Transcript 1ST YEAR LECTURE NOTES HISTORY OF THE CHEMICAL INDUSTRY

CM1100 LECTURE NOTES
HISTORY OF THE CHEMICAL INDUSTRY
M A MORRIS
E-MAIL [email protected]
Rm: 108 Kane Building
Industrial Inorganic Chemicals: Production and Uses, Ed. R
Thompson
The Chemical Industry, Ed. A Heaton
Introduction
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Chemicals were known by the ancients
Ancient Egyptians used ‘soap’
Soda (sodium carbonates, natron in Egypt) plus fats to wash corpses prior
to during mummification
Cement dates back to Egyptians passed to Romans and the Greeks
(forgotten for 2000 yrs) volcanic ash + rock + caustic soda (NaOH)
500 yrs ago Mayan Indians used latex balls in games and in clothing
Recipe for a mummy….
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Four jars hold the liver, lungs, intestines, and stomach. The heart is kept
inside the body and the other internal body organs fried.
The brain is pulled thru the nose with a hook. Stuff the head with tree resin
and sawdust.
Soak the body in natron for 40 days. The body is put on a inclined couch
and the liquids and natron fall to the bottom into a pan.
Rub the body with olibanum oil to make the skin supple.
Pack the body to make it more lifelike (with spices or sawdust).
Use wax to seal any incisions.
Tear fine linen into strips 16 yards long and 2-8 inches wide.
Wrap the smaller extremities (toes and fingers) first.
Next, wrap the limbs, and finally, the torso.
Sing appropriate chants over each body part.
Secure linen with tree resin.
Tuck in an amulet after every few layers.
Isis, Osiris, and Set
Modern Chemical Industry
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Began in UK around 1750-1800
Lead-Chamber Method was developed in England in 1749 to make
sulfuric acid.
Was sponsored by the industrial revolution with demands for chemicals for
other industries.
Soap manufacture (alkali + animal fat)
Cotton – bleach
Glassmaking – sand (SiO2) and soda (sodium carbonate)
Three key chemicals needed to be manufactured……..
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Sulphuric acid - oil of vitriol
Largest volume chemical in the world – used for steel processing, dehydration,
sulphate fertilizers, sugar treatment (after removal). Used in pharmaceutical and dye
manufacture. Lead acid batteries. Production of alum (Al2(SO4)3) for water
treatment. Around 200 Mt made very year.
Soda – sodium carbonate
Sodium Carbonate (Soda ash, Sal Soda, Washing Soda) (Na2CO3) & Sodium
Bicarbonate (baking soda) (NaHCO3) are used to manufacture glass, soap, textiles,
paper, and as a disinfectant, cleaning agent, and water softener
Caustic soda – sodium hydroxide
Alkali Hydroxides (usually just called "Alkali") are used to produce glass, paper, soap,
and dyestuffs for textiles, aid in oil refining, make bleaching compounds, and
preparing leather.
Johnny was a chemist's son, but Johnny is no more.
What Johnny thought was H2O was H2SO4.
Sulphuric acid an early route - copperas
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Jabir-Ibn-Hayyan (721-815) distinguished between green vitriol and blue vitriol,
ferrous sulphate and copper sulphate respectively
Green vitriol (FeSO4.7H2O) was used extensively in the textile (as dyestuffs)
and metallurgical industries and for a number of other purposes.
17th C manufacture copperas containing stones were collected from the beach
placed in oak vessels and packed with chalk. After several years a liquor a
mixture of sulphuric acid (source of this for many years) and iron sulphate
solution was collected. Further iron was added to bring it up to stoichiometery.
Sulphate crystals were collected by drying in sun. Twigs etc were added to
promote crystallisation processes.
Took place at Tankerton in Kent and in Dorset but soon move to the NW of
England
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It was the first heavily capitilised industry requiring large scale investments
Tankerton, nr. Whitstable,
Kent. : Copperas industry.
Sulphuric acid
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First chemical process on an industrial scale
This source became green vitriol ( FeSO4.7H2O) recovered from mineral
pyrites and was first material that Joshua Parr attempted to make at
Mynydd Parys - Angelsey (1795).
FeS2(s) + 11O2 → 2Fe2O3(s) + 8SO2(g)
Eventually sulphide/S mines in N. Wales sent material to Liverpool (Garston
sulphuric Acid Co.). Start of the NW chemical industry.
Parr was never successful and direct oxidation of S (as pyrite also) was in
air to give SO2 became the economically better route. Saltpeter (KNO3)
was used as catalyst releasing NOx
Water in reaction chamber absorbed gases
Reactions took place in small glass lined vessels but scale of production
was increased by Roebuck and Gardner (1749) using large lead lined
chambers.
Roebuck took no patent protection and eventually his business collapsed
View of Carron Works, 19th century (Roebuck)
Roebuck later worked with Watt on 1st steam engine
Nitrates
• Potassium Nitrate (saltpeter, Nitre) (KNO3) Was obtained primarily
from India and used to prepare matches, explosives, and
fertilizers.
• Chile saltpeter, an impure form of sodium nitrate (NaNO3), which
was deposited along the Pacific coast by large flocks of birds.
• Lime saltpeter (Norwegian saltpeter) which is composed of
calcium nitrate (CaNO3)
• These are only source of nitrates until Haber process
• They were extensively used in manufacture of explosives – the
Haber process was developed to reduce German reliance on Chile
saltpeter during WW1 (UK blockaded ports) and extended war.
Sulphuric acid improvements
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Gay-Lussac towers (1837)– introduced oxygen to form SO3 in increased
amounts and recovered NOx reducing requirement for the KNO3. Improved
by Glover (UK) and towers common in 1870s
1880s saw further increases. Phillips (UK vinegar merchant) patented Pt
catalysed oxidation of SO2 to SO3. Was not used until catalyst reactor built
in Germany in 1875. But technology widely used by 1890.
In the 20C Pt replaced by vanadium oxides
Absorption tower
Modern Contact process
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Most of the sulfuric acid manufactured is produced using the Contact
Process, a process involving the catalytic oxidation of SO2 to SO3.
Solid sulfur, S(s), is burned in air to form sulfur dioxide SO2
S(s) + O2(g) -----> SO2(g)
The gases are mixed with more air then cleaned by electrostatic
precipitation to remove any particulate matter
The mixture of SO2 and air is heated to 450oC and subjected to a
pressure of 1 - 2 atmospheres in the presence of a vanadium catalyst
(V2O5) to SO3(g), with a yield of 98%.
2SO2(g) + O2(g) -----> 2SO3(g)
Any unreacted gases from the above reaction are recycled
SO3(g) is dissolved in 98% (18M) sulfuric acid, H2SO4, to produce
disulfuric acid or pyrosulfuric acid, also known as fuming sulfuric acid or
oleum, H2S2O7.
SO3(g) + H2SO4 ------> H2S2O7
This is because if water is added directly to SO3 to produce sulfuric acid
SO3(g) + H2O(l) -----> H2SO4(l)
the reaction is slow and tends to form a mist in which the particles refuse
to coalesce.
Water is added to the disulfuric acid, H2S2O7 to produce H2SO4
H2S2O7(l) + H2O(l) -----> 2H2SO4(l)
Soda ash manufacture
• By 1800 the only native source of soda ash on the British Isles was kelp
(seaweed). Imports of Alkali, from America in the form of wood ashes
(potash) or Spain in the form of barilla (a plant containing 25% alkali) or
from soda mined in Egypt, were all very expensive due to high shipping
costs.
Needed an industrial process for generating soda.
• Based on the synthesis of H2SO4
• Leblanc process (1810):•
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2NaCl + H2SO4 → Na2SO4 + 2HCl
Na2SO4 + CaCO3 + 2C → Na2CO3 + CaS + 2CO2
• The salt came from the Cheshire salt plain
• NaOH was prepared from the sodium carbonate:
• Na2CO3 + Ca(OH)2 → 2NaOH + CaCO3
Pollution
• The HCl was a major problem. James Muspratt (the most important
figure in developing the NW chemical industry). The fumes were so
dense that visibility in the area was <90m.
• A petition against the Le Blanc Process in 1839
complained that "the gas from these manufactories is of such a
deleterious nature as to blight everything within its influence, and is
alike baneful to health and property. The herbage of the fields in
their vicinity is scorched, the gardens neither yield fruit nor
vegetables; many flourishing trees have lately become rotten naked
sticks. Cattle and poultry droop and pine away. It tarnishes the
furniture in our houses, and when we are exposed to it, which is of
frequent occurrence, we are afflicted with coughs and pains in the
head...all of which we attribute to the Alkali works."
• Led to the Alkali Act in 1863 first legislation to limit air pollution.
Solvay process
• John Hutchison – pioneered NW chemical industry recognising
efficiency of scale
• 1847 founded chemical works (Halton – Runcorn)
• Three key recruits:
Towers – analysis; Brunner – manager; and Mond from Germany as
scientific officer
In 1872 formed Brunner-Mond (part of the giant ICI)
1874 introduced the Solvay process
Ernest Solvay 1838-1922
Solvay process
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Ernst Solvay Belgium 1838-1922
Several similar processed but
difficult on large scale (Muspratt
had almost gone bankrupt). Used
to much NH4 which was not widely
available
Advantages of Solvay were:- use
of brine, less waste (low volume
CaCl2 vs high vol CaSO4),
CO2/NH3 recovered, costs some
70% less. However, plant cost
was greater
1890 Solvay was 90% of market
Process centred on iron towers
where rising CO2 was mixed with
brine spray
Solvay process
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CO2(g) + H2O(l) + NH3(g) + Na+(aq) →NaHCO3(s) + NH4+(aq) at 0-15°C
NaHCO3(s) → Na2CO3(s) + CO2(g) + H2O(g) at 300°C
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CO2 could be recycled and NH3 could be recovered. Ammonia is required to make sure
mixture remains non-acidic (i.e. prevents HCl formation which would convert all carbonate
to CO2)
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NH4Cl + Ca(OH)2 → CaCl2 + 2NH3 + 2H2O
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The Solvay reaction is carried out by passing concentrated brine through two towers. In
the first, ammonia bubbles up through the brine and is absorbed by it. It the second, CO2
bubbles up through the brine and precipitates sodium bicarbonate. CO2 for this step is
produced by heating calcium carbonate:
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In 1938, large natural deposits of the mineral trona were discovered near the Green River
in Wyoming. Sodium carbonate can be mined from this source less expensively than it
can be produced by the Solvay process, and since 1986, there have been no Solvaybased plants operating in North America. Throughout the rest of the world, however, the
Solvay process remains the major source of soda ash.
(1)
(2)
Schematic diagram of the manufacturing process
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Ammonia production
• Vital chemical in several industries
• Dyes, cotton treatments, plastics, fertilizer and Solvay process
• It was difficult to make – hydrogen is expensive and the N2/H2
reaction was very high temperature
• Before 1800s from distillation of natural products
• 1800s Distillation of coal became primary source for organics and
ammonia and town gas. All towns had a gas works.
• 1880s Solvay designed his own coke ovens (source of C for iron).
• Coal was heated at very high temperatures in reducing atmospheres
(coal hydrocarbons)
• In this very reducing atmosphere significant quantities of ammonia
were produced.
• First fertilizer was ammonia sulphate from reaction of NH4Cl plus
sulphuric acid
The Haber process
The Haber Process is a method of producing
ammonia developed in WWI. The Germans
needed nitrogen to for making their explosives
but the Allies blocked off all sources of sodium
nitrate and potassium nitrate. The chemist Fritz
Haber developed the Haber Process in WWI via
reaction of nitrogen and hydrogen
N2(g) + 3H2(g) <--> 2NH3(g) + 92 kJ.
This uses an iron oxide catalyst.
Nitrates are made by ammonia oxidation using a
rhodium-platinum wire gauze catalyst, the
primary product is nitric oxide:
4NH3 + 5O2 -> 4NO + 6H2O
This NO is oxidised to NO2 in air and dissolved
in water to yield nitric acid
Nitrates used in fertilizer and explosive
production
The laboratory apparatus designed by Fritz
Haber and Robert Le Rossignol for producing
ammonia from hydrogen and nitrogen, which
was scaled up in the Haber-Bosch process. The
catalytic process took place in the large cylinder
on the left.
Fritz Haber
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By 1905 Fritz Haber (1868–1934) had developed the catalyst
for fixing nitrogen from air. The process was soon scaled up by
BASF's great chemist and engineer Carl Bosch—hence the
name "Haber-Bosch" process. The nitric acid produced from
the ammonia was then used to manufacture agricultural
fertilizers as well as explosives.
He studied at several German universities, earning a doctorate
in organic chemistry in 1891. In 1911 he was invited to become
director of the Institute for Physical Chemistry and
Electrochemistry at the new Kaiser Wilhelm Gesellschaft in
Berlin, where academic scientists, government, and industry
cooperated to promote original research.
During the war he further supported the German side and
developed a new weapon—poison gas, chlorine, and
supervised its initial deployment on the Western Front at Ypres,
1915. His promotion of this frightening weapon precipitated the
suicide of his wife who shot herself with his gun
Controversy reigned when he got Nobel Prize in chemistry for
1918 for the synthesis of ammonia
He was a Jew and proud German and had to resign German
positions in view of Nazi sentiment and was on his way to
senior research job in Palestine when he died.
Cement and lime
• Lime (limestone CaCO3, lime CaO and slaked lime) were central to
most chemical processes in the 1800s
• Also central to cement – Portland cement was the first advanced
materials.
• Joseph Aspdin (Leeds bricklayer) patented Portland cement in 1824
• Limestone came originally from S Coast of UK
• Most common preparation of cement is mixture of limestone, clay
and sand heated (1500C) in a Kiln to produce klinker pellets, a
mixture of calcium silicates, calcium aluminates and calcium
aluminosilicates
• CaCO3 = CaO + CO2
• These are ground to a fine powder with gypsum and iron oxides.
Chlorine
• Is a strong bleaching agent and disinfectant used in textiles and
medical application. Was originally used as chlorine water.
• Charles Tennant (Glasgow) opened a factory there in 1799 that
produced bleaching powder which was much less harmful than the
bleach based on chlorine in an aqueous solution
• At the time Cl2 was produced by reaction of salt with sulphuric acid
and manganese dioxide
• In the 1860's two industrial chemists, Walter Weldon and Henry
Deacon, devised a way of recovering chlorine from the waste
hydrochloric acid produced by the Leblanc soda factories.
• MnO2 + 4HCl → Cl2 + MnCl2 + 2H2O
Chlorine
• The MnO2 could be recovered. The manganese chloride was
treated with milk of lime (a thin cream of slaked lime and water) to
make ‘Weldon Mud’ (a mixture of calcium manganite CaO.2MnO2
and manganese manganite MnO.MnO2).This was separated from
the CaCl2 solution and used again in the chlorine production
process.
• 1870 Deacon developed the process
2HCl + 1/2O2 → H2O + Cl2 used copper as a catalyst
• Gaskell, Deacon & Company based at Widnes exploited this
technology
• Eventually all of the Leblanc companies merged to form United
Alkali Company who later where one of the companies merged to
form ICI
Chlorine
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All of the chlorine technologies were dirty
Electrochemistry would be cleaner and first observed by Cruikshank in 1800
First patent based on a porous diaphragm was 1851 to Watt
However, the lack of domestic electricity supplies limited technology
United alkali company operated first membrane cell in 1890
Cell technologies
NaCl + H2O → NaOH + ½H2 + ½Cl2
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Regardless of cell type, the evolution of chlorine takes place at the anode
(positive electrode) of the cell:
Based on cell type, hydrogen and the hydroxide ions to form sodium
hydroxide are generated, directly or indirectly, at the cathode (negative
electrode) of the cell: