OTHER MISCELLANOUS INORGANIC COMPOUNDS

INTENDED LEARNING OUTCOMES

1. Describe the fundamental operations and processes involved in the different chemical manufacturing
industries.
2. Illustrate and outline a process flowchart for all the fundamental operations and processes involved in
the different chemical and manufacturing process.
3. Explain the processing of raw materials into usable and profitable products.
4. Relate chemical engineering concepts in the solution of real industrial process.

ALUMINUM SULFATE AND ALUMS

Definition of terms
True alum - a double sulphate of aluminium or chromium and a monovalent metal
Aluminum sulfate – often called either alum or paper-maker’s alum; also known as soda alum

HISTORICALS
Egyptians – uses alum as a mordant for madder and in certain medical preparations
Romans – employed alum to fireproof their siege machines and probably prepared it form alunite,
K2Al6(OH)12(SO4)4

USES AND ECONOMICS

USES
ALUMS  water treatment and sometimes in dyeing

ALUMINUM SULFATE  employed in dilute solution as a mild astringent and antiseptic

for the skin (pharmaceuticals)
 clarifying water
 sizing of paper
 as a mordant (dye industry)
 chemical manufacturing, concrete modification,
pharmaceutical preparations, soaps and greases, fire
extinguishing solutions, tanning and cellulosic insulation
 used in some baking powders

SODIUM ALUMINATE  basic; sometimes used in aluminum sulfate, which is acid, to

produce the aluminum hydroxide floc

MANUFACTURE

 Alums and aluminum sulfate are now made from bauxite by reaction with 60°Bè sulfuric
acid
 Potash alum – first prepared from alunite by the ancients
 Sources of Alums:
1. Shales
2. Alumina-bearing materials e.g. clay

Manufacture of Aluminum Sulfate:

1. Bauxite is ground until 80% passes 200 mesh
2. Ground bauxite is conveyed to storage bins
3. In lead-lined steel tank, the reactants are thoroughly mixed and heated with the aid of agitators and
live stream
4. Into the last reactor, Barium sulfide is added in the form of black ash to reduce ferric sulfate to the
ferrous state and to precipitate the iron.
5. This mixture is sent through a series of thickeners, operated concurrently, which remove undissolved
matter and thoroughly wash the waste so it will contain practically no alum.
6. Clarified aluminum sulfate solution is concentrated in an open, steam-coil heated evaporator.
7. The concentrated liquor is poured into flat pans, where it is cooled and completely solidified.
8. The solid cake is broken and ground to size for shipping.

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Summary:

GRINDING STORAGE BINS MIXING AND HEATING ADDITION OF BaS

COOLING AND
SOLIDIFICATION CLARIFICATION
(LIQUOR)

GRINDING (SOLID
CAKE)

SHIPPING

 To make the various true alums, it is necessary only to add the sulfate of the
monovalent metal to the diluted aluminum sulfate solution in proper amount

ALUMINUM CHLORIDE

ALUMINUM CHLORIDE
CHARACTERISTICS USES
 white solid when pure  Catalyst in the alkylation of
 Sublimes on heating paraffins and aromatic
 In the presence of moisture, hydrocarbons
anhydrous aluminum
chloride decomposes with
the evolution of hydrogen
chloride
 Manufactured primarily by
the reaction of chlorine
vapour on molten aluminum

COPPER SALTS

Copper Sulfate
 most important compound of copper and more than 29000t was produced in 1976
 commonly known as blue vitriol
 prepared by the action of sulfuric acid on cupric oxide or sulfide ores
 its poisonous nature is utilized in the fungicide Bordeaux mixture
 added to water reservoirs to kill algae
 employed in electroplating and finds mirror applications as a mordant, germicide, and agent in
engraving

MOLYBDENUM COMPOUNDS

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 Approximately 10% of the total molybdenum production of over 51,000 t/year goes into
compounds

Molybdenum Disulfide - dispersed in greases and oils for lubrication

- in volatile carriers, it is used to form dry coatings of lubricant

Sodium Molybdate - an especially effective corrosion inhibitor on aluminum surfaces

- dissolved in cooling solutions to protect aluminum motor blocks in automobiles

Molybdenum Salts
 used as catalysts including:
1. Cobalt Molybdate – for hydrogen treatment of petroleum stocks for desulfurization
2. Phosphomolybdates – promote oxidation

Compounds used for dyes:

 Sodium  Potassium  Ammonium Molybdates

Phosphomolybdic Acid – employed in basic dyes

Molybdenum Orange - a pigment; from mixture of crystal lead chromate and lead molybdate

Sodium Molybdate - also known as molydic oxide

- added to fertilizers as a beneficial trace element

Zinc and Calcium Molybdate - serves as inhibitory pigments in protective coatings and paint for metals
subjected to a corrosive atmosphere

Compounds used for better adherence of enamels:

 Molybdenum Trioxide  Sodium  Barium
 Ammonium  Calcium  Lead Molybdates

Molybdenite - mineral raw material

- through roasting, furnishes a technical grade of molybdenum trioxide of 80 – 90% purity

BARIUM SALTS

Mineral Carbonate or witherite - most common naturally occurring barium compounds

- Fairly abundant in England

 The most important domestic source of barite is Nevada.

USES

Barium Carbonate  sometimes employed as a neutralizing agent of sulfuric acid

 for making bricks
 immobilizes the calcium sulfate
 producing whitish surface discoloration
 TV picture tubes
 flux for ceramics
Witherite  used to prepare other compounds
Barium Sulfate  useful white pigment, particularly in the precipitated form, blanc fixe
 filler for paper, rubber, linoleum, and oilcloth
 in purified form, used in contour photographs of the digestive tract
Barium Sulfide and  gives precipitate of barium sulfate and zinc sulfide
Zinc Sulfate Solution
Barium Chlorate  used in pyrotechnics to impart green flame
and Nitrate
Barium Saccharate  used in recovering sugar from discarded molasses
MANUFACTURE

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Enough witherite available:

TREATMENT WITH THE PROPER ACID

FILTRATION TO REMOVE INSOLUBLE IMPURITIES

CRYSTALLIZATION OF SALT

Little Witherite Available:

HIGH TEMPERATURE REDUCTION OF BARIUM

LEACHING PRECIPITATION

TREATMENT WITH PROPER CHEMICAL PURIFICATION

 Much barite is ground, acid-washed, lixiviated, and dried to produce a cheap pigment or paper
or rubber filler, or changed to blanc fixe.

STRONTIUM SALTS

Strontium Carbonate - widely used as an x-ray screening agent in television picture-tube face plate glass
and has no commercial alternative

Strontium Sulfate - finely ground and converted to the carbonate boiling with 10% sodium carbonate
solution

LITHIUM SALTS - during WW II, lithium hydride was reacted with seawater to produce a convenient
lightweight source of hydrogen for the inflation of air-sea rescue equipment

King’s Mountain, North Carolina - largest known lithium ore reserve in the world
- currently large part of the free world’s output of lithium oxide comes
from this source as spodumene

2 producers of Lithium and Lithium Salts in USA:

1. Foote Mineral Co. – produces lithium from the ore in North Carolina and from subsurface brines in
Nevada
2. Lithium Corp. of America – all its production is from North Carolina sources

USES

Lithium Carbonate  employed in the production of lithium metal and frits and
enamels
 together with Lithium Fluoride, it serves as an additive for
cryolite in the electrolytic pot line production of primary
aluminum

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 addition to the electrolytic bath causes the formation of a
eutectic mixture that lowers the bath temperature, power
consumption, and rate of volatilization of fluoride salts
 as a drug to treat manic depression
Lithium-base Greases  efficient over wide temperature range – 51°C to 160°C
Lithium Hydroxide  employed in the removal of carbon dioxide in submarines and
space capsules
Hypochlorite  used in commercial and home laundries
Lithium Chloride  in demand for low-temperature batteries and for aluminum
brazing
Other Lithium Compounds  catalyst, glass manufacture, and nuclear energy

 The Food and Drug Administration (FDA) approved the use of Lithium Carbonate for treating
mind disorders in 1970

MANUFACTURE

Manufacture of Lithium Carbonate:

1. Spodumene ore is converted form alpha form to the beta form by heating to over 1000°C
2. Alpha form is not attacked by hot H2SO4 and the beta is treated as follows:

3. The water soluble lithium sulfate is leached out and reacted with sodium carbonate to yield lithium
carbonate.

BORON COMPOUNDS

Colemanite and Boracite – important naturally occurring ores of boron

USES

BORAX OR TINCAL  most important industrial compound of

boron
BORIC ACID  weak acid that finds some use in the
manufacture of glazes and enamels for
pottery
 used as fire retardant for cellulosic
insulation
 manufacture of borosilicate glasses and
textile grade glass fibers

MANUFACTURE

MIXING WITH HOT

CRUSHING BLENDED TO B2o3 DISSOLVING PLANT
RECYCLE LIQUIOR

CRYSTALLIZATION PRIMARY THICKENER

Kerr-McGee Chemical Corp. – uses a process that involves the use of an organic solvent to extract the
borax from the Searles Lake Brines

1. Boric Acid is extracted with kerosene.

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2. In a second mixer-settler system, dilute sulfuric acid strips the borates from the chelate.
3. Purification by carbon treatment and evaporation in two evaporator-crystallizer: pure boric acid and a
mixture of sodium and potassium sulfates

RARE-EARTH COMPOUNDS

Rare earths - chemical elements with atomic number 58-71 which are only separated with difficulty
- the name is misnomer, since they are neither rare nor earths
-
Cerium and Thorium - have not been able to compete with the richer monazite sands found in Brazil
and in Travancore-Conchin, India

Preliminary Separation - accomplished by the use of jigging, in this case the valuable material is denser
than the worthless fraction

Lanthanum and Cerium - separated by fractional crystallization and the others are by liquid-liquid
extraction or ion-exchange process

Molycorp. Inc. – developed a solvent extraction process for the production of the oxides of lanthanum,
cerium, gadolinium, terbium, praseodymium, neodymium, yttrium, and europium in tonnage quantities

Bastnasite – concentrated by hot-froth flotation and then subjected to solvent extraction

 Glass industry is the largest consumer of rare-earth compounds, mostly as oxides for rapid
polishing of plate glass, as well as precision optical equipment and eyeglasses

Yttrium and Europium oxides – used in ton quantities as phosphors for TV screens.

Other uses of Rare-Earth Compounds:

 Coloring  UV television tubes
 Decoloring  Lasers
 Opacifying glass  X-ray intensifying screens

Fluorides and Oxides – consumed in the production of carbon electrodes for arc lighting of high
intensity and good color balance

Thorium – of interest in nuclear reactions

SODIUM DICHROMATE

Chronite – starting material for the manufacture of sodium dichromate and other chromium
compounds
- a chromium iron oxide containing approximately 50% Cr2O3

Sodium Dichromate – consumed as the starting material for making the solutions of chromium salts
employed in chrome leather tanning and in chrome mordant dyeing of wool cloth

Yellow lead chromate - manufactured basically from sodium dichromate

Green Chromium oxides – for ceramic pigments

 Other half of the chromium enters the metal field as stainless steel and other high-chromium
alloys for the chromium plating of other metals, the balance being about equally divided
between chrome refractories and chrome chemicals.

Manufacture of Sodium Dichromate

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1. Ore is ground in 200-mesh.
2. Ground ore is mixed with ground limestone and soda ash.
3. The mixture (in #2) is roasted at approximately 1200°C.
4. The sintered mass is crushed and leached with hot water to separate the soluble sodium
chromate.
5. Treatment of enough sulfuric acid to convert the chromate to dichromate , with the resulting
formation of sodium sulfate
6. Crystallization of sodium sulfate in the anhydrous state from the boiling hot solution during
acidification, and the remainder drops out in the evaporators on concentrating the dichromate
solution
7. Saturated dichromate solution is fed to the crystallizer, and then to the centrifuge and dryer.

HYDROGEN PEROXIDE

Hydrogen Peroxide – most widely used peroxide compound

 Originally produced by the reaction of barium peroxide and sulfuric acid for use as
an antiseptic
USES

HYDROGEN PEROXIDE  Commercial bleaching, dye oxidation, manufacture of organic and

peroxide chemicals and power generation
 Bleaching wood, textile-mill bleaching of practically all wood and
cellulosic fibers as well as of major quantities of synthesis and paper-
and pulp-meal bleaching of groundwood and chemical pulps
 Organic applications: manufacture of epoxides and glycols
 Source of oxygen in municipal and industrial wastewater treatment
systems
 Oxidant for in-place solution mining of low-grade uranium ores

 The advantage of hydrogen peroxide in bleaching is that it leaves no residue and

generally results in excellent product whiteness, with little or no deterioration of the
organic matter that is bleached.

MANUFACTURE

Manufacture of Hydrogen Peroxide

 All hydrogen peroxide manufacturing plants utilize the autooxidation of an
anthraquinone
Process:
1. The quinone is hydrogenated to the hydroquinone using either Raney nickel or palladium as
catalyst.
2. Subsequent oxidation with air produces hydrogen peroxide and regenerates quinone.
3. The H2O2is water-extracted and concentrated.
4. Quinone is recycled for reconversion to the hydroquinone.

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Other Organic process:

1. Oxidation of liquid isopropyl alcohol at moderate temperatures and pressures to hydrogen
peroxide and an acetone co-product.
2. Distillation.
3. After distillation of the acetone and unreacted alcohol, the residual hydrogen peroxide is
concentrated.

By:
Balitaan, Riczel Mariz A.
ChE-3301