deep drawing, etc. are performed, the phosphatization-saponification treatment is first performed on the surface of a workpiece, and then the friction between the workpiece and a mold can be reduced to achieve a good lubricating effect.
  • The specific phosphatization process flow is as follows: firstly, the surface of a metal workpiece is degreased and derusted by an acid and a base, and the surface of the treated metal workpiece is washed with water; secondly, zinc-series phosphorization is performed, and the surface of the treated metal workpiece is washed with water; and thirdly, the surface of the metal workpiece is saponified with sodium stearate and then dried. The reasons for zinc-series phosphatization are as follows: firstly, a zinc-series phosphatized film is saponified to form a zinc stearate layer with excellent lubricity; and secondly, zinc-series phosphatization is carried out at a relatively low operating temperature and can be performed at 40, 60 or 90°C.
  • When a metal workpiece is derusted by the above process, derusting is performed by washing respectively with hydrochloric acid, nitric acid and sulfuric acid according to different metals, which produces toxic and smoky yellow and red smog, causes serious corrosive three-waste pollution, and easily allows that an outer layer of the metal of the washed workpiece is dissolved to form over-etching and the inside of the metal itself undergoes hydrogen permeation to cause hydrogen embrittlement, thus endangering the safety in use and shortening the service life. In addition, the whole process requires water washing for multiple times, and washing with water to dilute the waste working liquid may consume and lose a lot of water resources, resulting in serious pollution and great waste.
  • EP1314799A1 relates to a novel electrochemical reaction method and an electrochemical reaction apparatus thereof with small or zero in amount of generation of liquid waste such as electrolytic solution, using matter shifted into a supercritical or subcritical state and an electrolytic solution.
  • CN1283710C relates to a process for phosphonating iron and steel includes pickling, water washing, phosphonating, drying in air, saponifying and natural drying and CN105018920A discloses a phosphorus saponification production process to improve the production efficiency, the safety, the reliability, the heating efficiency, the quality, to save energy and reduce the production cost. These processes are not in a closed circulation system, causing the problem of pollution and waste.
    • SUMMARY OF THE INVENTION
  • To solve the problems existing in the prior art, the invention provides a high-pressure closed circulation system and a method for zero-discharge phosphatization and saponification using the system.
  • To achieve the above object, the invention employs the following technical solution:
    a method for zero-discharge phosphatization and saponification based on a high-pressure closed circulation system comprises an autoclave, a separation kettle, a buffer kettle, a hydraulic pump and a recovery vat. The method comprises the following steps:
    • step 1: a workpiece is fed into the autoclave and then sealed such that the pressure range of the autoclave is above 20 MPa;
    • step 2: degreasing and derusting by CO2: carbon dioxide is buffered by the buffer kettle and then delivered to the autoclave by the hydraulic pump, and then the workpiece is derusted and degreased by spraying a high-pressure carbon dioxide gas stream via a Venturi nozzle in the autoclave;
    • step 3: cyclic separation: supercritical CO2 is delivered to the autoclave for cyclic cleaning by means of the buffer kettle and the hydraulic pump until the autoclave is clean, and oil stains and solid residues are pushed into the separation kettle by the supercritical CO2;
    • step 4: high-pressure phosphatization: a phosphatizing solution is pressurized and injected into the autoclave by the hydraulic pump, and then mixed and diluted with high-pressure fluid in the autoclave under the action of a stirrer of the autoclave; the autoclave is warmed up to the reaction temperature to phosphatize the surface of the workpiece; the phosphatizing solution undergoes a chemical reaction on the surface of the workpiece to form a phosphatized film; and after the reaction is completed, the fluid in the autoclave is discharged to the separation kettle to separate and collect residues obtained after phosphatization;
    • step 5: cyclic separation II: supercritical CO2 is delivered to the autoclave for cyclic cleaning by means of the buffer kettle and the hydraulic pump until the autoclave is clean;
    • step 6: high-pressure saponification: a saponifying solution is pressurized and injected into the autoclave by the hydraulic pump, and then mixed and diluted with high-pressure fluid in the autoclave under the action of the stirrer of the autoclave; the autoclave is warmed up to the reaction temperature to saponify the surface of the workpiece; the saponifying solution undergoes a chemical reaction on the surface of the workpiece to form a saponified film; and after the reaction is completed, the fluid in the autoclave is discharged to the separation kettle to separate and collect residues obtained after saponification;
    • step 7: cyclic separation III: supercritical CO2 is delivered to the autoclave for cyclic cleaning by means of the buffer kettle and the hydraulic pump until the autoclave is clean; and
    • step 8: drying: the autoclave is opened for aeration drying.
  • A further improvement is that the carbon dioxide separated from the separation kettle in the step 5 and the step 7 is refrigerated, pressurized and then introduced to the autoclave for cyclic washing.
  • Compared with the prior art, the invention has the following beneficial effects: after the technical solution of the present application is employed, the solubility of oil stains, phosphoric acid, phosphate and sodium stearate can be changed by adjusting the temperature and pressure changes to achieve the purpose of cyclic separation and collection, the amount of acids, bases and industrial water used is greatly reduced, the chemical solution flows in a closed pipeline without volatilization and leakage, no sewage and waste liquid are discharged to the environment, good working conditions are provided, and production residues can be conveniently collected and treated without environmental pollution.
    • BRIEF DESCRIPTION OF THE DRAWINGS
    • Fig. 1 is a functional block diagram showing the steps of a method for zero-discharge phosphatization and saponification based on a high-pressure closed circulation system; and
    • Fig. 2 is a functional block diagram of the system for the method for zero-discharge phosphatization and saponification based on a high-pressure closed circulation system.
    DETAILED DESCRIPTION OF THE INVENTION
  • A preferred embodiment of the invention will be further described below with reference to the drawings.
  • As shown in Figs. 1 and 2, a method for zero-discharge phosphatization and saponification based on a high-pressure closed circulation system comprises an autoclave, a separation kettle, a buffer kettle, a hydraulic pump and a recovery vat. The method comprises the following steps:
    • step 1: a workpiece is fed into the autoclave and then sealed such that the pressure range of the autoclave is above 20 MPa;
    • step 2: degreasing and derusting by CO2: carbon dioxide is buffered by the buffer kettle and then delivered to the autoclave by the hydraulic pump, and then the workpiece is derusted and degreased by spraying a high-pressure carbon dioxide gas stream via a Venturi nozzle in the autoclave; wherein, in this step, mainly the kinetic energy and momentum of the generated carbon dioxide "snow" (containing small particles of dry ice) are used for derusting, and the chemical dissolution action of the carbon dioxide "snow" is used for degreasing; and then supercritical carbon dioxide fluid is introduced, and the dissolution and scouring actions of the supercritical fluid allow oil stains and solid particles in the container to be discharged to the separation kettle for separation and collection;
    • step 3: cyclic separation: supercritical CO2 is delivered to the autoclave for cyclic cleaning by means of the buffer kettle and the hydraulic pump until the autoclave is clean, and oil stains and solid residues are pushed into the separation kettle by the supercritical CO2;
    • step 4: high-pressure phosphatization: a phosphatizing solution is pressurized and injected into the autoclave by the hydraulic pump, and then mixed and diluted with high-pressure fluid in the autoclave under the action of a stirrer of the autoclave; the autoclave is warmed up to the reaction temperature to phosphatize the surface of the workpiece; the phosphatizing solution undergoes a chemical reaction on the surface of the workpiece to form a phosphatized film; and after the reaction is completed, the fluid in the autoclave is discharged to the separation kettle to separate and collect residues obtained after phosphatization;
    • step 5: cyclic separation II: supercritical CO2 is delivered to the autoclave for cyclic cleaning by means of the buffer kettle and the hydraulic pump until the autoclave is clean; and the carbon dioxide separated from the separation kettle is refrigerated, pressurized and then introduced to the autoclave for cyclic washing;
    • step 6: high-pressure saponification: a saponifying solution is pressurized and injected into the autoclave by the hydraulic pump, and then mixed and diluted with high-pressure fluid in the autoclave under the action of the stirrer of the autoclave; the autoclave is warmed up to the reaction temperature to saponify the surface of the workpiece; the saponifying solution undergoes a chemical reaction on the surface of the workpiece to form a saponified film; and after the reaction is completed, the fluid in the autoclave is discharged to the separation kettle to separate and collect residues obtained after saponification;
    • step 7: cyclic separation III: supercritical CO2 is delivered to the autoclave for cyclic cleaning by means of the buffer kettle and the hydraulic pump until the autoclave is clean; and the carbon dioxide separated from the separation kettle is refrigerated, pressurized and then introduced to the autoclave for cyclic washing; and
    • step 8: drying: the autoclave is opened for aeration drying.

Claims (2)

  1. A method for zero-discharge phosphatization and saponification based on a high-pressure closed circulation system, comprising an autoclave, a separation kettle, a buffer kettle, a hydraulic pump and a recovery vat; the method comprising the following steps:
    step 1: a workpiece is fed into the autoclave and then sealed such that the pressure range of the autoclave is above 20 MPa;
    step 2: degreasing and derusting by CO2: carbon dioxide is buffered by the buffer kettle and then delivered to the autoclave by the hydraulic pump, and then the workpiece is derusted and degreased by spraying a high-pressure carbon dioxide gas stream via a Venturi nozzle in the autoclave;
    step 3: cyclic separation: supercritical CO2 is delivered to the autoclave for cyclic cleaning by means of the buffer kettle and the hydraulic pump until the autoclave is clean, and oil stains and solid residues are pushed into the separation kettle by the supercritical CO2;
    step 4: high-pressure phosphatization: a phosphatizing solution is pressurized and injected into the autoclave by the hydraulic pump, and then mixed and diluted with high-pressure fluid in the autoclave under the action of a stirrer of the autoclave; the autoclave is warmed up to the reaction temperature to phosphatize the surface of the workpiece; the phosphatizing solution undergoes a chemical reaction on the surface of the workpiece to form a phosphatized film; and after the reaction is completed, the fluid in the autoclave is discharged to the separation kettle to separate and collect residues obtained after phosphatization;
    step 5: cyclic separation II: supercritical CO2 is delivered to the autoclave for cyclic cleaning by means of the buffer kettle and the hydraulic pump until the autoclave is clean;
    step 6: high-pressure saponification: a saponifying solution is pressurized and injected into the autoclave by the hydraulic pump, and then mixed and diluted with high-pressure fluid in the autoclave under the action of the stirrer of the autoclave; the autoclave is warmed up to the reaction temperature to saponify the surface of the workpiece; the saponifying solution undergoes a chemical reaction on the surface of the workpiece to form a saponified film; and after the reaction is completed, the fluid in the autoclave is discharged to the separation kettle to separate and collect residues obtained after saponification;
    step 7: cyclic separation III: supercritical CO2 is delivered to the autoclave for cyclic cleaning by means of the buffer kettle and the hydraulic pump until the autoclave is clean; and
    step 8: drying: the autoclave is opened for aeration drying.
  2. The method for zero-discharge phosphatization and saponification based on a high-pressure closed circulation system according to claim 1, wherein the carbon dioxide separated from the separation kettle in the step 5 and the step 7 is refrigerated, pressurized and then introduced to the autoclave for cyclic washing.
EP18187806.7A 2018-07-02 2018-08-07 Method for zero-discharge phosphatization and saponification based on high-pressure closed circulation system Active EP3591091B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810709238.XA CN108754479B (en) 2018-07-02 2018-07-02 Zero-emission phosphating and saponification method based on high-pressure closed circulation system

Publications (2)

Publication Number Publication Date
EP3591091A1 EP3591091A1 (en) 2020-01-08
EP3591091B1 true EP3591091B1 (en) 2021-07-21

Family

ID=63975326

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18187806.7A Active EP3591091B1 (en) 2018-07-02 2018-08-07 Method for zero-discharge phosphatization and saponification based on high-pressure closed circulation system

Country Status (3)

Country Link
EP (1) EP3591091B1 (en)
CN (1) CN108754479B (en)
TW (1) TWI668328B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111089454B (en) * 2019-12-27 2022-02-11 科源动力科技有限公司 Working medium pump drying method in ORC low-temperature waste heat power generation equipment
DE102022108314A1 (en) * 2022-04-06 2023-10-12 Ecoclean Gmbh Method for passivating a surface of a workpiece and device for passivating workpieces
WO2023219827A2 (en) * 2022-05-10 2023-11-16 Henrici Gerald Apparatus and method of orifice inspection and carbon dioxide cleaning thereof

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5339844A (en) * 1992-08-10 1994-08-23 Hughes Aircraft Company Low cost equipment for cleaning using liquefiable gases
JPH0780772A (en) * 1993-09-16 1995-03-28 Nippon Steel Corp Surface treatment method of steel and its device
TW508375B (en) * 1998-09-08 2002-11-01 Nihon Parkerizing Alkaline degreasing liquid formetallic material and the method of using the same
CN1155736C (en) * 2000-08-02 2004-06-30 暨南大学 Phosphonating liquid for cold deformation of iron and steel and its phosphonation process
US6793793B2 (en) * 2000-08-24 2004-09-21 Hideo Yoshida Electrochemical treating method such as electroplating and electrochemical reaction device therefor
CN105299335A (en) * 2014-07-31 2016-02-03 上海天阳钢管有限公司 Manufacturing method of carbon steel stainless steel double-metal polymerization pipe
CN105603415A (en) * 2014-11-19 2016-05-25 重庆江东摩托车配件有限公司 Saponification process
CN105695980A (en) * 2014-11-28 2016-06-22 重庆基石机械有限公司 Steel wire surface treatment process
CN105018920B (en) * 2015-08-04 2018-03-09 常熟市金华机械股份有限公司 A kind of phospholeum metaplasia production. art
CN105908208B (en) * 2016-03-28 2018-04-10 绵阳维克切削液有限责任公司 A kind of cold rolled silicon steel normal temperature zero-emission degreaser and preparation method thereof
CN105665469B (en) * 2016-03-30 2018-06-22 江门市蓬江区永华金属线材厂 A kind of pickling-free derusting phosphating continuous wire drawing equipment and its wire drawing production method
CN106216955B (en) * 2016-08-18 2018-01-23 无锡苏嘉法斯特汽车零配件有限公司 special steel transmission shaft tube manufacturing process

Also Published As

Publication number Publication date
EP3591091A1 (en) 2020-01-08
CN108754479B (en) 2020-04-21
TWI668328B (en) 2019-08-11
CN108754479A (en) 2018-11-06
TW202006185A (en) 2020-02-01

Similar Documents

Publication Publication Date Title
EP3591091B1 (en) Method for zero-discharge phosphatization and saponification based on high-pressure closed circulation system
CN104451727B (en) Anti-rusting agent
CN101654785A (en) Steel surface compact oxide layer scavenging agent
CN104005038A (en) Pretreatment method in aluminum alloy surface treatment and alkaline etching solution adopted by same
CN104609088B (en) A kind of manufacture method of the well for storage device storing special gas
CN104674263A (en) Metal surface cleaning method
CN106119869A (en) A kind of High Efficiency Rust Remover
CN101294287A (en) Formula and technique for neutral rust remover for rust cleaning of sheet material
CN111822464B (en) Membrane cleaning system for preferential organic matter permeation of oil tank truck and operation process
RU2691363C2 (en) Method and system for processing stainless steel strip, primarily for etching
CN102134723A (en) Neutral oil removing and rust removing agent
CN103422051A (en) Method of removing copper-nickel/aluminum-graphite composite seal coating material
CN101328587A (en) Hydraulic tubing three-in-one acid cleaning process
CN103726042A (en) Treating agent for cleaning and performing coating conversion and rust prevention on inner wall of nuclear power plant used 559 ton acrylic acid reactor
CN204097570U (en) Spray overflow pickling machine
CN110639896A (en) Method for cleaning surface of steel pipe before corrosion prevention
CN105755491A (en) Neutral agent for removing oil and rust
CN105713753A (en) Hydrocarbon cleaning agent for cleaning and separating water-soluble cutting fluid
CN109957809A (en) The method of the fungi-proofing antirust inhibition of oil pipeline inner wall
CN104498968A (en) Efficient rust remover
CN104233338A (en) Neutral deoiling rust remover
CN114392570A (en) Cutting fluid oil atomization microwave plasma treatment device and treatment process thereof
CN102978597A (en) Spraying type comprehensive phosphate treating agent for cold-rolled sheet workpiece spraying coating and preparation method of spraying type comprehensive phosphate treating agent
CN110857473B (en) Safe, environment-friendly and zero-emission metal continuous oil removing method and device
CN103074636A (en) Zero-emission cleaning agent (HW and HM series) for metal surface derusting, descaling, phosphorization, passivation, and antioxidation anticorrosion-Hansy ecological cycle method Steps 2-6

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200330

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

RIC1 Information provided on ipc code assigned before grant

Ipc: C23G 5/00 20060101ALI20201217BHEP

Ipc: C23C 22/73 20060101ALI20201217BHEP

Ipc: C23C 22/83 20060101ALI20201217BHEP

Ipc: C23C 22/00 20060101AFI20201217BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20210210

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018020314

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1412692

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210815

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210721

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1412692

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210721

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211021

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211021

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211122

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211022

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018020314

Country of ref document: DE

Ref country code: BE

Ref legal event code: MM

Effective date: 20210831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210831

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210831

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210807

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

26N No opposition filed

Effective date: 20220422

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210807

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210831

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20220803

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20220808

Year of fee payment: 5

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20220807

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20180807

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220807

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602018020314

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230831

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721