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US2532308A - Process of recovering copper oxide and a d-tartrate from a spinning solution - Google Patents

Process of recovering copper oxide and a d-tartrate from a spinning solution Download PDF

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Publication number
US2532308A
US2532308A US689150A US68915046A US2532308A US 2532308 A US2532308 A US 2532308A US 689150 A US689150 A US 689150A US 68915046 A US68915046 A US 68915046A US 2532308 A US2532308 A US 2532308A
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US
United States
Prior art keywords
copper
acid
tartrate
solution
slurry
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
US689150A
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English (en)
Inventor
Hofmann Hugo
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.)
Beaunit Mills Inc
Original Assignee
Beaunit Mills Inc
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
Priority to NL69975D priority Critical patent/NL69975C/xx
Priority to BE475206D priority patent/BE475206A/xx
Application filed by Beaunit Mills Inc filed Critical Beaunit Mills Inc
Priority to US689150A priority patent/US2532308A/en
Priority to GB20833/47A priority patent/GB647350A/en
Priority to ES0179244A priority patent/ES179244A1/es
Priority to CH274800D priority patent/CH274800A/fr
Priority to DEB11754A priority patent/DE966600C/de
Application granted granted Critical
Publication of US2532308A publication Critical patent/US2532308A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
    • D01F2/04—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts from cuprammonium solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/14—Complexes with ammonia
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives

Definitions

  • the present invention relates to a process of simultaneously recovering copper and tartaric acid in the form of salts from waste solutions formed during the manufacture of cuprammonium cellulose products, such as filaments, yarns, foils, films, etc.
  • One object of. this invention is the simultaneous recovery of copper salts and salts of tartaric acid in such a manner that the recovered chemicals can be used, in the production of cuprammonium cellulose spinning solutions.
  • Another object of the present invention is a process of simultaneously recovering copper oxide and tartrates of dextro (d-) tartaric acid in a facile and economical manner.
  • cuprammonium cellulose spinning solutions are extruded through the orifices of spinnerets mounted in funnels into substantially neutral water circulating therein.
  • Such spinning processes are disclosed in U. S. Patents Nos. 1,828,497; 1,867,297; 1,871,704; 1,947,159 and 2,036,089.
  • my invention is not limited to this type of spinning since it can be used in the simultaneous recovcry of copper salts and salts of tartaric acid from any other waste solution containing the same.
  • it is necessary to add one or more stabilizing agents to the spinning solution for example, tartaric acid which forms a tartrate therein.
  • Tartaric acid occurs in four distinct modifications, namely: (1) dor dextrotartaric acid, (2) lor laevo-tartaric acid, (3) d-l or racemic tartaric acid and (4) ior inactive (meso-) tartaric acid.
  • dor dextrotartaric acid (2) lor laevo-tartaric acid, (3) d-l or racemic tartaric acid and (4) ior inactive (meso-) tartaric acid.
  • 1-, d-l, and itartaric acids are operative when added to cuprammonium cellulose solutions, nevertheless it has been found by exhaustive experimentation 2 Claims. (o1. 1ot 1s7) that dextro- (d-) tartaric acid offers outstanding advantages as an addition agent to such spinning solutions.
  • the invention is illustrated in the flow sheet constituting the single figure in the drawing.
  • the alkaline water leaving the spinning funnels contains one or more copper salts apparently in com; bination with ammonia, a salt of tartaric acid and hydroxyl ions originating from the cupram monium' cellulose spinning solution, and it is called bluewater in the art.
  • This blue water? i together with waste copper solutions for example, waste spinning solutions, 2 and other alkaline wastes herein referred to as alkaline waste waters form sources of the alkaline solutions used in the present recovery process. All of these waste copper solutions contain copper salts and tartrates.
  • cuprammonium cellulose solution 23 is extruded through the orifices of spinnerets into a plurality of funnels 28 to form a plurality of thread bundles 38 which are treated with, a dilute acid solution, for example sulphuric acid 3!.
  • This acid hardens the still plastic threads and removes substantial amounts of copper salts and tartrate ions therefrom.
  • This dilute acid solution is usually recirculated in order to maintain a substantially constant amount of copper and acid ions therein. A portion of this acid solution is removed from the circulating system. It is called waste acid overflow 3 and forms one source of the waste acid solutions used in this process.
  • the treated thread bundles containing a plurality of filaments are wound in package or skein form 32 and treated with a dilute acid solution, for example sulphuric acid, 33, to remove more copper and 'tartrate ions therefrom before being Washed with water,
  • a dilute acid solution for example sulphuric acid
  • skein wash solutions 4 Water running off from the packages orskeins called skein wash solutions 4, constitutes an other source of the waste acid solutions.
  • suitable amounts of blue water I, waste copper solutions, 2, waste acid overflow 3 and skein wash solutions 4 are mixed at about room temperature (15-30 C.) and a pH of about 6.4 to 7.8. This results in the precipitation of a slurry 5 containing copper and tartrate ions.
  • the slurry is allowed to settle, and the solution overflow, containing soluble am.- monium salts, 6, is removed therefrom.
  • the aforesaid overflow may be used in the recovery of ammonia therefrom.
  • the slurry 5 is pumped into another settling tank 1 for further concentration.
  • Overflow solution ,8 is run off from tank I, and chemicals may be recovered therefrom.
  • the concentrated slurry is pumped into a re.- action vessel 9 and treated therein with caustic at an elevated temperature and a pH of about 10.5 to 11.0 to convert it into copper oxide while preserving the tartrate ions.
  • Overflow solution I3 is removed, and chemicals may be recovered from this solution by suitable means.
  • the copper oxide slurry I2 is removed vfrom vessel 9 to vessel 14 and converted therein by means of a suitable acid I5, preferably sulphuric acid, with heat 15, into a copper salt solution which contains also tartaric acid. Copper sulphate crystals 18 and tartaric acid I9 may be added to the solution to bring it to a proper copper and tartaric acid content.
  • a soluble alkali for example, soda ash NazCOs 2
  • the copper salt solution IT in vessel 20 in an amount suflicient to precipitate the copper in the form of a basic copper salt, for example basic copper sulphate 20, and at the same time the tartaric acid in the solution is converted into a salt of tartaric acid.
  • the precipitate is then decanted 22 preferably several times to remove soluble salts therefrom, and it may then be used in conventional manner in the production of cuprammonium cellulose solutions suitable for spinning.
  • Such spinning solutions contain generally 6-9% cellulose, 4.8% ammonia and'25% copper.
  • such solutions should contain for the aforesaid reason also about 0.2-1.0 part of tartaric acid, preferably d-tartaric acid, calculated on the cellulose content'of the spinning solution.
  • the mixing process was controlled by'pH recordinginstrumenta'and a constant level of 1iq-. Hid was maintained in the mixing tank.
  • a slurry was formed evidently comprising a mixture of cupric hydroxide, basic copper sulphate'and com!- plex copper tartrates.
  • the mixture of slurry and solution was pumped into several basins in which the slurry was allowed to settle.
  • the overflow (48.5 liters/min.) containing 0.023 gram of copper per liter was allowed to escape.
  • the precipitated slurry containing about 3.6 grams of copper per liter, was pumped at the rate of '7 liters per minute from the bottom of the basin into another settling basin where it was further concentrated.
  • the overflow (1 liter/min.) containing 0.023 gram of copper per liter was allowed to run off.
  • the concentrated slurry containing about 4.2 grams of copper per liter, was pumped into a reaction vessel at the rate of 6 liters per minute into which a sufficient amount of a sodium hydroxide solution grs. NaOH/liter of water) was introduced together with open steam. Steam was used to heat the mixture for reasons of economy.
  • the reaction vessel may be heated of course by other means to maintain the reacting temperature of about 60'75 C.
  • the pH of the mixture was maintained between 10.5 and 11.0.
  • a compact copper oxide was formed, which was pumped from the bottom of the reaction vessel into several settling basins.
  • the overflow (6.9 liters/min.) containing 0.025 gram of copper per liter was run off.
  • the compact copper oxide contained about 55% of the original tartrate used in the spinning solution.
  • 77.8 kilograms of the compact copper oxide, 50.9 kilo.- grams of CuSO45H2O and 270 liters of a sulphuric acid solution (521 grams of H2804 per liter of water) were mixed together with vigorous stirring at boiling temperature to form a copper sulphate solution. After cooling d-tartaric acid was added to compensate for the amount lost in the recovery process.
  • Example II Blue water having the composition set forth in Example I, was mixed with a lime solution containing about 0.6 gram of calcium. Rate of flow of blue water was 21 liters per minute, and the lime solution flowed at a rate of 0.2 liter per minute to maintain a pH of about 10 to 10.5. The reaction was carried out at temperatures ranging from about 15'to 30 C. The reaction mixture was run into a settling tower, and a slurry was precipitated containing about 2.0 grams of copper per liter. This slurry was pumped at a rate of about 0.9 liter per minute into a reaction vessel together with the slurry obtained in accordance with the process set forth in Example I. The oxide was then worked up as set forth above. This modification allowed the working up of excess blue water obtained during spinning.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Removal Of Specific Substances (AREA)
  • Paper (AREA)
US689150A 1946-08-08 1946-08-08 Process of recovering copper oxide and a d-tartrate from a spinning solution Expired - Lifetime US2532308A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL69975D NL69975C (fr) 1946-08-08
BE475206D BE475206A (fr) 1946-08-08
US689150A US2532308A (en) 1946-08-08 1946-08-08 Process of recovering copper oxide and a d-tartrate from a spinning solution
GB20833/47A GB647350A (en) 1946-08-08 1947-07-31 Recovery of salts of copper and tartaric acid from waste cuprammonium cellulose solutions
ES0179244A ES179244A1 (es) 1946-08-08 1947-08-06 UN MÉTODO QUiMICO DE RECUPERACIoN
CH274800D CH274800A (fr) 1946-08-08 1947-08-07 Procédé de fabrication d'articles en cellulose régénérée, par extrusion d'une solution cupro-ammoniacale de cellulose contenant des ions tartriques.
DEB11754A DE966600C (de) 1946-08-08 1950-10-03 Verfahren zur gleichzeitigen Rueckgewinnung von Kupfer- und Weinsaeuresalzen aus Abfallfluessigkeiten, die sich bei der Erzeugung von Celluloseprodukten aus Kupferoxydammoniakcelluloseloesungen ansammeln

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US689150A US2532308A (en) 1946-08-08 1946-08-08 Process of recovering copper oxide and a d-tartrate from a spinning solution

Publications (1)

Publication Number Publication Date
US2532308A true US2532308A (en) 1950-12-05

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Family Applications (1)

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US689150A Expired - Lifetime US2532308A (en) 1946-08-08 1946-08-08 Process of recovering copper oxide and a d-tartrate from a spinning solution

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US (1) US2532308A (fr)
BE (1) BE475206A (fr)
CH (1) CH274800A (fr)
DE (1) DE966600C (fr)
ES (1) ES179244A1 (fr)
GB (1) GB647350A (fr)
NL (1) NL69975C (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2666688A (en) * 1951-05-05 1954-01-19 Copper Res Method of making stable cupric hydroxide
US2904399A (en) * 1954-10-09 1959-09-15 Bemberg Ag Recovery of copper and ammonia from waste liquors from the manufacture of regenerated cellulose
US3017506A (en) * 1959-01-07 1962-01-16 Sylvania Electric Prod Selective signal eliminator
US3301542A (en) * 1963-12-04 1967-01-31 Western Electric Co System for treating acidic etching solutions
CN102286798A (zh) * 2010-06-17 2011-12-21 罗莱家纺股份有限公司 一种宾霸纤维及其制备方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US866371A (en) * 1906-03-22 1907-09-17 Rudolf Linkmeyer Removing copper salts from alkaline liquors.
US1049201A (en) * 1911-01-14 1912-12-31 Glanzstoff Ag Process for recovering copper from the wash liquors employed in the cuprammonia-cellulose process.
US1490499A (en) * 1923-10-20 1924-04-15 Glanzstoff Ag Process for working up copper cellulose sludge
CH144295A (de) * 1928-06-05 1930-12-31 Ig Farbenindustrie Ag Verfahren zur Ausfällung von Kupferhydroxyd aus einer ammoniakalischen Lösung einer Kupferverbindung.
US1920208A (en) * 1930-03-29 1933-08-01 Firm American Bemberg Corp Process for the recovery of copper compounds from the waste liquors of the cuprammonium silk stretch spinning process
US2141763A (en) * 1935-11-23 1938-12-27 Ig Farbenindustrie Ag Process for recovery of copper from waste liquors of the artificial silk industry
US2148895A (en) * 1935-10-04 1939-02-28 Ig Farbenindustrie Ag Shaped articles from cellulose
US2162176A (en) * 1934-10-13 1939-06-13 Duisburger Kupferhuette Regeneration of copper from cuprammonium artificial silk waste lyes
US2322778A (en) * 1940-05-01 1943-06-29 American Rayon Company Inc Method of removing copper and ammonia from cuprammonium yarn
US2370157A (en) * 1940-05-01 1945-02-27 American Rayon Company Inc Recovery and reuse of copper sulphate from wash liquors
US2395015A (en) * 1940-08-27 1946-02-19 Rayonier Inc Cuprammonium process

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE236537C (fr) *
DE237816C (fr) *
DE535649C (de) * 1928-06-06 1931-10-14 I G Farbenindustrie Akt Ges Gewinnung von Schwermetallhydroxyden durch Zerlegung der komplexen Ammoniakverbindungen

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US866371A (en) * 1906-03-22 1907-09-17 Rudolf Linkmeyer Removing copper salts from alkaline liquors.
US1049201A (en) * 1911-01-14 1912-12-31 Glanzstoff Ag Process for recovering copper from the wash liquors employed in the cuprammonia-cellulose process.
US1490499A (en) * 1923-10-20 1924-04-15 Glanzstoff Ag Process for working up copper cellulose sludge
CH144295A (de) * 1928-06-05 1930-12-31 Ig Farbenindustrie Ag Verfahren zur Ausfällung von Kupferhydroxyd aus einer ammoniakalischen Lösung einer Kupferverbindung.
US1920208A (en) * 1930-03-29 1933-08-01 Firm American Bemberg Corp Process for the recovery of copper compounds from the waste liquors of the cuprammonium silk stretch spinning process
US2162176A (en) * 1934-10-13 1939-06-13 Duisburger Kupferhuette Regeneration of copper from cuprammonium artificial silk waste lyes
US2148895A (en) * 1935-10-04 1939-02-28 Ig Farbenindustrie Ag Shaped articles from cellulose
US2141763A (en) * 1935-11-23 1938-12-27 Ig Farbenindustrie Ag Process for recovery of copper from waste liquors of the artificial silk industry
US2322778A (en) * 1940-05-01 1943-06-29 American Rayon Company Inc Method of removing copper and ammonia from cuprammonium yarn
US2370157A (en) * 1940-05-01 1945-02-27 American Rayon Company Inc Recovery and reuse of copper sulphate from wash liquors
US2395015A (en) * 1940-08-27 1946-02-19 Rayonier Inc Cuprammonium process

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2666688A (en) * 1951-05-05 1954-01-19 Copper Res Method of making stable cupric hydroxide
US2904399A (en) * 1954-10-09 1959-09-15 Bemberg Ag Recovery of copper and ammonia from waste liquors from the manufacture of regenerated cellulose
US3017506A (en) * 1959-01-07 1962-01-16 Sylvania Electric Prod Selective signal eliminator
US3301542A (en) * 1963-12-04 1967-01-31 Western Electric Co System for treating acidic etching solutions
CN102286798A (zh) * 2010-06-17 2011-12-21 罗莱家纺股份有限公司 一种宾霸纤维及其制备方法

Also Published As

Publication number Publication date
NL69975C (fr)
DE966600C (de) 1957-08-22
GB647350A (en) 1950-12-13
BE475206A (fr)
CH274800A (fr) 1951-04-30
ES179244A1 (es) 1947-10-01

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