EP0015478B2 - Tannins au chrome stables au vieillissement - Google Patents
Tannins au chrome stables au vieillissement Download PDFInfo
- Publication number
- EP0015478B2 EP0015478B2 EP80100936A EP80100936A EP0015478B2 EP 0015478 B2 EP0015478 B2 EP 0015478B2 EP 80100936 A EP80100936 A EP 80100936A EP 80100936 A EP80100936 A EP 80100936A EP 0015478 B2 EP0015478 B2 EP 0015478B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- mol
- tanning agents
- formic acid
- chrome tanning
- dried
- 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.)
- Expired
Links
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 14
- 230000032683 aging Effects 0.000 title description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims 4
- 229910021653 sulphate ion Inorganic materials 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 40
- 239000011651 chromium Substances 0.000 description 35
- 235000019253 formic acid Nutrition 0.000 description 21
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 18
- 229910052804 chromium Inorganic materials 0.000 description 13
- 229940044170 formate Drugs 0.000 description 9
- 239000007921 spray Substances 0.000 description 8
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 7
- 239000010985 leather Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 101100348017 Drosophila melanogaster Nazo gene Proteins 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical class [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 210000004197 pelvis Anatomy 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010633 broth Nutrition 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004674 formic acids Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
- C14C3/06—Mineral tanning using chromium compounds
Definitions
- the present invention relates in particular to age-resistant chrome tanning agents, the solubility of which is retained in water even over a long period of time.
- Tanning agents of this type are characterized by a mild tanning effect and good colorability of the leather produced with them. They are easily soluble in water, but lose this property when stored for a long time. This is disadvantageous for practical use, since chrome tanning agents are generally added to the tanning drums in powder form without prior dissolution. Tannins of the type mentioned which have been stored for a long time then dissolve too slowly or only incompletely in the time available for tanning. This can result in delayed tanning or the formation of spots due to undissolved tanning agent particles on the tanned leather, and the commercial value of the leather is thereby reduced.
- powdery chrome tanning agents with a formate content of 1.8-2.6 mol / mol Cr 2 0 3 and a basicity of at least 42%, preferably about 50%, which, before drying, have a sulfate content of at least 1, 8 moles of SO 3 / Cr 2 O 3 have been adjusted and then spray-dried, and their solubility is maintained even after prolonged storage.
- the present invention therefore relates to age-resistant spray-dried chrome tanning agents with a formate content of about 1.8-2.6 mol Cr 2 0 3 and a basicity of at least 42%, which are characterized in that they are spray-dried to a sulfate content of at least 1 , 8 mol S0 3 / mol Cr 2 O 3 can be set.
- the known powdery chrome tanning agents mentioned at the outset with a formate content of about 2 mol / mol Cr 2 0 3 and a basicity of about 50% have only a sulfate content of about 1.6 mol SO 3 / mol Cr 2 0 3 .
- the products according to the claims are produced by processes known per se (cf., for example, Ullmann, Enz. Der Techn. Chemie, 4th edition 1975, vol. 9, pp. 614-615).
- the known chrome tanning agents with a formate content of about 2 mol formate / mol Cr 2 0 3 with a sulfate content of about 1.6 mol SO 3 / mol Cr 2 O 3 can be spray dried to a sulfate content of at least 1.8 mol SO Adjust 3 / MolCr 2 O 3 and then spray dry.
- the tanning properties of the tanning agents according to the invention do not differ from those of the known formate-masked tanning agents with a lower sulfate content. Accordingly, the tanning agents according to the invention can be used in a customary manner.
- the tanning agents according to the invention can be used as such, or else in a mixture with base agents, such as magnesium oxide, sodium hydrogen carbonate or dolomite or / and with other masking agents, such as, for. B. salts of dicarboxylic acids.
- the chrome tanning agents according to the invention are particularly suitable for a tanning process in which very good exhaustion of the chrome broths is achieved by pretanning the pickled pelts with chromium (III) salts and tanning with chromium (III) salts and acid-binding agents.
- the total amount of chromium oxide offered is about 1.0 to 1.8%, based on the pelvis weight, and the tanning is at a fleet length ⁇ 100% (again based on pelvis weight) and up to a final pH of ⁇ 3 , 6 performed.
- Powdery chrome tanning agents which are particularly valuable in the practice of leather production and have a particularly long shelf life with regard to solubility in water contain about 1.8-2.4 mol of formate / mol of Cr 2 O and 1.8-2.8 mol of S0 3 / mol of Cr 2 0 3 with a basicity of 48-52%.
- the present invention is to be explained in more detail with the aid of the following examples.
- the percentages for the compositions relate to% by weight.
- 5000 kg of chromium sulfate liquor containing 11% Cr 2 O 3, 14.4% SO 3 , 11.2% NazO and 6.8% formic acid are dried in a spray dryer at an inlet temperature of 200 ° C. and an outlet temperature of 90 ° C.
- the dried product contains 21.5% Cr 2 O 3 , 13.3% formic acid (2.0 mol formic acids / mol Crz0 3 ) and 2.5 mol SO 3 / mol Cr 2 O 3 with a basicity of 50%.
- the undissolved residue is 0% when tested immediately and 0.1% after 30 days of rapid aging.
- the rapid aging and the examination of the release are carried out as described below.
- the dried product is stored under lock and key in a drying cabinet at 50 ° C. for a period of 30 days.
- 20 g of the fresh or the so aged product are mixed with 200 ml of water and dissolved for 1 hour at room temperature with shaking Then the residue is determined by weight by filtering through a suction filter.
- chromium sulfate liquor containing 13% Cr 2 0 3 , 12.6% SO 3 , 6.4% NazO and 8.7% formic acid are dried in a spray dryer at an inlet temperature of 190 ° C. and an outlet temperature of 120 ° C.
- the dried product contains 28% Cr 2 O 3 , 18.7% formic acid (2.2 mol formic acid / mol Cr 2 0 3 ) and 1.85 mol SO 3 / mol Cr 2 0 3 with a basicity of 50%.
- the undissolved residue is 0% when checked immediately and 2% after 30 days of rapid aging.
- chromium sulfate liquor with a content of 11.1% Cr 2 0 3 , 12.2% S0 3 , 8.2% Na 2 O and 7.3% formic acid are in a spray dryer at 190 ° C inlet and 110 ° C outlet temperature dried.
- the dried product contains 24.4% Cr 2 O 3 , 16% formic acid (2.2 mol formic acid / mol Cr 2 0 3 ) and 2.4 mol SO 3 / mol Crz0 3 with a basicity of 50%.
- the undissolved residue is 0% when tested immediately and 0.3% after 30 days of rapid aging.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19792908967 DE2908967A1 (de) | 1979-03-07 | 1979-03-07 | Alterungsbestaendige chromgerbstoffe |
DE2908967 | 1979-03-07 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0015478A1 EP0015478A1 (fr) | 1980-09-17 |
EP0015478B1 EP0015478B1 (fr) | 1981-09-16 |
EP0015478B2 true EP0015478B2 (fr) | 1985-07-31 |
Family
ID=6064761
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80100936A Expired EP0015478B2 (fr) | 1979-03-07 | 1980-02-26 | Tannins au chrome stables au vieillissement |
Country Status (12)
Country | Link |
---|---|
US (1) | US4298344A (fr) |
EP (1) | EP0015478B2 (fr) |
JP (1) | JPS6017400B2 (fr) |
AR (1) | AR219218A1 (fr) |
BR (1) | BR8001342A (fr) |
CA (1) | CA1131409A (fr) |
DE (2) | DE2908967A1 (fr) |
ES (1) | ES489246A1 (fr) |
MX (1) | MX155156A (fr) |
NZ (1) | NZ193032A (fr) |
YU (1) | YU65180A (fr) |
ZA (1) | ZA801325B (fr) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57100200A (en) * | 1980-12-15 | 1982-06-22 | Nippon Chemical Ind | Manufacture of chromium tanning agent |
DE3306374A1 (de) * | 1983-02-24 | 1984-08-30 | Basf Ag, 6700 Ludwigshafen | Verfahren zum gerben von haeuten mit einem hochbasischen chromgerbstoff |
FR2721619B1 (fr) * | 1994-06-22 | 1996-08-23 | Toulouse Inst Nat Polytech | Produit de masquage pour sels métalliques à propriétés tannantes tels que sels de chrome, et procédé de tannage de peaux en milieu aqueux. |
KR970010423B1 (ko) * | 1995-09-19 | 1997-06-26 | 엘지전자 주식회사 | 식기세척기의 오물 처리방법 및 그 장치 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1230170B (de) * | 1960-10-28 | 1966-12-08 | Bayer Ag | Gerbverfahren |
FR1304531A (fr) * | 1961-10-26 | 1962-09-21 | Bayer Ag | Procédé de fabrication de cuir |
-
1979
- 1979-03-07 DE DE19792908967 patent/DE2908967A1/de not_active Withdrawn
-
1980
- 1980-02-15 US US06/121,863 patent/US4298344A/en not_active Expired - Lifetime
- 1980-02-26 EP EP80100936A patent/EP0015478B2/fr not_active Expired
- 1980-02-26 DE DE8080100936T patent/DE3060022D1/de not_active Expired
- 1980-03-04 NZ NZ193032A patent/NZ193032A/xx unknown
- 1980-03-05 JP JP55026813A patent/JPS6017400B2/ja not_active Expired
- 1980-03-05 CA CA347,016A patent/CA1131409A/fr not_active Expired
- 1980-03-05 MX MX181442A patent/MX155156A/es unknown
- 1980-03-06 ZA ZA00801325A patent/ZA801325B/xx unknown
- 1980-03-06 BR BR8001342A patent/BR8001342A/pt not_active IP Right Cessation
- 1980-03-06 ES ES489246A patent/ES489246A1/es not_active Expired
- 1980-03-07 YU YU00651/80A patent/YU65180A/xx unknown
- 1980-03-07 AR AR280216A patent/AR219218A1/es active
Also Published As
Publication number | Publication date |
---|---|
MX155156A (es) | 1988-02-01 |
EP0015478B1 (fr) | 1981-09-16 |
AR219218A1 (es) | 1980-07-31 |
DE2908967A1 (de) | 1980-09-18 |
JPS6017400B2 (ja) | 1985-05-02 |
NZ193032A (en) | 1982-03-16 |
YU65180A (en) | 1983-01-21 |
BR8001342A (pt) | 1980-11-04 |
ES489246A1 (es) | 1980-08-16 |
JPS55120699A (en) | 1980-09-17 |
CA1131409A (fr) | 1982-09-14 |
DE3060022D1 (en) | 1981-12-03 |
EP0015478A1 (fr) | 1980-09-17 |
US4298344A (en) | 1981-11-03 |
ZA801325B (en) | 1981-04-29 |
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