1ST YEAR LECTURE NOTES HISTORY OF THE CHEMICAL INDUSTRY M A MORRIS E-MAIL [email protected] [email protected] Rm: 108 Kane Building.

1ST YEAR LECTURE NOTES1ST YEAR LECTURE NOTESHISTORY OF THE CHEMICAL HISTORY OF THE CHEMICAL

INDUSTRYINDUSTRY M A MORRISM A MORRIS

E-MAIL E-MAIL [email protected]@ucc.ie

Rm: 108 Kane BuildingRm: 108 Kane Building

SynopsisSynopsis

Start with initial use of chemicals and the Start with initial use of chemicals and the industrial revolution in the UK. industrial revolution in the UK.

Importance of resources. Importance of resources. Inorganic chemicals and industry. Inorganic chemicals and industry. Look at advent of catalysis in bulk chemical Look at advent of catalysis in bulk chemical

synthesis. synthesis. Petroleum industry and organics. Petroleum industry and organics. Start of the pharma-chem sector. Start of the pharma-chem sector. Materials market development.Materials market development.

IntroductionIntroduction

Chemicals were known by the ancientsChemicals were known by the ancients Ancient Egyptians used ‘soap’Ancient Egyptians used ‘soap’ Soda (sodium carbonates, natron in Egypt) plus Soda (sodium carbonates, natron in Egypt) plus

fats to wash corpses prior to during fats to wash corpses prior to during mummificationmummification

Cement dates back to Egyptians passed to Cement dates back to Egyptians passed to Romans and the Greeks (forgotten for 2000 yrs) Romans and the Greeks (forgotten for 2000 yrs) volcanic ash + rock + caustic soda (NaOH)volcanic ash + rock + caustic soda (NaOH)

500 yrs ago Mayan Indians used latex balls in 500 yrs ago Mayan Indians used latex balls in games and in clothinggames and in clothing

Recipe for a mummy….Recipe for a mummy…. Four jars hold the liver, lungs, intestines, and stomach. The heart is kept Four jars hold the liver, lungs, intestines, and stomach. The heart is kept

inside the body and the other internal body organs fried. 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 The brain is pulled thru the nose with a hook. Stuff the head with tree

resin and sawdust. resin and sawdust. Soak the body in natron for 40 days. The body is put on a inclined couch 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. and the liquids and natron fall to the bottom into a pan. Rub the body with olibanum oil to make the skin supple. Rub the body with olibanum oil to make the skin supple. Pack the body to make it more lifelike (with spices or sawdust). Pack the body to make it more lifelike (with spices or sawdust). Use wax to seal any incisions. Use wax to seal any incisions. Tear fine linen into strips 16 yards long and 2-8 inches wide. Tear fine linen into strips 16 yards long and 2-8 inches wide. Wrap the smaller extremities (toes and fingers) first. Wrap the smaller extremities (toes and fingers) first. Next, wrap the limbs, and finally, the torso. Next, wrap the limbs, and finally, the torso. Sing appropriate chants over each body part. Sing appropriate chants over each body part. Secure linen with tree resin. Secure linen with tree resin. Tuck in an amulet after every few layers. Tuck in an amulet after every few layers.

Modern Chemical IndustryModern Chemical Industry

Began in UK around 1800Began in UK around 1800 Was sponsored by the industrial revolution Was sponsored by the industrial revolution

with demands for chemicals for other with demands for chemicals for other industries.industries.

Soap manufacture (alkali + animal fat)Soap manufacture (alkali + animal fat) Cotton – bleachCotton – bleach Glassmaking – sand (SiO2) and soda Glassmaking – sand (SiO2) and soda

(sodium carbonate)(sodium carbonate)

Some key chemicals needed to be Some key chemicals needed to be manufactured……..manufactured……..

Sulphuric acid - oil of vitriolSulphuric acid - oil of vitriol Soda – sodium carbonateSoda – sodium carbonate Caustic soda – sodium hydroxideCaustic soda – sodium hydroxide

CopperasCopperas Green vitriol (FeSOGreen vitriol (FeSO44.7H.7H22O) was used extensively in the O) was used extensively in the

textile and metallurgical industries and for a number of textile and metallurgical industries and for a number of other purposes.other purposes.

Jabir-Ibn-Hayyan (721-815) distinguished between green Jabir-Ibn-Hayyan (721-815) distinguished between green vitriol and blue vitriol, ferrous sulphate and copper vitriol and blue vitriol, ferrous sulphate and copper sulphate respectivelysulphate respectively

17th17th C manufacture copperas containing stones were C manufacture copperas containing stones were collected from the beach placed in oak vessels and collected from the beach placed in oak vessels and packed with chalk. After several years a liquor a mixture packed with chalk. After several years a liquor a mixture of sulphuric acid (source of this for many years) and iron of sulphuric acid (source of this for many years) and iron sulphate solution was collected. Further iron was added sulphate solution was collected. Further iron was added to bring it up to stoichiometery.to bring it up to stoichiometery.

Sulphate crystals were collected by drying in sun. Twigs Sulphate crystals were collected by drying in sun. Twigs etc were added to promote crystallisation processes.etc were added to promote crystallisation processes.

Took place at Tankerton in Kent and in Dorset but soon Took place at Tankerton in Kent and in Dorset but soon move to the NW of Englandmove to the NW of England

Sulphuric acidSulphuric acid First chemical process on an industrial scaleFirst chemical process on an industrial scale This source became green vitriol ( FeSOThis source became green vitriol ( FeSO44.7H.7H22O) O)

recovered from mineral pyrites and was first material that recovered from mineral pyrites and was first material that Joshua Parr attempted to make at Mynydd Parys (1795). Joshua Parr attempted to make at Mynydd Parys (1795).

FeSFeS22(s) + 11O(s) + 11O22 →→ 2Fe 2Fe22OO33(s) + 8SO(s) + 8SO22(g)(g) Eventually sulphide/S mines in N. Wales sent material to Eventually sulphide/S mines in N. Wales sent material to

Liverpool (Garston sulphuric Acid Co.). Start of the NW Liverpool (Garston sulphuric Acid Co.). Start of the NW chemical industry. chemical industry.

S (as pyrite also) was oxidised in air to give SOS (as pyrite also) was oxidised in air to give SO22. . Saltpeter (KNOSaltpeter (KNO33) was used as catalyst releasing NOx) was used as catalyst releasing NOx

Water in reaction chamber absorbed gasesWater in reaction chamber absorbed gases Reactions took place in small glass lined vessels but Reactions took place in small glass lined vessels but

scale of production was increased by Roebuck and scale of production was increased by Roebuck and Gardner (1746) using large lead lined chambers.Gardner (1746) using large lead lined chambers.

Sulphuric acid improvementsSulphuric acid improvements

Gay-Lussac towers (1837)– introduced oxygen Gay-Lussac towers (1837)– introduced oxygen to form SOto form SO33 in increased amounts and recovered in increased amounts and recovered NONOxx reducing requirement for the KNO reducing requirement for the KNO3. 3.

Improved by Glover (UK) and towers common in Improved by Glover (UK) and towers common in 1870s1870s

1880s saw further increases. Phillips (UK 1880s saw further increases. Phillips (UK vinegar merchant) patented Pt catalysed vinegar merchant) patented Pt catalysed oxidation of SO2 to SO3. Was not used until oxidation of SO2 to SO3. Was not used until catalyst reactor built in Germany in 1875. But catalyst reactor built in Germany in 1875. But technology widely used by 1890.technology widely used by 1890.

In the 20C Pt replaced by vanadium oxidesIn the 20C Pt replaced by vanadium oxides

Soda ash manufactureSoda ash manufacture

Based on the synthesis of HBased on the synthesis of H22SOSO4 4

Leblanc process:-Leblanc process:-

2NaCl + H2NaCl + H22SOSO4 4 → → NaNa22SOSO4 4 + 2HCl+ 2HCl

NaNa22SOSO4 4 + CaCO+ CaCO33 + 2C → Na + 2C → Na22COCO33 + CaS + 2CO + CaS + 2CO22

The salt came from the Cheshire salt plainThe salt came from the Cheshire salt plain

NaOH manufactureNaOH manufacture

From the sodium carbonate:From the sodium carbonate: NaNa22COCO33 + Ca(OH) + Ca(OH)22 → 2NaOH + CaCO → 2NaOH + CaCO33

The HCl was a major problem. James Muspratt The HCl was a major problem. James Muspratt (the most important figure in developing the NW (the most important figure in developing the NW chemical industry). The fumes were so dense chemical industry). The fumes were so dense that visibility in the area was <90m. that visibility in the area was <90m.

Led to the Alkali Act in 1863 first legislation to Led to the Alkali Act in 1863 first legislation to limit air pollution.limit air pollution.

Solvay processSolvay process John Hutchison – pioneered NW chemical John Hutchison – pioneered NW chemical

industry recognising efficiency of scaleindustry recognising efficiency of scale 1847 founded chemical works (Halton – 1847 founded chemical works (Halton –

Runcorn)Runcorn) Three key recruits:Three key recruits:

Towers – analysis; Brunner – manager; and Mond Towers – analysis; Brunner – manager; and Mond from Germany as scientific officerfrom Germany as scientific officer

In 1872 formed Brunner-Mond (part of the giant In 1872 formed Brunner-Mond (part of the giant ICI)ICI)

1874 introduced the Solvay process1874 introduced the Solvay process

Solvay processSolvay process Ernst Solvay Belgium 1838-1922Ernst Solvay Belgium 1838-1922 Several similar processed but difficult on large Several similar processed but difficult on large

scale (Muspratt had almost gone bankrupt). scale (Muspratt had almost gone bankrupt). Used to much NHUsed to much NH44 which was not widely which was not widely availableavailable

Advantages of Solvay were:- use of brine, less Advantages of Solvay were:- use of brine, less waste (low volume CaClwaste (low volume CaCl22 vs high vol CaSO vs high vol CaSO44), ), COCO22/NH/NH33 recovered, costs some 70% less. recovered, costs some 70% less. However, plant cost was greaterHowever, plant cost was greater

1890 Solvay was 90% of market1890 Solvay was 90% of market Process centred on iron towers where rising COProcess centred on iron towers where rising CO22

was mixed with brine spraywas mixed with brine spray

Solvay processSolvay process

NHNH33 + H + H22O + COO + CO22 → NH→ NH44HCOHCO33

NaCl + NHNaCl + NH44HCOHCO33 → NaHCO → NaHCO33 + NH + NH44ClCl

COCO2 2 and NHand NH33 could be recovered could be recovered

2NaHCO2NaHCO33 → Na → Na22COCO33 + H + H22O + COO + CO22

NHNH44Cl + Ca(OH)2 → CaClCl + Ca(OH)2 → CaCl22 + 2NH + 2NH3 3 + 2H+ 2H22OO

Ammonia productionAmmonia production Vital chemical in several industriesVital chemical in several industries Dyes, cotton treatments, plastics, fertilizer Dyes, cotton treatments, plastics, fertilizer

and Solvay processand Solvay process It was difficult to make – hydrogen is It was difficult to make – hydrogen is

expensive and the Nexpensive and the N22/H/H22 reaction was very reaction was very

high temperaturehigh temperature Before 1800s from distallation of natural Before 1800s from distallation of natural

productsproducts

Ammonia productionAmmonia production 1800s Distillation of coal became primary source 1800s Distillation of coal became primary source

for organics and ammonia and town gas. All for organics and ammonia and town gas. All towns had a gas works.towns had a gas works.

1880s Solvay designed his own coke ovens 1880s Solvay designed his own coke ovens (source of C for iron).(source of C for iron).

Coal was heated at very high temperatures in Coal was heated at very high temperatures in reducing atmospheres (coal hydrocarbons)reducing atmospheres (coal hydrocarbons)

In this very reducing atmosphere significant In this very reducing atmosphere significant quantities of ammonia were produced.quantities of ammonia were produced.

First fertilizer was ammonia sulphate from First fertilizer was ammonia sulphate from reaction of NHreaction of NH44Cl plus sulphuric acidCl plus sulphuric acid

Cement and limeCement and lime Lime (limestone CaCO3, lime CaO and Lime (limestone CaCO3, lime CaO and

slaked lime) were central to most chemical slaked lime) were central to most chemical processes in the 1800sprocesses in the 1800s

Also central to cement – Portland cement Also central to cement – Portland cement was the first advanced materials.was the first advanced materials.

Joseph Aspdin (Leeds bricklayer) patented Joseph Aspdin (Leeds bricklayer) patented Portland cement in 1824Portland cement in 1824

Limestone came originally from S Coast of Limestone came originally from S Coast of UK UK

CementCement

Most common preparation is mixture of Most common preparation is mixture of limestone, clay and sand heated (1500C) in a limestone, clay and sand heated (1500C) in a Kiln to produce klinker pellets, a mixture of Kiln to produce klinker pellets, a mixture of calcium silicates, calcium aluminates and calcium silicates, calcium aluminates and calcium aluminosilicatescalcium aluminosilicates

CaCOCaCO33 = CaO + CO = CaO + CO22

These are ground to a fine powder with gypsum These are ground to a fine powder with gypsum and iron oxides. and iron oxides.

Used to seal and rebuild the Thames tunnelUsed to seal and rebuild the Thames tunnel

ChlorineChlorine Is a strong bleaching agent and disinfectantIs a strong bleaching agent and disinfectant used in used in

textiles and medical application. Was originally used as textiles and medical application. Was originally used as chlorine water.chlorine water.

Charles Tennant (Glasgow) opened a factory there in Charles Tennant (Glasgow) opened a factory there in 1799 that produced bleaching powder which was much 1799 that produced bleaching powder which was much less harmful than the bleach based on chlorine in an less harmful than the bleach based on chlorine in an aqueous solutionaqueous solution

At the time ClAt the time Cl22 was produced by reaction of salt with was produced by reaction of salt with sulphuric acid and manganese dioxidesulphuric acid and manganese dioxide

In the 1860's two industrial chemists, Walter Weldon and In the 1860's two industrial chemists, Walter Weldon and Henry Deacon, devised a way of recovering chlorine Henry Deacon, devised a way of recovering chlorine from the waste hydrochloric acid produced by the from the waste hydrochloric acid produced by the Leblanc soda factories.Leblanc soda factories.

MnOMnO22 + 4HCl + 4HCl →→ Cl Cl22 + MnCl + MnCl22 + 2H + 2H22OO

ChlorineChlorine The MnOThe MnO22 could be recovered. The manganese chloride could be recovered. The manganese chloride

was treated with milk of lime (a thin cream of slaked lime was treated with milk of lime (a thin cream of slaked lime and water) to make ‘Weldon Mud’ (a mixture of calcium and water) to make ‘Weldon Mud’ (a mixture of calcium manganite CaO.2MnOmanganite CaO.2MnO22 and manganese manganite and manganese manganite MnO.MnOMnO.MnO22).This was separated from the CaCl).This was separated from the CaCl22 solution solution and used again in the chlorine production process. and used again in the chlorine production process.

1870 Deacon developed the process1870 Deacon developed the process2HCl + 1/2O2HCl + 1/2O22 →→ H H22O + ClO + Cl2 2 used copper as a catalystused copper as a catalyst

Gaskell, Deacon & Company based at Widnes exploited Gaskell, Deacon & Company based at Widnes exploited this technologythis technology

Eventually all of the Leblanc companies merged to form Eventually all of the Leblanc companies merged to form United Alkali Company United Alkali Company who later where one of the who later where one of the companies merged to form ICI companies merged to form ICI

ChlorineChlorine All of the chlorine technologies were dirtyAll of the chlorine technologies were dirty Electrochemistry would be cleaner and Electrochemistry would be cleaner and

first observed by Cruikshank in 1800first observed by Cruikshank in 1800 First patent based on a porous diaphram First patent based on a porous diaphram

was 1851 to Wattwas 1851 to Watt However, the lack of domestic electricity However, the lack of domestic electricity

supplies limited technologysupplies limited technology United alkali company operated first United alkali company operated first

membrane cell in 1890membrane cell in 1890

Cell technologiesCell technologies Membranes were required for efficient Membranes were required for efficient

production of Cl2 and NaOH from salt production of Cl2 and NaOH from salt solution.solution.

Anode: NaCl Anode: NaCl → Na+ + Cl-; Cl- → Cl. + e→ Na+ + Cl-; Cl- → Cl. + e 2Cl. → Cl22Cl. → Cl2