CHEMICAL PROCESS INDUSTRIES CPI 201T-9 - F-T 2013

By

Dr Alex Sofianos
Bsc Chem Eng, Msc, PhD Ind Chem (GERMANY), MBL (UNISA)

Course Contents
1. 2. 3. 4. 5. 6. 7. 8. 9. Introduction Inorganic Bulk Commodity Chemicals Synthesis Gas Processes Petroleum Refining Polymerisation and Petrochemicals Organic Chemical Process Industries Cement, Glass, Dyes Manufacturing Hydrometallurgical Processes Environmental Issues and Green Chemistry
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Introduction
What is industrial chemistry (CPI)?

The development, optimization and monitoring of fundamental chemicalprocesses used in industry for transforming raw materials and precursors into useful commercial products for society.
Why is it relevant to you?

Industrial chemistry plays a vital role as an applied science in diverse areas that influence human society ranging from economic, environmental and political stability through job creation
1. Goals we set to achieve with this course

2. 3.

Define, describe, and apply basic chemical processes involved in the production of major commercial products used in society. Develop critical skills at analyzing the cost/benefit/impact of traditional industrial chemical processes on society as a whole. Appreciate the role of green chemistry for efficient yet sustainable industrial chemical processes with low impact on the environment and human health.
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Introduction II
Course strategy: Hints on how to succeed in this course (CPI)?

Try to attend every class on time and conscientiously do assigned reading and problem sets. This is particularly important as there are no textbooks for this course Actively participate in class/group discussions. Relate knowledge gained in class which can be applied to real-world problems. Creative contributions to group project and presentations. During the course, compile a concise set of notes from lecture and material that includes basic principles and equations of chemical analysis (useful for final exam). Questions or doubts about the material being taught can be discussed in class, drop-by for a visit in my office or send an e-mail message. Working in groups for support throughout the term is very important. But most important of all, do not get scared of the material keep an open mind, relax and try to have fun!
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Inorganic Bulk Chemicals

Sulphuric Acid Contact Process Phosphoric Acid Lurgi- Fisons Process Ammonia Haber-Bosch Process Nitric Acid Ostwald Process Urea and Fertilizers Sodium Hydroxide Chloralkali Process Chlorine Chloralkali Process Soda Ash Solvay Process
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Synthesis Gas Processes

Synthesis Gas Production
Coal Gasification Steam Reforming of Methane

Water Gas Shift Reaction Fischer-Tropsch Process Methanol Synthesis Methanol Conversion to Chemicals
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The Fischer Tropsch Process

Conventional oil reserves are not located where demand is growing No one technology can address the overall issue fossil fuel demand is too large Availability of infrastructure limits the use of many alternatives A large readily-available resource is needed to offset near-term implications of peak oil Alternatives must be clean, easily distributed and economically viable in todays environment
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The Fischer Tropsch Process 0. General

The Fischer Tropsch (FT) process is a chemical reaction between Carbon Monoxide CO and Hydrogen H2, facilitated by a catalyst (usually Iron or Cobalt Oxides), and which produces hydrocarbons (their type depends on the catalyst used, the conditions at which the reaction occurs and the reactor type utilised). The mixture of CO and H2 used in this reaction is called syngas and can be produced in various ways using organic materials as feedstocks. Raw materials are typically coal, natural gas, biomass, oil shales, solid residues from refineries etc

The Fischer Tropsch Process 1. General

The FischerTropsch process (or FischerTropsch synthesis) is a set of chemical reactions that convert a mixture of carbon monoxide and hydrogen into liquid hydrocarbons. The process, a key component of Gas to Liquids Technology, (GTL) produces a crude petroleum substitute for use as a synthetic fuel (substitute for gasoline, diesel) or a lubrication oil. The FT process has received intermittent attention as a source of low-sulfur diesel fuel and to address the supply or cost of petroleum-derived hydrocarbons. In RSA (current world champion of FT Technology!) FT process is the base of the SASOL group of industries.
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The Fischer Tropsch Process 1. General (continued)

FT process was discovered by two German scientists in 1925 in order to produce liquid fuels from coal feedstock (indirect coal liquefaction) A process in which a synthesis gas (i.e. syngas) consisting of hydrogen and carbon monoxide is reacted with a cobalt catalyst under certain pressures and temperatures to produce a liquid distillate
The feedstock which is referred to as a syngas can come from coal, methane or gasified biomass such as gasified black liquor

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The Fischer Tropsch Process 2. Definition

The FischerTropsch process involves a series of chemical reactions that lead to a variety of hydrocarbons. Useful reactions give alkanes by hydrogenation

(2n+1) H2 + n CO CnH(2n+2) + n H2O

where n= 1, 2, 3, 4 . is a positive integer. Example: n=1 CnH(2n+2) gives CH4 (methane!)

Formation of methane; unwanted reaction

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The Fischer Tropsch Process 2. Definition (continued) Most of the alkanes produced tend to be straight-chain alkanes, Some branched alkanes are also formed (why do we need branched alkanes?) In addition to alkane formation, competing reactions result in the formation of:
Alkenes Alcohols Ketones and other oxygenated hydrocarbons.
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Green Chemistry - Renewable Raw Materials

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The Fischer Tropsch Process 3. Existing Plants

Sasol is the leading company in the commercialization of synthetic fuel is a company based in South Africa. Sasol operates the world's only commercial Fischer Tropsch coal-to-liquids facilities at Sasolburg and at Secunda, with a capacity of 150,000 barrels per day (24,000 m3/d). Sasol's Oryx Fischer Tropsch gas-to-liquids (GTL) plant in Ras Laffan Industrial City, Qatar, is running at 29,000 barrels per day (4,600 m3/d) capacity, near its anticipated 34,000 barrels per day (5,400 m3/d) nameplate capacity. Royal Dutch Shell operates a 14,700 barrels per day (2,340 m3/d) Fischer Tropsch gas-to-liquids plant in Bintulu, Malaysia.[
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Sasol Secunda Plants

150,000 BPD Coal to Liquids (CTL)

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Sasol Secunda Plant

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Mossgas Plant
47,000 BPD Gas to Liquids (GTL)

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Shell Bintulu (Malaysia)

15,000 BPD Gas to Liquids (GTL)

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CHOREN Freiberg
500 BPD Biomass to Liquids

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The Fischer Tropsch Process

3. Existing Plants (continued)
The Mossgas gas-to-liquids plant in Mosselbay, South Africa produces 45,000 barrels per day (7,200 m3/d) of Fischer Tropsch synthetic fuels. Other companies that have developed CTL (coal- to-liquids) or GTL (or gas-to-liquids) processes (at the pilot plant or commercial stage) include: ExxonMobil StatoilHydro Rentech and Syntroleum South Africa is the world leader company in the commercialization of synthetic fuels
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The Fischer Tropsch Process 2. Existing Plants (continued)

The Mossgas gas to liquids plant in Mossel Bay, South Africa produces 45,000 barrels per day (7,200 m3/d) of Fischer Tropsch synthetic fuels. Other companies that have developed CTL (coal- to-liquids) or GTL (or gas-to-liquids) processes (at the pilot plant or commercial stage) include: ExxonMobil StatoilHydro Rentech and Syntroleum South Africa is the world leader company in the commercialization of synthetic fuels
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The Fischer Tropsch Process

4. Plants under Construction
The Pearl GTL project a joint venture of Shell and Qatar Petroleum is under construction in Ras Laffan, Qatar, and will produce 140,000 barrels per day (22,000 m3/d) of FT petroleum liquids starting in 2012 (two trains) The Escravos GTL project in Nigeria (a 75:25% joint venture of Chevron Nigeria (CNL) and National Nigerian Petroleum Company (NNPC) is expected to produce 34,000 barrels per day (5,400 m3/d) of Fischer Tropsch synthetic fuel by 2013. Shenhua expected to begin operation in July 2009 of their 1 million ton per year (roughly 22,200 barrels per day (3,530 m3/d)) direct coal liquefaction plant Erdos CTL, in Ejin Horo Banner in north China's Inner Mongolia autonomous region.
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The Fischer Tropsch Process

4. Plants under Construction (conued)
Shenhua also expects to complete a 6 Million ton per year (3 Million TPY first phase) coal-to-fuel project using its own Fischer Tropsch indirect conversion technology next to the Ejin Horo Banner plant in north China's Inner Mongolia area American Clean Coal Fuels, in their Illinois Clean Fuels project, is developing a 30,000 barrels per day (4,800 m3/d) Fischer Tropsch biomass and coal to liquids project with carbon capture and sequestration in Oakland Illinois. Baard Energy, in its Ohio River Clean Fuels project, is developing a 53,000 barrels per day (8,400 m3/d) Fischer Tropsch coal and biomass to liquids project with the carbon capture and sequestration
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The Fischer Tropsch Process

5. Economics

The economics of synthetic fuel manufacture vary greatly depending on:

the feedstock used, the precise process employed, site characteristics such as feedstock and transportation costs, cost of additional equipment required to control emissions.

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The Fischer Tropsch Process

5. Economics

Examples described below indicate a wide range of production costs between $20/BBL for large-scale gas-to-liquids, to as much as $240/BBL for smallscale biomass-to-liquids In order to be economically viable, projects must do much better than just being competitive head-tohead with oil. They must also generate a sufficient return on investment to justify the capital investment in the project.
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The Fischer Tropsch Process

5. Economics (conued)
A synthetic fuel manufactured from natural gas (GTL), in a large scale plant in the Middle East (where gas is relatively inexpensive), is expected to be competitive with oil down to approximately $20 per barrel Recent advances by the oil company Shell have seen synthetic fuels start to become profitable. The company is building a GTL (gas-to-liquid) plant in Qatar, due to come online in 2011. It will be capable of producing 300,000 barrels per day (48,000 m3/d) of synthetic fuels and other products, using natural gas as a feedstock. Shell claims the process will remain competitive with traditional diesel unless the price of crude falls below $20 per barrel.
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The Fischer Tropsch Process

5. Economics (conued)
A medium scale (30,000 BPD) coal-to-liquids plant (CTL) sited in the US using bituminous coal, is expected to be competitive with oil down to roughly $5256/bbl crude-oil equivalent. Adding carbon capture and sequestration to the project was expected to add an additional $10/BBL to the required selling price

In South Africa: Sasol Mossgas

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The Fischer Tropsch Process 6. Sasol In South Africa:

Sasol is an integrated energy fuels and chemicals company The worlds largest producer of synthetic fuels World leader in GTL (gas-to-liquids) and CTL (coal-toliquids) technologies Over 60 year experience in CTL and 30 years in GTL Operating, technical and commercial expertise About 300 PhD holding scientists and engineers Strong intellectual property portfolio (300 patent families)

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Sasol Secunda Plant

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The Fischer Tropsch Process

6. Sasol (conued) Economics of Sasol
Turnover: R142 billion or $18 billion (2011) Market Capitalization: R231 billion or $31 billion Listed on JSE and NYSE SASOLS SOUTH AFRICAN FACILITY Presence in 38 countries worldwide Employees 34 000 (worldwide)

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Steam Reforming
A typical modern GTL plant (gas-to-liquids-plant) first converts natural gas (i.e., methane) or LPG (liquified petroleum gases such as propane and butane) or naphtha into a mixture of gaseous carbon monoxide and hydrogen. The method is referred to as

"Steam Reforming CH4 + H2O CO + 3H2

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Steam Reforming II
The methane is first cleaned, mainly to remove sulfur oxide and hydrogen sulfide impurities that would poison the catalysts. The clean methane is then reacted with steam over a catalyst of nickel oxide. This is called: Primary steam reforming CH4 + H2O CO + 3 H2 Secondary reforming 2 CH4 + O2 2 CO + 4 H2 CH4 + 2 O2 CO2 + 2 H2O addition of air to complete conversion of the methane
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Coal Gasification
Coal or Biomass gasification is the process of producing coal gas a type of syngas a mixture of CO, hydrogen (H2), carbon dioxide (CO2) and water vapour (H2O) from coal or biomass Coal gas, which is a combustible gas, was traditionally used as a source of energy and the hydrogen obtained from gasification can be used for various purpose such as making ammonia, powering a hydrogen economy or upgrading fossil fuels. Alternatively the coal gas can be converted into transportation fuels (gasoline and diesel) through further treatment via the FT process. 35

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LURGI Coal Gasification

In this type of gasifier, coal must be compacted into briquettes of 5 to 50 mm size. It is then introduced at the top of the gasifier. Pure oxygen and steam are injected at the bottom of the vessel. The reaction takes place on a grate (set of horizontal iron bars). There can be a mechanical device to move this grate and accelerate the reaction ('Moving bed gasifier'). The reaction takes place at relatively low temperature (500 oC). This technology is in use in Sasol's plants

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Coal Gasification II
During gasification, the coal is blown through with oxygen and steam while also being heated (and in some cases pressurized). If the coal is heated by external heat sources the process is called "allothermal", while "autothermal" process assumes heating of the coal via exothermal chemical reactions occurring inside the gasifier itself. It is essential that the oxidizer supplied is insufficient for complete oxidizing (combustion) of the fuel.

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Coal Gasification III

During the reactions mentioned, oxygen and water molecules oxidize the coal and produce a gaseous mixture of carbon dioxide (CO2), carbon monoxide (CO), water vapour (H2O), and molecular hydrogen(H2). By-products like tar, phenols, etc. are also possible end products, depending on the specific gasification technology utilized The desired end product is usually syngas (i.e., a combination of H2 + CO)
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Coal Gasification IV
3C + O2 + H2O H2 + 3CO Coal Gasification Reaction Syngas is a combination of H2 + CO + CO2, but it includes also a variety of impurities, such as sulphur Sulphur is a catalyst poison the produced coal gas needs to be further refined to remove impurities, dust, sulphur etc.

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Water Gas shift Reaction

If as in the case of ammonia production, hydrogen is the desired end-product, the coal gas (primarily the CO product) undergoes the water gas shift reaction where additional quantities of hydrogen are produced by the reaction with water vapor: CO + H2O CO2 + H2

High temperature WGS reaction Low temperature WGS reaction

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Water Gas Shift Reaction II

If as in the case of ammonia production, hydrogen is the desired end-product, the coal gas (primarily the CO product) undergoes the water gas shift reaction where additional quantities of hydrogen are produced by the reaction with water vapor: CO + H2O CO2 + H2

High temperature WGS reaction Low t temperature WGS reaction

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Gas Purification I
Raw syngas contains many contaminants, which must be removed to protect: the environment, the workers at the facility, the equipment (some of these contaminants are corrosive), and also to avoid poisoning the catalysts in the case of a FischerTropsch, an Ammonia converter or a Methanol Sythesis reactor

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Gas Purification I
1. Removal of the solid particles (dust). With cyclones: the flow of gas + particles enters a cylindrical container in which a cyclone forms. The rotational effects and gravity entrain the particles to the bottom of the cylinder, while the clean gas exits at the top.
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Gas Purification II
1. Removal of the solid particles (continued).
With fabric filters: This is the cheapest way to remove small diameter particles. The flow of gas and particles circulates through a 'filter bag' filled with fabric (cotton, synthetic, glass fiber) in which the particles accumulate. This filter bag must be replaced periodically. With Electrostatic precipitators: The flow of gas and particles enters a chamber with high voltage electrically charged wires. In this chamber, the solid particles get an electrical charge. Then the flow enters an other chamber with vertical plates, charged electrically as well, but with an opposite voltage: thus the particles get attracted by the plates and accumulate in this chamber while the clean gas exits the system.
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Electrostatic Precipitator
Precipitator contains a row of thin vertical wires, followed by a stack of large flat metal plates in a vertical position with the plates typically spaced about 10 cm apart The gas stream flows horizontally through the spaces between the wires, and then passes through the stack of plates.
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Gas Purification III

1. Removal of the solid particles (continued).

With scrubbers (also efficient to remove ammonia and heavy metals such as mercury, etc...): the flow of gas and particles passes through a bath of water + solvent. While the gas bubbles through the liquid, the pollutants get dissolved in the liquid, and clean syngas exits at the top. The liquid (water + solvent) is renewed regularly and the contaminants recovered in a solid form via precipitation or other chemical reaction. The efficiency of these systems depends mostly on the size of the particles, and most of the time they will be combined to reach maximum efficiency.
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Gas Purification IV
2. Removal of the sulfurous gases (H2S, COS) and eventually carbon dioxide (CO2): this is done by passing the flow of gas through a solvent that will dissolve these contaminants. Sulfurous compounds may be converted into Sulfuric acid or Solid sulfur. Carbon dioxide, if it is recovered, may be injected underground in a salt deposit (carbon capture and storage), or in an oil reservoir to increase the recovery of oil. Once the syngas is clean, it can be converted into liquid hydrocarbons in the case of Indirect coal liquefaction, or converted into ammonia, methanol or ethanol via various catalytic processes. 49

Fischer Tropsch Synthesis

Reactions I
Chemical reactions involved The main reaction that occurs in a Fischer Tropsch reactor is the formation of alkanes CnH2n+2: (2n+1) H2 + n CO -> Cn H2n+2 + n H2O (1)

It's an exothermic reaction (it liberates heat: 39.4 kcal / mole of CO). Hence the reactor has to be cooled down.

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Fischer Tropsch Synthesis

Reactions II
Chemical reactions involved Other Reactions yield other products in created: alkenes CnH2n and alcohols CnH(2n+1)OH: nCO + 2n H2 -> CnH2n + n H2O nCO + 2 nH2 -> CnH(2n+1)OH + (n-1) H2O (2) (3)

(depending on the catalyst and the process)

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Fischer Tropsch Synthesis

Products
Types of products Two types of catalysts may be used in the FT reaction: Iron or Cobalt based Iron based catalysts and a high operating temperature (330-350 oC) will produce mostly light hydrocarbons, the final product will be mostly Gasoline. Cobalt based catalysts and a lower operating temperature (200 oC ) will produce heavier hydrocarbons, the final product will be mostly Diesel.
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Fischer Tropsch Synthesis Quality of Products

Since the syngas has been cleaned before entering the FT reactor (which means that the sulfur compounds and the dust particles have been removed )), the product of the reaction is a very pure and high quality hydrocarbon Less than 1ppm of sulfur (10 to 500 ppm for regular fuels) Less than 1% of aromatics (saturated hydrocarbons which contributes to the pollution) in mass (10% for regular fuels) FT diesels have a high cetane number (which means that they auto-ignite faster and more easily in the engine): 70 to 80 versus 40 to 50 in regular diesels A high energy density (7% higher than standards fuels).
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Fischer Tropsch Synthesis Reactors

Slurry Bubble Column Reactor Other Fischer-Tropsch technologies use a fixed bed reactor. A fixed bed reactor is the original reactor design used in the 1920s and still used by some companies today (Sasol 1). A slurry bubble reactor is simpler in design, less expensive to build and operate, and also provides for an easier scale up than the alternative fixed-bed reactor. Additionally, we believe a slurry-bed reactor provides better product yield than the alternative.
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Fischer Tropsch Synthesis Reactors

The FT reaction takes place in a pressurized vessel called the reactor. The reactor contains the catalyst, which will facilitate the reaction, The input of the reactor is syngas and its output a mixture of hydrocarbons. The reactor has to maintain constant pressure & temperature (the exothermic FT reaction releases heat, which is removed by water cooling systems). Various types of reactors have been developed. Each different type requires a different type the catalyst, different form of the catalyst used and different operating conditions (P, T, carrier)
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Packed Bed Reactor

Packed Bed (Arge) Reactor

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Sasol Synthol Reactors (in parallel)

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F-T Reaction with Synthol Reactor

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Sasol Advanced Synthol (SAS) Reactor

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Slurry Bubble Column Reactor

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Sasol Slurry Phase Distillate (SPD) Reactor

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Fischer Tropsch Synthesis The Catalysts

Various types of catalyst can be used in the various types of FT reactions: 1. Iron based catalysts will produce mostly lighter components (Gasoline). They are optimal with a low H2/CO ratio (i.e. when there is more Carbon Monoxide than Hydrogen in the syngas). This occurs when the syngas is produced with coal or other carbon-rich organic materials (bitumen, oil shales, residues from refineries etc...) Iron based catalyst are thus being used in the indirect coal liquefaction plants, mainly Sasol and the US company Rentech.
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Fischer Tropsch Synthesis The Catalysts II

2. Cobalt`- based catalysts produce heavier components (Diesel, Waxes). They are optimal with a high H2/CO ratio (more hydrogen than carbon monoxide in the syngas), which happens when the syngas is produced with natural gas (mostly made of methane CH4), such as in the Gas To Liquids process(GTL) The catalyst itself is not pure Iron or pure Cobalt, but a complex oxide molecule, comprising the active component and a series of promoters
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Fischer Tropsch Synthesis The Catalysts III

FT Catalyst components:
an oxidation promotor (Potassium K or Zirconium Zr) which initiates the FT reaction, an active metal (Iron, Cobalt, Nickel or Rubidium) which facilitates the FT reaction, a reduction promotor (Platinum Pt or Rubidium Rb) which allows to re-activate the active metal after it has been oxidized, and a support (Oxides of Aluminum, Silicium or Titanium).

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Fischer Tropsch Synthesis

THANK YOU

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