The sulfuric acid industry has a history of more than 200 years. The early sulfuric acid production used the nitrification method. This method can be divided into lead chamber method and tower method according to the evolution of the main equipment. In the late 19th century, the contact method gained industrial application and has now become the main method for producing sulfuric acid.
Early sulfuric acid production In the second half of the 15th century, B. Valentine mentioned in his works two methods: heating green vitriol and sand, and burning a mixture of sulfur and saltpeter. A method of producing sulfuric acid. Around 1740, the Englishman J. Ward first used glass vessels to produce sulfuric acid, with a volume of 300l. A mixture of sulfur and saltpeter is burned intermittently in a vessel, and the sulfur dioxide and nitrogen oxides produced react with oxygen and water to form sulfuric acid, which is the precursor to sulfuric acid produced by the nitrification process.
The rise and fall of the nitrification method. In 1746, the Englishman J. Roebuck built a 6ft (lft=0.3048m) square lead chamber in Birmingham. This was the first factory in the world to produce sulfuric acid using the lead chamber method. . Around 1805, a furnace was set up outside the lead chamber for the first time to burn sulfur and saltpeter, making the lead chamber method a continuous operation. In 1827, the famous French scientist J.L. Guy-Lussac suggested setting up a nitrate absorption tower after the lead chamber and using the lead chamber product (65% H2SO4) to absorb nitrogen oxides in the exhaust gas. In 1859, the Englishman J. Glover added a denitrification tower in front of the lead chamber and successfully removed nitrogen oxides from nitric sulfuric acid, and the product concentration of the tower reached 76% H2SO4. The combination of these two inventions realizes the recycling of nitrogen oxides and basically perfects the lead chamber process.
In the second half of the 18th century, the textile industry made significant technological progress. Sulfuric acid was used for bleaching linen fabrics, acidifying cotton fabrics, and dyeing woolen fabrics. The success of Lubulan's method requires the production of large amounts of sodium sulfate from sulfuric acid and salt. The rapidly growing demand has opened up a smooth development path for the emerging sulfuric acid industry.
Early lead-chamber factories used sulfur from Sicily, Italy as raw material. As the demand for sulfuric acid continued to increase, the supply of raw materials became increasingly tight. Since the 1830s, Britain, Germany and other countries have successively switched to using pyrite as raw material. Later, the use of smelting flue gas to produce sulfuric acid was also successful. The expansion of raw material sources adapted to the rise of the fertilizer industry with superphosphate and ammonium sulfate as the main products at that time, thus enabling greater development of the sulfuric acid industry. In 1900, world sulfuric acid production (based on 100% H2SO4) reached 4.2Mt. In 1916, the Tennessee Copper Smelting Company in the United States built a lead chamber method with a daily output of 230 to 270 tons (based on 100% H2SO4). It has four lead chambers connected in series, each with a volume of 15,600m3. This is the largest giant lead chamber in the world. Due to the low production efficiency, high lead consumption and high investment of the huge lead chamber, various improvement suggestions and inventions have been proposed since the second half of the 19th century, which eventually led to the advent of various tower-type devices that used filling towers instead of lead chambers. .
In 1911, Austrian C. Opple built the world's first tower method device in Hrushau. The total volume of the six towers is 600m3, with a daily output of 14t of sulfuric acid (based on 100% H2SO4). In 1923, H. Petersen built a seven-tower device in Mazarovar, Hungary, consisting of a denitrification tower, two acid-forming towers and four nitrification towers. In the acid liquid circulation process and the gas-liquid contact in the tower, There have been innovations in methods and other aspects to improve production efficiency.
The five-tower process was widely used in the Soviet Union and Eastern Europe. In the 1950s, the Soviet Union developed a more enhanced seven-tower process, which added an acid tower and a nitrate absorption tower. Its production intensity was doubled compared to the old tower method, and it could be used Ordinary steel replaces expensive lead in manufacturing production equipment.
The concentration of the lead chamber method product is 65% H2SO4 and the tower method is 76% H2SO4. When pyrite and smelting flue gas are used as raw materials, the product also contains a variety of impurities.
Since the 1940s, the demand for concentrated sulfuric acid and oleum in dye, chemical fiber, organic synthesis and petrochemical industries has increased rapidly. Many industrial sectors have also put forward higher requirements for the purity of concentrated sulfuric acid products, so the contact method has gradually It plays a leading role in the sulfuric acid industry.
The latecomer contact method In 1831, P. Phillips of England first invented a method of mixing sulfur dioxide and air and extracting sulfur trioxide through a hot porcelain tube filled with platinum powder or platinum wire. In 1870, the success of the alizarin synthesis method led to the rise of the dye industry, and the demand for oleum increased sharply, providing impetus for the development of the contact method. In 1875, German E. Jacob built the first contact method device for producing oleum in Kreuznach. He once thermally decomposed the product of the lead chamber method to obtain a mixture of sulfur dioxide, oxygen and water vapor. The remaining gas after condensation and dehydration passed through the catalyst layer to produce oleum containing 43% SO3.
Initiated in 1881, R. Knitch of the Baden Aniline Soda Ash Company in Germany conducted 10 years of research on the contact method and systematically tested the performance of platinum and other catalysts under various process conditions. And the technical key to production using pyrite as raw material has been comprehensively solved in industrial equipment. Contact-method devices at that time all used platinum catalysts that showed excellent activity at lower temperatures. However, it is expensive and easily poisoned and loses activity (see catalyst poisoning, catalytic activity). For this reason, early contact method devices, whether using sulfide ore or sulfur as raw materials, must fully purify the gas entering the conversion process in advance to remove various harmful impurities. In 1906, American F.G. Cottrell invented the technology of high-voltage electrostatic capture of mineral dust and acid mist, which was successfully used in contact method factories and became an important breakthrough in purification technology.
The outbreak of World War I caused European and American countries to rush to build contact method devices, and the products were used in the manufacture of explosives. This had considerable influence on the development of contact methods. In 1913, the Baden Aniline Soda Ash Company invented a vanadium catalyst with added alkali metal salts. It has good activity, is not easy to be poisoned, and has a low price. It has shown excellent results in industrial applications. Since then, vanadium catalysts with continuously improved performance have emerged one after another and have rapidly become widely used, finally completely replacing platinum and other catalysts.
Development in the past 30 years After the Second World War, the sulfuric acid industry has achieved great development, and the world's sulfuric acid production has continued to grow.
Modern sulfuric acid production technology has also made significant progress. In the early 1950s, the Federal Republic of Germany and the United States simultaneously developed pyrite boiling roasting technology. Farben Bayer Company of the Federal Republic of Germany took the lead in realizing the application of the double reforming process in 1964, and built the first boiling reformer with a diameter of 4m in 1971. In 1972, the first pressurized device using sulfur as raw material built by the French company Huguene-Kulmann was put into operation, with an operating pressure of 500kPa and a daily output of 550t (100% H2SO4). In 1974, the Swiss Ciba-Geigy Company developed an improved tower process to process low-concentration flue gas containing 0.5% to 3.0% SO2. In 1979, it built a 10km3 per hour treatment plant in the Federal Republic of Germany. Industrial device for roasting molybdenum sulfide ore flue gas (0.8% ~ 1.5% SO2).
The development of China's sulfuric acid industry In 1874, the Tianjin Machinery Bureau's Nitrogen Leaching Factory built China's earliest lead chamber method device. It was put into operation in 1876, with a daily output of about 2 tons of sulfuric acid, which was used to manufacture smokeless gunpowder. In 1934, China's first contact method device was put into production at the Gongxian Arsenal Branch in Henan.
Before 1949, China’s highest annual sulfuric acid output was 180kt (1942). In 1983, the output of sulfuric acid reached 8.7Mt (excluding Taiwan Province), ranking third in the world after the United States and the Soviet Union. In 1951, vanadium catalyst was successfully developed and mass-produced. Since then, several new varieties have been developed. In 1956, pyrite boiling roasting technology was successfully developed and venturi scrubbers were used for purification operations. In 1966, an industrial device with two transformations was built, becoming the first country to apply this new technology.
Fruitful results have also been achieved in areas such as thermal energy utilization, environmental protection, automatic control and equipment technology