US2639967A - Deliming hides with citric acid fermentation liquor - Google Patents

Deliming hides with citric acid fermentation liquor Download PDF

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Publication number
US2639967A
US2639967A US247370A US24737051A US2639967A US 2639967 A US2639967 A US 2639967A US 247370 A US247370 A US 247370A US 24737051 A US24737051 A US 24737051A US 2639967 A US2639967 A US 2639967A
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US
United States
Prior art keywords
citric acid
deliming
acid
hides
fermentation
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 - Lifetime
Application number
US247370A
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English (en)
Inventor
Rudy Hermann
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.)
Joh A Benckiser GmbH
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Joh A Benckiser GmbH
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Filing date
Publication date
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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
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S435/00—Chemistry: molecular biology and microbiology
    • Y10S435/8215—Microorganisms
    • Y10S435/911—Microorganisms using fungi
    • Y10S435/913—Aspergillus
    • Y10S435/917—Aspergillus niger

Definitions

  • This invention relates to a process for removing lime and other alkalies, such as sodium sulfide, and to deliming baths and deliming compositions useful therein. More particularly the application relates to deliming processes, deliming baths and deliming compositions utilizing unrefined citric acid.
  • Ammonium salt deliming agents have also been suggested for deliming hides and skins including ammonium salts of inorganic and organic acids, such for example, as ammonium sulfate, ammo nium lactate, ammonium tartrate, ammonium citrate, and the like.
  • ammonium salts of inorganic and organic acids such for example, as ammonium sulfate, ammo nium lactate, ammonium tartrate, ammonium citrate, and the like.
  • ammonium salts of inorganic and organic acids such for example, as ammonium sulfate, ammo nium lactate, ammonium tartrate, ammonium citrate, and the like.
  • unrefined citric acid produced by fermentation of carbohydrates is to be understood to mean the fermentation liquor produced in the Well known citric acid fermentation process or compositions containing the active ingredients of such liquor.
  • This liquor is also identified by the term citric acid fermentation liquor. It consists of the unrefined citric acid produced by the well known fermentation process and the liquid medium, or citric acid waste fermentation liquor in which the citric acid has been produced by such a process.
  • the advantages of the present invention are due, in part at least, to the fact that the citric acid fermentation liquor has a combined deliming and antiswelling effect.
  • the citric acid fermentation liquor has a combined deliming and antiswelling effect.
  • it is not necessary to neutralize the citric acid content of the citric acid fermentation liquor only a very small quantity of the liquor per unit of dry material is required.
  • a deliming bath will require only about 1.5% of the citric acid fermentation liquor although concentrations of the order of 0.3% to 2. may be used in such baths.
  • equivalent quantities of concentrated citric acid fermentation liquor may be used instead of the citric acid fermentation liquor produced in the fermentation process.
  • the citric acid fermentation liquor is mixed with additional Waste fermentation liquors remaining after the citric acid content has been removed from the unrefined fermentation liquor.
  • the added waste fermentation liquors serve not only to dilute the citric acid fermentation liquor but to exert a further complementary action when used in deliming baths.
  • Such waste liquors. may be obtained advantageously by precipitating the citric acid content of a citric acid fermentation liquor as calcium citrate, and then separating the precipitate from the mother liquor thereby leaving the waste fermentation liquor.
  • the fermentation liquor present with produced citric acid, or remaining after the separation of the citric acid content or compositions containing the active ingredients thereof, are referred to herein as citric acid waste fermentation liquor.
  • the deliming baths having appropriate strength of unrefined citric acid for deliming purposes may be obtained by diluting the unrefined acid entirely with Waste fermentation liquors or by diluting it partially with waste fermentation liquors and partially with conventional" dil'u-nts such as water.
  • deliming compositions by diluting and complementing the unrefined citric acid with liquors obtained after the separation of tartaric acid or salts of tartaric acid from their unrefined solutions during the refining process.
  • Tartaric acid may be separated from wine lees, for example, by converting tartaric acid or salts thereof to calcium tartrate, dissociating the calcium tartrate into tartaric acid, and recovering the tartaric acid by crystallization.
  • Such liquors left after the recovery of tartaric acid or compositions containing the active ingredients thereof are called herein tartaric acid waste liquors.
  • the unrefined citric acid may bediluted to a strength suitable for deliming purposes by adding citric acid waste fermentation liquors in combination with citric or tartaric acid waste liquors.
  • the deliming bath is diluted with either of these waste liquors, and especially when mixed with both types of waste liquors, the deliming composition exerts both a delir'ning'and bating effect.
  • the unrefined citric acid of this invention may be used, if desired, conjointly with other organic acid deliming agents, for example, lactic acid, acetic acid, tartaric acid, or with deliming ammonium salts, such as ammonium sulfate, ammonium tartrate, ammonium lactate, and ammonium citrate, or with deliming polymeric polyphosphates and the like.
  • organic acid deliming agents for example, lactic acid, acetic acid, tartaric acid, or with deliming ammonium salts, such as ammonium sulfate, ammonium tartrate, ammonium lactate, and ammonium citrate, or with deliming polymeric polyphosphates and the like.
  • the separation of the active deliming components in accordance with prior art practice, may involve, for example, (1) the production of the calcium salt (2) the decomposition of the calcium salt by sulfuric acid and (3) crystallization and separation of the pure acid.
  • the fermentation liquors including the citric acid
  • the reaction of the unrefined citric acid with calcium compoundsas in deliming would result in the formation of a very slightly soluble precipitate '4 which would be formed in the hide, resulting in leather damage, as is true when such salts are formed in tanning operations.
  • This surprising result may be attributed to unknown attributes of the fermentation liquors associated with the citric acid.
  • Example 1 Goat skins were soaked and washed in a cask for ashort time after liming. The goat skins were then introduced into a deliming bath containing1.5% of an unrefined citric acid.
  • the unrefined citric acid constituted a fermented liquor containing 15% citric acid. Deliming took place very quickly. The pelts had an especially smooth feel, and the glazed kid made therefrom had an especially fine grain.
  • Example 2 A calf skin limed and washed as usual was introduced into a solution containing 10 grams of unrefined citric acid and 3 grams of ammonium sulfate per liter and it was delimed in the solution until a sample of the pelt was free of lime. The process took nearly an hour. Then the skin was bated and worked up to box calf in the usual manner. The resulting leather showed an especially fine and smooth grain.
  • Example 3 An unrefined citric acid was produced by fermenting a carbohydrate with Aspergillus niger and 10 parts thereof were diluted with parts of citric acid waste fermentation liquors obtained in the production of refined citric acid. The resulting solution formed a superior deliming bath for cow hides being processed for sole leather. During the deliming operation additional unrefined citric acid was added to maintain its concentration in the bath at about 2%.
  • a process for deliming hides and skins which comprises contacting the hides in the limed condition with a solution containing approximately 0.3% to 2.0% of citric acid fermentation liquor.
  • a process for deliming hides and skins which comprises contacting the hides in the limed condition with a solution containing approximately 0.3% to 2.0% of citric acid fermentation liquor for a period of the order of one hour.
  • a process for deliming hides and skins which comprises contacting the hides in the limed condition with a solution containing approximately 0.3% to 2.0% of citric acid fermentation liquor produced by the fermentation of molasses, said liquor containing about 15% of citric acid.
  • a process for deliming hides and skins which comprises contacting the hides in the limed condition with a solution containing approximately 0.3% to 2.0%01? a commercial citricacid fermen 6 tation liquor and a lesser quantity of ammonium Number Name Date sulfate. 1,772,258 Le Petit Aug. 5, 1930 HERMANN RUDY. 2,132,579 Rohm Oct. 11, 1938 References Cited in the file of this patent 5 N b EOREIGl: PATENTS t um er Coun ry Da.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
US247370A 1950-04-07 1951-09-19 Deliming hides with citric acid fermentation liquor Expired - Lifetime US2639967A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEC793A DE925605C (de) 1950-04-07 1950-04-07 Entkaelkungsmittel

Publications (1)

Publication Number Publication Date
US2639967A true US2639967A (en) 1953-05-26

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US247370A Expired - Lifetime US2639967A (en) 1950-04-07 1951-09-19 Deliming hides with citric acid fermentation liquor

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US (1) US2639967A (zh)
BE (1) BE505164A (zh)
DE (1) DE925605C (zh)
DK (1) DK80394C (zh)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4213760A (en) * 1978-06-08 1980-07-22 Basf Aktiengesellschaft Deliming of hides
US4221564A (en) * 1978-05-20 1980-09-09 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Water-insoluble alkali metal aluminosilicates and polycarboxylic acids in the tanning process for the production of leather
US4229175A (en) * 1977-04-02 1980-10-21 Basf Aktiengesellschaft Lime-free and sulfide-free liming process
CN111842310A (zh) * 2020-07-22 2020-10-30 浙江农林大学 一种生物质梯级脱灰预处理的方法
WO2022124892A1 (en) * 2020-12-09 2022-06-16 Stahl International B.V. Process for deliming of hides, skins or pelts

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US223200A (en) * 1879-12-30 Improvement in processes of tanning
US515033A (en) * 1894-02-20 Carl wehmer
US873074A (en) * 1905-09-16 1907-12-10 Nowak Mfg Company Substance for treating hides and process of making same.
US996509A (en) * 1905-06-14 1911-06-27 Dermiforma Company Of America Tanning process.
US1570383A (en) * 1925-07-22 1926-01-19 Mccandlish Douglas Treatment of hides and skins for manufacture into leather
GB266414A (en) * 1925-10-26 1927-02-28 Auguste Fernbach Improvements in and relating to processes for the production of citric acid
US1679186A (en) * 1923-12-19 1928-07-31 Montan Und Industrialwerke Vor Process for producing citric acid by means of fermentation
US1772258A (en) * 1925-04-18 1930-08-05 Rohm & Haas Process for unhairing and preparing hides for tanning
US2132579A (en) * 1935-04-02 1938-10-11 Rohm Otto Method for producing unhaired hides with the aid of mold tryptases

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE268236C (zh) *
FR360854A (fr) * 1905-12-22 1906-05-05 Ottokar Henry Nowak Substance pour le tannage des peaux et le mordancage des tissus
GB409599A (en) * 1933-11-03 1934-05-03 Filippo Perciabosco A process for the purging of skins and hides in tanning

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US223200A (en) * 1879-12-30 Improvement in processes of tanning
US515033A (en) * 1894-02-20 Carl wehmer
US996509A (en) * 1905-06-14 1911-06-27 Dermiforma Company Of America Tanning process.
US873074A (en) * 1905-09-16 1907-12-10 Nowak Mfg Company Substance for treating hides and process of making same.
US1679186A (en) * 1923-12-19 1928-07-31 Montan Und Industrialwerke Vor Process for producing citric acid by means of fermentation
US1772258A (en) * 1925-04-18 1930-08-05 Rohm & Haas Process for unhairing and preparing hides for tanning
US1570383A (en) * 1925-07-22 1926-01-19 Mccandlish Douglas Treatment of hides and skins for manufacture into leather
GB266414A (en) * 1925-10-26 1927-02-28 Auguste Fernbach Improvements in and relating to processes for the production of citric acid
US2132579A (en) * 1935-04-02 1938-10-11 Rohm Otto Method for producing unhaired hides with the aid of mold tryptases

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4229175A (en) * 1977-04-02 1980-10-21 Basf Aktiengesellschaft Lime-free and sulfide-free liming process
US4221564A (en) * 1978-05-20 1980-09-09 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Water-insoluble alkali metal aluminosilicates and polycarboxylic acids in the tanning process for the production of leather
US4213760A (en) * 1978-06-08 1980-07-22 Basf Aktiengesellschaft Deliming of hides
CN111842310A (zh) * 2020-07-22 2020-10-30 浙江农林大学 一种生物质梯级脱灰预处理的方法
CN111842310B (zh) * 2020-07-22 2021-11-30 浙江农林大学 一种生物质梯级脱灰预处理的方法
WO2022124892A1 (en) * 2020-12-09 2022-06-16 Stahl International B.V. Process for deliming of hides, skins or pelts
NL2027083B1 (en) * 2020-12-09 2022-07-07 Stahl Int B V Process for deliming of hides, skins or pelts

Also Published As

Publication number Publication date
BE505164A (zh) 1952-12-19
DK80394C (da) 1956-01-09
DE925605C (de) 1955-03-24

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