EP0065984A1 - Pulpage a l'acide formique - Google Patents

Pulpage a l'acide formique

Info

Publication number
EP0065984A1
EP0065984A1 EP82900276A EP82900276A EP0065984A1 EP 0065984 A1 EP0065984 A1 EP 0065984A1 EP 82900276 A EP82900276 A EP 82900276A EP 82900276 A EP82900276 A EP 82900276A EP 0065984 A1 EP0065984 A1 EP 0065984A1
Authority
EP
European Patent Office
Prior art keywords
formic acid
bark
pulp
wood
lignin
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.)
Withdrawn
Application number
EP82900276A
Other languages
German (de)
English (en)
Inventor
Robert K. Jordan
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of EP0065984A1 publication Critical patent/EP0065984A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/003—Pulping cellulose-containing materials with organic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K10/00—Animal feeding-stuffs
    • A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
    • A23K10/32—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms from hydrolysates of wood or straw
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/10—Chemical features of tobacco products or tobacco substitutes
    • A24B15/16—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof

Definitions

  • This invention relates to digesting wood and bark in formic acid of atleast 35% concentration to produce wood pulp, bark pulp, lignin and lignin based chemicals including benzene, phenol and polyols.
  • Wood is conventionally delignified in aqueous alkaline medium by the kraft and soda processes that require pulping temperatures of over 150°C, give poor yields of pulp of typically 42% to 50% based on dry wood weight result in a high molecular weight modified lignin condensation product and is often malodorous.
  • the kraft process employs a mixture of aqueous sodium hydroxide and sodium sulfide at about 170°C/10 atmospheres for 2 to 3 hours to result in pulp yields averaging 47% and is accompanied by sulfide odors.
  • the spent liquor from the process is comprised of sodium salts of lignosulfonates, glucose and sugars from hydrolyzed cellulose and hemiceilulose, and residual inorganic chemicals.
  • Wood pulp is widely employed in the pulp and paper industry, by far most used in the production of paper and cardboard, but there are numerous other uses. Indeed, wood pulp has been used to feed ruminants. Bark is a major byproduct of pulping; it has a few minor uses and for the most part is burned as a poor fuel.
  • the lignin now recovered from the conventional wood pulping processes is largely burned because it is difficult to recover economically and is rather intractable because of its very high molecular weight and chemical modification.
  • an acid which may be costly in terms of both that of the acid itself and the loss of sodium which reacts with the acid, i.e. sodium ion.
  • Neutralization or acidification precipitates the highly condensed high molecular weight lignin from the spent liquor, leaving a solution of some sodium salt, usually sodium sulfate, and glucose and sugars that resulted from the hydrolysis of the mostly hemicellulose present in the wood.
  • the lignin is highly condensed to high molecular weight and, in the case of the kraft process, further ified by sulfide groups it is difficult to degrade; hence relatively useless. Disclosure of the Invention
  • My invention is a process for digesting wood and bark to the corresponding pulps in formic acid of ideally 65% to 90% concentration at its refluxing temperature, about 100°C, and further ideally using a surfactant and agitation to effect largely delignified pulp in about 1 hour to result in a some 70% yield of pulp and a liquor of essentially lignin in formic acid.
  • Practically all of the formic acid is easily recovered, for example by distillation, and the surfactant by minimal water extraction, leaving a low molecular weight lignin that is quite soluble in many solvents and easily hydrodeal kylated to benzene and phenol, or dealkylated to phenol and substituted phenols.
  • Bark pulp made by the process is an excellent ruminant feed and further an excellent replacement for tobacco as a smoking material.
  • the formic acid can be made from essentially carbon monoxide and water via methyl formate , as carbon monoxide is becomming widely available via coal gasification and no doubt will become even more available with the development of the oxygen-blown, coal fired blast furnace process.
  • Formic acid is usually obtained as 88% or 90% formic acid, the remainder water which is the preferred diluent for the formic acid employed in the process; although essentially pure formic acid may be employed, and the concentration may be as low as 35%, the preferred concentration range is 50% to 90% while the ideal ranges from about 65% to 90%.
  • Both soft and hard-woods may be used in the process, for examples Douglas fir, loblolly, oak, poplar, ash, maple and cherry.
  • the weight ratio may range from 2:1 to 1:20 dry wood :mediurn, ideally 1:3 to 1:8.
  • the softwoods are somewhat more difficult to pulp while the hardwoods pulp very rapidly.
  • the temperature of the del ignification may range from about 20°C to about 180°C, preferably from about 50°C to about 150°C and ideally from about 80°C to 130°C.
  • wood can be easily pulped in 75% formic acid at refluxing while at atmospheric pressure, about 100°C, with agitation in about 3 to 4 hours.
  • atmospheric pressure about 100°C
  • the yields by my process are, under such conditions, usually over 70% which indicates a very high selectivity of formic acid for dissolving out the lignin. Only smallish quantities of glucose and sugars are found in the the liquor after removing the pulp, mostly from sap.
  • Tree bark is readily pulped under about the same conditions as are employed for wood. Usually bark pulp is of shorter fiber length and quite dark in spite of the very extensive delignification. As measured by the so-called "K" number both wood and bark pulp are very low, but bark pulp is not bleachable to while by smallish amounts of bleaching agents. The use of surfactants has about the same effect on bark pulping as on wood pulping.
  • any of the common and even uncommon surfactants may be employed to accelerate the process very substantially, such as anionic, cationic, amphoteric and nonionic surfactants may be used.
  • examples include sodium dodecylbenzene sulfonate, sodium lauryl sulfate, cetyltrimethylammonium bromide, alkoxylates nonylphenol, e.g. C 9 H 19 C 6 H 4 O(C 2 H 4 O) 9 H, and perfluoroalkyl-alkyl cationic, anionic, amphoteric and nonionic surfactants.
  • concentrations of surfactants vary with the kinds employed and range from about 0.1% to about 5% for effectiveness although larger concentrations may be used, but wastefully.
  • the rate of pulping wood and bark is affected strongly by agitation at these and intermediate temperatures. At high temperatures the, formic acid-surfactant medium readily pulps without any agitation, but at lower temperatures the need for agitation, especially mechanical stirring or some kind of mixing becomes evermore greater. Probably this is a function of the decomposition of the hemicellulose in the wood and bark.
  • the amount of mixing or stirring desired is also limited by the pulping time and strength of the paper required of the wood pulp, or its other intended uses. Sawdust needs little or no agitation at atmospheric refluxing.
  • the lignin obtained is of low molecular weight, averaging well under 1,000, soluble in ethylene glycol dimethyl ether, other solvents and partly so in methanol.
  • the optimum temperatures lies about or below the glass transition temperature of the lignin as it exists in the wood. This ranges from about 110°C to about 140°C for most woods.
  • a judicious balance must be used that may require sacrificing low pulping times to obtain the desired lignin minimal quantity of contained glucose, sugars and other soluble carbohydrates in the liquor obtained after separating the pulp.
  • Formic acid and any water is easily recovered from the liquor, for example by simple distillation or extraction or other means.
  • Any surfactant if employed, may likewise be easily removed as may minor amounts of carbohydroates with a minor quantity of water by extraction since the lignin is insoluble in water.
  • the lignin may be used as a diluent for phenolic resin phenols or for producing polyols for polyuretha ⁇ e foams by alkylene oxide addition as is well known in the art. Such polyols of hydroxy! numbers of 50 to 700 may be used for both flexible and rigid polyurethane foams.
  • the lignin from my process may also be easily directly hydrodealkylated thermally or catalytically, using catalysts known in the art, to benzene and phenol. And it can also be dealkylated using such as aluminum aryloxide catalysts to phenol and substituted phenols in the liquor phase, for example using phenol as a solvent at from about 50°C to about 300°C.
  • the thermal or catalytic hydrodealkylation may be conducted by injecting the lignin alone or in a mixture with other chemicals to be hydrode- alky!ated, for example toluene, and therein combined with hot hydrogen. short residence time is desirable to obtain the best yields of phenol, which is more valuable than benzene.
  • the bark pulp of my process is of special interest in that 60% pulp yields are realized and the material is useful as a foodstuff for ruminants such as sheep, goats, elephants, cattle and the like.
  • the pulping process of my invention removes the lignin and some of the other chemicals from bark it does not remove some of the chemicals that provide flavor since by taste and on burning a characteristic flavor and aroma is realized.
  • the bark pulp is unique as a feed for ruminants and an additive to feeds for other animals, fowl and marine creatures. Indeed, as a feed for ruminants it is further highly superior for another reason, that the easily digestible hemicellulose contained in the bark, and wood, is retained in the pulp.
  • the efficiency of the bark pulp, or wood pulp, of my process as a ruminant feed is far superior to conventionally pulped wood and bark; and the pal atibil ity of my bark is evidenced by simply chewing on it. Birch hickory, oak and the others tasted have distinctive flavors.
  • the bark pulps emit fumes having aromas characteristic of the bark and wood from which they were derived. Hickory, cherry, birch, maple, oak and others yield distinctive aromas on burning; as they contain practically no lignin the smoke is inoffensive. And those tested contained contained no significant detectable amounts of nicotine. These are excellent smoking materials, as such, or in admixtures with tobacco. As pipe smoking materials, as rolled into cigarettes or cigars, the bark pulps are pleasant and apparently harmless in that in spite of their flavor they are largely holocellulose. Humectants, binding agents and other materials known in the art of utilizing tobacco may be employed in compounding the bark pulps; indeed, even other flavoring materials may be added, for example for menthol flavor. And of course, they may be combined with filters as in making cigarettes. To minimize chemical proliferation in testing some bark pulps were made without the benefit of a surfactant; thus Example I is typical.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Biotechnology (AREA)
  • Materials Engineering (AREA)
  • Animal Husbandry (AREA)
  • Zoology (AREA)
  • Botany (AREA)
  • Molecular Biology (AREA)
  • Food Science & Technology (AREA)
  • Physiology (AREA)
  • Wood Science & Technology (AREA)
  • Mycology (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paper (AREA)

Abstract

Procede de pulpage du bois et de l'ecorce dans de l'acide formique avec une concentration d'au moins 35 , la concentration ideale se situant entre 65 et 90 , avec reflux a la pression atmospherique, pour produire de la pulpe de bois et d'ecorce d'une teneur elevee en hemicellulose et des rendements tres eleves d'holocellulose, donnant une liqueur de tres faible teneur d'hydrate de carbone qui, lors de la recuperation de l'acide formique, laisse de la lignine de faible poids moleculaire, inferieur a 1000; la pulpe de bois est utile dans l'industrie du papier et comme aliment pour les animaux, la pulpe d'ecorce est un produit alimentaire ideal pour les ruminants, un produit de substitution du tabac a pipe, de cigarettes et de cigares, tandis que la lignine peut etre utilisee comme une base pour les polyols ou peut etre desalkylee ou hydrodesalkylee en phenol, phenols substitues et benzene.
EP82900276A 1980-12-05 1981-12-07 Pulpage a l'acide formique Withdrawn EP0065984A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US21323680A 1980-12-05 1980-12-05
US213236 1980-12-05

Publications (1)

Publication Number Publication Date
EP0065984A1 true EP0065984A1 (fr) 1982-12-08

Family

ID=22794270

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82900276A Withdrawn EP0065984A1 (fr) 1980-12-05 1981-12-07 Pulpage a l'acide formique

Country Status (2)

Country Link
EP (1) EP0065984A1 (fr)
WO (1) WO1982001902A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8721528D0 (en) * 1987-09-14 1987-10-21 Shell Int Research Pulping lignocellulose-containing material
FI80191C (fi) * 1988-03-30 1990-05-10 Valio Meijerien Foerfarande och konserveringsmedel foer ensilering av foder.
FI85510C (fi) * 1990-05-29 1992-04-27 Kemira Oy Foerfarande foer aotervinning av laegre alifatisk syra.
FI85511C (fi) * 1990-05-29 1992-04-27 Kemira Oy Foerfarande foer aotervinning av alifatiska syror och sockrar.
DE4228171C2 (de) * 1992-08-25 1995-06-14 Kaemmerer Projekt Agentur Gmbh Verfahren zur Gewinnung von Zellstoffen
DE19516151A1 (de) 1995-05-03 1996-11-07 Sven Siegle Verfahren zur Herstellung einer Pulpe aus zellulosehaltigem Material, die Pulpe selbst und deren Verwendung
WO2011138355A2 (fr) * 2010-05-07 2011-11-10 Basf Se Procédé de production de cellulose et d'au moins une matière valorisable organique liquide ou liquéfiable avec recyclage des effluents gazeux
JP5996842B2 (ja) * 2010-08-31 2016-09-21 ユニ・チャーム株式会社 ペットフード
CN102153763B (zh) * 2010-09-27 2013-10-16 天津大学 一种木质纤维素酸碱耦合预处理方法
CN102675581B (zh) * 2012-03-12 2016-08-10 北华大学 树皮粉、木质素液化改性制备可降解聚氨酯泡沫塑料的方法
JP2015198653A (ja) * 2014-03-31 2015-11-12 日本製紙株式会社 反芻動物用飼料

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB477842A (en) * 1936-07-03 1938-01-03 Henry Dreyfus Improvements in or relating to the manufacture of cellulose from lignin-containing cellulosic materials
US2516447A (en) * 1947-02-24 1950-07-25 Elmer R Burling Method and apparatus for chemical treatment
US2645633A (en) * 1949-11-14 1953-07-14 Masonite Corp Process for extraction of lignin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8201902A1 *

Also Published As

Publication number Publication date
WO1982001902A1 (fr) 1982-06-10

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Effective date: 19830214