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3,072,521 United States Patent 1 . 2 p The cooked and de?bered pulp is thendiluted to less 3,072,521 " than 1% ‘concentration and rif?ed and screened to re-' , NON-AQUEOUS DEINKING PROCESS move oversized objectsand unde?bered pieces of paper, Gilbert J. Samuelson, Webster Groves, and Kenneth J. Lissant, St. Louis, Mo., assignors to Petrolite Corpora This’mate'rial is then washed with voluminous amounts of Water, an average of 20,000 gallons of water per ton -' tiou, Wilmington, Del., a corporation of Delaware ‘ N0 Drawing. Filed July' 27,1959, Ser. No. 829,498 ' 19 Claims. ‘ Patented Jan. 8, 1953 (Cl. 162—5) of pulp, to separate the?ber from‘ other substances by washing or screening or by a?otation process; The dis _ posal of large amounts of water used inthe process poses This invention relates to an essentially non-aqueous a stream pollution problem which must be remedied in process of deinking cellulosic materials, such as, paper 10 most areas of the country.‘ __ l . p , _ H v = p products, which comprises treating imprinted cellulosic The problem’ of deinking has been further‘ complicated by certain recent changes in the paper industry which" materials such as paper products with a surfactant-con taining organic solvent. 1 have increased the dif?culty of deinking', among which Paper manufacture does not damage or alter the char acter of the essential ?ber from which the paper is orig inally made; hence, such‘ ?ber may be recovered from used paper and reused, time after time, in’ the manufac ture of fresh‘ paper stock. The limitations in respect of changes are the following: (1) The increased use of groundwood containing slivers of wood rubbed from pulp wood present, jagged sawtooth‘ends which affordexcellent crevicesfor'trapping; ' the carbon particles of the printer’s ink, thus making'jit" practical recovery of ?ber from used paper are to be increasingly di?icult to produce a reuseable pulp of high found in the di?iculty and consequent expense of thor 20 quality of whiteness, _ _ Y A’ ,_ ,, oughly deinking printed paper stock to upgrade it to the (2) ‘Many of the improved new inkscurrently in use color and quality of the original paper stock. are‘ non-saponi?able with caustic, and generally'require Many processes have been used for ‘deinking cellulosic more drastic cooking conditions during deinking, thus' materials, such as waste paper to make the c'ellulosic content thereof useful in a pulp for reuse informing pa‘ per or other cellulosic products. These processes, how tending to further degrade‘ the cellulosic ?ber. v I n ' (3) ' Certain paper coatings such as casein andsoybean proteins, hardened with formaldehyde require for their ever, are expensive, laborious, time-consuming, complicat ed, and present pollution problems in disposing of the removal higher temperatures which also degrade the‘ wastes thereof. (4) The increased ?ller content of paper, (now, ap In general, in preparing used paper for deinking and 30 proaching an average of 25%, results in increased shrinki. recovery of ?ber, the stock to be salvaged is ?rst thor age during deinking which increases the cost of deinked oughly cleansed’ of super?cial dirt and macerated by means of any suitable system or apparatus; stock.‘ Then‘ the - ' Among the disadvantages of prior processes are the maceratum is boiled, subjected to the cooking and de?ber ing in a suitable aqueous alkali to soften ‘the paper ?bers, following: , _ _ ' , p g V H (1) Longv cooking periods at‘ elevated temperatures re, loosen and disintegrate atileast part of the ink and other ' _ quite large expenditures of energy with increased ex matter adheringr'to the ?bers‘, and thoroughly agitated, either while‘ in the‘ alkaline solution or‘ subsequently, to (2) High‘temperatures and strong chemicals employed disintegrate and de?ber the stock as thoroughly as“ possi' in these processes tend to deleteriously affect the ?bers ble. Thereafter, the pulp is rit?ed and screened and‘ sub so' that they are not always of the same quality as those pense. sequently dewatered, preferably through suitable rolls, from freshpaper pulp. ?lters, or the like, to remove a.considerable portion of Thus,‘ all commercially successful processes for deink ing waste paper involve thefollowing steps: p I I v p solutions thereof can be found, for example, in the fol~ lowing patents: , 60 (3) Ri?iing and screening (4) Washing I . pollution problem" whichvrequires expensive pollution‘ control systems. Arstatement of“ the deinking problems andproposed many times as may be practical‘ and expedient; (2)‘ Alkali cooking and de?bering V v , (3) The use ‘of large amounts of water poses a'strearn the loosened ink. Itis then washed and dewatered ‘for removal of additionalv quantities ‘of the loosened ink as‘ ' (l) Dusting and maceration , 7 4 2,607,678 2,077,059; 23,580,161 , . 2,112,561 2,673,798 2,005,742 2,219,781 ‘1,993,362, etc: In general, the sorted, dusted and macerated paper is ‘ We have now discovered an‘ essentially non-aqueous cooked with an aqueous’ deinking agent at a temperature 55 process of deinkingcellulosic materials, suchQa's’impi-inti of from 140° F. to its boiling point for 25-48. hours at ed'paper products, which comprises treating ink-contain concentrations of 4-25 %. by weight of paper in the al ing celluolsic materials with a" surfactant-containing’or kali solution. Heat consumption willvary ' inversely with‘ ' ganic' solvent. Since this, process can be carried‘ out‘at the concentration and viscosity of the stock. ‘ De?bering' room temperature in a shortperiod’of time, no‘expedi is generally accomplished during the cooking'operation. 60 .ture of heat energy nor long holding periods‘a‘re required: ’ In general, the deinking agent employed containsl‘an Since no strong‘ chemicals,‘high temperatures no extended‘ aqueous alkali solution which may in addition contain reaction‘ periods are required, little, if- any, degradation’ ‘one or more of the following: a detergent,.for example of the pulp occurs, with obvious advantages; Since no: sodium. soaps of fatty acids orabietic'acid, sulfonated‘oil; etc.; a dispersing agent to preyenta'gglom‘er'ation- of the‘ pigment after release and to emulsify any ‘unsaponi?a ble material; a softening'age'nt suchasikerosine or mineral water washes are required,“ or if they are. employed, they‘ 65 are carried out at room temperatures,‘ little,"if any, stream pollution results" from the aqueous“ e?‘luent: These andv - , other advantages will‘ become evidentr-as'the» process?‘ is" oil‘, etc} to" soften‘ the‘ vehicle of the ink‘sf'an' agent such as clay,“ a silicate‘, etcl, for selective adsorption after re-_ The facility with‘ which‘ the“ ink isremoved from3 the? lease from thej?ber. a; prevent reiiepositidn‘ on the ?ber; 70 paper by the present invention is‘ indeed unexpected in a" basic exchange chemical to" prevent formation of ‘cal the party since organic ‘solvents themselves, without‘the sur-‘ cium soaps, etc. i i ' ' ’ fac'tant, effect little, if any, separation of-the ink—-in fact; ~ described. , . 3,072,521 . . . , 4 3 they tend to further darken the paper. Furthermore, to tally or substantially totally non-aqueous systems of any kind have never been successfully employed. In addi tion, the present effect of a surfactant in a non-aqueous I. Anionic A. Carboxyllc acids: (1) Carboxyl joined directly to the hydrophobic group (subcalssiil cation on basis of the hydrophobic group, e.g., fatty acid soaps, rosin soaps, etc. (2) Oarboxyl joined through an intermediate linkage. system is unexpected since one generally employs sur factants to affect the properties of a dual aqueous-organic system and not those in which the system is essentially (a) Amide group as intermediate link. (1)) Ester group as intermediate link. (c) Sulfonan'iide group as intermediate link. (11) Miscellaneous intermediate links, ether, —-S0a--, —S—-, etc. organic. THE SOLVENT 10 The non-aqueous solvent employed in the present proc ess may vary widely although, in general, the more non polar oraguic solvents are most advantageously employed. This does not preclude the use of polar type solvents, par ticularly where polarity is masked by an organic group, 15 or groups having a relatively large hydrocarbon group or groups. A convenient test of suitable polarity of the sol vent is its solubility in water. Those solvents which are relatively insoluble, for example, will dissolve less than about ?ve percent by volume, but preferably less than 20 about one percent by volume, of water are most advanta B. Sulfuric esters (sulfates): (l) Sulfate joined directly to hydrophobic group. (a) Hydrophobic group contains no other polar structures (sul fated alcohol and suliated ole?n type). (b) Sulfuric esters with hydrophobic groups containing other polar structures (suliated oil type). (2) Sulfate group joined through intermediate linkage. (a) Ester linkage (Artie Syntex M. type). (b) Amide linkage (Xynomine type). (c) Ether linkage (Triton 770 type). _ (d) Miscellaneous linkages (e.g., oxyalkylirnidazole sulfates). O. Alkane sulionic acids: (1) Sulionic group directly linked. (a) Hydrophobic group bears other polar substitutents (“highly suliatcd oil” type). Chloro, hydroxy, acetoxy, and ole?n suli‘onic acids (Nytron tvpe). (b) Unsubstitutcd alkaue sulionic acids (MP 189 type; also ce taue sulio acid type). (0) Miscellaneous sulionic acids of uncertain structure, e._g., oxidation products of suliurized ole?ns, sull’onated rosin, etc. (2) Sulfonic groups joined through intermediate linkage. (a) Ester linkage. geously employed. (l) RCOO—X—SO;H (Igepon AP type). Based on commercial considerations, the solvent should ' _ (2) ROOC—X—SO3II (Aerosol and sulioacctate type). (b) Amide linkage. (1) RCONH——X—SO3H (Igeoon T type). be inexpensive and relatively low boiling, for example, boiling below about 200° C., but preferably below about 25 (2) RNHOC~'X_SO3H (suliosuccinamide type). (c) Ether linkage (Triton 720 type). .110’0 C. I However, this does not preclude the use of- high (11) Miscellaneous linkages and two or more linkages. boiling solvents since various methods can be used for their recovery, such as by reduced pressure, steam distil D. Alkyl aromatic sulionic acids: , (1) Hydrophobic group joined directly to sulionated aromatic nu cleus (subclasses on basis of nature of hydrophobic group. lation, etc. ' Examples of suitable solvents include straight and 30 branched chain alkanes, for example hexanes, heptanes, octanes, nonanes, decanes, undecanes, etc.; cycloalkanes, for example cycle-hexane, terpenes, etc., the reduced Alkyl phenols, terpene, and rosin-aromatic condensates, alkyl aromatic ketones, etc). (2) Hydrophobic group joined to sulionated aromatic nucleus through as intermediate linka e. (a) Ester linkage (suliophthalates, suliobenzoates). (b) Amide and imide linkages. (i) R-CONH-ArSO?I type. (2) Sult‘obenzamide type. aromatic compounds such as those of benzene and naph (c) Ether linkage (alkyl phenyl ether type). thalene such as di-, tetra-, and hexahydrobenzene, tetra-, 35 (d) Heterocyelic linkage (Ultravon type, etc). (e) Miscellaneous and two or more links. and decahydronaphthalene; aromatic compounds, for ex E. Miscellaneous anionic hydrophilicgroups: ample benzene, toluene, ethylbenzene, xylene, etc. and 21) Phosphates and phosphonic acids. 2) Persuliates, thiosuliates, etc. (3) Sulionamides. (4) Suliamic acids, etc. ample, petroleum ethers, gasoline, kerosine, naphtha sol II. Cationic vents, white spirits, etc. In addition, other water insoluble A. Amine salts (primary, secondary, and tertiary amines): (1) Amino group joined directly to hydrophobic group. or substantially water insoluble organic solvents can be (a) Aliphatic and aromatic amino groups. employed, for example halocarbons, alcohols, ethers, (b) Amino group is part of a heteroeycle (olkaterge type). (2) Amino group joined through an intermediate link. ketones solvents having more than one of these groups, for (a) Esther link. example keto-alcohols, etc. Although the solvent em 45 (It) Amide link. (c) Ether link. ployed is a non-aqueous solvent, the presence of small (d) Miscellaneous links. amounts of water which do not interfere with the es B. Quaternary ammonium compounds: (1) Nitrogen joined directly to hydrophilic group. sentially organic nature of the solvent is within the scope (2) Nitrogen joined through an intermediate link. of this invention. (a) Ester link. (b) Amide link. 50 (a) Ether link. (d) Miscellaneous links. THE SURFACTANTS 0. Other nitrogenous bases: (1) N on-quaternary bases (classi?ed as guanldine, tbiuronium salts, A wide variety of surfactants can be employed in this mixtures thereof that occur naturally or result from in dustrial processes or which are arti?cially mixed, for ex 40 etc. (2) Quaternary bases. invention. The chemical nature and structure of the sur Non-nitrogenous bases: factant are not important except as they relate to their 55 D. (1) Pbosphonium compounds. function in the present process. In general, all classes of surfactants can be employed in (2) Sulionium compounds, etc. III. N 011-] onto A. Ether linkage to solubilizing groups. B. Ester linkage. C. Amide linkage. this'invention including anionic, cationic, non-ionic and ampholytic surfactants, provided they are sui?ciently soluble in the organic solvent to be e?ective. As is evident, the subclasses and species under the above D. Miscellaneous linkages. E. Multiple linkages. IV. Ampholytic classes are legion. To enumerate all surfactants that can A. Amino and carboxy: be employed in this invention would be unnecessary and would render the speci?cation too voluminous. Therefore, we shall merely present the general types of surfactants which can be employed in this invention and more fully describe certain preferred types of surfactants which are (l) (2) (1) (2) Non-quaternary. Quaternary. Non-quaternary. Quaternary. B. Amino and sulfuric ester: C. Amine and alkane sulionie acid. D. Amine and aromatic sulfonic acid. E. Miscellaneous combinations of basic and acidic groups. illustrated by speci?c examples. An excellent discussion of surfactants can be found Examples of speci?c commercial surfactants useful in in the texts, “Surface ‘Active Agents and Detergents” by 70 the present invention include those disclosed in “Emulsions Schwartz et al. (vol. I, 1949, vol. II, 1958), Interscience Theory and Practice,” by Paul Becker, ACS Monograph Publishers, New York, which volumes are by. reference No. 135, Rhinhold Publishing Corp., 1957, pp. 337-371, incorporated into the present application. In vol. I of which are hereby incorporated by reference into the present speci?cation. these textbooks is a classi?cation scheme that is useful in a general representation of useful surfactants. 75 One class of surfactant advantageously employed in 3,072,521 6 5 The nature of the oxyalkylatable starting material used in the preparation of the emulsi?er is not critical. Any species of such material can be employed. By proper additions of alkylene oxides, this starting material can be eludes the non-ionic surfactants. Because it is a preferred class, we will discuss it in detail. . The most typical representatives of this class are the oxyalkylated surfactants or more speci?cally polyalkylene ethers or polyoxyalkylene surfactants. Oxyalkyl-ated sur factants as a class are well known. rendered suitable as a surfactant in the present process. The possible sub TABLE I.-—-REPRESENTATIVE EXAMPLES OF Z classes and speci?c species are legion. The methods em ployed for the preparation of such oxyalkylated sur No. factants are also too well known to require much elabora tion. Most of these surfactants'contain, in at least one 10 place in the molecule and often in several places, an Z 0 ll 1 _________ __ RO—O-—— 2 --------- —- a, 3 _________ __ R—~O~— 4 _________ __ R-S 5 _________ _- R—‘O-- alkanol or a polyglycolether chain. These are most com monly derived by reacting a ‘starting molecule, possessing one or more oxyalkylatable reactive groups, with an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, or higher oxides, epichlor-ohydrin, etc. o 15 However, they may be obtained by other methods such as shown in U.S. Patents 2,588,771 and 2,596,091-3, or by esteri?cation or amidi?cation with an oxyalkylated ma terial, etc. Mixtures of oxides or successive additions 20 of the same or different oxides may be employed. Any 0 II oxyalkylatable material may be employed. As typical starting materials may be mentioned alkyl phenols, phenol E —' O / 6 _________ __ R—g-'-—N' ic resins, alcohols, glycols, amines, organic acids, carbo hydrates, mercaptans, and partial esters of polybasic acids. \ In general, the art teaches that, if the startingmaterial is water-soluble, it may be converted into an oil~solub1e sur~ i‘ 7 _________ ._ factant by the addition of polypropoxy or polybu-toxy chains. If the starting material is oil-soluble, it may be converted into a water-soluble surfactant by the addition of polyethoxy chains. Subsequent additions of ethoxy , units to the chains tend to increase the water solubility, R-—N— 8_________ __ RN/ 9; _______ _. Phenol-aldehyde resins 10 ........ _. —O— (EX7 Alkylene oxide block polymers) while subsequent additions of higher alkoxy chains tend to increase the oil solubility. In general, the ?nal solubility R R and surfactant properties are a result of a balance between 35 the oil-soluble and water-soluble portions of the molecule. 11 ------- Since the present invention relates to non-aqueous systems, the oxyalkylated surfactant employed herein should be organically soluble. '1 ' In general, the compounds are oxyalkylated surfactants of the general formulav _ . r . . . ll .. x_o-, ~s~, -—CHz-'~, éonr??ete. ‘ O > ' wherein Z is the oxyalkylatable material, R is the radical derived from the alkylene oxide which can be, for exj 45 ample, ethylene, propylene,.buty1ene, epichlorohydrin and ‘ ll’ 1-2. _______ .- R—S—CH2O—-O— 13.;...... _- RPO4‘H 14,. ______ _- RPOA/ ‘ the like, n is a number determined by the moles of alkyl =_ ene oxide reacted, for example 1: to 2000 or more and ‘m a whole number determined by the number of reactive oxyalkylatable groups. Where only one group is oxy 50 15 ________ __ ' '\ 04: 1s.- ....... _- . RF'Q-somL ‘ alkylatable as in the case of a monofunctional phenol or alcohol, R’OH, then m=1. Where Z iswater, or a glycol, 171:2. Where Z is glycerol, m=3, etc. ' 17‘. _______ -_ \ RFC>so2N= In. certain cases, it is advantageous to react alkylene oxides with the oxyalkylatable material in a random fash 55 .‘ (I? H ‘ ion‘ so as to form a random copolyrner on the oxyalkylene ....... .. ace-MGM chain, i.e. the‘ [ (OR) nOH] m chain such as ‘ 19 ........ __ Polyohdcrived (‘Exz'glyceroh glucose‘, peritae'ritliytol)‘ AABAAABBABABBABBA+ _ In addition, the alkylenel oxides can be reacted. in an alternate fashion to form block copolymers on the chain, 60 for example BBBAAABBBAAAABBBB~ or 20; _______ .. Auhydrohexitan or anhydrohexide‘derived 2i ________ __ , Polycarboxylic derived 22.‘_._.-._.. lenienmL \ 1] -BBBBAAACCCAAAA-BBBB— where A is the unit‘ derived from one alkylene oxide, for example ethylene oxide, and B is the unit derived from‘ a Ha amine second alkylene oxide,.for example propylene oxide, and C ‘is the unit derived from’a third alkylene oxide, for.eX-‘ ample, butylene oxide, etc. Thus, these compounds in- ' elude terpolymers or higher copolymers polymerized randomly or in: a block-wise fashion or in. many varia- ' ' THE PROCESS “ dusted. and. macerated, with the surfactantscontaining' or ganic solvent. ' In practice, the waste papef to be treated1 is preferably subdivided in relatively small pieces .as‘ by passing. the waste paper vthrough a» conventional shred-" r575. ding machine. The exact» size of theipieces-is'rndt mater —-A,,B1,C;,— or any variation thereof, wherein a, b and! c are 0 or a number providedthat at leastone of‘ them- is i > by treating used paper, which’ has preferably been sorted,. tions of sequential additions. Thus, (OR)-n in the above formula can‘ be Written‘ greater-than 0. I . In general, the process of this‘ invention is-carrie‘d out‘ 3,072,521 rial, it being advisable merely to so subdivide the waste 8 paper as to avoid the presence of a thick bulky mass which able in some instances to subject the recovered ?ber to a bleaching operation in which case it is advantageous to might damage the beater in which the waste paper is sub pass the ?ber from the continuous ?lter to a chest where sequently treated and to expose the inked paper to inti mate contact with the surfactant-containing solvent. the ?ber is subjected to the action of a bleaching agent, for example 1% chlorine bleach, after which the bleached ?ber is thoroughly washed with water. This washing may After the paper has been shredded, it is introduced into the surfactant-containing solution in an operating beating engine in su?icient quantity to provide a suspension which also be advantageously conducted by the use of a con tinuous ?lter of the Oliver type although other conven the beater can satisfactorily handle. In practice, we em tional means may be employed. ploy a suspension of approximately from about one to 10 The process can also be carried out continuously such ten percent by weight, or higher, solid content, but pref as by removing the ink from the solvent-surfactant me erably about two to ?ve percent, with an optimum of dium, by any suitable means, for example, by ?ltration, about 2.5 to 4 percent. settling and decantation, distillation, etc., and combina The ratio of surfactant to organic solvent will vary tions thereof and thereupon reusing the solvent-surfac depending on various factors: for example, the particular tant medium to deink additional paper. In other words, solvent employed, the particular surfactant employed, etc. the solvent-surfactant medium is separated from the paper However, in practice, we employ a concentration of sur pulp, freed of ink or other undesirable matter, and reused factant in organic solvent of about 2 to 20 volume percent, to treat additional waste paper. The reuse of the solvent or higher, for example about 4 to 12 percent with an surfactant system can be carried out batchwise or con optimum of about 6 to 10 percent. Of course, it should tinuously. be realized that the surfactant can be added to the solvent prior to addition to the heater or any time thereafter, provided the combination of surfactant and solvent is placed in intimate contact with the paper. The temperature of the reaction mass is not critical. Other variations on the above process can also be em ployed, for example, counter current extraction, etc. As is quite evident, the ef?ciency of the present process will vary with the speci?c solvent-surfactant system as Any temperature can be employed which is convenient. Well as the ratios of each employed. For example, a speci?c class or species of solvent may be more effective In practice, we carry out the treatment at room tempera~ as compared with other solvents employing the same sur ture although there is no reason why higher or lower tem factant while another solvent may be more effective with peratures cannot be employed, if desired, for example, one particular class or species of surfactant as compared below room temperature or above the boiling point of the 30 to other surfactants. In addition, certain surfactants are solvent if pressure equipment is employed, in certain more effective as deinkers in an organic system which is instances. not followed by a water Wash, while others are more effec The mass in the beater is circulated around the heater tive when followed by a water wash. An advantage of and subjected to the action of the beater wheel until the present invention is the fact that the surfactant can “shiners” have practically disappeared from the mass. be “custom built” to perform whatever function one de The time required for this operation will vary with the sires as to the system employed where no water wash is particular apparatus employed. Further beating promotes employed or where a water wash is employed. In addi an excess of ?ne ?bers which may not be desirable in tion, the surfactant can be “custom built” for optimum preparing paper. Beating time varies with the particular system and apparatus employed, but ordinarily in the laboratory the beating'of the mass is continued from about one-half to three minutes, or longer, for example about one to two minutes with an optimum of about one to one and one-half minutes, or until the ?ber is com pletely freed of ink and other extraneous material pres ent. However, these times will vary in the plant, depend ing on the effectiveness of the apparatus employed. vAfter completion of the beating action the mass is withdrawn from the heater and the excess liquid is sepa rated from the ?ber content which is then washed, if de sired, with an organic solvent. The separation and work ing of the ?bers may, for example, be advantageously accomplished by passing the mass from the beater di rectly to a continuous ?lter of the Oliver type. In this type of ?lter a perforated drum rotates in a tank con taining the suspension and by the action of reduced pres sure or suction the liquid is drawn through the perfora tions leaving a mat of ?ber on the surface of the drum, performance in any particular solvent. As is quite evident, new surfactants will be constantly developed which could be useful in our invention. It is, therefore, not only impossible to attempt a comprehensive catalogue of such compositions, but to attempt to describe the invention in its broader aspects in terms of speci?c chemical names of its components used would be too voluminous and unnecessary since one skilled in the art could by following the description of the invention herein select a useful surfactant. This invention lies in the use of suitable surfactants in conjunction with suitable organic solvents in deinking paper and their individual composi tions are important only in the sense that their properties can a?ect this function. To precisely de?ne each speci?c useful surfactant and solvent in light of the present dis closure would merely call for chemical knowledge within 55 the skill of the art in a manner analogous to a mechani cal engineer who prescribes in the construction of a ma chine the proper materials and the proper dimensions through which subsequent ?ltering takes place. During thereof. From the description in this speci?cation and Heat as well as reduced pressure can also be used to re and solvents suitable for this invention by applying them the rotation of the drum the mat of ?ber on the surface 60 with the knowledge of a chemist, one will know or deduce with con?dence the applicability or speci?c surfactants thereof can be subjected to sprays of organic solvent. cover the solvent. Other types of apparatus can also be in the process set forth herein. In analogy to the case employed. of a machine, wherein the use of certain materials of con struction or dimensions of parts would lead to no prac ~ If desired, the mat can also be water washed. Whether a water wash is desirable will depend on many factors, for example, the nature of the surfactant employed, tical useful result, various materials will be rejected as inapplicable where others would be operative. We can whether one wishes to remove water soluble material from obviously assume that no one will wish to use a useless the ?bers, etc. Alternatively the mat can be reslurried surfactant or a useless surfactant-solvent system nor will in water and then ?ltered and rematted on the Oliver ?lter. 70 be misled because it is possible to misapply the teachings After separation and washing, the ?ber is conveyed to a of the present disclosure to do so. Thus, any surfactant storage chest for use in the manufacture of paper or it is or surfactant-solvent system that can perform the func suspended in water and passed over a drum or screen to tion stated herein can be employed. form laps or sheets of pulp. While the foregoing process The following tests were devised to evaluate the process results in the production of white pulp, it may be desir 75 of the present invention: 3,072,521 10" ‘Although newsprint has been used to illustrate our process, any imprinted cellulosic material can be salvaged _' Ten grams of newsprint cut into approximately one for reuse by the process of the present invention, for ‘inch squares, the solvent and the surfactant were placed example various kinds of imprinted paper, suchras im 1n a one pint Mason jar ?tted with a Hamilton Beach cutter head and stirred on the Hamilton Beach blender 5 printe‘i newsprint’ Iotogravure newsprint’ bopkstocli’ from one to three minutes. The pulp was then ?ltered, “Pagan” stock’ ledger Stock’ cardboard’ etc‘ In addl' Process I using a 500 ml. ?lter ?ask and a Biichner ?lter funnel, non’ the PIPES? may.be used to d‘a‘wax paper apt-he with a wire Screen in place of ?lter paper. same time it demks, since the solvent-surfactant system The pulp was then washed twice with water by placing the ?ltered alslo 1s ggil?ble (If rim??? waxlgugmi the grocgss' 1 for one minute_ After each wash’ the pulp was then vents and surfactants aremerely exemplary _of a wide ?ltered to remove the water_ A clean pulp was obtained variety of other surfactants and. solvents which can be pulp in the blender with 300 ml. of water and stirring 10 - - - ~ v ‘ - n a 1 Ion’ 1 s on e rea-lze it at t e a We 5.01’ employed to yield a clean pulp. Pmcess H . Deinked paper is a very important source of rawlma Ten grams of newsprint cut into approximately one ‘15 terial for the manufacture of book and magazine papers, inch squares, the solvent and the surfactant were placed in‘ a one pint Mason jar ?tted with a Hamilton Beach labels’ coated Papers’ etcf' was? Edger papeis’ bonds.’ etc" can be ‘Flaked makmapmslble this riaducnon 11.1. the cutter'head and stirred on the Hamilton Beach blender amount of Vlrgm Pulp reqmred m suchgrades as Patent from one to three minutes. The pulp was then ?ltered, F°ated'b°ards# Pnstols, envelope Papers’ etc" as' We,“ as using a 500 ml. ?lter ?ask and a ‘Biichner ?lter funnel, 20 111 book’ magazme, and Cover Papem Delnked ground with a wiere screen in place of ?lter paper. _ The pulp ' wood Papers can b‘? usFd'advantagewsly as Summits?“ was then washed twice-With Solvent by placing the pulp patent-coated, r‘nulticyllnder boards and as a substantial in the blender with 300 ml. of solvent and stirring for one minute. After each wash, the'pulp was then ?ltered Porno“ of Phe hnerfurnlsh, 1n maml'a'hmf'd b°ards~ They are also’ bemg usifd 111' consldelzable quantlty for the Flam-1' to remove ‘the solvent. A clean pulp was obtained. 25 facture of hangmgs, newspnm, 199st‘?r PQPQY, mlmeo" It is to be noted that Process I and Process II are carsraphraper, catalog P?PerS,_t1SS,u¢S, and slmllar Papers ried out in exactly. the same manner except for the ?nal mFVhmh groundwoqd ‘5 ordmanlyv USed- Othe? uses of wash. Thus, both Processes I and II are inessence nondemke?i Paper are “(Q11 known Po the_ art_ aqueous processes, differing only in the ?nal step after Havmg thus flescnbed our mventlona What _We clalm the completion of the non-aqueous treatment and as 30 as new and deslre to 3?“? bl’ Leiters Patent 151 much of the solvent as possible is removed for economic reasons_ , ‘1- A Process‘ of delnklng _1mpf1nted Pallet Products ‘ without any prior contact with water consisting essen In Process I a terminal aqueous wash is e?ected, whereas in Process II a solvent wash is effected, With some tially of contacting said products with a waterless sur factant-contammg organic solvent, said surfactant being surfactants, Process I is preferred, with others Process II 35 substautlally S0111b1e in Sald Organic SOIVent is preferred, and with still others Process I or Process II 2. The Process of Clalm 1 Whef?ln the SOIVeIlt is a is equally e?ective. liquid hydrocarbon. The following examples were run according to the 3. The process of claim 2 wherein the surfactant is above procedures and are presented for purposes of illus~ non-ionic. tration and not of limitation. 40 ' TABLE II Solvent Surfactant Ex. No. ' Pro cedure ‘ Name Amt, ml. 1 ____ _- Kerosine ________ _- Tradename Chemical name Amt., ml. 270 .............................. .. Dingnylphenoeplusethyleneoxide(weightratio 1.0 to 1.31)... . _....do ____________________ .. . .. 3(5) 1 I 30 I Dincnylpnenol plus ethylcn e(we ati Dinonyl phenol plus ethylene oxide (weight ratio 1. Dinonyl phenol plus ethylene oxide (weiaht ratio 1. Dinonyl phenol plus ethylene oxide (weight ratio 1. Dinonyl phenol plus ethylene oxide (weight ratio 1. Dinonyl phenol plus ethylene oxide (Weialit ratio 1. Dinonyl phenol plus ethylene oxide (Weight ratio 1. 30 30 30 30 30 30 30 I I I I I I I Dinonyl phenol plus ethylene oxide (weizht ratio 1.0 30 I 270 Triton X—171 (Rohm & Haas). Blend of alkyl aryl polycther alcohols with organic sull‘onates. 30 I 275 Victarnul20 (Victor Chem)..- Oxyethylated phosphoric ester ______________________________ .. 25 I 275 Span-85 (Atlas) _____________ .. 25 I Sorbitan trioleate ___________________________________________ ._ 275 Surfynol 'I‘G. (air reduction)-. Mixture of ditcrtiary acetylenic glycol, alkyl phenyl ether of 25 I 275 275 Span-20 (Atlas) ............. .. Sorbitan monolaurate _______________________________________ ._ .............................. __ Dinnoyl phenol (1.011.31) plus ethylene oxide _________ ._ ... 25 25 I I 275 Surfynol104E (air reduction). Ethylene glycol solution oiaditertiary acetylenic glycol ..... -_ 25 II 275 Span-85 (Atlas) _____________ .. Sorbitan trioleate 25 II 275 Span-20 (Atlas) _____________ -. Sorbitan monolaurate _______________________________________ .. 25 II 275 Victamul 20 (Victor Chem)-.- Oxyalkylated phosphoric ester..- 25 II 275 Victamul 89 Oxyethylated phosphoric ester ________ .. . 25 II 275 Arquad 16 (Armour) n-Palmityl t‘rimethyl ammonium chloride . 25 I Gocoyl ammonium acetate ............ -. . 25 I . 25 I l-hydroxyethyl, 2-heptadecenyl glyoxalidine ................ __ 25 I polyethylene glycol and ethylene glycol. ‘ ‘ .. 275 ArmacO (Armour)... 275 Arquad 2-0 (Armour) ______ -- di-Oocoyl dimethyl ammonium chloride“ 275 Aglln? 220 (Carbide and Caron . ' ‘ ‘ . . Dinonylphenolplus Et0(1.0:1.31) .......................... ....__ 30.._.. Xylene .......... .- 31.____ Tur entine/ xy ene 50:50 by ' ‘270 . Deriphat 1700 (General O_____ ' % N-lauryl?-amlno propionicacid _________________________ __,..__ 25 I Nonyl phenol oxyethylated and suliated ____________________ _. 25 I n-LaurylB-amino propionic acid ............................. -- 30 I Mills). volume. 32"--- Cyclohexanone.__. 270 33 ________ __do .......... .- 270 .............................. __ Delirl‘liir?rstt S '44 _____do__ - 270 ‘ . 1600 ' ______ -. Nonylphenoloxyethylated and sulfated ...... ._ . 30' I (General Partialsodium salt oin-laurylB-iminodipropion _ 30 I . . _ _ . .- 30 I > Dinonyl phenol plus ethylene oxide (1.021.31) _ _ . . . . 3,072,521 11 ' 4. The process of claim 2 wherein the surfactant is cationic. 5. The process of claim 2 wherein the surfactant is anionic. 6. The process of claim 2 wherein the surfactant is ampholytic. 7. The process of claim 2 wherein the surfactant is an oxyalkylated phenolic compound. 12 16. The process of claim 15 wherein the surfactant is oxyalkylated alkyl phenol. 17. The process of claim 16 wherein the surfactant is an oxyethylated dinonyl phenol. 18. The process of claim 14 wherein the surfactant is an oxyalkylated phosphoric ester. 19. The process of claim 14 wherein the surfactant is a sorbitan ester. 8. The process of claim 7 wherein the surfactant is an oxyalkylated alkylphenol. 9. The process of claim 2 wherein the surfactant con tains an organic sulfonate. 10. The process of claim 2 wherein the surfactant is an oxyalkylated phosphoric ester. 11. The process of claim 2 wherein the surfactant is References Cited in the ?le of this patent UNITED STATES PATENTS 1,833,804 2,390,695 Watanabe ___________ .... Nov. 24, 1931 Dean _______________ _._ Dec. 11, 1945 401,145 545,113 Germany ___________ __ Aug. 28, 1924 Canada ____________ _. Aug. 20, 1957 a sorbitan ester. 12. The process of claim 11 wherein the surfactant is sorbitan trioleate. 13. The process of claim 11 wherein the surfactant is sorbitan monolaurate. 14. A process of deinking imprinted paper products without any prior contact with water consisting essential 1y of contacting said products with a waterless surfactant containing low boiling petroleum hydrocarbon solvent, said surfactant being substantially soluble in said solvent. 15. The process of claim 14 wherein the surfactant is an oxyalkylated phenolic compound. FOREIGN PATENTS OTHER REFERENCES CA41, #1103, 1947, Removal of Synthetic Finishes From Papers To Be Recovered. CA35, “4205, Regeneration of Pulp From Waste 5 Printed Papers,” Japanese Patent 133,421, Nov. 21, 1939.