ANTHRAQUINONE

1144

-UNTAPPED

INDUSTRIAL A N D ENGINEERING CHEMISTRY

Vol. 46, No. 6

RESOURCES

UNTAPPED RESOURCES Dirtributfonr of Abillty.of a Current Age Group and of Tho.

The existence of a large pool of persons of above average intelligence who do not go beyond high school haa been established through A m y General Classi5catim Tests (AGCT). These tests show that the higher the e d u c a t i d attainment, the higher the intelligence level. Average AGCT test scores are as follows: Total population100 High school graduates-110 College entrants115 College graduates121 Ninety per cent of college graduates score above 100, So%, 121 or higher; and 12%, 140 or higher. For various reasons, a Bignificant number of most capable young people are not

4 AGCT Score OURCE COMMI5SION ON HUMAN RESOURCE5 AND ADVANCfD TRAININ

above situations wanted. One significant trend noted in mid1953, however, waa that situations open and situations wanted dropped sharply. In the latter part of 1953, both h k an upward swing which is still going on. Demand for engineers by both Government and industry was approximately the eame in 1953 ss in 1952, the Engineering Manpower Commission hss reported. This conclusion was baaed on a survey of industries and government agencies employing about 125,000 engineere, 26% of the total number in the United States. Although signs of a softening in d e mand were noted, the need was substantially greater than the number of graduates, who total 21,612.

New Demand Shdy The chemical, rubber, and petroleum industries were still encountering difficulty in locating chemists, chemical engineers, and other scientists and engineers in 1963, according to a special study by the Burmu of Labor Statistics. The pilot study, sponsored by the Air Force, was made in 1953 to determine the factors dectiing industrial demand for chemists and chemical engineers. Three industries were cove&chemicals, petroleum, and rubber-which together employ nearly half of all chemists and about three fifths of d chemical engineem in the United States. The 132 companies surveyed employed about 18,000 chemists and more than 14,000 chemical enginem, or about one fifth of all chemists and nearly one third of all chemical engineers. Sales of reporting companies totaled over S20 billion in 1952, more than two fifths of the total d e s of the chemicals, petroleum, and rubber industries. The study showed that one out of every 12 employees in chemical companie is an engineer or scientist. The figure for petroleum industry is one out of 15, while that for rubber is one out of 40. I n recent years employment of scientists has risen sharply in chemicals and petroleum and to a much leas extent in rubber. Between 1948 and 1953, for emnple, chemical companies increased employment of chemists 25%, chemical enginem 45%, and other scientists and engineers

getting the education that their capaciQ seems to warrant. Of the top 2% of h i school graduates, in terms both of high intelligence and high grades, only two thirds graduate from college. Of the top quarter of higb school graduates, agah in terms of intelligence and grades, only 42% graduate . from college. Manpower experts emphasize the deairabiliQ of identifying these persons of high mental abiliQ and giving them an opportuniQ to reach their greatest potential. Tbis applies particularly to those persons with great mechanical ability or inventiveness who could contribute to technological or industrial development

62%. Corresponding figures for petroleum are 26, 40, and 44%. In rubber the figures are 6, 26, and 46%. This expansion has extended to all types of scientific activity including research and development, production, administration, and technical sales. The companies surveyed indicated that the increases would have been still greater, particularly in mearch and development, had there not heen shortages of manpower. In 1953, when the survey waa conducted, surveyed companies were aaked to indicate their planned expansion of manpower in 1953. Chemical companies indicated that they planned a 7% increase in chemists and 12% in chemical engineers-greater than in %vera1 prior years. A similar increase is indicated for rubber. In petroleum expansion in 1953 is less than in earlier years. Need for chemists and chemical engineers to 811 vacancies created by death, retirement, or transfers to other firms is about 5%. Thia accounts for more than half of the total hiring of chemists and chemical engineers by petroleum companies and 30 to 40% of hiring planned by chemical and rubher companies. The surveyed companies expected to meet 70% of their needs for chemists and 8% of their needs for chemical engineers from the 1953 gnrduating clsas. Estimated need for 1953 chemistry graduates is approximately equal to the numher of 1952 graduate hired. The estimated need for 1953 chemical engineering graduates wna nearly one t h i d greater than the number hired in 1952. Becawe the total number of chemical engineering graduates dropped sharply between t h e e two years, the proportion of thesegraduate needed in 1953 is two thirds greater than the proportion actually hired in 1952. For graduates in chemistry the proportion is appmximately the m e in both years. In the last half of 1963 all petroleum companies surveyed and half of the chemical and rubber companies had vacancies for chemists and chemical engineers difficult to fill. One third of the companies reported greater dficulty in reoruiting needed chemists and chemical enginem in 1953 than in 1952.

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:D ..y;

Vot dyes are now about 40% of U. S. synthetic dyestuffs. Cibo Stotes mnkes 4,000,000 pounds of anthmquinone pastes in 35 colors

Brown Dyer and Many Others. Vat dyeatuffa are not made in vats. They are so named becsw of thek ability to form a soluble alkali

Lc

salt, or vat, from the insoluble dye. CIBA

A a e i t Editor &vin Bradley's collaborator this month, Phil Kmnowitt, who is waiutant manager at Toms River, waa a Scientific Adviser to the Military Qovemment after the war, and participated inwriting this FIAT report, which provided Kevin wi$h much source mSterial.

(Society of the Chemical Industry in Bade)

Kronowitt not only helped build the plant;

haa been making anthraquinoue vat dyes for he a h helped design it, and Bradley found bk almost half a century. Just a yesr ago its own previous industrial experience aa a pigU. 8.plant, Ciba States Ltd., a t Toms River, ment and dye chemist helpful in preparing the N. J., built b e c a w of expanded American article. He was slready pretty well 80markets for t h e e dyeatuiTs, went into opera- quainted at C i h States, k c e this is the thiid t i n . . ,' . I/. :,:,' story on that plant he bas written. Two It has bean mid that a large part of the others, one on the effluent treatment system American dyestuffs plants built since World and the other on special fork trucks and silos, .on Fwr Final &part appeared in C&EN last summer. Brown BR War II .wmi 1313 Snd its 'British BIOS counterpart. is the specific dye in this h r y . ' '

COKE-BED DUST FILTER. Bureau of Mines has applied the method of Ernst Sachrsa to give an efficient p t i n u w s pmceu far removing dust entrained in synthesis gas. The movinpbed coke fllter removes 9.8% a t a pressure drop of 3.5 inches of water.

CALCULATINGOPERATION COST of a complex of production units for minimum cost at any desired output is on ever-otiroctivesubject to management . . Nine articles comprise the published version of the I&EC Christmas Symposium "Flow through Porous Medio." (Permeability of kaolinite is added) . Other articles in this section include mechanism of solute transfer from droplets . Pumpability of residual fuel

.

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. .

oils

4

...

Two-Plant Standby Cod Bolonce

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.

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RED FBB

0 1

A Staff-Industry

c=o I I

H-N

*

.

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Collaborative Report

:

.

.

I

GOLDEN ORANGE 3G

GOLDEN YELLOW GK 1146

Anthraquinone SINCE

WORLD WAR 11, the most outstanding increase in synthetic dye&& production in the United Ststas bas been in the class of vat dyea. Output aver8ged 30.9% of total U.8. synthetic dyad& production in the yesrs 1946 to 1950. It incregded to 36.2% in 1051 and to 39.4% in 1952. I n 1962,24.8% ofall aynthatiodyes produced in thin wuntry were anthraquinone vat dyes (4). These dyes, in the commercial range, are outatanding for faetnessto light, washiog, and many other agencies. They sre second only to am dyes in quantity of production but probably lnvpaas the am8 in money value. Pmduotion of anthraquinone vat dyes was relatively high in 1951 but fall off wnsiderably the following year (Table I). Thie was largely due to the demand for anthraquinone vate for colohg military d o m in 1951 and the practical disappearmw of thst business in 1952. Khaki 2G, Olive T, Olive 2B, Bmwn Bff, Olive 2R, and Brown BR were most Seriously affected by this demand fluctuntion. Rene B o b , in 1901, eydtheaised the &st members of the anthraquinone vat family, mdantbrene (now called indanthrone) and hvanthrene ( 8 , 6 ) . Tha ~ a m ey w , both dyes were placed on tha &kat by the Bsdiscbe Anilin- und fhh-Fabrik. These were the 6rst dyea possessing not only a carbon skeleton di6ering from indigo but slso an entirely diffarent chromophoric &due (a). An adequate number of dyes faat to wool and silk were

I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY

Vol. 46. No. 6

"

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0 II

C

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1

BLUE GCD

I

BROWN BR

M a r M Expansion Imd CIBA lo Bulld In (IN U n W Stabs

K M N J. BRADLEY, Assistant Mifor in col&rafion

wifh

PHILUP KRONOWIF Ciba Sfatar Lirnifed, Toms River,

N. J.

Vat - y e s

.

available, but until the advent of the anthraquinone’vats, there were no reliable, fast dyes for cotton. Indanthmne is aeldom used today because of its seneifvity to bleaching agents. Vat dyestutra me so w e d because of their ability to form a soluble alkali salt or vat from the insoluble dye (6). This is usually accomplished by an slksline reducing agent, and the affinity of tbe co~orlessleu00 d t for textile fibers, e s p i d y celldosic fibers, is characteristic of the group. The insoluble dye is regenerated on the fiber hy oxidation,usually with atmospheric oxygen. F’ractically all antiuaquinone vat dyes contain a pair of carbonyl groups, either as a 1,4-quinoneor as part of a complex quinone system in a polycyclic aromatic compound. Most anthraquinone derivatives conbin two or more anthraquinone ring ~ystems. Prior to World War I, anthraquinone vat dyes were made almost exclusively in Germany. Since 1W7,they have been manufactured at Bade, S w i b e r h d , by CIBA (Society of the Chemical Industry in Basle). The w a ~ t i m u l a t a dgrowth of the chemical industry resulted in &e manufactureof vat dyes in Great Britain, the Unitad States, Frsnce, Italy, and Japan, in the World War I years and in the twenties. However, Germany &d the leader, a position strengthened by the amalgamation of the German dyemakers into the IG in 1924.

JUM 1951

Expsnsion of the American market for anthraquinone vat dyeEtufia in the M o d after World War I1 encourage3 CIBA to look for a plant site on thin amtinent. Lead w.w purahssea in June 1949 at T o m I(iver, N. J. Space for expsneion and n e w nwa to raw materiale and market were 4etmninhg factors in the choice. Of the 1250 auw pumhml, a b u t 36 nam have been cleared of ha. Althougb the location is near the North Jersey heavy manufaolwing arean, cranberries, blueberriw, podtry, and vsostioniste m the msin income producers of the immediate neigbhrhood. Water ia availsble from the river, but it has been found that the ground water in the tuea is of such superior quality that a minimum of t r e a h e n t ia raquired for ite uae ~d procesa water. T o m River, acned by two railroads and e x d e n t bnnl-nurtaced highways, is 53 miles from Philadelphia and 70 milea from New York. It is d y accessible to major markets and principal distribution centers along the Atlantic coast. The plant, built at a cost of SlS,OOO,OOO,is designed for a normalproduction Cspsojty of 4,OOO,OOO pounds of paste dyestuffs a year. About 36 colors can be produced, depending on market requirements. Besides those liated in Table 111, several new dyes, developed recently by CIBA, w i l l be made. The whole lisl includes dyes ranging from yellow6 to blacks, but almost all have a common denominator in anthraquinone. Economics at preeent favor purchase of this material from large manufackem; however, CIBA could make ita own anthraquinone a t Tome River from phthalic anhydride and bensene.

Table I.

Production and Sales of Anthraquinone Vat Dyes (4) Bdea

Production. Thou. Lb.

wun&

Thous. dollam

AII Anthwuinone Dye8 43.831 43.587 83.317 51.578 41.484 80.023 40.742 35,878 ES.081 2n.aio 40 518 28 288 31.R73 27:861 88:m 27.182 25.7m 32,506

1852 1851 1850 1848 1848 1847 1852 1861 1850 1848 1848

Thoua.

310 ’

688 588

514

528

Bmnn BR 336 440 457 450 416

INDUSTRIAL A N D ENGINEERING CHEMISTRY

688 886

1,014 870 768

Unit Vdue par Lb.

1.46 1.44 1.47 1.41 1.37 1.26 1.07

2.24 a.22

2.16 1.85

1147

ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT Manufocturing Processes Requiring Use of Flammable Solvents Carried Out in Soporoh Building

The manufacturing part of the Toms River plant is composed of three buildings: two production units and, located between them and connected to each by two-story bridge+ the five-~tory standardization building. Although the standardization building is higher than its two companions, it contains less floor SF. Each of the production buildings contain about l,sM),OoG cubic

Battery of Glass-lined and Cast-iron Reaction Vessels

feet, while the ~ t a n d a r d i ~ a t ibuildinpr ~n contains 950,ooO cubic feet. The production buildings are very similar to each other; they are three storiea in height and contain much the aame equipment. One is designed for processes that can be carried out in aqueous or other nontlammable reaction media. Its twin is intended for t h w processes that involve the use of organic solvents, and it ia equipped with the latest devices to reduce b a r d from bmmnble and toxic solventa. Stairways in both buildings are of the fire tower type, constructed outside the building proper and independent of it. The solvent building fire towers have an open balcony on each Boor. All windows in the solvent building are equipped with explosion latches so that an exploaion will blow them open easily and d i e aipate its force. AU electrical apparatus in this building is exploaionpmf. Every reaction veasel in both proeess b u i l d w is connected to a plantwide vent system leading to washer type fume exhausts on the roofs. Hinged vent ducts e m be mung directly onto the vessel outlets and hitched with quick-closing connections. All ventilation ducts are of lead sbeet or p h t i c . Both process buildings are of central well construction, facilitat ing the shifting of equipment and making ventilation easier.

There is one maintenance man for every production worker in the plant. Volunteers from the 325-man working force comprise a trained 6re brigade to NU the high pressure fog-type fire pumper. Periodic 6re drills are held. The planLwide fire alarm system recorda all &ma on tape in the pump house. Maintenance workers entering a vessel wear a eafety bamess and are under continuous supervision by a person outside the v d . The equipment is cleaned and ventilated before entrance is permitted. Fresh air ia supplied continuously to the interior of the vessel. Grinding and mixing of dry powders is done in a closed circuit. Powder loading, unloading, filling, and weighing are carried out under hoods with exhausters and duakollecting equipment. A control laboratory ia on the top floor of the central finishing building. Fleactions are sampled in the process buildings, and samples are cheeked in this laboratory. Use kats on the finished dyes are also carried out here. Cloth swatches or lengtha of yarn are dyed on a laboratory scale, and the dyed material i s checked for M e , strength, fastneae to light, w a e h i , snd other agents and ease of application. Particle size is checked here by sieve U S tests tests and microscopic examination, and V ~ ~ ~ Ofiltration are made to determine insoluble residue. Liquid raw materiale are stored in a tank farm consisting of eight 12,aoCrgallon tanks, located adjacent to the railhead. Two of the t a n k s contain sulfuric acid and two more are for oleum, Caustic, aqueous ammonia, hydrochloric acid, and benzene are also stored in the farm. Pumps ( 8 E ) are mounted directly on these storage tanks. Liquid chemic+ are pumped from the tank farm to the proceae buildinga through overhead pipelines, whicb include mild steel, rubber-lined, and lead-lined ducts. Most organic solvents are stored in an underground tank farm adjacent to the solvent building. Processes in both the production buildings begin on the second floor. Liquids pumped from the tank farm are held in storage tanke mounted in a tower section. These storage tanks can hold 2500 gallona, from 2 day’s to a week’s supply. Measuring t a n k s (19E)are located on a platform between the second and third floors directly behind the reaction kettles. These tanka are equipped with teller gages for vohme mwurement and are fed from the storage tanks by gravity flow. Both storageand m e w uring tanks are made in different materials for different liquids. Those designed to bold hydrochloric acid are rubberlined; for caustic or concentrated sulfuric acid they are mild steel; stainless steel is used for aqueous ammonia and lead linings for dilute s~lfuricacid.

Table No. Vwsb Nooiacketed 8 1

80 I1

Jaaketed 20 2 4

1

18

II. Reaction Vessels

Description

Size, Gallono

Mild steel CWt iron Mild steel,acid roof brick-limed Mild steel. rub&-liid

4WOtoMXx) 4wo

C.st iron

Mild stool l e d - l i i [it.idm:tool Mild .bel. nickelclad Mild &el, enameled

smtom 2SW to loDD

250 to 1500 loo0

750 750

250 to 15W

Production Buildings Equipped with Motor-Driven Roof Ventilators

There are about 100 reaction kettlea varying in capacity from 250 to 5wo gaU~ns(Table 11) in the two pmceae buildings.

In case of emergenciea such as broken fume lines, motowlriven ventilators mounted on the roofs of the production buildings can change the air in an entire building in 5 minutes. Portable explosimeters and electronic vapor detectors are llsed to indicate any potential hasard. Gas masks, emergency showers, eye rimera, and other conventional eafety equipment are readily available.

They are set into the second floors, which serve as working p l a t forma. Kettles are grouped in batteries deaigned for a given type of reaction (~igureI). ~ulfonations,halogenations, aminations, rednctiom, condensations, oxidations, saponi6cationa, and nitrations are carried out in these kettles. Many are jacketed for heating or m l i n g by hot or cold water, brine, or steam; others have provimon for beating and cooling by means of mile or

1148

INDUSTRIAL A N D ENGINEERING CHEMISTRY

Vol. 46, No. 6

a wool filter cloth and the third, ootton. The pornus stone doea the best filtration job but ia aubjeot to clogging when filtrate

luna 19w

alurriea, agitated for m v q of solventepy direct atmob phezia distillation, agitated stesm stills, or reaction veaaela

INDUSTRIAL A N D B N Q I N E B R I ' N O C H B P I % T R Y

la@

ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT

1190

INDUSTRIAL A N D ENGINEERING CHEMISTRY

Val. 46.No. 6

PLANT PROCESSES-Anthraquinone ~

Table Ill. Cibanone Vat Dyes Produced at Toms River

Red 6B Red FBB Red R K

Vat Dyes

pounds of various raw materials. Chief among these are sulfuric acid, caustic soda, hydrochloric acid, phthalic anhydride, ammonia, benzene, nitrobenzene, glycerol, and alcohol. Typical of the many anthraquinone vat dyes produced a t Toms River is Cibanone Brown BR (Figures 2 and 3), a carbazole derivative of anthraquinone. It is produced from two intermediates that are also made and kept in stock, l-chloroanthraquinone and 1,4-diaminoanthraquinone. Phthalic Anhydride Condensed with p-Chlorophenol Makes Quinizarin for Amidation to 1,4-Diaminoanthraquinone

the tank to the neutralization compartments as needed. The unslaked lime residue is dumped several hundred yards from the treatment plant. Lime consumption may approach 10 tons per working day. The neutral liquid Aows from the neutralization basin into a 16,000,000-gallon lake where suspended color particles, calcium sulfate, and excess lime settle out. Capacity of this sedimentation basin can be increased to 29,000,000 gallons by raising the overflow level. If trouble arises in the handling of the effluent, the overflow from the sedimentation basin can be shut off. Several weeks would be required to fill the remainder of the basin; meanwhile the problem could be evaluated and corrections made. When the effluent Aows over the restraining barrier from the sedimentation basin, it falls into a pipe which leads to the 4,000,000-gallon aeration basin. Walls of this basin are asphalt and the floor is of fine gravel. Rows of pipes along the floor bubble air up through the effluent, effectively aerating it. A small portion of the effluent from the digester is circulated through the aeration basin to promote aerobic digestion. Finally, the effluent is chlorinated in an asphalt-lined tank, with wooden baffles for thorough mixing. A concrete duct leads several hundred feet from the chlorination tank to a small pond. Here, fish are raistd to demonstrate to the neighbors that the effluent is harmless. Actually, the discharge will be of higher purity than the Toms River itself, which is highly colored by cedar swamps and has a fairly low (4.5 to 5.5) pH. The effluent is continuously sampled a t all stages of treatment.

Sulfuric acid is charged into a 500-gallon enameled reactor (10E) from a measuring tank ( 1 9 E ) ; then boric acid is added, followed by phthalic anhydride from a drum suspended from a chain hoist. At 60' C. p-chlorophenol i s added. By means of a Dowtherm heating system the reaction is heated to 194" C. over 5 hours and held for 7 hours to complete condensation The charge is then blown through a blow leg with compressed air, into a 4000-gallon tank (22E) lined with acidproof brick (17 E ) and equipped with a lead-coated steel agitator and a lead-lined top, containing cold water. Quinizarine precipitates upon this drowning. Hot water a t 80" C. is added to the suspension, and the mixture is heated to 130" C. with open steam. I t is held a t that temperature for 3 hours. After further dilution with water the suspension is blown with compressed air to the third floor, where it is filtered and washed acid-free with hot water on a wood filter press (143). The quinizarin is dried in either air ( 1 f E )or vacuum ovens (.$E). Yield is about 145 pounds of quinizarin for each 100 pounds of p-chlorophenol. The purity of the product varies with the yield and can be raised to as high as 90 to 95% by sacrificing yield, Organic Reactions in Great Variety The chief adulterants are purpurin and 2,7-dichlorofluoran in Are Carried Out at Toms River small percentages, and they are not removed. This quinizarin is amidated with 18% aqueous ammonia and sodium hydroTemperatures varying from below 0 to over 500' F., and pressulfite, including some leuco-1,4-diaminoanthraquinone from a sures ranging from 29 inches of vacuum to over 600 pounds gage previous charge. The ammonia is run into the reaction kettle are encountered in the various reactions. Besides about 35 from a measuring cylinder (19E).The reaction takes place in a dyes normally produced (Table III), many intermediates are 750-gallon mild steel vessel (%E). The mixture is heated from made and stocked. Equipment flexibility is necessary for such a room temperature to 90°C. over 5 hours and held a t that temperavariety of products and processes (Figure 1). The capacity of ture, under 30 to 45 pounds gage pressure, for 2 hours. Micro4,000,000 pounds of dyestuffs a year requires about 22,000,000 scopic examination of the reaction mixture should show no crystals of leuco quinizarin but only the brownish crystals of leuco1,4 diaminoanthraquinone. This test is carried out in the control laboratory. The reaction mixture is cooled to 20 C. and blown to a suction filter ( 2 3 8 ) on the third floor with compressed air. I t is washed ammoniafree with cold water and dried in a vacuum chamber dryer (4E) under 29 inches of vacuum a t 90' C. Yield is 91% of theory. Pulp Is Moved Throughout Plant in Covered Cake Cars Drawn by Tractors

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O

June 1954

INDUSTRIAL AND ENGINEERING CHEMISTRY

1153

ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT

Dry Powder Blending

Intermediates Can Be Purified by Sublimation Vacuum sublimer i s cooled by outside water spray and jacketed inner cylinder

In the solvent building, the leuco-1,4-diaminoanthraquinone is oxidized in a jacketed 750-gallon steel kettle ( 2 2 E ) . The leuco intermediate is added to nitrobenzene at room temperature, with some piperidine as a catalyst. The reaction is heated slowly to 150' C. It is stirred a t that temperature until control tests show that the reaction is complete. A sample of leuco-1,4-diaminoanthraquinonedissolved in pyridine gives a dirty olive color, while the oxidized compound produces a clear, reddish blue solution. The test sample is compared with standards for evaluation. When the reaction is complete the charge is blown into a rotary vacuum dryer ( 2 l E ) with inert gas. The solvent is vacuum distilled and recovered through a steel shell- and tube-condenser ( 6 E ) and a coil aftercooler (15E). The yield of 1,4-diaminoanthraquinoneis 96% of theory. The finished intermediate usually contains a small amount of 1-hydroxy-4-aminoanthraquinoneand about 1% of ash.

Horizontal ribbon powder mills in standardization building are charged from silos carried b y special fork trucks. Silos or mills can be fllled from grinding mills on floor above through flexible hose connections

tion filter (I7E, 23E) and washed acid-free. The filtrate is collected in a brick-lined receiver ( I 7 E , 2dE) where addition of concentrated potassium chloride solution precipitates anthraquinone-1-potassium sulfonate. This precipitate is filtered on a brick-lined suction filter and washed with 0.5% potassium chloride solution. About 50% of the anthraquinone charged is actually sulfonated. Chlorination to 1-chloroanthraquinoneis carried out in a 3000gallon brick-lined kettle (IYE, 2dE) heated by open steam through a porcelain inlet. The anthraquinone-1-potassium sulfonate is charged in paste form, and 1500 gallons of water are added. The proper volume of hydrochloric acid is run in from a measuring

Sulfonation and Chlorination of Anthraquinone leads to 1-Chloroanthraquinone

0

II

0

0 S03H ii

I1

0

0 11

I

0

SOJC

0

71

I1 0

A mixkre of new and recovered anthraquinone is sulfonated with 20% oleum in the presence of mercuric sulfate. The oleum is fed from a steel measuring tank (198) into the casbiron sulfonator (18E). Mercuric sulfate is added and dissolved by agitation at 50" to 60" C. for a half hour. Anthraquinone is charged from chain-hoisted drums. The mixture is heated to 120" C. over an hour and a half. After 4 hours at this temperature, about half the anthraquinone has been sulfonated. Compressed air then blows the sulfonation mass into a 4000gallon, acidproof brick-lined precipitation kettle (17E, 2dE). Hot wash water from previous batches is run slowly into the hot sulfonation mass, with agitation from a large, heavy-duty, anchor-type stirrer. When the mass becomes too thick for efficient agitation, the stirrer is raised until it just clears the surface of the charge. Wash water addition is continued as the agitator works the water into the heavy mass from above. The stirrer is lowered into the mass as rapidly as the viscosity will permit, until it has once again reached the bottom of the tank. Unreacted anthraquinone is filtered out in a brick-lined suc1154

Solvent Recovery by Vacuum Distillation A battery of rotary vacuum dryers (Venuleths) i s flanked by condensers, coolers, and receivers

INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 46, No. 6

PLANT PROCESSES-Anthraauinone

Vat

Dves

tank (19E). After heating to 100" C., sodium chlorate is added in solution over about 16 hours. Temperature is held at 100" C. A test for completion of the reaction is carried out by the control laboratory. A sample of the reaction mixture is filtered, and an excess of chlorate solution is added to the filtrate. If a yellow precipitate appears on boiling, chlorination is not yet complete and more chlorate is needed. The filtrate from another sample is made alkaline with sodium hydroxide. If unchlorinated anthraquinone-1-sulfonate is present, addition of sodium hydrosulfite will produce a red color. If no exposed iron is present, chlorination usually can be completed in less than 24 hours. If exposed metal or metal salts are included, the reaction will stop at 70 to 75% of completion. When the reaction is over, the chlorinator is filled to capacity with water. The product is filtered a t 80' 6. on an acidproof brick-lined suction filter (17E, 2SE) and washed acid-free with hot water. It is dried in an air dryer (11E). Yield is approximately 94% of theory. Intermediates Are Condensed to Trianthrimid

top Carbazolation to Brown BR

Vacuum Chamber Dryers These dryers are used for heat-sensitive substances; stoinless steel troys are placed on steam-heated shelves

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J In a glass-lined reactor (IOE), 1-chloroanthraquinoneand 1,4diaminoanthraquinone are condensed to form the trianthrimid of Brown BR, 1,4-( dianthraquinony1amino)-anthraquinone. Nitrobenzene is used as the solvent, so the reaction must be carried out in the process building equipped to handle toxic and flammable solvents. Sodium acetate and soda ash are added to neutralize and buffer the hydrogen chloride given off in the condensation. A colloidal copper catalyst is included in this reaction. The nitrobenzene is run into the reaction vessel from a measuring tank (19E), and 1-chloroanthraquinone, 1,Pdiaminoanthraquinone, sodium acetate, soda ash, and the copper catalyst are added. The batch is heated to 210" C., and held for 10 to 15 June 1954

hours. Compressed inert gas then blows the contents of the kettle to a rotary vacuum dryer (21E)where the nitrobenzene is distilled off and recovered. The dry trianthrimid is ground in a micropulverizer (18E) and boiled in dilute hydrochloric acid to remove salts. This purification step is carried out in an acidproof brick-lined kettle ( 17E, 22E). The purified trianthrimid is filtered and washed in a filter press (14E)and dried in a vacuum chamber dryer (4E). Carbazolation is effected in a glass-lined jacketed kettle (10E). Pyridine is fed into the tank from a measuring tank (19E). Aluminum chloride is poured in from a chain-hoisted drum, and the temperature is held between 100" and 130' C. while the trianthrimid is added. The temperature is held a t 135' C. until a sample taken from the melt shows the same appearance as a standard sample. The melt sample is boiled with 30% sodium hydroxide, diluted, and filtered. The residue is dried on a porous plate and compared with the standard. When the reaction is complete, compressed inert gas blows the mixture into a 4000-gallon acidproof brick-lined vessel (17E, 22E) containing caustic soda solution charged from a measuring tank (19E). Pyridine is distilled off with direct steam and recovered in a liquid-liquid extraction column (9.73). A solution of sodium hypochlorite is run in from another measuring tank (19E), and the slurry is boiled for about an hour. An excess of sodium bisulfite is added to remove excess bleach, and the slurry is filtered in an iron filter press (14E). The Cibanone Brown BR is washed to neutrality and standardized. Standardization Includes Treatment of Chemically Finished Dye to Ensure Proper Physical Form

Manufacture of anthraquinone vat dyes has probably changed very little over the past 30 years, but great progress has been made in solving the problems of putting the dye in the proper form for easiest and most economical use. The physical form of anthraquinone vat dyes affects markedly the ease of vatting and affinity for the fiber ( 5 ) . Dyes separated in crystalline form from

INDUSTRIAL AND ENGINEERING CHEMISTRY

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ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT laboratory scale in stainless steel dye beakers. T h e dyed fibers are checked for shade and strength and for fastness to light, washing, and crocking. Particle size is checked by microscopic examination, filter, and sieve tests. Filter tests with cheesecloth or filter paper determine the amount of difficultly soluble residue. Crystal structure is studied with microscopes. Research Should Be Directed Toward Making Anthraquinone Vat Dyes less Expensive, Easier on Fabric, and Brighber

N o r e than 50 years after their discovery, there is still much room for improving anthraquinone v a t dyes. Although these are the fastest growing dyes and least affected by t h e present slump in the textile industry, they are expensive and not yet comparable in brightness with other classes of dyes t h a t do not, holvever, possess their fastness. T h e application of v a t dye9 requires considerable skill. This would be another fruitful field for research. Some anthraquinone dyes, especially those used for the production of lemon or greenish yellow shades with the maximum light fastness, show a pronounced tendering effect on the dyed fiber. Elimination of this defect and development of light shades having good light fastness ip one of the most important problems facing the dye chemists. Literature Cited (1) Chela. Eng. A\rews, 31, S o . 36, p. 3691 (1953). ( 2 ) Thorpe and Ingold, “Vat Colours,” p. 175, London, Longmans,

Laboratory Where Dye Colors Are Tested in Small Stainless Steel Vats organic solvents are usually difficult to vat. Poor shades and wasted material may result. Different treatments have been developed to prepare dyes for different end uses, Only 12 to 15% of v a t dye production is sold as dry powders. T h e overwhelming majority of the output is sold in paste form in varying concentrations, from 10 to 30% dye. Surface-active agents, humectants, or other additives may be included. Dissolving the crystalline dye in concentrated sulfuric acid and reprecipitating by drowning in water is a standard and effective method of improving the vatting and dyeing properties. Treatment with oxidizing agents such a s sodium hypochlorite or dichromate solution near boiling, for an hour or more, with vigorous mechanical agitation markedly improves the shades of many dyes. T h e standardization of dye pastes usually consists of conventional paste grinding, with the addition of conditioning agents to regulate the fluidity of the paste. Aryl sulfonic acid derivatives are among the conditioning agents used. Glycerol is added to printing pastes. T h e shade and strength of the pastes are standardized in mixing kettles. T h e product is then strained into drums ready for shipment. When the chemical synthesis of Brown BR is complete, the pulp is charged into stainless steel 1500-gallon kettles and the concentration is adjusted approximately. It is ground in a micropulverizer until the desired particle size and consistency are attained and then returned t o the pasting kettle. Samples are examined in the laboratory, and the strength and shade are finally adjusted. T h e finished paste is p u t through a 200-mesh screen into drums for shipping. Powders are also ground in a micropulverizer, but they are blended in horizontal ribbon powder mills (15E). Quality Control Includes laboratory Scale Dyeings

Every batch of dyestuff turned o u t at Toms River is subjected to actual use tests in the laboratory. Yarn or cloth is dyed on a

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Green and Co., 1923. (3) U. S.DeDt. Commerce, OTS, Washinaton 2 5 , D. C., FIAT Final Rept.,-1313, Vol. 11, 1949. (4) U. S. Tariff Commission (Supt. Documents, Washington 2 5 , D. C.), “Synthetic Organic Chemicals-U. 8. Production and Sales,” 1947-1952. ( 5 ) Venkataraman, “Chemistry of Synthetic Dyes,” Vol. 11, New York, Academic Press, 1952. Processing Equipment (1E) A. 0. Smith Co., Milwaukee, Wis., custom-built autoclave, mild steel, clad with 316 stainless steel, 500 t o 2500 gallons. (2E) Blaw-Knox Co., Pittsburgh, Pa., custom-built sublimer, 304 stainless steel-clad mild steel. (3E) Chemical Engineering Catalog, Iieinhold, Kew York, 1952-54, Croll-Reynolds Co., steam-jet Evactor, 321- JJ, three-stage, cast-iron, 304 stainlezs steel nozzle, hard bronze throat. (4E) Ihid., J. P. Devine Mfg. Co., KO. 27 vacuum chamber dryer. (5E) Ibid., Dowtherm Div., Dow Chemical Co., Dowtherin A. (6E) Ihid., Doyle and Roth Manufacturing Co., Shell-and-tube condenser, 2081-53, 304 Stainless steel. (7E) Ibid., Haynes Stellite Co., Hastelloy B and C. (8E) Ihid., La Bour Co., centrifugal pump Type BG, vertical, packingless, self-priming, size 12. (9E) I b i d . , Otto H. York Co., York-Scheibel multistage extractor, 9-stage, 3-inch diameter, 304 Stainless steel. (10E) Ibid., Pfaudler Co., custom-made glass-lined reaction kettle. (11E) I b i d . , Proctor and Schwartz, two-compartment truck dryer, hot-air circulation, automatic temperature control (10 it. x 12 ft. X 9 i t . 6 inches). (12E) Ibid., Pulverizing Machinery Co., Nikro-Pulverizer 3TH. (13E) Ihid., Roots-Connersville Blower Div., Dresser Industries. inert gas generator, 6000 cubic feet per minute, blower type AF, gas pump type XA. (14E) I h i d . , T. Shriver and Co., plate-and-frame filter press, threeeyed, top-center feed, washing-type open delivery, hydraulic closing device. (15E) Ibid., Sprout-Waldron and Co., Style B horizontal ribbon-andpaddle agitator batch blender. (16E) I h i d . , Worthington Corp., Type HBV dry vacuum pump, single horizontal feather valve, piston displacement 22 by 9 inches, 300 r.p.m. (17E) Chemsteel Construction Co., Pittsburgh, Pa., acidproof brick lining. (18E) Lynchburg Foundry Co., Lynchburg, Va., custom-built, castiron reactor. (19E) Struthers Wells Corp., Warren, Pa., custom-built measurnig cylinder, 250 gallons. (20E) Ibid.,custom-built mild steel pressure filter. (21E) Ihzd., custom-built mild steel rotary vacuum dryer. (22E) Ibzd., custom-built mild steel reaction kettle. (23E) Ihzd., suction filter box, mild steel, 100 and 150 sq. ft (24E) Ibid., Dowtherm liquid heater, 5,000,000 B.t.u./hour. (25E) Wall-Derkiss Fabricators, Linden, N. J., coil-type aftercooler.

I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY

Vol. 46, No. 6