Decolorization of Glycosides

Europaisches Patentamt 0 338 151 European Patent Office v\) Publication number: A1 Office europeen des brevets

EUROPEAN PATENT APPLICATION

@ Date of filing: 19.04.88

© Date of publication of application: © Applicant: HENKEL CORPORATION 25.10.89 Bulletin 89/43 300 Brookside Avenue Ambler Pennsylvania 19002(US) © Designated Contracting States: AT BE CH DE ES FR GB GR IT LI LU NL SE @ Inventor: McDaniel, Robert S., Jr. 968 Montgomery Court Oecatur Illinois 62526(US) Inventor: McCurry, Patrick M. 3146 Lake Bluff Drive Decatur Illinois 62521 (US) Inventor: Short, Rolland W.P. 2657 Gregory Court Decatur Illinois 62526(US) Inventor: Glor, Paul R. 448 Ewing Avenue Decatur Illinois 62522(US)

©" Representative: Harle, Horst, Dr. et al c/o Henkel KGaA TFP/Patentabteilung Postfach 1100 Henkelstrasse 67 D-4000 Dusseldorf(DE)

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Xerox Copy Centre EP0 338 151 A1

Decolonization of glycosides

This patent deals with the decolorization of the average polysaccharide chain length exceeds glycosides which are useful as surfactants and for about 20. United States Patent 4,393,203 to Leslie other purposes. issued July 12, 1983 describes the treatment of Glycosides are known to have several uses glycosides with a wipe film evaporator to assist in including their incorporation into detergent products 5 color reduction. Rau in United States Patent as nonionic surfactants. Lower glycosides, that is 4,465,828 issued August 14, 1984 suggests using those materials having a short hydrophobic moiety hydroxy carboxylic acids to minimize color forma- attached to the saccharide backbone as later de- tion when preparing glycosides. scribed, are useful as intermediates for manufactur- A general method of preparing glycosides is ing higher glycosides. The lower glycosides are 70 found in Untied States Patent 3,219,656 to Boettner also useful for such purposes as mold release issued November 23, 1965. Descriptions of produc- agents, for polymers which require a hydroxyl func- ing alkyl glycosides are also found in United States tionality, and as a formaldehyde scavenger in var- Patent 3,547,828 to Mansfield issued December ious products which utilize formaldehyde as a reac- 15, 1970 and United States Patent 3,598,865 to tant. 75 Lew issued August 10, 1971. Roth also describes Glycosides are typically formed from a lower the preparation of glycosides in United States Pat- saccharide which may be either monomeric or ent 4,223,129 issued September 16, 1980. polymeric with regard to the saccharide unit. For It is also known that glycosides may be decol- reasons which are not fully understood the orized by using a bleaching material. Suitable glycosides obtained from most processes are dark 20 bleaches include materials such as hydrogen per- colored. The color ranges from dark yellow to cof- oxide for bleaching. It has been observed, however, fee black depending upon the conditions under that upon exposure to high temperature, a which the glycoside is produced. The color is not bleached glycoside product can revert to a darker inherent to the glycoside per se but rather to the color product upon standing. presence of humins which are co-produced with 25 • Hydrogenation of saccharides to form polyols ' the glycoside. ■ has been known as evidenced by Kool in United It has been suggested that the color bodies States Patent 2,609,399 issued September 2, 1952. (humins) in the glycoside composition may be re- It is not the intent of the present invention to form moved by adsorption with resinous components. polyols by hydrogenation as this destroys the ke- This process requires that the entire glycoside 30 tone and aldehyde functionality desired for composition be mixed with a resin in sufficient glycoside formation. volume to substantially remove the color forming It has now been discovered that hydrogenation, materials. preferably catalytic hydrogenation, of a glycoside It has also been suggested that the color bod- composition can substantialy reduce the color. The ies present in a glycoside composition may be 35 hydrogenation of the glycoside composition ac- eliminated by treatment with various reducing according to the present invention allows for consid- ids. The acid reduction has its limitations in that the erably greater stability after color removal than acidic material must be neutralized or removed does bleaching. That is, the hydrogenation of the from the end products. This is the case with laun- color forming bodies in the glycoside composition dry detergents. Typically laundry detergent pro- 40 leads to a more stable product than does bleaching ducts are formulated in the alkaline pH range to which gives products capable of reversible reac- facilitate removal of body soil. Thus while there is tions. some market for glycosides in the acid pH range it Throughout the specification and claims per- is desired not to incorporate any more acid than is centages and ratios are by weight, temperatures necessary. For a description of the use of reducing 45 are degrees Celsius and pressures are in KPascals acids to produce glycosides see European Patent unless otherwise indicated. To the extent that any Application No. 82305286.5 to Arnaudis published of the references mentioned in this application are as 0 077 167 on April 20, 1983. applicable to the present invention they are herein Further discussion of treating a glycoside com- incorporated by reference. position to reduce color is found in European Pat- so In one aspect, the present invention provides a ent Application No. 83200572.2 to Mao published process for reducing the color of a glycoside com- as 0 092 875 on November 2, 1983. In Mao the position containing colored humins having conju- acid catalyst employed is stated to be destroyed gated unsaturation, characterized in that said pro- after at least 90% of the short chain alkyl monosac- cess comprises subjecting said composition to hy- charide (glycoside) has been destroyed and before drogenating conditions whereby to decrease the EP 0 338 151 A1 color of components of said composition, conve- ably from about 2 to about 18 carbon atoms. Spe- niently by contacting said composition with hy- cific alcohols which may be utilized herein include drogen or a hydrogen source under humin hy- methyl, ethyl, propyl, isopropyl, butyl, pentyl, drogenating conditions preferably in the presence hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, of a hydrogenation catalyst, and, if appropriate, by 5 tridecyl, tetradecyl, pentadecyl, hexadecyl, hep- subsequently recovering the glycoside composition tadecyl, and octadecyl. herein of reduced color, e.g. after separating any hy- Further alcohols which may be utilized drogenation catalyst from the composition. In the include benzyl alcohol, phenol, and the sterol al- cholesterol, sitosterol, stig- process of the invention, the step of subjecting the cohols including glycoside composition to hydrogenating conditions, io masterol, and the like. Also valuable herein are both aromatic and aliphatic e.g. a step of contacting the composition with hy- alcohols containing an drogen or a hydrogen source and, preferably, a structure such as nonylphenol. Similarly, alkoxylat- hydrogenation catalyst under hydrogenation con- ed alcohols may be utilized which include materials ditions is effected for sufficient time to effect a such as the ethylene and propylene oxide adducts decrease in the color of the composition but prefer- 75 of any of the aforementioned alcohols or the poly- ably is not effected for so long or under such merized forms of the aforementioned oxides, e.g. conditions as to cause substantial polyol formation. polyethylene glycol or polypropylene glycol. Typically, hydrogenation times where a catalyst is The glycosides which are suggested for use in selected from used will range from 5 minutes to 16 hours, prefer- the present invention include those ably 10 minutes to 12 hours, especially 15 minutes 20 the group consisting of fructoside, glucoside, man- to 9 hours and more particularly 30 minutes to 6 noside, galactoside, taloside, aldoside, altroside, hours. idoside, arabinoside, xyloside, lyxoside and In a further aspect, the invention provides a riboside and mixtures thereof. Preferably the glycoside composition containing hydrogenated glycoside is a fructoside and most preferably a humins. 25 glucoside. All of the aforementioned glycosides with The glycoside may be obtained through, for may be obtained from sugars (saccharides) example, the methods of the Mansfield, Lew, Boett- the preferential fructose and glucose starting ma- ner or Roth patents previously incorporated by terials being obtained from corn syrup. Complex reference. A glycoside is a material containing a glycosides, those containing one or more different saccharide structure which may be represented by 30 saccharide units, may also be used as starting the formula materials. ,; R(OG)X The glycoside has the ability to utilize the where R is a hydrophobic moiety, 0 an oxygen monomeric saccharide unit to promote chain atom and (G) is the saccharide structure growth of the glycoside. Thus x in the above for- (backbone) of the glycoside. The value x is the 35 mula may vary between 1 and 10, preferably from number of monosaccharide units in the glycoside. about 1.2 to about 5, and most preferably from The value also be The oxygen atom shown in the formula above about 1.3 to about 3.5. x, may is typically derived from an alcohol with R being referred to as the degree of polymerization (DP.) the hydrophobic moiety of the alcohol. The oxygen of the glycoside. This number is an average de- atom is attached to the saccharide in an ether 40 gree of polymerization. In obtaining a glycoside, linkage. Where the aldehyde or ketone structure of polymerization of the monosaccharide units occurs the saccharide is involved in the glycoside forma- to some extent usually through a 1,6 linkage. The tion the product may be termed an acetal or ketal saccharide portion of the glycoside molecule en- respectively. The favored reaction is the acetal or hances water solubility and thus for detergent pur- ketal formation to give the glycoside with the oxy- 45 poses it is advantageous to have the D.P. some- also desirable for deter- gen being attached to the carbon in the one posi- what greater than 1. It is tion. It is less likely that the hydrophobic moiety gents that the hydrophobic moiety have sufficient will be attached through one of the remaining length to give a proper HLB (hydrophilic/lipophilic hydroxyl groups present on the starting saccharide. balance), e.g. C* and above. Suitable hydrophobic moieties which are at- so Inherent in the glycoside formation is the gen- tached to the saccharide as previously described eration of color bodies referred to as humins which include primary or secondary alcohols having are believed to be polymers of levulinic acid, fur- straight or branched chains which can be either fural or hydroxymethyl furfural. The monomers of saturated or unsaturated and may contain ether these polymers are obtained as a by-product when linkages. Preferably, the alcohols are primary satu- 55 the saccharides are partially degraded by heat or rated alcohols. Examples of such materials include other processing conditions. These monomers are those alcohols containing from 1 to about 30, pref- then polymerized through a not fully understood erably from about 1 to about 20, and most prefer- mechanism into polymers which contain conjugat- EP0 338 151 A1 ed unsaturation which strongly absorbs light in the metals. Where desired the catalyst may be re- visible range. The removal of such components is duced and sulfided prior to its use. This may be extremely difficult. The reversibility of the glycoside accomplished during its synthesis or in situ prior to formation to give an alcohol and the starting sac- admixing with reactants. charide allows the generation humins throughout 5 Most conveniently the hydrogenation catalyst the process. Thus the practice of this invention is will be employed with a direct source of hydrogen preferred over pretreating the saccharide or even to maintain the reaction and the catalyst in its intermediate glycosides to remove or eliminate the active state. By maintaining the catalyst in its ac- color forming bodies. tive state the process of decolorizing a glycoside The glycoside within the glycoside composition 10 composition may be conducted on a continuous is typically present on a dry solids basis during the basis. It is noted that some catalysts such as hydrogenation reaction at from about 10% to about Raney nickel contain hydrogen within the structure 75%, preferably from about 20% to about 60% by of the catalyst and thus may be used without weight of the composition to be hydrogenated. The additional hydrogen. Of course, Raney nickel may remainder of the glycoside composition includes 15 also be used with added hydrogen such that the saccharides, alcohols, water or other convenient catalyst is maintained effective for longer periods solvents. During the hydrogenation reaction, the of time. It is suggested that when conducting the glycosides are preferably dispersed in a solvent reaction on a continuous basis that the catalyst be selected from the group consisting of polar and continuously removed and replaced with fresh non-polar solvents, for example water or fatty al- 20 amounts of catalyst to continue optimum process- cohols, e.g. C6-30 alcohols, preferably C6-2+ al- ing. cohols and especially Cs or Cs to Cis alcohols. The source of hydrogen for the hydrogenation Where a hydrogenation catalyst is employed, is most conveniently hydrogen gas although other this may be any material suitable for such purpose. hydrogen sources may be utilized such as lithium As the materials involved are organic, and for the 25 aluminium hydride or an alkali metal borohydride, most part carbohydrates, it is desirable that the e.g. sodium borohydride. catalyst be sufficiently active to allow saturation of In those instances wherein reactive hydrogen the conjugated double bonds present in the sources (such as, for example, alkali metal alumin- glycoside composition. One skilled in the art in ium hydrides or alkali metal borohydrides) are di- selecting the catalyst should be aware of the po- 30 rectly employed as hydrogenation reagents in the tential for the poisoning or inactivation of the cata- absence of a separately added hydrogenation catalyst by the glycoside or trace components within lyst, it is generally preferred to conduct the result- the giycoside composition. ing hydrogenation at a temperature of from about Where a hydrogenation catalyst is employed, it 20 to about 75 (preferably from about 30 to about typically is selected from groups IB, IIIB, IVB, VI, 35 60 and most preferably from about 40 to about 50) ° VII and VIM of the periodic table. Conveniently the C and for a treatment period of from about 1 to catalysts are based on nickel, platinum, palladium, about 1 00 (preferably from about 4 to about 50 and molybdenum, chromium, osmium, iron, ruthenium, most preferably from about 8 to about 24) hours. In rhodium, cobalt, copper, silicon, platinum, alumin- addition, when this particular type of hydrogenation ium, silver, manganese, lead, tin, rhenium, gallium, 40 reaction is conducted utilizing the discolored yttrium, lanthanum, and other rare earths, and ce- glycoside composition in the form of an aqueous rium, and mixtures thereof. solution thereof, it is generally preferred to conduct The preferred catalysts which are employed the hydrogenation reaction at a pH of at least about herein are based on nickel, platinum, palladium, 8, more preferably in the range of from about 10 to cobalt, and molybdenum. Furthermore, the hydro- 45 about 13 and most preferably in the range of from genation catalyst may employ combinations of the about 1 1 to about 1 2. foregoing metals to provide a balance of activity Where a catalyst is employed in the present and selectivity. For example, a promoter may be invention it may be supported or unsupported and used selected from the group consisting of molyb- may be utilized in a heterogeneous or homoge- denum, chromium, osmium, iron, rhodium, 50 neous catalytic system. Most preferably, the cata- rhenium, cobalt, copper, silicon, platinum, alumi- lysts employed herein are heterogeneous catalysts. num, silver, manganese, yttrium, lanthanum, and In a heterogeneous catalyst system the catalyst other rare earths and cerium and mixtures thereof. constitutes a separate phase. Supported catalysts In addition, unwanted side reactions such as are always heterogeneous catalysts; however, het- isomerization and decomposition to carbonaceous 55 erogeneous catalysts also exist which are not sup- materials, etc. may be suppressed by the use of ported. For example, a Raney nickel may be em- attenuators such as phosphorous, gallium, germa- ployed in a supported function or may be dis- nium, tin, lead, and sulfided forms of the active persed throughout the glycoside composition. One EP0 338 151 A1 aspect of the present invention allows the catalyst palladium on barium carbonate powder; ruthenium to be utilized in a fixed bed which is in fact a on carbon; nickel, cobalt or molybdenum alone, or heterogeneous supported catalyst system. In a pre- in combination, and on alumina; ruthenium on alu- ferred embodiment, the catalyst is employed in one mina; and rhodium on carbon and rhodium on or more fixed bed reaction zones through which the 5 alumina. reactants are passed on a continuous basis and in The following catalysts may be utilized in a include the presence of hydrogen. pelleted or granular form. These catalysts The use of hydrogen as previously described palladium on 4-8 mesh (4.76 to 2.38 mm) granular is typically carried out at from ambient pressure carbon, palladium on 1/8 inch (0.32 cm) alumina (101 KPa) to about 10,000 KPa. Preferably the io pellets, palladium on 28-150 mesh (595 to 105 hydrogen pressure will be from about 101 KPa to micrometers) carbon. Platinum (sulfided) on 0.32 about 2,000 KPa. In practice the process may be cm (1/8 inch) alumina pellets, ruthenium on 4-8 conducted by maintaining sufficient hydrogen at mesh (4.76 to 2.38 mm) granular carbon, ruthenium the reaction zone, e.g. the catalytic site, to sustain on 0.32 cm alumina pellets and rhodium on 0.32 the reaction. 75 cm alumina pellets. In addition to the foregoing The parameters of conducting a hydrogenation iridium may be employed on a support which is reaction may vary substantially in the present in- carbon, calcium carbonate or alumina. vention due to the selection of the catalyst of this The following unsupported powdered catalysts particular hydrogenation reaction. These factors in- may also be employed herein. These catalysts clude, the amount of the color bodies (humins) in 20 include palladium oxide, palladium black, platinum the glycoside composition to be hydrogenated; the oxide, platinum black and ruthenium dioxide. partial pressure of the hydrogen gas (which deter- Metals of Group VIII which are conveniently mines concentration in the reaction phase); the used herein are iridium trichloride in the form of its temperature in the reaction vessel; the activity and hydrates, and osmium tetroxide. Palladium com- amount of any catalyst utilized; and the duration of 25 pounds usable herein include ammonium palladium the contact of the glycoside composition with the (IV) hexachloride, palladium (II) chloride; palladium catalyst and hydrogen. The degree of color im- (II) diamino dichloride, palladium diamino dinitrite, provement sought is also a factor. In practice, the palladium (II) nitrate, sodium palladium (II) chloride, dark brown state of the glycoside composition is and palladium (II). conveniently converted to at least a straw yellow or 30 Frequently used metal catalyst compounds in- amber liquid by the hydrogenation. As the clude ammonium platinum (IV) hexachloride, glycosides have several uses, it is entirely possible chloroplatinic acid, platinum (II), platinum diamino during production to separate streams of the dinitrite; potassium platinum (II) tetrachloride and glycosides and to decolorize each stream to the potassium platinum (IV) hexachloride. Also useful desired extent depending upon the end usage. 35 herein are rhodium trichloride in the form of its The temperature of the glycoside composition hydrates, ruthenium dioxide, ruthenium nitrate, during the hydrogenation, in particular catalytic hy- ruthenium trichloride and rhenium. drogenation, is conveniently maintained between The following nickel catalysts from Alfa (Morton about 10° C and 250° C, preferably from about Thiokol) are useful herein: Nickel coated aluminum; 25° C to 120° C, most preferably from about 30° C 40 nickel coated diatomaceous earth; nickel coated ° to about 90 C. As the function of the catalyst is to graphite; nickel on kieselguhr skirts; nickel on silica lower the activation energy for the hydrogenation alumina; nickel molybdate on alumina; nickel, co- reaction, the exact parameters of temperature are balt, iron oxide on alumina; nickel oxide on silica- dependent upon the hydrogenation catalyst (if one alumina; nickel, tungsten on silica-alumina. is employed) and on the hydrogen concentration. It 45 Metal powders of the Raney type-aluminum is desired to operate in the lower temperature alloys are also useful herein. Such materials are ranges for hydrogenation. Low temperature oper- the powdered alloys of aluminum with a base met- ations on the glycoside composition are desired to al. The aluminum is leached with a strong caustic minimize side reactions including the formation of solution followed by careful water washing in the further humins during the hydrogenation. so absence of air. These so-called Raney type cata- Hydrogenalysis of the glycoside is also minimized lysts are finely divided powders which are by low temperatures. pyrophoric when exposed to the air. The typical The following are suggested hydrogenation aluminum-metal ratio in the alloy is 1:1. Such alloys catalysts which may be employed in the present include aluminum-cobalt; aluminum-copper and invention. These catalysts include palladium on 55 aluminum-nickel. These materials may be preac- carbon; palladium on alumina or calcium carbonate; tivated and stabilized so that they are non- platinum on alumina; platinium on carbon; sulfided pyrophoric. Of course, Raney nickel of the palladium on carbon; palladium on barium sulfate; pyrophoric type may also be utilized, however, this EP 0 338 151 A1 10 material should be handled to avoid contact with any convenient means such as filtration, decanting, free oxygen. or using a support. The glycoside is thus recovered The following disclosure of catalysts suitable in a less colored state. herein is found in Catalysis of Organic Reactions The invention will now be illustrated by means edited by William R. Moser published by Marcel 5 of the following non-limiting Examples:- Dekker, Inc. copyright 1981 New York and Basel. (Pages 383 et seq.) Further disclosures of suitable catalysts herein EXAMPLE include Raney-type nickel catalysts prepared from a ternary nickel-silicon-cobalt alloy. Similarly, 10 nickel-aluminum-molybdenum, nickel-aluminum-co- A suggested exemplification of the present in- balt and nickel-aluminum-chromium alloys are also vention involves the treating of a glycoside com- useful herein. Further ternary alloys of interest in- position comprising n-butyl glucoside which is pre- clude those of Ishikawa reported at Nippon Kagaku pared from starch according to the Roth patent Zasshi 81_ (1960) and 82 (1961). Ishikawa describes 75 previously incorporated herein by reference. ternary alloys of silver, copper, iron, manganese, The n-butyl glucoside in the amount of 100 lead and tin. Further descriptions in the Catalysis of parts (28.29 parts solids in butanol) is placed in a Organic Reactions include quaternary and quinary reaction vessel containing 0.52 parts of 20% aque- alloys. ous sodium hydroxide. Also present in the hy- The following materials described in Raney Ac- 20 drogenation vessel are 1.47 parts of wet Raney tive Metal Catalysts and Alloys of the Davison nickel. The system is sealed such that the later Chemical Division of W. R. Grace & Company are described hydrogen gas will not be vented to the also useful herein. These products described as atmosphere. Raney active catalysts include Raney 2400- The hydrogen gas is generated in this experi- chromium-promoted; Raney 27-cobalt; Raney-28- 25 ment by introducing sodium borohydride (dissolved nickel; Raney-29-copper, Raney-30-molybdenum- in aqueous sodium hydroxide) to a second reaction promoted; Raney 3000-molybdenum-promoted; vessel containing sufficient 5N sulphuric acid to Raney 200-nickel (highly active nickel fines); Raney generate the required amount of hydrogen gas. In 4100-nickel; Raney 4200-nickel; and Raney 4300- the present case, the hydrogen gas is generated molybdenum-promoted. 30 over a sufficient period of time to obtain the maxi- Raney alloys also available from W. R. Grace mum color reduction possible in the glucoside. A include 2413-chromium-promoted nickel-aluminum conduit is employed between the reaction vessel powder; 2713-cobalt-aluminum powder; 2813- which is generating the hydrogen gas and the nickel-aiuminum alloy powder; 2913-copper-alumi- reaction vessel containing the butyl glucoside. Suf- num alloy powder; 5842-crushed-granular nickel- 35 ficient agitation is maintained in each vessel so that aluminum alloy; and 5830-crushed granular molyb- the hydrogen gas is evolved, and second, ade- denum promoted nickel aluminum. The catalysts quately dispersed in the butyl glucoside composi- found in Raney Active Metal Catalysts and Alloys tion. The initial reaction is conducted over a period Davison Chemical Division, W. R. Grace & Com- of approximately 3 1/2 hours at 25° C. The reaction pany are herein incorporated by reference. 40 mixture is then treated for an additional four hours Further suggested hydrogenation catalysts in- at from 70 'C to 75° C to increase the amount of clude those described in Volume 2, A Bibliography hydrogen gas reacted in the glucoside composi- of Research in Catalysis with the Rare Earth Ele- tion. ments (1971- 1976) entitled~ApplJcation Report 7907 The hydrogenated glucoside composition is Molycorp, Inc. 6 Corporate Park Drive, White 45 then tested for transmittance using a 2 centimeter Plains, New York 10604 pages 19-21. Still further cell at 470 nanometers. discussions on the preparation of Raney nickels The improvement over the starting glucoside W2; W4; W6; W7; and W8 for deuteration are compared to the end hydrogenated glucoside com- discussed in Catalytic Hydrogenation Techniques position showed a 62% transmittance increase. and Applications in Organic Synthesis, Robert L. 50 Augustine 1965, Marcel Dekker, Inc. which is herein incorporated by reference. The disclosures on EXAMPLE II the preparation of of Raney nickel catalyst by Au- gustine are found in the appendix at pages 147- 149. Other useful Raney catalysts include W1; W3; 55 A second glucoside composition is prepared as and W5. in Example I with the exception that the caustic is The catalyst may be separated from the omitted in the vessel containing the glucoside and glycoside composition following hydrogenation by the catalyst is platinum on charcoal. The amount of 11 EP 0 338 151 A1 12

50° catalyst employed is 0.1 part of 5% platinum on ing the temperature at C. The color improve- charcoal. ment of the hydrogenated composition over the ° The reaction is conducted at from about 70 C starting material gives a 66% decrease in the ex- to 75° C over a period of 6 hours. The color reduc- tinction coefficient, i.e. much higher light transmit- tion of the glucoside mixture is visibly noticeable. tance, for the finished product. An as is color comparison of the starting glucoside to the hydrogenated end-product shows a transmittance increase of greater than 100%. EXAMPLE VI Example II is repeated by dispersing the glycoside prior to hydrogenation in 5 parts of butyl 10 Two hundred parts by weight of an aqueous contains 50 alcohol per part of glycoside. The hydrogenated alkyl glucoside solution which weight composition will have approximately the same color percent (i.e. 100 parts by weight) of a C12-13 alkyl as in Example II but will be easier to process due glucoside having an average degree of polymeriza- to a more fluid nature. tion of about 2 and which has a pH of about 3.7 75 and an extinction coefficient of 1.32 is thoroughly admixed with 3.3 parts by weight of a 14N NaOH EXAMPLE solution containing 12 weight percent of sodium borohydride (i.e. 0.4 parts by weight of sodium borohydride hydrogenation reagent per 100 parts The hydrogenation of the glucoside composi- 20 by weight of alkyl glucoside solids). The resulting tion of Example I may be repeated utilizing any of aqueous mixture has a pH of about 11.6 and is 25° the hydrogenation catalysts listed hereinbefore. held at ambient temperature (i.e. about C) for a The glucoside compositions are observed to be time period of 4 days. At the end of that time improved in color as a result of the hydrogenation. period, the resulting hydrogenated aqueous A further variable in the present invention is to 25 glycoside solution has an extinction coefficient of use Raney nickel in a batch process where no 0.64 and thus exhibits substantially improved color color lev- outside hydrogen gas is included. A further vari- characteristics (i.e. substantially reduced ation of the present invention is to utilize hydrogen els) relative to that of the untreated starting ma- gas with Raney nickel or platinum on charcoal. terial. This example is repeated using Raney nickel 30 with each of the promoters described herein with similar results. EXAMPLE VII Example III is successfully repeated by having present 5 parts of water per part of glycoside in the The hydrogenation process of Example VI is hydrogenation vessel. 35 repeated except that the treatment period is reduced from four days to one day. The resulting sodium borohydride treated product is found to EXAMPLE IV have a substantially lower extinction coefficient (i.e. substantially lighter coloration) than the untreated 40 starting material. A long chain glucoside is hydrogenated to reduce color according to the following. Butyl glucoside is prepared and transetherified with a Claims C12-13 primary alcohol (Neodol 23) to give a long chain glucoside suitable for detergent uses. 45 1. A process for reducing the color of a This material is hydrogenated in accordance glycoside composition containing colored humins with each of the processes described in Examples having conjugated unsaturation, characterized in t, II and III. Upon conducting the hydrogenation, it that said process comprises subjecting said com- is observed that lighter colored products are ob- position to hydrogenating conditions. tained over the starting glucoside. 50 2. A process as claimed in claim 1 wherein said composition is contacted with hydrogen or a hydrogen source under humin hydrogenating con- EXAMPLE V ditions. 3. A process as claimed in either one of claims Twenty-five parts of a C12-13 DP3 glucoside 55 1 and 2 comprising contacting said composition are dispersed in forty parts water. Twenty parts with a hydrogenation catalyst and hydrogen or a Raney nickel are introduced and the entire mixture hydrogen source under hydrogenation conditions is stirred over a period of five hours while maintain- 13 EP 0 338 151 A1 14 whereby to decrease the color of components of 18. A process as claimed in any one of claims said composition and thereafter recovering a 3 to 17 wherein said hydrogenation catalyst com- giycoside composition of reduced color. prises a material selected from molybdenum, chro- 4. A process as claimed in any one of claims 1 mium, osmium, iron, ruthenium, rhodium, cobalt, to 3 which process comprises contacting said 5 copper, silicon, platinum, aluminium, silver, man- giycoside composition with a hydrogenation cata- ganese, lead, tin, yttrium, lanthanum, rare earths lyst in the presence of hydrogen or a hydrogen and cerium and compounds and mixtures thereof. source at a temperature of about 10 to 250° C at a 19. A process as claimed in any one of claims pressure of about 101 to 10,000 KPa whereby to 1 to 18 wherein an alkali metal borohydride is decrease the color thereof and thereafter separat- w employed as a hydrogen source. ing the hydrogenation catalyst from the giycoside 20. A giycoside composition at least partially composition and recovering the giycoside composi- decolorized by hydrogenation. tion of reduced color. 5. A process as claimed in any one of claims 1 to 4 wherein said giycoside composition comprises 75 an alkyl giycoside. 6. A process as claimed in any one of claims 1 to 5 wherein said giycoside composition comprises an alkyl glucoside. 7. A process as claimed in any one of claims 1 20 to 6 wherein during hydrogenation said giycoside composition contains from about 10% to about 75% by weight of giycoside on a total giycoside composition weight basis. 8. A process as claimed in any one of claims 1 25 to 7 wherein during hydrogenation said giycoside composition contains from about 20 to about 60 weight percent of giycoside on a total giycoside composition weight basis. 9. A process as claimed in any one of claims 3 30 to 8 wherein as said hydrogenation catalyst is employed a homogeneous catalyst. 10. A process as claimed in any one of claims 3 to 8 wherein said hydrogenation catalyst is supported. 35 11. A process as claimed in any one of claims 3 to 10 wherein said hydrogenation catalyst comprises nickel, platinum, palladium or a compound thereof. 12. A process as claimed in claim 11 wherein 40 said hydrogenation catalyst is a Raney-type nickel. 13. A process as claimed in any one of claims 3 to 8 and 10 to 12 wherein said hydrogenation catalyst is employed in a fixed bed. 14. A process as claimed in any one of claims 45 3 to 8 and 10 to 13 wherein as said hydrogenation catalyst is employed a heterogeneous catalyst. 15. A process as claimed in any one of claims 1 to 14 wherein during hydrogenation said giycoside composition is dispersed in a solvent so selected from the group consisting of polar and non-polar solvents. 16. A process as claimed in claim 15 wherein said solvent comprises water. 17. A process as claimed in claim 15 wherein 55 said solvent comprises a fatty alcohol. Patent Application Number J European EUROPEAN SEARCH REPORT Office EP 88 30 3525

DOCUMENTS CONSIDERED TO BE RELEVANT Citation of document with indication, where appropriate, Relevant CLASSIFICATION OF THE Category of relevant passages to claim APPLICATION ant. CI.4) EP-A-0 077 167 (ROHM AND HAAS) Y,D C 07 H 15/04 * Abstract; claim 1 *

Y ORGANIC CHEMISTRY, 3rd edition, 1970, page 745, McGraw-Hill Book Co., New York, US * Page 745, table 18.3 *

EP-A-0 165 721 (A.E. STALEY) * Page 5, line 7 - page 8, line 11; claim 1 *

W. WARD PIGMAN et al . : "Chemistry of the carbohydrates", 1948, Academic Press, Inc., Publishers, New York, US * Page 71, lines 1-10 *

TECHNICAL FIELDS SEARCHED (Int. C1.4)

C 07 H 15/00

The present search report has been drawn up for all claims Place of search Date of completion of the search Examiner THE HAGUE 28-10-1988 BRENNAN J.

2 CATEGORY OF CITED DOCUMENTS T : theory or principle underlying the invention 3 E : earlier patent document, but published on, or X : particularly relevant if taken alone after the filing date Y : particularly relevant if combined with another D : document cited in the application S document of the same category L : document cited for other reasons A : technological background I O : non-written disclosure & : member of the same patent family, corresponding P : intermediate document document