WO2016209093A1 - Procédé de séparation de chrome à partir de déchets de tannage - Google Patents

Procédé de séparation de chrome à partir de déchets de tannage Download PDF

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Publication number
WO2016209093A1
WO2016209093A1 PCT/PL2015/000099 PL2015000099W WO2016209093A1 WO 2016209093 A1 WO2016209093 A1 WO 2016209093A1 PL 2015000099 W PL2015000099 W PL 2015000099W WO 2016209093 A1 WO2016209093 A1 WO 2016209093A1
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WO
WIPO (PCT)
Prior art keywords
chromium
acid
insoluble
organic acids
salts
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Ceased
Application number
PCT/PL2015/000099
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English (en)
Inventor
Piotr Grzybowski
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23 Rs Coras Sp ZOO
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23 Rs Coras Sp ZOO
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 23 Rs Coras Sp ZOO filed Critical 23 Rs Coras Sp ZOO
Publication of WO2016209093A1 publication Critical patent/WO2016209093A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the subject of the invention relates to a method for Cr 3+ separation from sewage, in particular tanning sewage.
  • the chromium Cr 3+ salts are commonly used in leather tanning.
  • the tanning process involves cross-linking of collagen proteins comprising the main ingredients of animal skin using chromium ions, leading to the formation of extremely strong bonds.
  • the leather becomes resistant to moisture as well as to action of bacteria and fungi.
  • Salts of metals other than chromium are also used, but leather tanned using the chromium techniques are of very high quality and, nowadays, it is the dominating tanning technology. While soaking leather in tanning worts, as well as during leather cutting or thinning, sewage and wastes containing chromium are generated. Chromium is a heavy metal causing intoxication if consumed in its ionic form, and even deaths in higher amounts.
  • Chromium ions penetrating into the environment become gradually oxidised to their Cr 6+ form, in which they additionally show carcinogenic properties. Chrome elimination from tanning waste and sewage is thus very important both from the point of view of environment and from the point of view of health.
  • chromium is expensive and its recovery from waste has an additional, economic aspect. Returning chromium separated from wastes back to the production cycle seems to be the most proper approach. Theoretically, separation of chromium seems to be very simple, since when warm, chromium in its Cr 3+ form forms its completely insoluble hydroxide Cr(OH) 3 that can be separated from the waste stream. Unfortunately, such hydroxide obtained from aqueous solutions forms strongly hydrated flocks forming compressible precipitates.
  • PL171 170 discloses a method of chromium(III) regeneration from used tanning solutions including subjecting chromium(III) compounds contained in used tanning solution to adsorption on a waste protein bed, preferably on a bed containing cuttings of chromium leathers, activated by treatment with alkaline substances, preferably lime, sodium carbonate of magnesium oxide, with the activation of protein bed and chromium compounds adsorption is performed at least twice, and chromium(III) is recovered as salts by treating the bed with acid, preferably with sulphuric acid.
  • Polish patent application P.299475 discloses a binding technology of post- neutralisation, high chromium content galvanic wastes, wherein ingredients of such wastes, hazardous to the environment, are permanently bound within ceramic products. In result such waste can be utilised in construction ceramics.
  • the utilisation method includes decreasing of chromium content achieved by appropriate mixing of high chromium content precipitates with wastes having different characteristics and by permanent chromium binding within a ceramic product by performing the sintering in reducing atmosphere and in that the chromium, calcium and alkali contents are lowered thanks to the use of appropriate raw materials, mixing of post-neutralisation wastes having various compositions in order to achieve proper balance between the metals, and finally, by optional addition of lead-containing compounds leading to chromate binding in the form of extremely insoluble compounds, followed by waste biding within a ceramic product.
  • Polish patent application P.307908 discloses a method wherein radioactive chromate waste is reduced with sugar, followed by neutralisation of sulphuric acid using sodium lye. Thus obtained solution, continuously mixed, is introduced into cement and the entire material hardens in a metal container.
  • US4340571 Al discloses a method of chromium recovery after tanning procedure. Chromium is recovered from the ash obtained after combustion of industrial wastes, in which chromium is substantially present in its hexavalent form only.
  • the disclosed method includes stages of ash mixing with sulphuric acid and water in order to obtain a suspension of ash in the acid; addition of a reducing agent to the suspension in order to transform the hexavalent chromium into trivalent chromium; filtration of the suspension and of the mixture of reducing agent in order to obtain the extraction solution of trivalent chromium and residues; washing the residues with water in order to remove residues of the extraction solution and to obtain an aqueous solution containing the recovered chromium.
  • US4483829 discloses a method of chromium recovery from tanning products, in which waste products from leather tanning using chromium are washed and then ground down in water, followed by hydrolysis at pH of at least 10.5, at the boiling point or at a temperature close to the boiling point.
  • the obtained suspension is filtered and a polypeptyde solution is obtained together with a cake containing solids, substantially containing chromium hydroxide.
  • the solution is neutralised, water is evaporated, the solution is cooled and filtrated in order to obtain substantially chromium- free protein material which can be used as feed for animals or as a plant fertiliser; solids are washed, filtrated and acidified obtaining chromium sulphate which may be re-used at the tanning factory.
  • US4569830 provides a method of trivalent chromium salts recovery from water obtained during leather tanning using so called "chromium" system, including stages in which all trivalent chromium salts in the form of chromium hydroxide are flocculated by treating them with an aqueous solution containing 15 to 30% (weight) of a salt obtained from a weak acid and a strong base, with pH of 6.9 to 7.2 at a temperature of 22°C to 26°C, followed by separation of thus obtained chromium hydrate from the aqueous dispersion by concentrating the dispersion in a device designed for purification and flocculation, followed by concentrate filtration until a precipitate containing ca. 20 %wt. of dry mass is obtained. Then, the precipitate is dissolved in sulphuric acid, at pH of 1.8 to 2 and at temperature over 50°C, preferably at 70°C.
  • the invention also presents an installation enabling implementation of said method.
  • the subject of the invention is a method of Cr 3+ isolation from sewage, including tanning sewage, by precipitating thereof as an insoluble salt with selected organic acids.
  • organic acids insoluble in water are used, more preferably organic acids are used, of which sodium, potassium and ammonium salts are soluble in water, said acids are selected from the group including terephthalic acid, salicylic acid, benzoic acid, stearic acid, palmitic acid, sebacic acid, azelaic acid and mono- or polycarboxylic aliphatic and/or aromatic acids.
  • a preferred embodiment of the method includes filtration, sedimentation and/or centrifugation of insoluble, crystalline chromium salts of organic acids.
  • chromium from insoluble, crystalline chromium salts of organic acids is recovered by treating chromium salts with mineral acid solutions, preferably with sulphuric acid.
  • the process includes pH adjustment of wastes, aimed at maintaining a pH value of 7 or lower, followed by introduction of soluble salts of appropriate organic acids to such wastes.
  • a double exchange reaction yields insoluble salts of chromium and organic acids which are very easy to filtrate and enable chromium separation from waste using this method.
  • Collected precipitates of chromium salts of some organic acids are then regenerated.
  • the regeneration includes treatment with aqueous solution of a mineral acid, e.g. sulphuric acid.
  • the reaction enables recovery of the organic acid in the form insoluble in water, and of a soluble chromium salt, e.g. chromium sulphate.
  • the chromium salt in aqueous solution can be easily isolated from the precipitate of the organic acid, and its solution after concentration may be used for separation of pure chromium salt.
  • This precipitate floated in the post-reaction mixture comprising an aqueous solution of amino acids and oligomers from collagen decomposition with the mixer running and precipitated on the bottom of the reactor when the mixer was switched off. Then, 250 kg of 20% H 2 S0 4 solution was added to the reactor, resulting in dissolution of the chromium hydroxide precipitate. Thus obtained solution was filtered through a cloth filter, removing all insoluble contaminations present in the processed waste, such as mineral particles as e.g. sand. 850 kg 20% of aqueous solution of disodium terephtalate was added to the clear, post-reaction solution. An exchange reaction yielded an insoluble salt of terephthalic acid and chromium(III).
  • Crystals of this salt were easily filtrated in a filter-press, and the filtration cake obtained was washed with hot water, removing residues of protein hydrolysate solution.
  • the precipitate of the salt of terephthalic acid and chromium was then washed using 430 dm J of 20% aqueous solution of sulphuric acid which washed chromium from its salt with terephthalic acid, leaving a precipitate of insoluble terephthalic acid on the filter. Then the precipitate was washed with a small amount of water in order to remove as much chromium(III) sulphate solution as possible, combining the washings with the previously collected solution.
  • Regeneration of the solution of sodium terephthalate included washing the terephthalic acid cake with 785 kg of warm water containing 65 kg NaOH.
  • the obtained solution of chromium(III) sulphate was concentrated and 218 kg of crystalline chromium sulphate Cr 2 (S0 4 )3 ⁇ 12 H 2 0 was obtained.
  • “Wet blue” tanning waste was used in a similar amount, and was subjected to hydrolysis as described in Example 1.
  • 150 kg of terephthalic acid was added to the reactor containing the post-reaction mixture comprising aqueous solution of collagen protein hydrolysis products and suspension of chromium(III) hydroxide.
  • the mixture was heated up to nearly 100°C and mixed for period of 3 hours.
  • the suspension was pumped to the filter-press and filtered.
  • the filtrate comprised an aqueous solution of protein hydrolysate.
  • the precipitate contained the chromium salt of terephthalic acid and the unreacted excess of terephthalic acid.
  • the filtration cake contained all contaminations present in the starting binarywet-blue" waste.
  • the filtration cake was washed with hot water to remove remaining of the hydrolysate solutions.
  • 430 dm 3 of 20% aqueous solution of sulphuric acid was passed through the filtration cake, wherein said sulphuric acid washed chromium from its salt with terephthalic acid, leaving a precipitate of insoluble terephthalic acid on the filter.
  • the precipitate was washed with hot water, and the washings were added to the previously obtained salt solution.
  • the recovered precipitate of terephthalic acid was ready to be used in the next batch.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Removal Of Specific Substances (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Abstract

La présente invention concerne un procédé de séparation de chrome à partir d'eaux usées, notamment d'eaux usées de tannage, suite à une réaction de double échange produisant des sels insolubles de chrome et d'acides organiques qui sont très faciles à filtrer et permettent une séparation de chrome à partir de déchets au moyen de ce procédé. Les précipités collectés de sels de chrome de certains acides organiques sont ensuite régénérés.
PCT/PL2015/000099 2015-06-23 2015-06-29 Procédé de séparation de chrome à partir de déchets de tannage Ceased WO2016209093A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PLP.412821 2015-06-23
PL412821A PL412821A1 (pl) 2015-06-23 2015-06-23 Sposób wydzielania chromu z odpadów garbarskich

Publications (1)

Publication Number Publication Date
WO2016209093A1 true WO2016209093A1 (fr) 2016-12-29

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PCT/PL2015/000099 Ceased WO2016209093A1 (fr) 2015-06-23 2015-06-29 Procédé de séparation de chrome à partir de déchets de tannage

Country Status (2)

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PL (1) PL412821A1 (fr)
WO (1) WO2016209093A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113788635A (zh) * 2021-10-09 2021-12-14 湖南先锋防水科技有限公司 一种不带入污染性铬元素的通用水泥生产方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4337227A (en) * 1981-09-10 1982-06-29 The United States Of America As Represented By The Secretary Of The Interior Recovery of chromium from waste solutions
US4340571A (en) 1978-06-19 1982-07-20 Saco Tanning Division Of Kirstein Leather Co. Process for chrome recovery from industrial waste and the like, as from chrome-ladened tannery waste
US4483829A (en) 1982-02-02 1984-11-20 Giuliano Guardini Process for recovering proteins and chromium from chrome-tanning waste
US4569830A (en) 1982-12-30 1986-02-11 Giovanni Tibaldi Method and plant to recover chromium salts from tannery reflux water
PL299475A1 (en) 1993-06-25 1994-12-27 Envira Przed Utylizacji Odpado Process for utilizing electroplating plant wastes of high chromium content
PL307908A1 (en) 1995-03-28 1995-09-18 Inst Energii Atomowej Method of neutralising the radioactive waste chromic acid cleaning mixture

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4340571A (en) 1978-06-19 1982-07-20 Saco Tanning Division Of Kirstein Leather Co. Process for chrome recovery from industrial waste and the like, as from chrome-ladened tannery waste
US4337227A (en) * 1981-09-10 1982-06-29 The United States Of America As Represented By The Secretary Of The Interior Recovery of chromium from waste solutions
US4483829A (en) 1982-02-02 1984-11-20 Giuliano Guardini Process for recovering proteins and chromium from chrome-tanning waste
US4569830A (en) 1982-12-30 1986-02-11 Giovanni Tibaldi Method and plant to recover chromium salts from tannery reflux water
PL299475A1 (en) 1993-06-25 1994-12-27 Envira Przed Utylizacji Odpado Process for utilizing electroplating plant wastes of high chromium content
PL307908A1 (en) 1995-03-28 1995-09-18 Inst Energii Atomowej Method of neutralising the radioactive waste chromic acid cleaning mixture

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113788635A (zh) * 2021-10-09 2021-12-14 湖南先锋防水科技有限公司 一种不带入污染性铬元素的通用水泥生产方法
CN113788635B (zh) * 2021-10-09 2022-08-16 贵州德隆水泥有限公司 一种不带入污染性铬元素的通用水泥生产方法

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