A.D. 659-686, during the Tang Dynasty in China, a collection of Taoist alchemy was published, named The Collection of Huangdi Jiuding Shen Dan Classics. Surprise is a professional book in ancient China, edited by officials for the emperor to read; "Jiuding" is a symbol of state power, indicating that this Dan is dedicated to the emperor. This book contains the alchemist Hu Gangzi (also known as Hu Gangzi) at the end of the Eastern Han Dynasty (AD 25-220), including the method of refining stone and extracting essence. The so-called "stone gall" refers to the pentacrystalline copper sulfate (CuSO4? 5H2O), it is still called gallstones in our country, because it is blue, just like gallstones. The method of refining gall bladder is to distill gall vitriol to produce sulfuric acid. Copper oxide (CuO), sulfur trioxide (SO3) and water are generated because the crystal of copper sulfate pentahydrate is decomposed by heat. Sulfur trioxide dissolved in water is sulfuric acid (H2SO4), which is expressed by modern chemical reaction formula:
CuSO4？ The original narrative of 5h2so4-→ CuO+SO3+5h2so3+H2O-→ H2SO4 is as follows: "Take the mound as two square-headed furnaces, separated by two feet, and make a hole on the side between the fine mud outside and the mud inside, so as to smoke it dry. Put the copper plate into the furnace and fix it, that is, seal it; Stone gall is burned with charcoal in the furnace, with charcoal as smoke and things as fans, and it is refined into copper plates. The fire in the furnace is waiting for the cold, and it is agreed that all the medicines are gods. " Here, "soil" is "adobe", "fine mud" is to seal the gap with fine mud, "fine fumigation" is to heat slowly, and "smoke" refers to the foggy sulfuric acid gas produced by the combination of sulfur trioxide and steam.
That is to say, around the 2nd century A.D., China has already created a method of manufacturing sulfuric acid by the earthen chamber method.
In Europe, the earliest record of sulfuric acid production appeared in Albertus, a Catholic priest, philosopher and natural scientist in the third century. In albertus magnus's works (1 193- 1280), it is obtained by distilling copperas. Chlorite is ferrous sulfate (FeSO4? 7H2O), named for its green color. The chemical process of distilling copperas to produce sulfuric acid is the same as that of distilling sulfuric acid. Therefore, Europeans called sulfuric acid copperas oil in the Middle Ages. /kloc-Valerius cordus, a German pharmacist in the 6th century (1515-1544), described in his works that large blue or green alum crystals were selected and heated in a casserole until the crystals turned red and turned into powder, leaving 6 pounds 12. Steam is introduced into a glass container containing 65,438+08 ounces (65,438+0 ounces = 65,438+0/65,438+06 pounds, and 65,438+0 pounds is about 0.453 kilograms) to form copperas oil (Figure 8-65,438+0).
/kloc-At the beginning of the 6th century, there was a method of burning sulfur to produce sulfuric acid in Europe, which was also called sulfur oil. Geissner (15 16- 1565), a Swiss professor of physics and natural history, described in his works that a porcelain basin was placed under a suspended glass bell jar, and a cup was placed in the basin, which was filled with sulfur. After sulfur is burned, sulfur is continuously added to generate sulfur trioxide (SO3) and sulfur dioxide.
The quality of sulfuric acid produced by this method is poor, because almost no sulfur trioxide (SO3) is produced.
By 1736, the Englishman Joshua Ward (1685- 17 1) set up a large-scale sulfuric acid plant in Twitchenham, England, and began to produce sulfuric acid on a large scale.
Wade is a quack. 17 17, he was convicted of trying to enter the British parliament and fled to France. 1733, he was pardoned and returned to England, where he made saltpeter and porcelain and practiced medicine. He thinks mirabilite has extraordinary effects in medicine, so he wants to make it. Sodium sulfate refers to sodium sulfate decahydrate crystal (Na2SO4? 10H2O) was discovered in the mineral water near Vienna, Austria on 1625 by the German chemist glauber in the 7th century. It was once used as a laxative, and people realized that it could be made of salt and sulfuric acid.
Morris Scofield. The early stage of sulfuric acid. Chemistry,1972,45 (9).
Wade made sulfuric acid to make sodium sulfate. He burns a mixture of sulfur and saltpeter to make sulfuric acid. This method was first invented by the Dutch inventor Lebel (1572- 1633). French pharmacist Nicolas lemerre (1645- 17 15) described this method in his works published in 1675- 1690. Wade may have learned this method during his escape from France.
Wade's equipment for manufacturing sulfuric acid is a spherical wide-mouth glass bottle with a capacity of 40~50 gallons (capacity unit, 1 gallon =4.546 liters). When operating, put a small amount of water in the bottle, put a small coarse clay pot, put a small iron plate on the pot, and put a mixture of sulfur and saltpeter. After igniting the mixture with a red-hot shovel, plug the bottle with a cork. After a period of time, the operation is repeated until the required concentration of sulfuric acid is produced.
Due to the harmful smoke and environmental pollution produced in production, Wade's sulfuric acid manufacturing workshop was opposed by local residents, and moved to Richmond in northern England in 1740, and obtained the British patent in 1749. Wade hired Welsh workers who could not speak English to keep his production secret. However, he told the secret to his friend John Page.
Wade's sulfuric acid manufacturing workshop used about 100 spherical tanks, which reduced the price of sulfuric acid to116 of the original price.
However, Wade's equipment and operation method for manufacturing sulfuric acid were soon replaced by the lead chamber method created by another Englishman, John roebuck (17 18- 1794).
Rob is a doctor of medicine 1764 Elected as a member of the Royal Society (equivalent to an academician of the Academy of Sciences). From 65438 to 1940s, he lived in Birmingham, an industrial city in England. He started a private clinic, an iron factory and a business of recovering gold and silver from jewelry waste. 1746, Rob and his partner Gabbert (,17 17- 1803) needed sulfuric acid to dissolve impurities when recovering gold and silver. They learned from chemistry textbooks that lead can resist the corrosion of sulfuric acid, so they used wood as the frame and lead plate as the wall. Form a cubic lead chamber with a length of 6 feet (65,438+0 feet =0.3048 meters) on each side. In operation, sulfur and saltpeter are put into the iron spoon, and then put into the iron plate in the lead room after ignition. The generated sulfur oxide gas is absorbed by the water sprayed on the inner wall of the lead room in advance to form sulfuric acid, and sulfur and saltpeter are continuously added. Take out the acid about every four weeks, and then put it in a glass container for heating and concentration.
By 1749, Robb set up Preston Pan Company in Preston Pan Cheng, Scotland, and built a bigger and more lead room, employing 50 workers, working day and night, making the output of sulfuric acid from pounds to tons, not only for British people, but also exported to the European continent.
Rob also built a high wall around his factory to keep the production technology secret, requiring every worker to swear secrecy. But under the temptation of money, Samuel Skey, a wealthy chemical manufacturer, bribed a worker, learned about the structure and operation process of the lead room, and established a cubic lead room with a side length of 10 foot. Then, he built lead rooms in London and other places, as well as in some parts of France. Lead chambers are being built larger and larger, and the number is also increasing. 1805, a sulfuric acid plant in Berndt Island, England, had 360 lead chambers, each with a volume of 192 cubic feet. Chaptal (1756- 1832), a professor at Montpellier University and a wealthy chemical industrialist, proposed that the largest lead chamber should be 25 feet long and each side 15 feet high, but he once built a large lead chamber 80 feet long, 40 feet wide and 50 feet high.
Sicily, Italy has long been the sole supplier of sulfur. 1838, the Italian government implemented the law of publicly selling sulfur, so the price of sulfur soared. Sulfuric acid manufacturers use the method of calcining pyrite containing iron sulfide and chalcopyrite containing copper sulfide instead of burning sulfur.
Some manufacturers are constantly improving their production equipment. If steam is sprayed into the lead chamber instead of water on the inner wall of the lead chamber; A separate furnace for burning sulfur or sulfur-containing minerals is set up, and it is not burned in the lead room. In this way, the production of sulfuric acid gradually changed from intermittent to continuous, and the output of sulfuric acid increased greatly. By 1878, the annual output of sulfuric acid in Europe has reached several million tons.
At one time, sulfuric acid manufacturers thought that the purpose of adding saltpeter when burning sulfur in sulfuric acid manufacturing process was to produce oxygen, and sulfur dioxide was used as sulfur trioxide. In 1806, two French chemists, Charles Bernard de Sormes (1777-1862) and Nicolas Clement (1779-1841), observed that sulfur dioxide. Therefore, it is determined that sulfur dioxide is not directly oxidized by oxygen in the lead chamber, but forms an intermediate product with nitrogen oxides, and the whole process of forming sulfuric acid is a cyclic process. This has attracted the attention of many chemists. After many studies, it is confirmed that sulfur dioxide, nitric oxide, oxygen and water in the lead chamber form crystalline nitrossulfonic acid (HOSO2ONO). Nitrososulfonic acid reacts with water to generate sulfuric acid and release nitrogen oxides, which can be expressed by the following chemical reaction formula:
2NO+O2-→ 2No24NO2+O2+SO2+2H2O-→ 4Hoso2Ono2Hoso2Ono+H2O-→ 2H2SO4+NO2+NO = Because nitrogen oxides can be reused, the problem of how to recover them arises. The famous French chemist Joseph Louis Gay-Lussac (1778- 1850) proposed to build a tower behind the lead room in 1827. The tower is filled with coke, and the gas released from the lead chamber is introduced from the bottom of the tower and dissolved and absorbed when it rises. However, the oxides of nitrogen can not be completely absorbed, because nitric oxide is not easily soluble in sulfuric acid and does not react chemically, while nitrogen dioxide is not easily soluble in concentrated sulfuric acid, but only in dilute sulfuric acid. In order to re-release nitrogen oxides and return them to the lead chamber for use, nitrogen oxides are initially diluted with water. This will dilute the generated sulfuric acid, and it is not economical to concentrate it again. Therefore, the tower designed by Guy Lussac is not widely used. This tower was later named Grusakta.
By 1859, a British plumber, john glover (18 17- 1902), proposed to set up a tower between the combustion furnace and the lead chamber, so that the high-temperature sulfur dioxide would flow upward and meet with the nitrogen-containing sulfuric acid sent from the top of Grusak tower, and the nitrogen oxides in it would be released by heating and enter the lead. In this way, not only the nitrogen oxides are completely recovered, but also the nitrogen oxides absorbed in Gelusakta are released again. This tower was later named Glover Tower, and was soon used in actual production (Figure 8-3). An ordinary worker perfected the design of a famous scientist and enjoyed a high reputation in the field of sulfuric acid manufacturing.
Since then, sulfuric acid manufacturers have made a series of improvements to the lead chamber. The lead chamber is no longer a cube, because the cube will form corners, and the materials may stagnate at these corners. Moreover, the flow speed of air is very slow, and the repeated contact efficiency of gas phase and liquid phase of tiny droplets is very poor, so the lead chamber is transformed into a cylindrical shape or a frustum shape, and the lead chamber is deformed into a tower shape.
The lead room is no longer empty, but full of porcelain beads. This can increase the contact surface of reactants.
The frame is no longer wood, but steel, and even the lead plate has been replaced by steel. They are as resistant to sulfuric acid as lead, and the lining made of acid-resistant bricks or orthoclase enhances the corrosion resistance.
In this way, the lead chamber method becomes a tower method, but the chemical principle of producing sulfuric acid is still the same.
The principle of manufacturing sulfuric acid by contact method is different. Contact method, that is, catalytic method or catalytic method, started from 183 1. In this year, Peregrine Phillips, a vinegar merchant in the southern port city of Bristol, submitted a patent application to the government. The project is "saving the cost of saltpeter and lead alum room". It uses platinum as a catalyst, directly oxidizes sulfur dioxide into sulfur trioxide with oxygen, and then dissolves sulfur trioxide in water to form sulfuric acid. Rudolf messer (1848- 1920), a chemist who was born in Germany and lived in Britain for a long time, first made fuming sulfuric acid by this method, that is, concentrated sulfuric acid obtained by lead chamber method absorbed sulfur trioxide to make fuming sulfuric acid. Sulfur trioxide can not be directly absorbed by water, because the chemical reaction between sulfur trioxide and hydration to produce sulfuric acid is exothermic, which generates a lot of heat to evaporate water, and the generated water vapor combines with sulfur trioxide to form an acid mist of sulfuric acid, which affects the absorption effect. 1875, Squier, a manufacturer of sulfuric acid, built a factory to produce sulfuric acid according to Messer's method.
However, platinum is quickly affected by impurities carried in sulfur dioxide gas and fails. 190 1 year, German chemist Knitt (1854- 1906) first proposed that purifying sulfur dioxide gas can keep platinum effective for a certain period of time.
However, platinum is expensive and easy to be poisoned, which urges sulfuric acid producers and chemists to find cheap and effective catalysts. 19 14 vanadium oxide was discovered in Germany, 1926 was adopted in the United States. Nowadays, sulfuric acid is widely produced by contact method in countries all over the world.
At present, in the production of sulfuric acid by contact method, fluidized bed roaster-fluidized bed roaster is also used to roast sulfur-containing ore. The mineral powder in the furnace boils in the blast, and the reaction is fierce. The sulfur dioxide content in the furnace gas obtained after roasting is 1.5 times higher than that of the mechanical furnace. Furnace gas purification is an important link in contact production. Arsenic trioxide will poison the catalyst and must be removed. There are many purification and refining procedures. First, remove most mineral dust with mechanical electrostatic precipitator, then wash with dilute sulfuric acid or water to completely remove residual mineral dust and gas impurities, and finally remove acid mist with demister (Figure 8-4).