HClO3Chem.

TK

LAB-SCALE INDUSTRIAL PROCESSES

Volume 2
Francis Glode

12

Table of Contents
Introduction .................................................................................................................................................. 2 Disclaimer: .................................................................................................................................................... 2 Sulphuric Acid ............................................................................................................................................... 3 Lead Chamber Process.............................................................................................................................. 3 Background: .......................................................................................................................................... 3 Theory: .................................................................................................................................................. 3 Experimental: ........................................................................................................................................ 3 Contact Process......................................................................................................................................... 5 Background: .......................................................................................................................................... 5 Theory: .................................................................................................................................................. 5 Experimental: ........................................................................................................................................ 5 Refractory Ceramics...................................................................................................................................... 7 Fused Silica................................................................................................................................................ 7 Background: .......................................................................................................................................... 7 Theory: .................................................................................................................................................. 7 Experimental: ........................................................................................................................................ 7 Carbon Refractory..................................................................................................................................... 8 Background: .......................................................................................................................................... 8 Theory: .................................................................................................................................................. 8 Experimental: ........................................................................................................................................ 8 Nitrogen ........................................................................................................................................................ 9 By Air Purification Process ........................................................................................................................ 9 Background: .......................................................................................................................................... 9 Theory: .................................................................................................................................................. 9 Experimental: ........................................................................................................................................ 9 Thanks to:....................................................................................................................................................11 Bibliography ................................................................................................................................................11

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Introduction
Industrial processes are made to be efficient and cheap. They usually require very common reagents such as air, carbon, and other common feedstock. They are also robust and can be continuous. Some of them can be adapted to be done in a lab at a reduced scale. Such processes have a number of advantages for the preparation of commonly used reagents, and need very small investments. This is the second volume and first edition of Lab Scale Industrial Processes. It contains a few processes that have been adapted. These processes are useful to make a large quantity of reagents cheaply. This book mainly explains experimentals, but if you think something needs to be changed or improved in the next version, contact me using the email address: hclo3@hotmail.com This book has been made by Francis Glode (Plante1999) in 2012

Disclaimer:
All experiments in this book should be done outside or in a fume hood with proper safety equipment. It must be done by or under the direct supervision of someone experienced with chemistry laboratory procedures. They must never be done in the presence of young children or animals.

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Sulphuric Acid
Lead Chamber Process
Background:
Sulphuric acid is a very important industrial chemical. It was, for a long time, produced by pyrolysis of sulphate salts but this process was inefficient and only small batch could be made at a time. The first process practical enough to be used on the industrial scale was the lead chamber process. It was invented by Joann Glauber and industrialized in 1736 by Joshua Ward. It used sulphur, air, and nitrogen oxides. It was a very robust process that can be adapted easily to lab work because all reagents are common in a lab.

Theory:
When nitrogen monoxides and oxygen in the air reacts it makes nitrogen dioxide (equation 1). If nitrogen dioxide is in presence of water it dissolves making nitric acid (equation 2). The nitric acid then react with the sulphur dioxide to make nitrosyl sulphuric acid (equation 3). Nitrosyl sulphuric acid hydrolyses in water to make sulphuric acid, nitrogen monoxide, and nitrogen dioxide (equation 4). All the nitrogen oxides react back with more sulphur dioxide, making nitrogen oxides a catalyst for sulphur dioxide oxidation. 2NO + O2 2NO2
Equation 1: Oxidation of Nitrogen monoxide

3NO2 + H2O NO + 2HNO3

Equation 2: Formation of nitric acid

SO2 + HNO3 NOHSO4

Equation 3: Sulphur dioxide reduction of nitric acid

2NOHSO4 + H2O 2H2SO4 + NO + NO2

Equation 4: Nitrosylsulphuric acid Hydrolysis

Experimental: Reagents:
-25% nitric acid (HNO3) Page | 3

- Sulphur (S8) or iron sulphide (FeS) -Air -Water (H2O) -Sodium carbonate (Na2CO3)

Materials:
-Propane torch or Bunsen burner -1-Liter glass bottle -A stopper with three holes for the 1-Liter glass bottle -500-ml beaker -Glass tubing -Vacuum pump -Combustion tube - Various stoppers -250-ml Erlenmeyer -500-ml glass bottle -Rubber tubing -Gas flow restricting clamp -Hotplate -A thermometer that can go to 300 degrees Celsius

Method:
The combustion tube is filled with sulphur or iron sulphide powder, about 70 g of active sulphur is needed. Pyrite can also be used. One side of the combustion tube have a stopper and a glass tube going to one hole of the stopper for the 1-Liter bottle. This tube goes to the bottom of the bottle. The 250-ml Erlenmeyer is filled with 150 ml of 25% nitric acid and a two-hole stopper. One hole of the stopper has a glass tube leading to the bottom of the 1-Liter flask, the other hole have a rubber tubing with an gas flow restricting clamp on it. This tube is used as the air and nitrogen oxides supply. When air passes through the nitric acid, it carries nitric acid that will react with the sulphur dioxide to make the nitrosylsulphuric acid, efficiently starting the reaction. The 250-ml flask is set on an hotplate. The third hole of the 1-Liter flask stopper have a glass tubing leading through a saturated solution of sodium carbonate in the 500-mL glass bottle. The bottle have a two-hole stopper, the first leading to the vacuum pump and the second to the top of the 1-Liter flask. The hot plate is set at 60 degrees Celsius and the vacuum pump is turned on. The combustion tube is heated to light the sulphur. If it is iron sulphide or pyrite, heating must be continued during all the experiment. Then, air flow is regulated in the nitric acid to get an appropriate amount of nitric acid for the sulphur dioxide. After an hour or two, all the sulphur will have burner and most of the nitric acid will have reacted. Add 100 ml of water to the 1-Liter flask and swirl vigorously. Then, pour the solution into Page | 4

the 500-ml beaker with the thermometer and boil it down using an hotplate (Caution: sulphur oxides, nitrogen oxides, and sulphuric acid fume is emitted in the process). When at 250 degree Celsius, stop heating, and lets the solution cool down. It should now be 95-96% Sulphuric acid of technical grade, suitable for most applications in the Lab.

Contact Process
Background:
The discovery of the catalytic effect of platinum made possible the development of the contact process. When it was discovered that sulphuric acid could be made using platinum catalyst. Some contact process-based sulphuric acid plants where constructed, but they didnt work as they should have, platinum was readily poisoned by the arsenic and antimony in the sulphur dioxide that came from the ore used to make it, and the platinum catalyst slowly eroded, making the process extremely costly. The lead chamber process was much more adapted for harsh conditions and significantly cheaper to run. Later, it was found that vanadium pentoxide-based catalysts could do the oxidation of the sulphur dioxide and was hardly poisoned. The discovery of Vanadium catalyst permitted the contact process to be the most-used process to make sulphuric acid.

Theory:
When sulphur dioxide contacts the hot platinum catalyst, it combines with the oxygen making sulphur trioxide (equation 1). Sulphur trioxide cant be reacted directly with water since the reaction is too exothermic. Instead it is dissolved in sulphuric acid where it form disulphuric acid in equilibrium (equation 2). Disulphuric acid is commonly named oleum. The disulphuric acid is then hydrolysed in water to make sulphuric acid (equation 3). Platinum catalyst is used but sublimed sulphur must be used to protect the catalyst. 2SO2 + O2 2SO3
Equation 1: Oxydation of sulphur dioxide

Equation 2: Equilibrum of sulphur trioxide and sulphuric acid

SO3 + H2SO4 H2S2O7

H2S2O7 + H2O 2H2SO4

Equation 3: Disulphuric acid hydrolysis

Experimental: Reagents:
-Sublimed sulphur (S8) -Air -A starting amount of sulphuric acid 95-96% (H2SO4) -Saturated sodium carbonate solution (Na2CO3) Page | 5

-1 ml 30% hydrogen peroxide (H2O2) -Distilled water -Ice

Materials:
-Glass tubing -4 250-mL flask -2 Combustion tube -Various stoppers -Air pump -Bunsen burner or propane torch -Platinized asbestos -500-ml beaker - A thermometer that can go to 300 degree Celsius

Method:
One flask is filled with 200g sulphuric acid and connected to the sulphur combustion tube. The two combustion tubes are connected in series using rubber stoppers and glass tubing. The first one is filled with 64 g of sulphur and the second with about a gram of platinized asbestos. The second stopper from the platinum catalyst tube is lead through three 250-ml flasks in series, the last one filled with saturated sodium carbonate solution. The inlet of the the sulphuric acid flask is lead to the air pump. It is recommended to use ice bath for the first two flasks after the catalyst tube. The air pump is turned on, and the combustion tube filled with sulphur is heated lo light the sulphur. Next, the catalyst tube is heated untill white fumes appear, and low heating is continued to get better yield. One could stop heating after seeing the white fumes because the sulphur dioxide oxidation is exothermic but yield would be lower. A liquid will start to collect in the two flask, this is sulphur trioxide. It must be noted that the rubber stopper after the catalyst tube will be seriously corroded and useless so it is better to make a large run. After all the sulphur have burnt, apparatus is dismantled but the two flask are keep for processing the sulphur trioxide.The 200g of sulphuric acid from the first flask is added to the second flask and swirled to dissolve the sulphur trioxide, then the oleum is poured in the third flask and swirled again. The 500-ml beaker is filled with 40ml of water. The oleum is slowly poured in the beaker, and then swirled to make an homogeneous mix and the acid is heated to 250 degree Celsius and 1 ml of 30% H2O2 is very slowly added drop by drop(Caution the reaction can be vigorous and make acid mists), all the acid will become colorless. When it have cooled it is stored. This acid is very pure and suitable for most lab preparations requiring reagent-grade acid.

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Refractory Ceramics
Fused Silica
Background:
In the laboratory, from time to time, ceramics that resist to high temperature are needed. Fused silica is a ceramic that resist up to 1400 degree Celsius. It exhibit little shrinkage during cooling and is very chemically resistant. It is unsuitable for basic pH condition. It can be easily made, but require to be partially melted which require a lot of heating.

Theory:
When calcium hydroxide is heated with silicon dioxide, it makes insoluble calcium silicate (equation 1) which make cement for all silica particles. Then the surfaces need to be melted to make the ceramic more resistant to abrasion and less brittle. Diatomaceous earth helps the ceramic to keep its water when curing and to make the ceramic less brittle. 2CaOH + 2SiO2 2CaSiO3 + H2O
Equation 1: Calcium oxide reaction with silicon dioxide

Experimental: Reagents:
-Calcium hydroxide (CaOH) -Water (H2O) -Diatomaceous earth (SiO2) -Silica sand (SiO2)

Material:
-Propane torch or Bunsen burner

Method:
75 g of silica sand is very finely ground, until it looks like flour. Then, 15g of calcium hydroxide is mixed with 25 g of diatomaceous earth and the silica. Water is added until It resembles a castable paste, and quickly it is casted in its shape, casting can be done in wax impregnated wood. The mix hardens in 5 minute, cures in 6 hour, and dries in one day or two. After two days, the piece is heated extremely strongly with a propane torch to melt the surface of the piece. It can be done by heating small surface at the time. When completely glassed, the ceramic is cooled down slowly. The piece is now ready for its service life. Page | 7

Carbon Refractory
Background:
Carbon ceramics are very resistant, with the major exception being susceptibility to degradation by oxygen. They can also serve as electrodes.

Theory:
When pitch is heated, it pyrolises to carbon, making hydrogen, water, carbon oxides, and various other volatile organic compounds. The carbon serves as a binder for carbon particles. The carbon must not be heated in oxidizing environment, so a reducing atmosphere is used.

Experimental: Reagents:
-Carbon powder -Pitch -Xylenes

Materials:
-crucible -Furnace/ wood fire/ Bunsen/propane torch

Method:
Make a paste of carbon powder and pitch to get a sort of paste then, cast it. It can take a week to dry. When the piece is dry, heat it in a crucible with a non-hermetic lid to 600 degree Celsius to pyrolise the pitch. You will obtain a porous carbon piece. Make a mix of Make a mixture of one part, by weight, of pitch for every one part of xylenes and impregnate the carbon with it and wait until it is dry. When dry you need to pyrolyse it. You may need to repeat the process many times to get a carbon with the porosity needed for the application. Very porous carbon is more isolating, but fragile.

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Nitrogen
By Air Purification Process
Background:
Nitrogen is a cheap inert gas. It can be used to make ammonia. Its usual industrial extraction is by the fractional distillation of liquid air, which is unsuitable for lab procedure, an old process for its production is described here.

Theory:
When a copper powder is heated in air it reacts with the oxygen but it does not react with the nitrogen effectively purifying it (equation 1). Heating the copper powder with carbon regenerates the copper powder (equation 2). 2Cu + O2 2CuO
Equation 1: Copper oxidation

CuO + C Cu + CO
Equation 2: reduction of copper oxide by carbon

Experimental: Reagents:
-Air -Copper powder/copper oxide (Cu / CuO)

Material:
-Combustion tube or copper tube -Various rubber stopper - Air pump -Non-pressurized or slightly pressurized gas container -Iron crucible -Charcoal powder -Bunsen burner or propane torch

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Method:
The combustion tube is filled with copper. Copper oxide can be roasted in an iron crucible with an equimolar amount of carbon to make copper powder. The pump is connected to the combustion tube and the other side of the tube to the gas container. The combustion tube is strongly heated, and the air pump is turned on. Each gram of copper powder purifies sufficient air to yield roughly 850 ml of nitrogen gas. When all the nitrogen is made for the amount of copper you used, turn off the air pump and dismantle the apparatus. The nitrogen still contains a small amount of oxygen and some other gases, but is suitable for most applications requiring nitrogen. The copper powder can be regenerated by the same process used to turn the copper oxide to copper powder.

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Thanks to:
Joe M Anderson (Hexavalent) Francisco Gomez (Vargouille) Daniel Finnemore (DJF90)
For the correction and review of the book

Bibliography
1. Ullmann, F. Ullmanns Encyclopedia of industrial chemistry, 5th ed.; John Wiley & Sons, 1999. 2. Pierson, H. O. Handbook of Carbon, Graphite, Diamond, and Fullerenes: Properties, Processing, and Applications, illustrated ed.; Noyes Publications, 1993. 3. William George Davenport, M. J. K. Sulfuric Acid Manufacture: Analysis, Control and Optimization, illustrated ed.; Elsevier, 2006; Vol. 13.

Adaptations are based upon my work