ALUMINA

Alumina, Al2O3, is an important chemical because it is the raw material for metallic aluminum.
Uses and Economics. Large quantities of alumina are produced yearly for the manufacture of
metallic aluminum. In 1954, 7,297,789 long tons of bauxite (dried bauxite equivalent) were
imported (73 per cent) or mined. Most of this went for the production of about 2,600,000 short
tons of Al2O3 (as 100 per cent) for conversion to the metal. Of the total bauxite consumption,
the alumina industry used approximately 90 per cent, the abrasive industry 4 per cent, the
chemical industry 4 per cent, the refractory industry 1 per cent, and all other industries 1 per
cent.

Manufacture. Figure 7 shows the essential steps in the production of alumina from bauxite by
the Bayer process. The steps involved may be divided into the following unit operations (Op.)
and "Unit processes (Pr.): Bauxite, a mineral containing about 55 per cent aluminum oxide and
less than 7 per cent silica, is crushed and wet ground to 100 mesh (Op.).

The finely divided bauxite is dissolved under pressure and heat in digesters with concentrated
spent caustic soda solution from a previous cycle and sufficient lime and soda ash (Pr.). Sodium
aluminate is formed and the dissolved silica is precipitated' as sodium aluminum silicate. The
undissolved residue (red mud) is separated from the alumina solution by filtration and washing
and sent to recovery (Op.). Thickeners and Kelly or Oliver filters are used.
The solution of sodium aluminate is hydrolyzed to aluminum hydroxide by Cooling and by
dilution with wash waters; the aluminum hydroxide is induced to crystallize by seeding with
the finest of the aluminum hydroxide from last thickener (Op. and Pr.).
The precipitate is separated from the liquor and clarified in foul thickeners and washed with
hot water. It is filtered in Dorrco or Vallez filters (Op.).
The aluminum hydroxide is calcined up to 1150°C. to alumina in a rotary kiln (Pr.).
The alumina is cooled and shipped to the reduction plants (Op.).
The dilute caustic-soda filtered from the aluminum hydroxide is concentrated for reuse (Op.).
The red mud may be reworked for recovery of additional amounts of alumina (Pr. and Op.).

While many other processes and raw materials have been investigated None of these has
proved to be commercially feasible except the red mud process for treating red mud or low-
grade bauxites, i.e., those containing up to about 15 per cent silica. In this process, the red mud
from the Bayer digestion is mixed with soda ash and limestone and sintered. This sinter is
reacted with water to form a sodium aluminate solution leaving the silica combined as an
insoluble dicalcium silicate. After separation from the insoluble residue, the sodium aluminate
solution is recycled to the Bayer digester.

ALUMINUM SULFATE AND ALUMS

The manufacture of alums entails just one step additional to the aluminum sulfate process.
This, along with the fact that the uses of aluminum sulfate and alums are similar and the
compounds are largely interchangeable, justifies their concurrent discussion. The term alum
has been very loosely applied. A true alum is a double sulfate of aluminum or chromium and a
monovalent metal (or radical, such as ammonium). Aluminum sulfate is very important
industrially and while it is not a double sulfate it is often called either "alum" or papermakers
alum. Alum has been known since ancient times. The writings of the Egyptians mention its use
as a mordant for madder and in certain medical preparations. The Romans employed it to
fireproof their siege machines and probably prepared it from alunite, K2Al6(OH)12(S04)4,
which is plentiful in Italy.
Uses and economics. Alums are used in water treatment and somewhat in dyeing.
They have been replaced to a large extent in these applications by aluminum sulfate which
has,a greater alumina equivalent per unit weight. Pharmaceutically, aluminum sulfate is
employed in dilute solution as a mild astringent and antiseptic for the skin. The most important
single application of it is in clarifying water, more than half of the total amount manufactured
being so consumed. Sodium aluminate,which is basic, is sometimes used with aluminum
sulfate, which is acid, to produce the aluminum hydroxide floc.
6NaAI02 + Al2(SO4)3 + 12H20 + 8Al(OH)3 + 3Na2SO.
Second inimportance is the application of aluminum sulfate to the sizing of paper. It reacts with
sodium resinate to give the insoluble aluminum resinate. For the sizing of paper, aluminum
sulfate must be free from ferric iron or the paper will be discolored. The ferrous ions do no
harm since they form a soluble, practically colorless resinate whic.h, however, would represent
a loss of the resinate. A small amount of aluminum sulfate is consumed by the dye industry as
a mordant. Soda alum or aluminum sulfate is used in some baking powders. In 1953, 731,039
tons of.aluminum sulfate and 38,229 tons of iron-free aluminum sulfate (both 17 per cent
Al203) were produced in the United States. In addition, municipally owned plants made about
13,600 tons of aluminum sulfate for their own use.

Manufacture. Practically all alums and aluminum sulfate are made now from bauxite by
reaction with 60°Be sulfuric acid. ,However, potash alum was first prepared from alunite by
the ancients. Other possible sources of alums are shales and other alumina-bearing materials
such as clay.
The bauxite is ground until 80 per cent passes 200 mesh; next it is conveyed to storage bins.
The reaction occurs in lead-lined steel tanks where the reactants are thoroughly mixed and
heated with the aid of agitators and live steam. These reactors are operated in series. Into the
last reactor barium sulfide is added in t.he form of black ash to reduce ferric sulfate to the
ferrous state and to precipitate the iron. The mixture from the reactors is sent through a series
of thickeners, operated countercurrently, which remove undissolved matter and thoroughly
wash the waste so that when discardpd it will contain practically no "alum" The clarified
aluminum sulfate solution is concentrated in an open, steam-coil-heated evaporator from
35°Be. to 59 or 62°Be. The concentrated liquor is poured into flat pans where it is cooled and
completely solidified.The solid cake is broken and ground to size for shipping. Another slightly
modified procedure uses, instead of reactors and thickeners, combined reaction and settling
tanks. The Dalecarlia rapidsand filter plant which supplies water to Washington, D.C., makes
its own filter alum. In this case concentration of liquor would be an unnecessary expense;
therefore, the aluminum sulfate is made and used in water solution.
To make the various true alums, it is necessary only to add the sulfate Of the monovalent metal
to the dilute aluminum sulfate solution in the proper amount. Concentration of the mixed
solution, followed by cooling, yields the alum crystals.

ALUMINUM CHLORIDE
Aluminum chloride is a white solid when pure. In the presence of moisture, anhydrous
aluminum chloride partly decomposes with the evolution of hydrogen chloride. This salt was
first prepared in 1825 by H. C.Oersted who passed chlorine over a mixture of alumina and
carbon and condensed the vapors of the aluminum chloride formed. Essentially the same
process is used today in the commercial preparation of aluminum chloride.The price in 1913
was $1.50 per pound, while the present price is below 8 cents per pound in carload lots.
Uses. Since modern methods of manufacture have reduced the price of aluminum chloride, it
has found increasing application in the petroieum industries and various phases of organic
technology. It is used to a considerable extent in certain petroleum processes. Aluminum
chloride is a catalyst in alkylation pf paraffins and aromatic hyarocarbons by olefins and also in
the formation of complex ketones, aldehydes, and carboxylic acid derivatives. In 1953, 48,434
tons of liquid, crystal and anhydrous, were manufactured.
Manufacture. There, are three important methods for the preparation of anhydrous aluminum
chloride. One of these is the direct reaction of liquid or gaseous chlorine with metallic
aluminum; the second consists of the simultaneous reduction by carbon and chlorination by
gaseous chlorine of alumina-bearing materials; and the third consists of the action of hydrogen
chloride on alumina. The reaction between aluminum and chlorine is exothermic. Enough heat
is given off to vaporize the aluminum chloride continuously as it is formed. The reaction
between carbon, bauxite, and chlorine, however, is endothermic and heat must be supplied to
cause the reaction to take place. In the United States bauxite is calcined, mixed with a
carbonaceous residue, briquetted, and recalcined to drive off all hydrocarbons that would form
corrosive hydrogen chloride later on. This material in a shaft kiln is heated up to 1600°C. by a
blast of air and chlorinated, the aluminum chloride being volatilized and condensed.
The reaction of HCI on alumina produces Al2Cl4 which sublimes off and must be condensed.
The product made from aluminum metal is of a very high purity but may be resublimed for the
highest-purity material available.