Where Everything Comes From: Industrial Chemistry 101

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Where Everything Comes FromIndustrial Chemistry
101

• William F. Carroll Jr.
• Occidental Chemical Corp.
• ACS President, 2005
• Indiana University

2
Goals for this discussion

• Understand the raw material streams leading to
  the highest volume industrial chemicals
• Review the chemical families derived from these
  streams
• Understand the ecology and interdependent
  nature of chemical products and processes

3
Ultimate Sources

• Four Elements
• Earth
• Air
• Fire
• Water

4
No, Really

• Inorganics
• Rocks
• Minerals
• Brine
• Organics
• Coal
• Oil
• Natural Gas
• Biomass

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High Production Volume Inorganics

• 48 Calcium Carbonate (Precipitated)
• 51 Carbon Black
• 55 Potassium Chloride
• 57 Titanium Dioxide
• 59 Calcium Chloride
• 60 Potassium Sulfate
• 64 Hydrogen
• 65 Sodium Silicate
• 66 Concd Superphosphate
• 68 Aluminum Sulfate
• Aluminum Hydroxide
• Calcium Phosphate
• Hydrogen Cyanide
• Sodium Chlorate
• Magnesium Chloride
• Sodium Bicarbonate
• 99 Sodium Sulfate
• 100 Potassium Hydroxide

• Sulfuric Acid
• 2 Nitrogen
• 3 Oxygen
• 5 Lime
• 8 Ammonia
• 9 Chlorine
• 10 Phosphoric Acid
• 11 Diammonium Phosphate
• 12 Sodium Carbonate
• 14 Sodium Hydroxide
• 16 Sulfur
• 19 Urea
• 21 Carbon Dioxide
• 23 Nitric Acid
• Ammonium Nitrate
• 30 Monoammonium phosphate
• 32 Hydrochloric Acid
• Aluminum Oxide
• Ammonium Sulfate

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High Production Volume Inorganics

• 48 Calcium Carbonate (Precipitated)
• 51 Carbon Black
• 55 Potassium Chloride
• 57 Titanium Dioxide
• 59 Calcium Chloride
• 60 Potassium Sulfate
• 64 Hydrogen
• 65 Sodium Silicate
• 66 Concd Superphosphate
• 68 Aluminum Sulfate
• Aluminum Hydroxide
• Calcium Phosphate
• Hydrogen Cyanide
• Sodium Chlorate
• Magnesium Chloride
• Sodium Bicarbonate
• 99 Sodium Sulfate
• 100 Potassium Hydroxide

• Sulfuric Acid
• 2 Nitrogen
• 3 Oxygen
• 5 Lime
• 8 Ammonia
• 9 Chlorine
• 10 Phosphoric Acid
• 11 Diammonium Phosphate
• 12 Sodium Carbonate
• 14 Sodium Hydroxide
• 16 Sulfur
• 19 Urea
• 21 Carbon Dioxide
• 23 Nitric Acid
• Ammonium Nitrate
• 30 Monoammonium phosphate
• 32 Hydrochloric Acid
• Aluminum Oxide
• Ammonium Sulfate

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Fertilizer chain K, N, P, S
Phosphate Rock (Ca5F(PO4)3) Sulfuric Acid (1)
Phosphoric Acid (10) CaSO4 HF (H2SiF6)
Sulfur (16) O2 (3) Spent acid or H2S burning
(SO2/SO3 )
Oxygen (3) Ammonia (8) CarbonDioxide (21)
Nitric Acid (23)
Nitrogen (2) Hydrogen (64)
Urea (19)
from synthesis gas
Potassium Chloride (55) Potassium Sulfate
(60) Calcium Phosphates (78) Superphosphates (66)
Ammonium Nitrate (24) Ammonium Sulfate
(41) Ammonium Phosphates (11,30)
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Chemicals from Brine

• Sources
• Seas, isolated lakes, underground deposits,
  solution mining
• Contents
• Metals Li, Na, Mg, K, Ca
• Nonmetals Cl, Br, borate, nitrate, sulfate
• Products
• NaCl, MgCl2 (93), KCl (55), CaCl2 (59), Li2CO3,
  Na2CO3 (12), Mg(OH)2, K2SO4 (60), Na2SO4 (99)
• By-Products
• CaCO3 (ppt 48), CaSO4

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Chloralkali
e-, one cell
Chlorine dioxide
SodiumChloride
Sodium Chlorate (82)
Sodium Hydroxide (14)
H2O
Potassium Chloride (55)
Chlorine (9)
CO2
Potassium Hydroxide (100)
Potassium Carbonate
Magnesium Chloride (93)
Magnesium Metal
Electrolysis, separate cells
Hydrogen (64)
Hydrochloric Acid (32)
Rutile,coke
Oxygen (3)
Titanium dioxide (57)
NaOH
Sodium Hypochlorite
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Carbonates Trona and Limestone

• Soda Ash
• Na2CO3/NaHCO3 ore/Solvay Process
• Generates Sodium Bicarbonate (95), Sodium
  silicate (65) (silica gel/detergent)
• Glass, chemical manufacture
• Lime
• CaCO3 CaO (5) CO2
• Flux, pollution control, cement

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Alumina

• Aluminum hydroxide (74) and aluminum oxide (34)
• Isolated from bauxitewith removal of ironand
  silicon oxides
• Papermakers Alum
• Al2O3 3H2SO4 Al2(SO4)3 (68) 3 H2O
• Hall electrochemical process
• 2Al2O3 3C 4Al 3 CO2
• Carried out in a Na3AlF6/AlF3 bath

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High Production Volume Organics

• 43 Phenol
• 44 Polyester Resins Fibers
• 45 Acetic Acid
• 46 Propylene Oxide
• 47 Phenolic Resins
• 49 Butadiene
• 50 Nylon Resins Fibers
• 52 Alpha Olefins
• 53 Acetone
• 54 Phosgene
• 56 Vinyl Acetate
• 58 Urea-Formaldehyde Resins
• 61 Polyurethanes (polyether polyols)
• 62 Engineering Thermoplastics
• 63 Acrylonitrile
• 67 Acrylic Acid
• 69 Nitrobenzene
• 70 Cyclohexane
• 71 Adipic Acid

• 3 Ethylene
• 6 Polyethylene
• 7 Propylene
• 13 Ethylene Dichloride
• 15 MTBE
• 17 Vinyl Chloride
• 18 Polypropylene
• 20 Benzene
• 22 Polyvinyl Chloride
• 25 Ethanol
• 26 Ethylbenzene
• 27 Styrene
• 28 Terephthalic Acid,
• 29 Formaldehyde
• 31 Xylenes
• 33 p-Xylene
• 35 Cumene
• 36 Ethylene Oxide
• 37 Methanol

75 Bisphenol A 76 Acetic Anhydride 77 Styrene-Buta
diene 79 Caprolactam 80 Methyl Methacrylate 83 Iso
propyl Alcohol 84 Polycarbonate 85 Adiponitrile 86
Methyl Diphenyl Diisocyanate 87 Styrene-Based
Latexes 88 Polybutadiene Rubber 89 Butyl
Acrylate 90 Acrylonitrile-Butadiene-Styrene
(ABS) 91 Hexamethylene- diamine 92 Methyl
Chloride 94 o-Xylene 96 Cyclohexanone 97 Propylene
Glycol 98 Phthalic Anhydride
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Sources of Organics Coal
Chemicals from Energy

• Coal tararomatics
• By-product of coke production
• Production of liquids by hydrogenation (H2 or
  solvent donor)
• Carbide/acetylene process
• 2CaCO3 5C 2CaC2 3CO2
• CaC2 H2O C2H2 CaO
• Products via Synthesis Gas

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Sources of Organics Natural Gas
Chemicals from Energy

• Methane, plus higher hydrocarbons
• Use as RM
• Synthesis gas
• Ethane, propane, butane
• Dehydrogenated by steam cracking
• Ethylene, propylene (and H2, CH4)
• US Ethylene 70 from NGL

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Your 60-Second PhD Program

• Chemistry A giant game of Scrabble
• Letters are not created or destroyed, just
  rearranged

FINE BET
BENEFIT
(
TIN BEEF)

• Petroleum Engineering Sorting Socks
• Separating big molecules from little ones on a
  huge scale

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Sources of Organics Crude Oil Distillation
Catalytic Reforming
Steam Cracking
Gases (ltC5)
START HERECrude Oil
Light (Str. Run Gasoline)
Naphtha(n-, i-, c- aro- to C9)
Heavy
Atmospheric Distillation
Atm. Gas Oil
Kerosene, Diesel, Heating Oil
Heavies
Vacuum Gas Oil
Residual Fuel Oil
Catalytic Cracking/Hydrocracking
Lub. Oil Feeds
Vacuum Distillation
Heavy Gas Oil
Pitch
Chemicals from Energy
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Sorting the Molecules
http//www.pafko.com/history/h_refine.html
This column is kept at a temperature that
continuously separates the molecules by size
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Some Processes

• Breaking molecules down, rearranging them,and
  building them up

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Steam vs. Catalytic Cracking

• Thermal/Steam Cracking
• Thermal process w/steam added
• Free radical mechanism
• Thermodynmically, C H2 are favored at these
  temps
• Yields typically C2-C5 materials, mostly olefins
• Catalytic Cracking/Reforming
• Ionic mechanism
• More rearrangement than fragmentation
• Yields typically C5-C12 materials

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Synthesis Gas CO H2
H2
To Make
CH4 H2O CO 3H2 ?H 49 kcal/mol
CnHm
(2n)H2 nCO n(CH2) nH2O
Fischer-Tropsch Fe, Ni, Cu catalyst
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Polymerization

• PolyMany
• Many units
• Categories
• Processing Thermoplastic vs. Thermoset
• Mechanism Chain vs Step-Growth
• Composition Homo- vs. Co-polymer

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Types of Polymers by Processing

• Thermoplastics
• Formed by heating, cooled to retain shape
• Large number of reshaping cycles
• Thermosets
• Cured by heating Crosslinked
• Typically not reshapable
• Chars before melting

e.g., Butter
e.g., Bread
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Chain Growth (Addition)
Types of polymers by mechanism

• Single units extend a single growing end of a
  molecule
• Synthesis Steps
• Initiator (FR, Cation, Anion)
• Addition usually via substituted ethylene monomer
• Chain terminates, transfers

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More on Monomers
XH, YH Poly(Ethylene) Milk Bottles XMe,
YH Poly(Propylene) Outdoor carpet XPh, YH
Poly(Styrene) Foam insulation XCOOH, YH
Poly(Acrylic Acid) Disposable Diapers XCOOMe,
YMe Poly(Methyl Methacrylate) Plexiglas
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Step-Growth Polymerization
Another kind...

• Sometimes called condensation
• Reaction proceeds from two active ends
• Reaction between bifunctional molecules
• Diacid or diester diol polyesters
• Diacid or acid chloride diamine
  polyamides
• Amino acid polyamide
• Isocyanate alcohol polyurethane
• Can eliminate small molecule

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Step-Growth Polymers

• Polyesters
• HOOC-Ar-COOH HOCH2CH2OH
• Polyamides
• Nylon 6,6

Polyethylene terephthalate
1st No.
2nd No.
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Step-Growth Polymers

• Nylon 6polycaprolactam
• ---CO-(CH2)5-NH---
• Polycarbonate phosgene Bisphenol-A

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Thermosets

• Phenolic resins
• Phenol formaldehyde
• Polyurethanes
• MDI, TDI polyols

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The Major Organic Families

• C1-C5, Benzene, Toluene, Xylene

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Methane/Syn Gas
Xylenes
Ethylene
CH4,CO H2
Propylene
Steam Cracking
Cat. Reforming
C4 Olefins
Nat. Gas Liquids
Toluene
Naphtha
Benzene
Pyrolysis GasC5 Olefins, Aromatics
Separation
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Ethylene (4) Chain
High, Low Density Polyethylene (6)
-HCl (32)
Ethylene Dichloride (13)
Cl2 (9)
Vinyl chloride (17)
Poly(vinyl chloride) (22)
-H2
FH (20)
Ethylbenzene (26)
Polystyrene (39), ABS (90) SBR (77, 87)
Styrene (27)
Polyethylene glycols
Ethylene Oxide (36)
Ethylene Glycol (42)
Nonionic surfactants
O2 (3)
Ag
Polyethylene terephthalate resins, fibers(40, 44)
Sterilant
Antifreeze
Soda bottles, Dacron, Mylar
AcOH (45)
Poly(vinyl Acetate), poly(vinyl alcohol,
poly(vinyl butyral)
Vinyl Acetate (56)
Pd
Elmers Glue, thickener, windshield laminate
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High Production Volume Organics Polymers

• 43 Phenol
• 44 Polyester Resins Fibers
• 45 Acetic Acid
• 46 Propylene Oxide
• 47 Phenolic Resins
• 49 Butadiene
• 50 Nylon Resins/Fibers
• 52 Alpha Olefins
• 53 Acetone
• 54 Phosgene
• 56 Vinyl Acetate
• 58 Urea-Formaldehyde Resins
• 61 Polyurethanes (polyether polyols)
• 62 Engineering Thermoplastics
• 63 Acrylonitrile
• 67 Acrylic Acid
• 69 Nitrobenzene
• 70 Cyclohexane
• 71 Adipic Acid

• 3 Ethylene
• 6 Polyethylene
• 7 Propylene
• 13 Ethylene Dichloride
• 15 MTBE
• 17 Vinyl Chloride
• 18 Polypropylene
• 20 Benzene
• 22 Polyvinyl Chloride
• 25 Ethanol
• 26 Ethylbenzene
• 27 Styrene
• 28 Terephthalic Acid,
• 29 Formaldehyde
• 31 Xylenes
• 33 p-Xylene
• 35 Cumene
• 36 Ethylene Oxide
• 37 Methanol

75 Bisphenol A 76 Acetic Anhydride 77 Styrene-Buta
diene 79 Caprolactam 80 Methyl Methacrylate 83 Iso
propyl Alcohol 84 Polycarbonate 85 Adiponitrile 86
Methyl Diphenyl Diisocyanate 87 Styrene-Based
Latexes 88 Polybutadiene Rubber 89 Butyl
Acrylate 90 Acrylonitrile-Butadiene-Styrene
(ABS) 91 Hexamethylene- diamine 92 Methyl
Chloride 94 o-Xylene 96 Cyclohexanone 97 Propylene
Glycol 98 Phthalic Anhydride
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The Take-Away

• All of industrial chemistry comes from just a few
  places
• Most pounds come from a few chemicals
• Most inorganic pounds become fertilizer most
  organic pounds become polymers
• Building block products are interdependent

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Chlorinated Organics Chain
See ethylene chain
Ethylene Dichloride (13)
Vinyl chloride (17)
Poly(vinyl chloride) (22)
Chlorinated ethanes, ethylenes
CH4
CH3Cl (92), CH2Cl2, CHCl3, CCl4
Chlorine (9)
Base
Propylene
Epichlorohydrin
Epoxy resin
Allyl Chloride
Polycarbonate (84)
CO
Phosgene (54)
Polyurethanes (61)
Benzene, phenol
Chlorinated aromatics
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Chemical Chains

• Syn Gas (C1)/Methanol
• Ethylene (C2)
• Propylene (C3)
• Butane/Butene (C4)
• Benzene
• Toluene
• Xylene

• Ammonia/Fertilizer
• Brine
• Chloralkali
• Sodium Carbonate
• Alumina
• Chlorinated Organics

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Cumene Hydroperoxide
O2

H
-H2O
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Other Processes

• Oligomerization
• Short chain olefins to branched C9-C12
• Alkylation
• Acid catalyzed reaction of olefins to branched
  alkanes
• Hydrocracking
• Hydrogenation of heavy oils
• Dehydrogenation
• Alkanes to alkenes
• Isomerization
• Straight to branched chains
• Metathesis
• Propylene to Ethylene, butene create novel
  alkenes
• Disproportionation
• Toluene to benzene, xylenes

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Catalytic Reforming
Hydrogenolysis
Cracked Prods(low MW)
Hydrogenolysis
Aromatics
Source Industrial Organic Chemicals, Wittcoff,
Reuben
42
Industrial Chemistry
Consumers
Export
Mining
Other Mfg
Top 100
Inorganic,OrganicRM
Intermediates, Finished Prods
ChemicalProcessing
ChemicalProcessing
Energy, Air, Water
Energy, Air, Water
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Sources of Inorganics

• Air
• Salt/Brine
• Phosphate rock
• Sulfur/Smelting off streams
• Limestone
• Trona
• Bauxite
• Rutile/Ilmenite

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Hydroformylation Oxo Process
Co(CO)3H
CH2CH2 HCo(CO)3
CO
CH3CH2COCo(CO)3
CH3CH2Co(CO)4
H2
H2O
CH3CH2CHO HCo(CO)3
CH3CH2COOH HCo(CO)3
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C1 Syn Gas, Methanol (37) chain
Phenol (43)
Phenolic resins (47)
See benzene chain
Formaldehyde (29)
Ag, -H2
Urea (19)
Urea-Formaldehyde resins (58) Melamine-Formaldehyd
e resins (Formica)
See fertilizer chain
t-butanol
MeOH
MTBE (15)
See C4 chain
CO
Acetic Acid (45)
Vinyl Acetate (56), Acetic Anhydride (76), other
acetates
See ethylene chain
H2O
46
Propylene (7) Chain
Polypropylene resins, fibers (18)
H2O, ?
Isopropanol (83)
Methyl meth-acrylate (80)
1) HCN (81) 2) H2SO4 (1)
MeOH (37)
FH
Acetone (53)
Cumene (36)
O2
Cumene Hydroperoxide
Phenol (43)
poly(MMA) Plexiglas
Propylene Glycol (97)
Safer Antifreeze
Propylene Oxide (46)
HOCl
Polyurethane polyols (61)
NH3, O2
Acrylonitrile (63)
ABS (90), SAN, pAN
See benzene, C4 chains
O2
O2
Acrylic acid (67)
Poly(Acrylic acid)
Superabs. diapers
H2
oxo
n-butyraldehyde
n-butanol (72)
PVB
Solvents, monomers
47
C4 Chain
Butadiene polymers, elastomers (77, 87, 88, 90)
Butadiene (49)
HCN (81)
Adiponitrile (85)
H2
Hexamethylenediamine (91)
Nylon (6,6) resins, fibers (50)
Adipic Acid (71)
See benzene chain
H2O, H
t-butanol
Isobutylene
MTBE (15)
MeOH
See methanol chain
Acid I-X
See ethylene chain
1-butene
Linear low-density polyethylene
48
Benzene (20) Chain
Ethylbenzene (26)
Styrene (27)
Polystyrene (39), etc
See ethylene chain
Acetone (53)
Bisphenol-A (75)
Cumene (35)
H
COCl2
Phenol (43)
Polycarbonate (84)
CDs, bottles
HCHO
Phenolic resins (47)
Sandpaper, plywood
O2 (3)
H2 (64)
Cyclohexanone (96)
Cyclohexane (70)
NH3 (8)
Caprolactam (79)
Nylon (50)
O2 (3)
HNO3 (23)
Adipic Acid (71)
cat
Nitrobenzene (69)
HMDA (91)
1) HCl (32) 2) HCHO (29)
H2 (64)
polyols
Polyurethanes (61)
Aniline (73)
3) COCl2 (54)
(MDI)
49
Toluene Chain
1) HNO3 (23) 2) H2SO4 (1)
COCl2 (54)
Toluene Diisocyanate
Diaminotoluenes
3) H2 (64)
Polyurethanes
Solvent, Benzaldehyde, Benzyl alcohol
Reforming
Benzene
See benzene chain
Reforming
Xylenes
See xylene chain
50
Xylene Chain
Phthalate plasticizers
Phthalic Anhydride (98)
DAP, Alkyd resins
o-Xylene
Solvent
m-Xylene
Alkyd resins, aramids--Nomex
Isophthalic Acid
Polyester resins, fibers (44)
p-Xylene
Terephthalic acid (28)
Aramids--Kevlar