US2694059A - Corrosion inhibition in chlorite bleaching of cellulose derivatives - Google Patents

Corrosion inhibition in chlorite bleaching of cellulose derivatives Download PDF

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Publication number
US2694059A
US2694059A US226936A US22693651A US2694059A US 2694059 A US2694059 A US 2694059A US 226936 A US226936 A US 226936A US 22693651 A US22693651 A US 22693651A US 2694059 A US2694059 A US 2694059A
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United States
Prior art keywords
cellulose
bleaching
bleaching agent
chlorite
slurry
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Expired - Lifetime
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US226936A
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English (en)
Inventor
Bayard T Lamborn
Richard A Leonard
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Hercules Powder Co
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Hercules Powder Co
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Filing date
Publication date
Priority to NL81768D priority Critical patent/NL81768C/xx
Priority to NLAANVRAGE7711775,A priority patent/NL169647C/xx
Application filed by Hercules Powder Co filed Critical Hercules Powder Co
Priority to US226936A priority patent/US2694059A/en
Application granted granted Critical
Publication of US2694059A publication Critical patent/US2694059A/en
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/22—Post-esterification treatments, including purification
    • C08B3/30—Stabilising
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/20—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen
    • D06L4/22—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents
    • D06L4/23—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents using hypohalogenites
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/20—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen
    • D06L4/22—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents
    • D06L4/24—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents using chlorites or chlorine dioxide

Definitions

  • This invention relates to a noncorrosive bleaching composition.
  • this nvention relates to a process for the bleachingof cellulose derivatives with a chlorite bleaching agent and to the composition of matter employed in the bleaching step.
  • this invention relates to a process for in hibiting the corrosive action of metal chlorites on metallic reaction chambers in a cellulose acetate bleaching process and to the noncorrosive bleaching composition employed in the bleaching step.
  • Cellulose derivatives for example, cellulose ethers and esters, and particularly cellulose acetate, are employed in high temperature operations, such as molding, for the formation of a wide variety of articles, and in such high temperature operations it is essential that the cellulose derivative have a high thermal color stability in order that the product resulting from the process will be color less. It has recently been found that cellulose derivatives that have been bleached with a chlorite, for example, an alkali metal or alkaline earth metal chlorite, have a thermal color stability higher than that of cellulose derivatives which have been bleached with other known bleaching agents.
  • a chlorite for example, an alkali metal or alkaline earth metal chlorite
  • an aqueous slurry of the cellulose derivative is formed, and the pH of this slurry is adjusted with an acid to obtain a pH lower than 7.
  • the cellulose derivative is then bleached by introduction of the chlorite bleaching agent.
  • Various acids can be used for the pH adjustment, but acetic acid is regarded as preferable since it is a relatively weak acid, and it has no appreciable oxidative action upon the cellulose derivative.
  • the chlorite when employed in the presence of an aqueous slurry of a cellulose derivative whose pH has been adjusted'with acetic acid, has an undesirable corrosive action upon the metallic surfaces of the reaction chamber, even when the reaction chamber is constructed of a corrosion resistant stainless steel.
  • the bleaching of various pulps, such as paper pulp and wood pulp is practiced extensively commercially, and among the bleaching agents employed is chlorine dioxide which is also corrosive upon.
  • chlorite or chlorine dioxide bleaching agent upon metal ,Massachusetts, 1936, prepared under the ICC surfaces can be inhibited by adding to such an aqueoussolution a phosphoric acid or a derivative of said acid whose aqueous solution has an acidic pH.
  • a phosphoric acid or a derivative of said acid whose aqueous solution has an acidic pH.
  • Solution contained 0.7 gram of sodium chlorite per liter and its pH Was .adlusted to 4 with phosphoric acid.
  • the stainless steels employed were of the auStenitic chromium-uiclgel type.
  • the stainless steel for run l contained a maximum of 0.08% carbon, 18-20% chromium, 55-11% nickel, and a maximum of 2% manganese.
  • the stainless steel for run 2 contained a maximum of 0.10% carbon, 16-18% chromium, 10-14% nickel, and 23% molybdenum, and this steel is considered to have a superior resistance to chemical corrosion.
  • the stainless steel for run 3 contained a maximum of 0.08% carbon, 17-49% chromium, and 9.l2% nickel. The following data were ob- From these data it is apparent that the phosphoric acid completely inhibited the corrosive action of the sodium chlorite on the ferrous metals.
  • EXAMPLE 4 Cellulose acetate was bleached in the manner set forth in Example 2 but nitric acid was employed to adjust the pH of the slurry instead of phosphoric acid. In a second run no nitric acid was employed for pH adjustment. The color of the cellulose acetate resulting from each of the runs was then noted. The data observed in each of the runs are tabulated below.
  • the above examples demonstrate the desirability of employing phosphoric acid for pH adjustment in a sodium chlorite bleaching operation of a cellulose ester instead of acetic acid.
  • the above examples also demonstrate that when phosphoric acid is employed in the bleaching process the bleached cellulose ester has a more desirable color than those cellulose esters resulting from operations wherein other acids are employed for pH adjustment.
  • the austenitic alloys employed in the foregoing examples were chosen because of their wide application in chemical vessel and apparatus fabrication.
  • the corrosion-inhibiting compounds that are employed in the practice of this invention are selected from the group consisting of the phosphoric acids and derivatives of said acids whose aqueous solutions have an acidic pH.
  • Phosphoric acid (H3PO4) is preferred because of its availability, but any of the phosphoric acids can be used.
  • Derivatives of the phosphoric acids within the scope of, this invention are inorganic salts and organic esters of the acids. For example, hydrogen atoms in the acids may be displaced by an ammonium ion or by a metal such as, sodium, potassium, calcium, magnesium, and the like.
  • ester salts or acid-ester salts.
  • the derivative of the phosphoric acid retains at least one hydrogen atom, and an aqueous solution of the derivative has an acidic pH.
  • the amount of corrosion-inhibiting agent employed is variable, depending largely upon the desired pH of the bleaching solution and upon the derivative. Actually, the amount employed is suflicient to adjust the pH of the bleaching solution to the desired range.
  • sodium chlorite was used as the bleaching agent.
  • Sodium chlorite is the preferred chlorite bleaching agent and it is available commercially.
  • the invention is applicable to processes employing chlorine dioxide and other chlorites as bleaching agents.
  • Typical examples or" other chlorites are ammonium chlorite and the alkali metal and the alkaline earth metal chlorites, such as potassium chlorite, calcium chlorite, magnesium chlorite, barium chlorite, and the like.
  • the bleaching process of this invention is quite useful for bleaching such cellulose derivatives as cellulose esters and cellulose ethers.
  • Typical cellulose derivatives are methyl cellulose, ethyl cellulose, cellulose acetate, cellulose propionate, cellulose butyrate, and the like.
  • mixed ester, mixed ether, and ether-ester derivatives can be bleached in this manner.
  • cellulose acetate propionate, cellulose acetate butyrate, carboxymethyl hydroxyethyl cellulose, acetylated hydroxyethyl cellulose, and the like are Within the scope of this invention.
  • the invention is applied to the bleaching of cellulose esters, preferably cellulose acetate, with sodium chlorite, and the invention will be described in further detail with reference to such a process.
  • the cellulose esters employed in practicing this invention can be prepared by any of the known methods.
  • a typical method for preparing these cellulose esters will be set forth by describing a method for preparing cellulose acetate.
  • One method of preparing cellulose acetate involves the preparation of a cellulose mix by spraying cotton linters with glacial acetic acid.
  • An acetylation mix is separately prepared by mixing together acetic anhydride, methylene chloride and catalytic amounts of zinc chloride and perchloric acid. This latter mix and the cellulose mix are combined and agitated for a period of time sufficient to effect the desired acetylation.
  • the bleaching process is effected at the highest slurry concentration that permits efficient agitation and mixing and this varies with the type of agitation available for use.
  • slurry concentrations In laboratory procedures the slurry concentrations have generally been below 10% and in commercial practice the usual range of slurry concentrations is from 13 to 15%.
  • slurry concentration is meant the relation ship between the amount of cellulose ester and the total amount of cellulose ester and slurrying medium.
  • the amount of bleaching agent that is employed is variable.
  • the prefered amount is the minimum amount required to provide adequate purification of the cellulose ester.
  • the actual amount of bleaching agent employed is within the range of 0.001 to 0.015 part of bleaching agent per part of cellulose ester. ⁇ Vood pulp esters require more bleaching than esters of cotton linters. When bleaching Wood pulp cellulose esters, the minimum amount of bleaching agent would not efiect as good a purification as would be effected on a cotton linters cellulose ester. However, with either type of ester, a bleaching thereof would take place With the minimum amount of bleaching agent.
  • the upper limit or 0.015 part of bleaching agent per part of cellulose ester is suflicient to provide an eflicient bleach for cellulose esters of all types in a period of two hours and at a temperature of 95 to 100 C.
  • Greater amounts of bleaching agent can be used, if desired, since the metal chlorites within the scope of this invention are for all practical purposes incapable of oxidatively damaging the cellulose ester. However, greater amounts of bleaching agent are not necessary for carrying out the process.
  • the bleaching agent is added to the water slurry of the cellulose ester in an aqueous solution.
  • This solution usually has a concentration of bleaching agent within the range of 3 to 5%.
  • higher concentrations of the aqueous solution of the bleaching agent can be used, and it is possible to effect a desired bleaching by adding the bleaching agent to the water slurry of the cellulose ester in the form of a solid.
  • the bleaching procedure is employed in a process for producing the cellulose ester, such as that described above for preparing cellulose acetate, it is preferred to effect the desired bleaching by contacting the bleaching agent with the cellulose ester at any point in the process after the precipitation of the cellulose ester by addition of excess water.
  • the cellulose ester is given a preliminary washing after precipitation with water, and it is then bleached in a water slurry as already described.
  • the cellulose ester can be prepared as a solid in the manner described above, and at a time subsequent to such preparation an aqueous slurry of the cellulose ester can then be prepared.
  • the cellulose ester in this slurry is then bleached in accordance with this invention.
  • this bleaching procedure is incorporated in the above process for producing a cellulose ester, the cellulose ester, after precipitation with water, is treated by washing with water. A water slurry of the washed ester is then formed, and the pH of the resulting slurry is adjusted to within the desired range with phosphoric acid.
  • ester is then bleached with sodium chlorite as already described.
  • an aqueous solution of the phosphoric acid and sodium chlorite in the required amounts can be formed, and the resulting solution is then added to an aqueous slurry of the washed ester to effect the desired bleaching.
  • the method of improving the thermal color stability of a cellulose derivative selected from the group consisting of cellulose esters and cellulose ethers and of inhibiting the corrosive action of the bleaching agent employed in the process which comprises treating said cellulose derivative with from 0.001 to 0.015 part of a metal chlorite bleaching agent per part of cellulose derivative, said metal chlorite bleaching agent being selected from the group consisting of alkali metal and alkaline earth metal chlorites in contact with stainless steel corrodible by said bleaching agent in an aqueous slurry containing essentially water, said cellulose derivative, said bleaching agent and a phosphoric acid, the pH of said slurry being from 3 to 6, and said bleaching agent and said phosphoric acid being present in amounts suflicient to improve the color of said cellulose derivative and to inhibit the corrosion of said stainless steel.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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US226936A 1951-05-17 1951-05-17 Corrosion inhibition in chlorite bleaching of cellulose derivatives Expired - Lifetime US2694059A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
NL81768D NL81768C (enrdf_load_stackoverflow) 1951-05-17
NLAANVRAGE7711775,A NL169647C (nl) 1951-05-17 Weergeefinrichting met een vloeibaar kristal.
US226936A US2694059A (en) 1951-05-17 1951-05-17 Corrosion inhibition in chlorite bleaching of cellulose derivatives

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2947700A (en) * 1953-12-15 1960-08-02 Hoechst Ag Inhibited chlorite baths and method
US3854958A (en) * 1972-09-14 1974-12-17 Dow Chemical Co Stabilization of ethyl cellulose with sodium omicron and rho nitrobenzoates

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1992045A (en) * 1932-07-01 1935-02-19 Grasselli Chemical Co Phosphoric acid metal cleaning and rust preventing solution
US2129719A (en) * 1937-09-13 1938-09-13 Mathieson Alkali Works Inc Bleaching method
US2194956A (en) * 1939-01-10 1940-03-26 Mathieson Alkali Works Inc Bleaching pulp
US2430674A (en) * 1943-01-11 1947-11-11 Mathieson Alkali Works Inc Method of bleaching
US2526839A (en) * 1947-02-01 1950-10-24 Olin Mathieson Method of repressing the generation of chlorine dioxide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1992045A (en) * 1932-07-01 1935-02-19 Grasselli Chemical Co Phosphoric acid metal cleaning and rust preventing solution
US2129719A (en) * 1937-09-13 1938-09-13 Mathieson Alkali Works Inc Bleaching method
US2194956A (en) * 1939-01-10 1940-03-26 Mathieson Alkali Works Inc Bleaching pulp
US2430674A (en) * 1943-01-11 1947-11-11 Mathieson Alkali Works Inc Method of bleaching
US2526839A (en) * 1947-02-01 1950-10-24 Olin Mathieson Method of repressing the generation of chlorine dioxide

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2947700A (en) * 1953-12-15 1960-08-02 Hoechst Ag Inhibited chlorite baths and method
US3854958A (en) * 1972-09-14 1974-12-17 Dow Chemical Co Stabilization of ethyl cellulose with sodium omicron and rho nitrobenzoates

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NL81768C (enrdf_load_stackoverflow)

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