WO2021074904A1 - Procédé de régénération d'eaux mères de décapage d'acide chlorhydrique - Google Patents
Procédé de régénération d'eaux mères de décapage d'acide chlorhydrique Download PDFInfo
- Publication number
- WO2021074904A1 WO2021074904A1 PCT/IB2020/059809 IB2020059809W WO2021074904A1 WO 2021074904 A1 WO2021074904 A1 WO 2021074904A1 IB 2020059809 W IB2020059809 W IB 2020059809W WO 2021074904 A1 WO2021074904 A1 WO 2021074904A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrochloric acid
- solution
- pickling
- regenerated
- pickling tank
- Prior art date
Links
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 238000000034 method Methods 0.000 title claims abstract description 46
- 235000021110 pickles Nutrition 0.000 title description 19
- 230000008929 regeneration Effects 0.000 title description 9
- 238000011069 regeneration method Methods 0.000 title description 9
- 238000005554 pickling Methods 0.000 claims abstract description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 21
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 21
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 19
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 19
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 13
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 238000004064 recycling Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 description 15
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 229960002089 ferrous chloride Drugs 0.000 description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 5
- 230000001172 regenerating effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 4
- 239000010953 base metal Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- -1 ferrous metals Chemical class 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910000677 High-carbon steel Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011785 micronutrient Substances 0.000 description 1
- 235000013369 micronutrients Nutrition 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
-
- 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
- C23G1/08—Iron or steel
-
- 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
- C23G1/36—Regeneration of waste pickling liquors
Definitions
- THIS invention relates to a pickling process, and in particular to regenerating spent pickling liquors.
- the process of pickling is a metal surface treatment used to remove impurities, such as stains, inorganic contaminants, rust or scale from ferrous metals, copper, and aluminum alloys.
- a solution called pickle liquor, which contains strong acids, is used to remove the surface impurities. It is commonly used to de-scale or clean steel in various steelmaking and steel processing processes.
- Acid reacts with the oxides and base metal to produce dissolved metal salts, thereby neutralizing the acid.
- Speed is an important requirement for integration in automatic steel mills that run production at high speed; speeds as high as 800 ft/min ( « 243 metres/min) have been reported.
- the pickling process generates a considerable quantity of spent pickle liquor (SPL) containing the dissolved metal salts as well as residual free acid (a weak ferrous chloride solution). This SPL must be disposed of by chemical neutralization with alkali or regenerated.
- SPL spent pickle liquor
- hydrochloric acid offers a number of potential advantages over sulfuric acid, including the following:
- Iron concentrations can be as high as 13%.
- Metals other than iron such as zinc, lead or chromium present in the SPL interfere with the regeneration process and may cause the SPL to be rejected by processors.
- the acid retardation ion exchange process can be used to reduce the acidity of the liquid ferrous chloride byproduct.
- a pickling process including the steps of:
- the solution is typically cooled to -1 °C to -15°C, -5°C to -15°C typically -10°C to -15°C.
- the dosing of sulphuric acid is preferably in molar proportion to the ferric chloride in the solution, at a molar ratio of 1 :1.
- the hydrochloric acid pickling liquor solution at Step 1 typically has an ambient temperature.
- the solution comprising hydrochloric acid containing ferric chloride (FeCh) removed from the pickling tank at step 2), and the regenerated hydrochloric acid solution recycled to the pickling tank at step 6) are passed through a cross-flow heat exchanger, for the solution comprising hydrochloric acid containing ferric chloride (FeCh) to heat the regenerated hydrochloric acid solution.
- Figure 1 is a flow diagram of a process of the present invention.
- Figure 2 is a graph showing a comparison of concentration of hydrochloric acid between the current method of regenerating SPL, and the process of the present invention.
- the present invention provides a process for the regeneration of spent pickle liquor that can be carried out on-site where the pickling process takes place.
- costs would be reduced as equipment on site would reduce down time, service costs would be less and product quality would be more consistent.
- the equipment may be containerized utilizing technology that operates by exploiting a double decomposition technique with additional technology to create an iron sulphate hepta-hydrate by-product and regenerated hydrochloric acid.
- the sulfuric acid reacts with the ferrous chloride according to equation (1 ) thereby liberating free hydrochloric acid in solution.
- the mixed acid is then cooled to below the freezing point of water, causing crystallization of ferrous sulphate hepta-hydrate.
- the drop in temperature converts crystallized ferrous sulphate mono-hydrate to crystallized ferrous sulphate hepta- hydrate.
- the mother liquor, now fortified with hydrochloric acid, but containing a residual of sulfuric acid is then separated from the crystals and recycled to the pickling process.
- the level of residual sulphuric acid in the regenerated hydrochloric acid is dependent on the concentration of iron and the temperature. This is controlled by computer to ensure that the dosing of sulphuric acid is in proportion to the iron content and the temperatures are controlled.
- the process according to the invention may be known as the NUgen process (Trade Mark).
- the ferrous sulphate hepta-hydrate is a readily marketable material. There are a number of markets for this material including water treatment coagulants as well as sewage de-odorization, animal feed soil micro-nutrients, catalyst manufacture, iron oxide pigments, magnetic oxides, heavy metal stabilization, cyanide destruction, arsenic stabilization and chrome control in cement.
- the process is more forgiving towards contamination with other metals such as zinc.
- steel (not shown) is continuously fed through a pickling line 10 including at least one pickling tank 11 initially containing 18wt% hydrochloric acid pickling solution.
- the picking tank may hold from 7,000 to 25,000 litres of pickling solution.
- Ferrous metal is submerged in the pickling tank 11 for a period of 10 to 40 mins.
- the hydrochloric acid reacts with the oxides and base metal to produce dissolved metal salts, thereby neutralizing the hydochloric acid.
- Solution 12 comprising hydrochloric acid containing ferric chloride (FeCh) is removed from the pickling tank 11 and regenerated hydrochloric acid/regenerated pickle liquor (RPL) 16 is recycled to the pickling tank to maintain the concentration of hydrochloric acid in the pickling tank 11 in the range of 15 to 16wt% and maintaining the concentrion of iron at about 10wt%.
- Solution 12 typically containing about about 10wt% iron (in the form of dissolved ferrous chloride) and 15 to 16wt% hydrochloric acid is withdrawn from the pickling tank 11 .
- the temperature of the exiting solution 12 is at ambient for a continuous pickle line but may be less for a batch pickling operation.
- the solution 12 is introduced to a cross-flow heat exchanger 14. The solution 12 exchanges heat with a regenerated pickle liquor (RPL) solution 16 returning to the pickling tank 11 in the pickling line.
- the acid solution to be regenerated 18 then flows into a reactor 20 where it is contacted with 98wt% sulphuric acid (H 2 SO 4 ) 22, thereby initiating Reaction (1 ) and obtaining a reaction mix 24 containg HCI and ferrous sulphate (FeSC ).
- the final temperature reduction is accomplished by chilling the reaction mix 24 to temperatures of -15 to -1 °C in a crystallizer tank 26 which is cooled by a chiller 28. This temperature reduction reduces the solubility of ferrous sulphate, causing it to precipitate out of solution, leaving behind the hydrogen ions from the sulphuric acid and the chloride ions from the ferrous chloride.
- ferrous sulphate drops out as the hepta-hydrate salt (FeS0 4 .7H 2 0) which is a coarse crystalline material 30, easily separated from the mother liquor by vacuum filtration 32.
- a small amount of water is used to wash the residual mother liquor from the crystals to provide a ferrous sulphate product 34. This water compensates for the water of hydration that is combined with the ferrous sulfate.
- Regenerated pickle liquor (RPL) 36 comprising hydrochloric acid with a concentration in the range of 15 to 18wt% flows to the heat exchanger 14 where it is heated, and heated regenerated pickle liquor (RPL) 16 is returned to pickling tank 11 .
- Figure 2 is a graph showing a comparison of concentration of hydrochloric acid between the current method of regenerating SPL, and the process of the present invention.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
La présente invention concerne un procédé de décapage conduit dans une cuve de décapage (11). Une solution de décapage comprenant de l'acide chlorhydrique contenant du chlorure ferrique est retirée de la cuve de décapage (11), de l'acide chlorhydrique est ajouté à la cuve de décapage. La solution prélevée (12) est traitée avec de l'acide sulfurique (22) pour obtenir une solution (24) comprenant de l'acide chlorhydrique régénéré contenant du sulfate ferreux ; de façon à obtenir un produit précipité de sulfate ferreux (34) ; et la solution d'acide chlorhydrique régénérée (16) est recyclée dans la cuve de décapage (11).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA2022/05500A ZA202205500B (en) | 2019-10-18 | 2022-05-18 | Process for the regeneration of hydrochloric acid pickle liquors |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA2019/06867 | 2019-10-18 | ||
| ZA201906867 | 2019-10-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2021074904A1 true WO2021074904A1 (fr) | 2021-04-22 |
Family
ID=75538061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2020/059809 WO2021074904A1 (fr) | 2019-10-18 | 2020-10-19 | Procédé de régénération d'eaux mères de décapage d'acide chlorhydrique |
Country Status (2)
| Country | Link |
|---|---|
| WO (1) | WO2021074904A1 (fr) |
| ZA (1) | ZA202205500B (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117735762A (zh) * | 2023-12-22 | 2024-03-22 | 连云港太平洋金沙石英有限公司 | 一种光伏用石英砂酸洗液的回收装置与方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001049901A1 (fr) * | 2000-01-05 | 2001-07-12 | United States Filter Corporation | Regeneration de liqueur de decapage usee |
| US7097816B2 (en) * | 2004-06-22 | 2006-08-29 | Alexander Kehrmann | Method of producing ferrous sulfate heptahydrate |
| US7351391B1 (en) * | 2000-12-19 | 2008-04-01 | Olsen Douglas R | System and method for converting the spent remnants of a first pickling acid solution into a usable second pickling acid solution |
-
2020
- 2020-10-19 WO PCT/IB2020/059809 patent/WO2021074904A1/fr active Application Filing
-
2022
- 2022-05-18 ZA ZA2022/05500A patent/ZA202205500B/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001049901A1 (fr) * | 2000-01-05 | 2001-07-12 | United States Filter Corporation | Regeneration de liqueur de decapage usee |
| US7351391B1 (en) * | 2000-12-19 | 2008-04-01 | Olsen Douglas R | System and method for converting the spent remnants of a first pickling acid solution into a usable second pickling acid solution |
| US7097816B2 (en) * | 2004-06-22 | 2006-08-29 | Alexander Kehrmann | Method of producing ferrous sulfate heptahydrate |
Non-Patent Citations (2)
| Title |
|---|
| BROWN ET AL.: "Regeneration of hydrochloric acid pickle liquors by crystallization", 31 January 2015 (2015-01-31), pages 831 - 843, XP055819189, Retrieved from the Internet <URL:https://www.researchgate.net/publication/267304672> [retrieved on 20201208] * |
| DEVI ANURADHA, SINGHAL ANUPAM, GUPTA RAJIV: "A review on spent pickling liquor", INTERNATIONAL JOURNAL OF ENVIRONMENTAL SCIENCES, vol. 4, no. 3, 2013, pages 284 - 295, XP055819192 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117735762A (zh) * | 2023-12-22 | 2024-03-22 | 连云港太平洋金沙石英有限公司 | 一种光伏用石英砂酸洗液的回收装置与方法 |
| CN117735762B (zh) * | 2023-12-22 | 2024-05-24 | 连云港太平洋金沙石英有限公司 | 一种光伏用石英砂酸洗液的回收装置与方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA202205500B (en) | 2024-06-26 |
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