Many plants contain potassium carbonate and sodium carbonate, especially those growing in saline-alkali land and coastal or marine areas, which absorb sodium ions (Na+) in soil or seawater. When they rot or burn into ashes, they contain a certain amount of sodium carbonate, the content of which can be as high as 30%. China wrote in Compendium of Materia Medica compiled by Li Shizhen of Ming Dynasty (15 18~ 1593) more than 400 years ago: "Collect Artemisia scoparia, dry it in the sun, burn it to ashes, juice it with raw water, and remove dirt. Hair noodles. "
Early artificial alkali production
Europeans have known for a long time to extract alkali from the ash juice of seaweed. However, with the industrial revolution from Britain in the middle of18th century, the demand for alkali in textile, paper-making, soap-making, glass, printing and dyeing industries has increased sharply. It is obviously not enough to rely solely on natural alkali and extract alkali from plant ash, and manual production is needed.
Chemists realized that salt and sodium carbonate contained the same sodium through analysis and research, and began to try to convert salt into soda ash.
1737, the French scholar hammel Dumont Su first heated salt with sulfuric acid to obtain sodium sulfate, and then heated sodium sulfate with charcoal to generate sodium sulfide and carbon monoxide. After sodium sulfide is converted into sodium acetate, the heat is strengthened and the vapor of acetone is released, leaving sodium carbonate.
He also first converted salt into sodium nitrate, and then put sodium nitrate and charcoal in a crucible to explode, producing sodium carbonate.
This is just an experiment in the laboratory.
1773, Swedish chemist Scheler heated salt solution and lead oxide powder together to form sodium hydroxide solution, which was exposed to air to absorb carbon dioxide gas, and then precipitated sodium carbonate and yellow lead oxychloride (PbOCl PbCl).
In this way, Kerr, an Englishman, established a factory in Dudley to produce soda ash and soap. 1780, another Englishman, Thule, obtained a patent to make lead oxide into yellow pigment, claiming that this pigment is Thule yellow.
In 1777, French priest Ma Houbi changed one salt into another, a salt, a salt, a salt, a salt, a salt, a salt, a salt, a salt 1779 Factory production, factory production, factory production, factory production. Copp, a French pharmaceutical professor, improved this method of making alkali by replacing iron with iron oxide. After his method spread to Britain, he immediately set up a factory for production, and the annual output of soda ash reached thousands of tons.
Others have proposed other methods.
Lubran soda process
1783, the French Academy of Sciences offered a reward of 1200 livres (the old name of French franc) to find a way to make soda ash to meet the needs of French soap, textile, bleaching and dyeing industries at that time.
1789, Lou Bran, a physician of the Duke of Orqi, France, modified some previous methods of alkali production and created a new method. 179 1 year, he obtained a patent and was funded by the Duke of Orleans to set up a soda factory with a daily output of 250-300 kg in Saint-Denis, a suburb of Paris. The raw materials used in Lubulan soda process are still salt, sulfuric acid, charcoal and limestone. The production operation process is mainly divided into three steps: ① salt reacts with sulfuric acid to generate sodium sulfate; (2) heating sodium sulfate, charcoal and limestone in rotary furnace to produce black melt, and cooling to form black ash; (3) soaking black ash, decanting the solution, and concentrating to separate out sodium carbonate crystals.
1793165438+1On October 6th, the Duke of Orleans was guillotined by the French bourgeois revolution,1October 28th, 1794 65438+ Saint-Denis factory was confiscated. Lubran didn't receive the bonus. Although he owned the Saint-Denis factory at 180 1, he was too poor to survive and had to enter the workhouse. He committed suicide on 1806. Eight years after his death, that is, 18 14 years later, the Paris Institute of Technology erected a statue for him as a memorial.
1823, the British government announced the duty-free of salt, which promoted the chemical industry production with salt as raw material in Britain. Musprat, an entrepreneur, seized this opportunity to introduce Lubran method to Britain and set up factories in Liverpool, Newton and Flemington successively. By 1886, Britain had produced millions of tons of soda ash by the Lubran method.
Hydrogen chloride gas, a by-product of Lubran process, is discharged into the atmosphere at the initial stage. Later, due to serious environmental pollution, the British Parliament passed management regulations, forcing producers to try to restore it. 1836, soap manufacturer Gesai built a washing tower filled with coke, so that the rising hydrogen chloride gas was absorbed by the falling water and hydrochloric acid was obtained. In 1866, production workers Deakin and Huldt mixed this hydrogen chloride gas with preheated air. It is a patent to use copper or manganese oxide (as a catalyst) to convert chlorine gas, and then use lime water to absorb this chlorine gas to make bleaching liquid. In 1822, industrial chemist Chance introduced the flue gas containing carbon dioxide into the waste, so that the calcium sulfide in the waste was converted into hydrogen sulfide and then oxidized into sulfur.
This not only revolutionized the Lubran process, but also obtained a series of by-products, which made the Lubran process form a chemical production system. The chemical industry is gradually emerging.
Survisu play
Although Lubran soda process has been popular for some time. However, there are many shortcomings, mainly because the melting process is carried out in solid, which requires high temperature, small equipment production capacity, serious corrosion, insufficient utilization of raw materials, poor working conditions of workers and poor quality of soda ash. Therefore, manufacturers are scrambling to study other methods of alkali production. This is the inevitable trend of scientific and technological development.
By 1859, after repeated experiments in the gas plant run by his uncle, the Belgian Sulvi finally mixed brine with ammonium carbonate to generate sodium bicarbonate precipitate, and heated the sodium bicarbonate to release carbon dioxide and water, leaving sodium carbonate. He first made sodium bicarbonate from crude ammonia, carbon dioxide gas and salt, and then heated it to make sodium carbonate. This is the so-called ammonia-alkali method.
186 1 In April, Sulvi was granted a patent by the Belgian government. 1in April, 863, he and his brother raised funds to set up Sulvi soda production company, and set up a factory in Coulette.1in June, 865, the daily output of soda ash was 1.5 tons. 1867, the products of this factory won the bronze prize of the Paris World Expo. 1876 won the medal of Vienna Expo, and this law was officially named Sulvesu style of play. 1869, the factory building expanded by 1 times, and the product volume increased by three times. At this time, the price of soda ash dropped sharply. This is how scientific and technological creation benefits mankind.
Sulvi doesn't know chemistry, nor is he an engineer. He didn't create the ammonia-alkali method either. As early as 18 10, Fresnel, a French optician, proposed this method. This method was put into production as early as 1838 in Britain, but it soon stopped because of the large ammonia loss and low economic benefit. The important point of Sulvi's success is to overcome this shortcoming. He set up a tower to make carbon dioxide rise from the bottom of the tower, meet with saturated brine flowing from the top of the tower, generate sodium bicarbonate precipitation and quickly transfer it to form continuous production. He also made the ammonium chloride in the product react with hydrated lime to regenerate ammonia.
Survey's success also lies in the fact that he transferred the patent license to British industrial chemist Mende and entrepreneur brenner. 1874, they set up Bunemen Alkali Company in England, and used Sulvi to produce alkali. Mende designed a rotary filter to precipitate sodium bicarbonate, installed a continuous ammonia steaming chamber, and controlled the temperature, pressure and concentration of reactants, which made the ammonia-alkali method more perfect and popular.
Sulvi has rich practical experience, which is one of the reasons for his success. When he worked in a gas plant, he was already familiar with the process of gas and liquid treatment. In his own words, he "grew up in ammonia". He escaped the damage caused by the explosion of the pipeline. It can be said that he was lucky to grow up in practice.
Sulvi attaches great importance to the welfare of workers, which also makes the alkali company obtain good economic benefits. He often provided financial support for scientists, researchers and students, and funded the establishment of a series of research institutes named after his surname, such as the Institute of Physiology, the Institute of Sociology and the International Institute of Physiology and Chemistry. 19110 In June, he invited outstanding scientists in the world at that time, including Madame Curie, to hold an international Sulvi conference in Brussels, Belgium, to discuss major issues in physics and chemistry. Later, this kind of meeting was held every few years, and it was called Sulvey Physics Conference and Sulvey Chemistry Conference.