September, 1933
INDUSTRIAL AND ENGINEERING CHEMISTRY LIMITINQ CONCN. %
COMPOUND p-Dichlorobenzene a-Chloronaphthalene 8-Chloronaphthalene p-Chlorophenol o-Chlorophenol
1.3-1.4 0.4-0.5 0.5-0.6 0.34.4 0.6-0.7
COMPOUND
LIMITINQ CONCN.
% 2-Chloro-5-hydroxytoluene Phenol o-Cresol Naphthalene
0.5-0.6 0.8-1.0 0.7-0.8 0.6-0.8
The present results agree with those of Curtin and Bogert in indicating an increase in fungicidal power upon the chlorination of the lower phenols, although the relative increase was very much less than was found by them. Contrary to their results, the writers find that the chloronaphthalenes appear to be better preservatives than is naphthalene itself, although the differences are not large. The discrepancies between our results and those of Curtin and Bogert are due, apparently, to the difference in the method used for the
991
determination of preservative efficiencies. The former investigators used the agar plate method, in which the results depend to a marked extent upon the solubi!ity of the preservative in water: in the mood pulp method (and probably also in service) slight variations in solubility have relatively less effect. LITERATURE CITED (1) Curtin a n d Bogert, ISD.ENG.CHEX, 19, 1231 (1927). (2) Rhodes a n d Gardner, Ibid., 22, 167 (1930). (3) Schmitz a n d others, Ibid., Anal E d . , 2, 361 (1930); see also Schmitz and Zeller, I N D .E N G .CHEM.,13, 621 (1921); Schmitz a n d Buckman, I b i d . , 24, 772 (1932). RECEIVED March 6, 1933. The work described here was done under a fellowship maintained a t Cornel1 University by the American Creosoting Company.
Dry Distillation of Residue of Waste Sulfite Liquor MAXPHILLIPS, Bureau of Chemistry and Soils, Washington, D. C.
I
X A PAPER recently published from this laboratory ( 7 ) results of an investigation were presented dealing ITith the dry distillation of alkali lignin in a reduced atmosphere of carbon dioxide. I n this paper the results are given of a similar study on the dry distillation of the residue of waste sulfite liquor. Ahrens (1) was the first to make a study of the products of the dry distillation of waste sulfite liquor. He neutralized the liquor with lime, then evaporated the solution to dryness, and subjected the residue to dry distillation. The distillate was found to contain acetone and acetic acid, together with an oil containing sulfur, The carbonized residue contained 33.6 per cent ash and 4.37 per cent total sulfur. Bantlin (2) partly separated the volatile sulfur compounds from waste sulfite lye by passing through it a current of air and steam. The solution was then evaporated t o dryness and the residue distilled. A small yield of liquid products was obtained and no methanol, while large quantities of hydrogen sulfide and mercaptans were evolved. I n view of the rather meager information found in the literature with respect to the composition of the distillate obtained when the dry residue of waste sulfite liquor is subjected to dry distillation, the investigation described in this paper was undertaken. EXPERIMENT.4L PROCEDURE
PREPARATION OF MATERIAL. Waste sulfite liquor concentrated to the consistency of sirup was kindly furnished by The Brown Company, of Berlin, N. H. The total solids in this product amounted to 51.37 per cent. The product was evaporated to dryness, dried a t 105" C., and ground to a powder. This dry material analyzed as folloas: Ash, 19.03 per cent; sulfur, 6.84 per cent; methoxyl, 6.54 per cent. APPARATUS.The apparatus described in a previous communication (7) was used for these experiments. The distillation experiments were carried out in a manner similar to that described in the article on the dry distillation of lignin from corncobs ( 7 ) . For each experiment, 300 grams of the dry residue from waste sulfite liquor were used. The air in the apparatus was first replaced with dry carbon dioxide and then evacuated to 25 mm. pressure. A small stream of dry
carbon dioxide a t the rate of about one bubble per second was passed through the apparatus during the distillation experiment. The temperature was gradually increased until the maximum of 400" C. was obtained. The gases given off had a very obnoxicus odor. The presence of hydrogen sulfide and mercaptans could be detected. The distillate consisted of a milky, aqueous liquid and an oil. Because of the relatirely small amount of oil in the distillate, no attempt was made to separate it from the aqueous portion of each individual experiment. In each experiment the weight of the distillate and of the carbonized residue in the retort was determined. No attempt was made to collect the gaseous products, and the weight of the latter was obtained by difTerence. The results of ten experiments are given in Table I. TABLEI. PRODUCTS OF DRY DISTILLATION OF SULFITELYE [300 gramm material used in each experiment (222.6 grams calculated on ash- and sulfur-free basis) I TOTALDISTILLATE (OIL AQWEOUBDISTILLATE) Yield (calcd. CARBONIZBD RESIDUE^ GASEOUS P'RODUCTBb OD ash- and SE X P T . Weight Yield free material) Weight Yield Weight Yield Grams Grama % Grama % % % 1 166 55.3 62.0 20.7
+
2 3 4 5 6 7 8 9 10
167 168 167 160 165 164 164 161 170 165
55.6 56.0 55.6 53.3 55.0 54.6 54.6 53.6 56.6 65.0
64.0 63.0 63.0 65.5 64.0 62.5 64.0 66.0 60.0 63.6
21.4 21.0 21.0 21.9 21.4 20.9 21.4 22.1 20.1 21.2
Mean A composite sample of the carbonized residue was sshed and found to yield 35.90 per cent ash. b By difference. (1
EXAMINATION OF AQUEOUS DISTILLATE The aqueous distillates from the ten experiments were combined. To this Norit was added, the mixture was well shaken and allowed to stand a t room temperature for 2 hours. This was filtered, and the filtrate made up to 1000 cc. in a volumetric flask; 250 cc. of this solution were treated with 4 per cent potassium permanganate until no further reduction took place. This was for the purpose of oxidizing volatile reducing substances, chiefly sulfurous acid. The product was made acid with sulfuric acid and distilled in a current of steam until the distillate coming over no longer reacted acid. The
992
INDUSTRIAL AND ENGINEERIXG CHEMISTRY
distillate was neutralized with sodium hydroxide and concentrated to a volume of 800 cc. Some tarry matter separated out in the course of this operation and was filtered off. The filtrate was acidified with sulfuric acid and distilled in a current of steam until all the volatile acids were driven over. The distillate was made up to a definite volume, and an aliquot titrated with 0.1 iL' sodium hydroxide solution, phenolphthalein being used as the indicator. -4 total of 1498.8 cc. of 0.1 .V sodium hydroxide vias used. This corresponds to 8.99 grams acid calculated as acetic acid, or 36.96 grams in total aqueous distillate (equal to 1.19 per cent yield calculated on the 3000 grams dry sulfite lye residue used, or 1.61 per cent calculated on the ash-free and sulfur-free material). The above-mentioned solution, containing the sodium salts of volatjle acids, was evaporated to dryness and a portion of the dry residue converted into the acid toluide according to the method described by Mulliken (5'). I t melted a t 148.6' C. (corrected), and, when mixed with a pure specimen of acetop-toluide, no depression in the melting point was observed. The optical properties of the crystals of the toluide prepared from the sodium salt of the volatile acid obtained in the steam distillation were found to be identical with those of a known and pure specimen of aceto-p-toluide. The volatile acid therefore consisted chiefly of acetic acid. Another 250-cc. sample of the aqueous distillate was made slightly alkaline with sodium hydroxide and distilled until about 150 cc. of distillate were obtained. The residual solution was acidified with phosphoric acid and distilled in a current of steam until the distillate coming over no longer reacted acid. The solution remaining in the distilling flask was filtered and exhaustively extracted with ether. The ether solution was dried over anhydrous sodium sulfate, and the ether removed by distillation. A small amount of sirup was obtained. This was subjected to distillation under reduced pressure. Sothing definite could be isolated from the small quantity of distillate obtained. Acetone Determination. The acetone in the aqueous distillate was determined by the method of Deniges ( 3 ) . The Messinger method (4) for determination of acetone could not be used because of the relatively large amounts of sulfurous acid and other sulfur compounds in the distillate. Three 25-cc. samples yielded 0.5772, 0.5677, and 0.5697 gram of precipitate, respectively. This corresponds to 0.0351, 0.0345, and 0.0347 gram acetone (mean = 0.0348 gram acetone = 1.3920 grams acetone in total aqueous distillate, or 0.046 per cent of the total weight of dry material distilled = 0.062 per cent calculated on the ash-free and sulfur-free material). The methanol in the aqueMETHANOL DETERMINATIOK. ous distillate was determined by a method referred to in a previous communication (6). Two 5-cc. samples gave 0.3837 and 0.4017 gram silver iodide, and 0.0623 and 0.0547 gram methanol (= 10.70 grams-mean value-in the total aqueous distillate = 0.35 per cent calculated on the 3000 grams material distilled and 0.48 per cent calculated on the ashand sulfur-free material.) EXAMINATION OF OIL. The oil which had been separated from the combined distillates of all the ten experiments amounted to 46 grams (= 1.53 per cent yield calculated on the 3000 grams material distilled, or 2.0 per cent calculated on ash- and sulfur-free material). The oil was diluted with approximately three times its volume of ether, and the solution extracted with a 5 per cent solution of sodium bicarbonate. This extract was acidified with sulfuric acid and distilled in a cuwent of steam until the distillate coming over no longer reacted acid. The total distillate was made up to a definite volume, and an aliquot was titrated with a 0.1 N sodium hydroxide solution; 311.7 cc. were required for the
Vol. 25, No. 9
total distillate. This corresponds to 1.87 grams acid calculated as acetic ( = 4.06 per cent of weight of total oil). The distillate was neutralized nith sodium hydroxide and the solution evaporated to dryness. Frcm a portion of the dry residue, the acid toluide n-as prepared by the method referred t o above. The toluide obtained was identified as the acetop-toluide by its melting point, mixed melting point, and by the optical properties of the crystals. The volatile acid present in the sodium bicarbonate extract ccnsisted, therefore, princirally of acetic acid. The acid liquid remainkg in the distilling flask from the steam distillation mentioned above was extracted with ether, the ether solution dried over anhydrous sodium sulfate, and the ether finally removed by distillation. A small quantity of a dark brown oil was obtained. This was distilled under reduced pressure, and a very small amount of liquid came over which, on standing, partly crystallized. The amount obtained v a f , however, too small to permit identification. The ethereal solution of the oil which had been extracted with a 5 per cent sodium bicarbonate solution was next exhaustively extracted with a 5 per cent sodium hydroxide solution. The alkaline extract was acidified with sulfuric acid and the solution extracted with ether. The ether solution was dried over anhydrous sodium sulfate and filtered, and the ether was distilled off, A dark brown oil was obtained. The yield was 7.5 grams ( = 16.3 per cent of weight of the oil = 0.25 per cent calculated on the 3000 grams material distilled, or 0.33 per cent calculated on ash- and sulfur-free material). The oil was distilled in a current of steam. In the distillation flask there remained some tarry matter from which nothing definite could be obtained. The distillate was extracted with ether, and, after removal of the ether by distillation, an oil was obtained which amounted to 1.5 granis. Cnder ordinary pressure it distilled over a t 200' to 210" C. The 3,5-dinitrobenzoyl derivative of this substance was prepared according to the method described in a previous communication (8). After three crystallizations from 95 per cent ethyl alcohol, cry.stals were obtained which melted a t 138" C. (corrected). This agrees closely with the melting point recorded for the 3,5-dinitrobenzoylguaiacol. The optical properties of the crystals also agreed with that of 3,5-dinitrobenzoylguaiacol. From the original mother liquor of the above, a second crop of crystals separated out. These were found to melt a t 115" C. The melting point of the 3,5-dinitrobenzoyl derivative of l-A~-propyl-3-methoxy-4-hydroxybenzene is 116.2 ' C. (corrected) (9). The optical properties of the crystals agreed with those recorded for l-N-propyl-3-methoxy-4-hydroxybenzene. The phenolic fraction of the oil, therefore, contained guaiacol and l-S-propyl-3-methoxy-4-hydroxybensene. ExAMIKATIOS OF
I~ECTRA FRACTION L
The ether solution of the oil which had been successively extracted with 5 per cent sodium bicarbonate solution and 5 per cent sodium hydroxide solution, was dried over anhydrous sodium sulfate and filtered, and the ether was distilled off. A dark brown oily residue was obtained which amounted to 37 grams (= 80.4 per cent of weight of oil). The oil was distilled in a current of steam, and a heavy yellow oil came oler. In the distilling flask there remained a black, hard, tarry residue from which nothing definite could be obtained. The distillate was extracted with ether, the ether solution was dried over anhydrous sodium sulfate, and the ether was removed by distillation, The oily residue amounted to 26.5 grams (= 57.6 per cent calculated on the 46 grams of oil obtained from all the distillation experiments). The oil had a rather offensive odor. It was distilled under ordinary pressure and the following fractions were obtained:
The frztctiou distillirig at 170" to 180" C. was redistilled, a fractionating coliinm heing used. Below 145", 6.5 grams distilled over. Tlic mercury column then rose rapidly, and the remaindcr of the oil rlistillcd o ~ c ar t 170" to 172'. ?'lie weight of this fraction nrnountcd to 6.5 grams. The fraction wliich distilled over below 145- was redistilled, and it dist,illed over a t 110" to 130"; as it. %vascvidently a Fractioii li0" to 172" was :inalysed ior cariron, Iryilrogen, and ailfor, and the following results wcre obtained: Substance, 0.1595, 0.1179, 0.1 103; water, 0.11659, 0.049:1, 0.0472; cnrhon dioxide, 0.1222, 0.0916, 0.0845. Found: carbon 20.'30, 21.18, and 2039 per cont; hydropn 4.62, 4.68, snd 4.78 per cent. iiubstnnce, 0.1669, 0.1452; Imium sulfate, 0.8618, 0.7486. Found: 71.15 and 71.04 per cent sulfur. Mean: carbon 20.99; hydrogen, 4.69; solfur, 71.09 per r e n t .
Tile ident,ity of this fraction was not established. ably it was not pure.
I'rcsim-
DI~CU~~ 01 I REWLTS ON
In studying the results obtained in the distillation experiments recorded in this paper, it is of interest to compare them with those obtained in the distillation oilignin. In the following table the results of both series of experiments are presented; those obtained in the distillation of alkali lignin are taken from an article previously published from this laboratory (7): . A ~ ~ I O nir.r ~ ~ ~
Alkali Iiyniu Residue from waste
1
c.~~oN-
Die-
Dra-
T~LLITB
TLLLITF.
rze" KEBID"E
70
90
%
11.7
28.3
50.5
sulfite 114uor ao.0" 2.0" Caieulalad on the ash- and auifur-free nialeriil.
55.0
T i l e dry rwidiie of waste sulfite liquor ! dist.illat.ion in a reduced atmwpliere of carlion dioxide at a maximum temporature of 400" C. The fnlknving results, representing the average of ten experiments (calculated on the lxsis of nreii-dry material) were olitained: Aqiicous distiiI&, 22.3 per ccnt; oily disl.illate, 1.5 per cent (30.0 and 2.0 per cent, respertively, calciilatcd on ash- and sulfur-free material): carbonized reidiie. 55.0 iier cent:, . em. , , 21.2 ner cent (13y ciitGrence). The aaueons distillatc contained acetic acid. acetone, and metlranoi. The yield of these three compoun~s(calculated on the Iiasis of the dry material distilled) amounted to 1.19, 0.046, and 03.5 per cent., respectiroly. When calculated uti the /)asis of asli- and sulfur-free material, thc yields amounted to 1.61, 0.06'2, and 0.48 per cent, respectively. The oil was successively extracted with 5 per cent sodium bicarbonate and 5 per cent sodium hydroxide solutions. In the sodium bicarbonate extract, acetic acid was identified. In the sodium hydroxide extract, guaiacol and 1-A'-propyl3-metlioxy-4-lrydroxy~nzenewere identified. The iractiori
