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EP4453101A1 - Procédé de production de pigments d'oxyde de fer - Google Patents

Procédé de production de pigments d'oxyde de fer

Info

Publication number
EP4453101A1
EP4453101A1 EP22843204.3A EP22843204A EP4453101A1 EP 4453101 A1 EP4453101 A1 EP 4453101A1 EP 22843204 A EP22843204 A EP 22843204A EP 4453101 A1 EP4453101 A1 EP 4453101A1
Authority
EP
European Patent Office
Prior art keywords
solution
iron
iron oxide
oxygen
production according
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.)
Pending
Application number
EP22843204.3A
Other languages
German (de)
English (en)
Inventor
Norbert Etzenbach
Matthias BOERS
Stefan RIDDER
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.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
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 Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP4453101A1 publication Critical patent/EP4453101A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/22—Compounds of iron
    • C09C1/24—Oxides of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide [Fe2O3]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)

Definitions

  • the present invention relates to a method for producing iron oxide pigments according to the Penniman process, characterized in that there is no separate nucleus production step, and to the use of such iron oxide pigments.
  • Iron oxide color pigments which are used as ecologically harmless colorants in ceramics, building materials, plastics, paints and paper, can basically be obtained in black, yellow, red, orange and brown shades.
  • Iron oxide pigments are obtained, as described in Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim 1992, Vol. A20, p. 298ff, by solid phase reactions (red, brown and black pigments), precipitation and hydrolysis reactions of iron salts (yellow, red, orange and black pigments) and by oxidation of iron with aromatic nitro compounds in the presence of hydrolyzable, polyvalent salts, the so-called Laux process, as disclosed, for example, in DE 4 63 773 A1 and DE 5 15 758 A1.
  • the solid-phase reactions are mainly used for the production of red iron oxides from black precursors (by calcination) or from FeSO4 (Copperas process).
  • the Laux process starts with nitrobenzene and Fe metal and leads first to iron oxide black or iron oxide yellow and aniline.
  • iron oxide black obtained is burned.
  • the process is technically complex and not easy to master, since variable proportions of control chemicals have to be used to set the desired particle size.
  • the required apparatus technology is demanding and correspondingly expensive.
  • the reaction produces aniline as a second product, which, due to its properties, requires special industrial hygiene measures.
  • Yellow, orange, red and black iron oxide pigments can be produced via the precipitation process (US Pat. No. 2,388,659 A1 for iron oxide yellow pigments and US Pat. No. 5,421,878 A1 for iron oxide red using a direct precipitation process).
  • Iron oxide pigments obtained via the precipitation process are produced from iron salt solutions and alkaline compounds in the presence of air and have the disadvantage that stoichiometric amounts of neutral salts are generated, which must be discharged with the waste water or processed in a time-consuming and costly manner.
  • the direct precipitation method is technically difficult because a-Fe2C>3 is accessible only in a narrow range and the reaction is not easy to control.
  • the iron oxide red produced by the precipitation process has the disadvantage of high salt loads, which pollute the waste water and are therefore ecologically questionable. c) hydrothermal process
  • iron oxide red pigments are produced by dissolving and oxidizing iron metal with the addition of an iron oxide red nucleus.
  • nitric acid is generally used to produce nuclei, so that there are nitrates or ammonia in the waste water, which have to be removed at great expense in terms of process technology.
  • WO 2016/038152 A1 also discloses a Penniman process which requires a separate nucleus production step.
  • the nucleus in the form of a suspension of hematite nuclei with a particle size of 100 nm or less and a BET specific surface area of 40 m2/g to 150 m2/g is produced separately by reacting metallic iron, oxygen and nitric acid and then together with Iron, iron (II) nitrate solution and oxygen built up to the pigment.
  • the Penniman process reduces the amount of neutral salts formed during the precipitation process by using metallic iron as the raw material, which is dissolved by liberated acid during the process.
  • a cost-effective method is available for the direct production of iron oxide pigments.
  • a further advantage of the Penniman process is the production of pigments with favorable color tones with a low accumulation of neutral salts.
  • the disadvantage of the Penniman process is that it requires two process steps: 1) nucleation and 2) pigment build-up. This production is therefore operationally complex. Toxic nitrous gases are formed during the production of the germs, which must be processed. There are also residues to be landfilled and waste water containing heavy metals. The Penniman process is also time-consuming to achieve the desired shade. The setting of a specific color also requires constant, complex monitoring of the manufacturing process by trained employees.
  • the present invention was therefore based on the object of producing iron oxide pigments by means of a significantly simplified Penniman process. Furthermore, the invention was based on the object of minimizing or preventing the disadvantages associated with the nucleus production step, such as toxic nitrous gases and residue to be landfilled and waste water containing heavy metals.
  • this object was achieved in that the iron oxide pigment was produced according to the Penniman process without a separate nucleus production step.
  • the feature "separate seed production step” is preferably defined in such a way that the seed production step is carried out in such a way that the seed - usually in the form of a suspension - is present as a product, for example in a separate reactor or container, and only then as a reactant is used in the process according to the invention for the production of pigments.
  • the iron oxide pigment is preferably produced in such a way that a) a solution containing iron, iron(II) nitrate and water is initially taken; b) the solution is heated; c) oxygen-containing gases are added to the solution during and/or after the heating in order to obtain a pigment suspension; and d) the pigment suspension is then filtered, washed and/or dried.
  • the proportion of iron, based on the total volume of the solution, is preferably from 1 to 250 g/l, preferably from 40 to 85 g/l, very particularly preferably from 50 to 75 g/l.
  • the proportion of iron(II) nitrate, based on the total volume of the solution is preferably from 1 to 250 g/l, preferably from 40 to 50 g/l, very particularly preferably from 44 to 46 g/l.
  • the proportion of iron(II) nitrate, based on the total volume of the solution is particularly preferably 45 g/l.
  • the solution is preferably heated under atmospheric pressure to from 60 to 100°C, preferably from 70 to 95°C, most preferably from 84 to 86°C. Most preferably, the solution is heated to 85°C under atmospheric pressure.
  • the solution is preferably heated to from 50 to 250.degree. C., preferably from 100 to 200.degree.
  • oxygen-containing gases/l solution Preferably from 1 to 200 l/h of oxygen-containing gases/l solution, preferably from 10 to 40 l/h of oxygen-containing gases/l solution, very particularly preferably from 25 to 35 l/h of oxygen-containing gases/l solution, particularly preferably 30 l /h oxygen-containing gases/1 solution supplied.
  • Air is preferably used as the oxygen-containing gas.
  • the oxygen-containing gas is preferably fed in over a period of 5 to 150 hours, preferably over a period of 50 to 120 hours, very particularly preferably over a period of 65 to 75 hours.
  • the iron oxide pigment resulting from the process is preferably deagglomerated and/or ground and/or thermally treated.
  • an additive that promotes processability is preferably added to the pigment.
  • the invention also includes the use of the iron oxide pigment according to the invention for coloring lime and/or cement-bound building materials, asphalt, paints, lacquers, color gels, paper, plastics, food colorings and/or pharmaceutical products.
  • the iron oxide pigment is preferably mixed with the lime and/or cement-bound building materials, asphalt, paints, varnishes, color gels, paper, plastics, food colorings and/or pharmaceutical products.
  • the iron oxide pigment is preferably used as a technical oxide in the area of catalysts, abrasives, etc.
  • the solution containing iron, iron(II) nitrate and water was placed in the steel kettle. This solution was then heated. The heated solution was aerated with air for a specified time. This gassing of the solution was carried out until the pigment suspension reached the desired volume. The resulting pigment suspension was then filtered and the pigment filter cake thus obtained was washed with water, dried and ground.
  • the color of the pigments was evaluated in Alkydal L 64® thixotropic (non-hardening alkyd resin from Bayer AG) at a pigment volume concentration of 10%.
  • the reflectance values and CIELAB data were determined using a measuring device with an integrating sphere (illumination conditions d/8", standard illuminant CI2") including surface reflection.
  • the reflectance values obtained were converted to the CIELAB color data system in accordance with DIN 5033, Part 3.
  • a spectrophotometer (“color measuring device") with the measuring geometry d/8 without a gloss trap was used. This measuring geometry is described in ISO 7724/2-1984 (E), point 4.1.1, in DIN 5033 part 7 (July 1983), point 3.2.4 and in DIN 53236 (January 1983), point 7.1.1.
  • a DATAFLASH® 2000 measuring device (Datacolor International Corp., USA) was used.
  • the colorimeter was calibrated against a white ceramic working standard as described in ISO 7724/2-1984 (E) point 8.3.
  • the reflection data of the working standard against an ideally matt white body are stored in the colorimeter so that after calibration with the white working standard, all color measurements are related to the ideally matt white body.
  • the black point calibration was carried out with a black hollow body from the color measuring device manufacturer.
  • the result of the color measurement is a reflection spectrum.
  • colorimetric quantities it is irrelevant which type of light was used for the measurement (except for fluorescent samples). Any desired colorimetric variable can be calculated from the reflection spectrum.
  • the colorimetric quantities used in this case are calculated according to DIN 6174 (CIELAB values) calculated.
  • the color value "b*" is calculated according to DIN 6174. The following applies to the color impression: the more negative b* is, the more bluish the color pigment is.
  • the residual iron was determined after the reaction by weighing the unused iron after rinsing with water and drying at 80 °C in the circulating air drying cabinet.
  • the Fe determination was carried out by means of cerimetry under inert conditions. After digestion of 2 to 10 cm 3 (depending on the solids concentration) of the sample in 20 cm 3 water and 20 cm 3 hydrochloric acid (37%), the iron(II),(III) chloride solution thus obtained was 10 cm 3 Sulfuric acid (approx. 48.5% by weight) added, made up to 200 cm 3 with deionized water and titrated potentiometrically on an automatic titrator (Mettler Memotitrator DL70).
  • the iron(II) was oxidized to iron(III) with cerium(IV) sulfate solution.
  • iron(III) is reduced to iron(II) with a small excess of 7% titanium(III) chloride solution (approx. 7% in 10% HCl).
  • the total iron was titrated with cerium(IV) sulphate solution in a 2-step titration, whereby first the titanium(III) excess from the reduction to titanium(IV) and then the iron(II) to iron( III) has been oxidized. The titration results were then determined from the raw data and output by the automatic titrator.
  • Example 5 Running time 59 h VI.
  • Example 6 Running time 59 h
  • Table II Summary of the experimental conditions of the examples ZA space-time yield or the amount of substance/hematite produced in g/l/h.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Iron (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un procédé de production de pigments d'oxyde de fer selon le procédé Penniman, caractérisé en ce qu'aucune étape de nucléation séparée n'est effectuée, et l'utilisation de tels pigments d'oxyde de fer.
EP22843204.3A 2021-12-21 2022-12-20 Procédé de production de pigments d'oxyde de fer Pending EP4453101A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21216439.6A EP4201999A1 (fr) 2021-12-21 2021-12-21 Procédé de production de pigments d'oxyde de fer
PCT/EP2022/087051 WO2023118182A1 (fr) 2021-12-21 2022-12-20 Procédé de production de pigments d'oxyde de fer

Publications (1)

Publication Number Publication Date
EP4453101A1 true EP4453101A1 (fr) 2024-10-30

Family

ID=79018655

Family Applications (2)

Application Number Title Priority Date Filing Date
EP21216439.6A Withdrawn EP4201999A1 (fr) 2021-12-21 2021-12-21 Procédé de production de pigments d'oxyde de fer
EP22843204.3A Pending EP4453101A1 (fr) 2021-12-21 2022-12-20 Procédé de production de pigments d'oxyde de fer

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP21216439.6A Withdrawn EP4201999A1 (fr) 2021-12-21 2021-12-21 Procédé de production de pigments d'oxyde de fer

Country Status (7)

Country Link
US (1) US20250066612A1 (fr)
EP (2) EP4201999A1 (fr)
JP (1) JP2025500381A (fr)
CN (1) CN118414388A (fr)
AU (1) AU2022420735A1 (fr)
CO (1) CO2024008046A2 (fr)
WO (1) WO2023118182A1 (fr)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1327061A (en) 1917-06-20 1920-01-06 West Coast Kalsomine Company Process of manufacturing iron compounds
US1368748A (en) 1920-01-05 1921-02-15 Nat Ferrite Company Process of manufacturing iron compounds and product
DE463773C (de) 1925-05-09 1928-08-02 I G Farbenindustrie Akt Ges Verfahren zur Herstellung aromatischer Amine
DE515758C (de) 1925-08-21 1931-01-12 I G Farbenindustrie Akt Ges Verfahren zur Herstellung aromatischer Amine
US2388659A (en) 1943-07-12 1945-11-06 Interchem Corp Manufacture of pigments
US5421878A (en) 1992-10-23 1995-06-06 Bayer Ag Pure-colored iron oxide direct red pigments, a process for their production and their use
DE19917786A1 (de) 1999-04-20 2000-11-23 Bayer Ag Eisenoxidpigmente, Verfahren zu ihrer Herstellung sowie deren Verwendung
IN2014DN01801A (fr) * 2011-09-30 2015-05-15 Lanxess Deutschland Gmbh
JP6440830B2 (ja) * 2014-09-11 2018-12-19 ランクセス・ドイチュランド・ゲーエムベーハー 改良された色値を有する赤色酸化鉄顔料

Also Published As

Publication number Publication date
JP2025500381A (ja) 2025-01-09
EP4201999A1 (fr) 2023-06-28
CN118414388A (zh) 2024-07-30
US20250066612A1 (en) 2025-02-27
AU2022420735A1 (en) 2024-08-01
CO2024008046A2 (es) 2024-06-27
WO2023118182A1 (fr) 2023-06-29

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