Preparation of Chromic Acid

INTRODUCTION
All chromic acid produced in this country is made by reacting bichromate of soda with sulfuric acid.
Bichromate of soda is the end-product of a process involving chromite ore, soda ash, lime, water and
sulfuric acid. The process with improvements in equipment, controls and techniques has been used
for over 25 years.

CHROMITE ORE
Chromite ore is available in many locations throughout the world, but there is a wide variation in
grade. That which is most suitable for the production of chromium chemicals is referred to as chemical
grade ore, and comes chiefly from the Transvaal area of the Union of South Africa. An average
analysis of chemical grade chromite is as follows:
Chromic Oxide, Cr2Os3, 44.18%
Ferrous Oxide, FeO, 19.01%
Aluminum Oxide, Al2O3, 14.74%
Magnesium Oxide, MgO, 11.48%
Silica, SiO2, 3.53%
The chromite ore is purchased on an assay basis through importers who have several sources of
supply. The chromium chemicals producing companies maintain large inventories of the ore to offset
the transportation hazards from the mines. Shipment from the mines to the port is by a single track
railroad because of the terrain. When the demand for chromium chemicals is greatest, other materials
are also in emergency supply and there is considerable competition for ore boats.
Beginning in 1946, there has been a steady gain in the world production of chromite ore. The Union of
South Africa has more than doubled production. The Philippines have better than quadrupled their
production while Cuba has experienced a slight decline. The production position of Southern
Ethodesia, Turkey and New Caledonia has strengthened. Yugoslavia has shown a substantial gain in
production while Russia has produced a large but fluctuating output. Other countries such as India,
Sierra Leone, Greece, Cyprus, Bulgaria, Canada, Japan, Albania and Brazil have turned out lesser
quantities of chromite ore.
The total world production of chromite ore is approximately 2 1/2 million short tons. The United States
imports from 22 to 50 per cent of this amount with chromium chemicals production requiring from 7 to
18 per cent of the imported ore.
THE MANUFACTURING PROCESS
Grinding and Roasting
The chromic acid manufacturing process is essentially the conversion of chromite ore to sodium
chromate solution, to bichromate of soda crystals, to chromic acid. The chromite ore, containing 42-50
per cent Cr2O3, is first dried and ground to a maximum coarseness of 100 mesh. This preparation
increases the efficiency of the succeeding reaction step of the process.
The dried and ground ore is mixed with soda ash, and lime or ground filter residue from a previous
operation. The ingredients are thoroughly blended in rotary mixers.
The mix is roasted in rotary kilns for about four hours in an oxidizing atmosphere, at a closely
controlled temperature of 1094-1149° C (2000-2100° F).
Sodium Chromate Step
After leaving the kiln the roast is cooled and then transferred to a leacher where water is added and a
nearly saturated solution of sodium chromate and sodium aluminate is obtained. The residue from
leaching contains the iron, magnesium and silicon impurities in the ore. Part of this residue, called
mud, is dried and ground for use in future mixes and the remainder is discarded.
The leached sodium chromate-sodium aluminate solution is passed through a polishing filter to
remove traces of suspended matter and then pumped into batch hydrolyzing tanks. Here sodium
chromate solution is slowly added to the sodium chromate-sodium aluminate solution to crystallize
hydrated alumina. The alumina is separated and washed on filters and either dried and marketed as
such, or the wet filter cake is dissolved in sulfuric acid and converted to aluminum sulfate.
The purified sodium chromate solution is either sold as a 40° Baume solution, evaporated to produce
anhydrous or hydrated sodium chromate crystals, or converted to bichromate of soda.
Sodium Bichromate Step
To produce sodium bichromate, the 40° Baume sodium chromate solution is treated with 66° Baume
sulfuric acid. Approximately half of the sodium sulfate formed in this reaction is precipitated during
mixing and the remainder drops out in the evaporator to which the solution is pumped for
concentrating. When a concentration of 13.5 to 14.0 lbs Na2Cr2O7· 2H2O per gallon is reached, the
solution is pumped into a battery of water-cooled crystallizers. When the temperature of a crystallizer
falls to 35° C (95° F), the batch is centrifuged and the mother liquor is either sent back to the
evaporators, the hydrolyzer, or sold in tank cars as a saturated solution containing 70 per cent by
weight, Na2Cr2O7· 2H2O. The crystals are dried in rotary dryers, care being taken not to drive out the
water of crystallization.
Chromic Acid Step
In the chromic acid process, bichromate of soda crystals are mixed with either 66° Baume or fuming
sulfuric acid in a kettle equipped with an agitator. Fuming sulfuric acid absorbs the water of
crystallization while this water has to be evaporated if 66° Baume acid is used. The temperature of the
mix is raised to 197° C (387° F) at which point the entire mass containing chromic acid and sodium
bisulfate is in the molten state. Chromic acid, being heavier than sodium bisulfate, collects at the
bottom and is drawn on and passed through water-cooled flaking rolls and packed in steel drums. The
sodium bisulfate contaminated with chromic acid is run out into pans to solidify before being
discarded.
The care exercised in the separation of the chromic acid from the sodium bisulfate determines the
sulfate content of the chromic acid. The quality control laboratory analyzes the ingredients for each
batch and the reaction time is adjusted, if necessary. The chromic acid is analyzed for CrO3 content
and impurities. The individual drums of chromic acid are rapidly segregated by a sulfate analysis. All
material showing sulfate higher than standard is rejected and reprocessed.
One hundred pounds of bichromate of soda yields 62.4 lb of salable chromic acid, which is 93 per
cent of the theoretically available amount. Loss in the bisulfate is about 5.5 per cent and up to 1.5 per
cent is lost in dust and handling. The weight of the contaminated bisulfate produced and discarded is
essentially equal to the weight of the bichromate of soda used.
It has been shown that the chromite ore contains iron, aluminum, magnesium and silicon in addition to
chromium oxide. Of these impurities only aluminum is obtained in a salable form. The reason for using
chemical grade ore is quite evident, since ores high in silica, iron, and magnesium mean the payment
of freight on materials destined to be discarded as waste products.
The impurities in the chromite ore are removed in the manufacture of bichromate of soda. This
material has been produced for sale in a highly competitive market for many years. Hundreds of man
hours have been expended over these years to produce as pure a technical grade of bichromate of
soda as it is chemically possible to achieve. This same bichromate of soda is used in the chromic acid
process. The principal problems concerning the purity of chromic acid are in heating the kettle and in
the separation of the sodium bisulfate and chromic acid layers. The temperature and time are
controlled by instruments. A mistake at this point may cause the formation of undesirable complex
chromium compounds. The correct separation of the layers controls the sulfate content. This
separation is performed manually by a trained operator. The operator is double-checked by an
analytical chemist and any chromic acid containing high sulfate is reprocessed.
Chromic acid is sold in flake form because it is the most economical anhydrous form to
produce. The flake is friable and, in shipment, some of it breaks up into a powder so that the
farther the material is shipped, the more powder may be found in a drum.
Two container sizes are packed. One hundred pound drums are more convenient for the
electroplating industry, while the 400 pound drum has proven more satisfactory for those
industries using chromic acid to manufacture other chromium compounds (Combs, 1953).

Works Cited
Combs, E. L. (1953, April). Chromic Acid Manufacture. Historical Articles.