In the early 1950s, Mr. Gao Shiyang participated in the salt lake scientific expedition of China Academy of Sciences led by Liu Gang, and found carnallite in the brine pit beside the Chaerhan Yantan Highway in Qinghai. Niobite was found in the bottom sediments of surface brine in Dachaidan Lake.
Participated in the Sino-Soviet cooperation project of "Exploration, Development and Utilization of Salt Lake in Qaidam Basin", and confirmed that Chaerhan Salt Lake is rich in potassium and magnesium salts, and carnallite and bischofite can be separated from brine by solar evaporation. Dachaidan Salt Lake is rich in potassium magnesium borate, which is a rare new borate salt lake in the world and has scientific research significance and development and utilization value. I have visited the United States, Chile, Australia and the former Soviet Union while studying many salt lakes in Qinghai-Tibet Plateau, Xinjiang and Inner Mongolia for many years, summed up the achievements of scientific and technological personnel in developing and utilizing salt lakes for many years, and put forward the proposition of salt-forming elements, namely, hydrogen, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, sulfur, oxygen, chlorine and bromine.
The research of salt lake chemistry is located in the field of resource inorganic chemistry from the chemical point of view, and is widely used by domestic counterparts.
In the series of research on borate chemistry of brine, the behavior of borate in the process of evaporation and freezing salting-out of brine was found out, the dynamic limit solubility of magnesium borate in concentrated brine was determined, the phase composition of borate precipitated from concentrated brine with high boron content was determined, and a new double salt, chlorite pillared magnesite, was determined, which solved the problem that Soviet scholars could not figure out, and put forward the comprehensive statistics that borate in brine was "tetraborate". Chlorine pillared magnesium borate can be transformed into pillared magnesium borate, mullite and fibrous magnesium borate when dissolved in water. No scholars have obtained these magnesium borate hydrates from brine before.
Mr. Gao Shiyang analyzed the long-term results of brine on the surface of salt lakes from 1950s to 1980s, and put forward a quadrilateral change law: sodium chloride (evaporation in summer) precipitated and dissolved (dilution in early winter); Glauber's salt is precipitated (frozen in early winter) and dissolved (warm in early summer);
In this paper, a chemical model of annual variation law of new salt lake brine in plateau is proposed. According to the formation and climatic characteristics of salt groups in plateau salt lakes and the annual variation law of surface brine concentration and dilution, combined with physical chemistry and geochemistry, the explanation that many magnesium borate hydrate salts in plateau salt lakes are diluted into salts is put forward. The mechanism of physical and chemical salt formation (positive and negative temperature effect and positive and negative concentration effect) is preliminarily expounded, which has been accepted and widely cited by domestic colleagues and attracted the attention of foreign scholars.
Mr. Gao Shiyang introduced the supersaturated dissolution phenomenon of magnesium borate observed in the field into the laboratory to prepare MgO with dissolution activity. The crystallization process of MgO-B2O3-MgCl2-H2O supersaturated solution was studied by kinetic method. The complex kinetic phenomena of crystallization and precipitation of different borates were observed, and the thermodynamic non-equilibrium phase diagram of the system was obtained for the first time, which was different from the equilibrium phase diagram and the evaporative metastable phase diagram. It broadens the research direction of the phase diagram of supersaturated area of concentrated salt solution, and the dissolution and transformation kinetics and phase chemistry of magnesium borate double salt (chlorite brucite, etc.). ) has been studied. It is found that the supersaturated solubility of component salts can be formed during the dissolution of double salts, but similar phenomena have not been observed abroad for many years, which provides a physical and chemical basis for solving the causes of pillared brucite and other salts in plateau salt lakes. In the inorganic chemistry of salt, the research methods of salt dilution with water and crystallization kinetics of supersaturated saline solution were established.
A variety of pure magnesium borate compounds were synthesized by the crystallization method of MgO n B2O3 supersaturated salt solution, the dissolution transformation method of magnesium borate in chlorine column and the high-temperature hydrothermal phase interaction method, which were used to determine the heat of solution and calculate the heat of formation.
The conclusion that boron oxide particles exist is verified by borate thermochemical method. He and doctoral students studied the FT-IR, B-NMR and Raman spectra of 30 kinds of borates and their aqueous solutions, gave some new spectra, learned that there were fewer boron oxide particles in aqueous solutions than in solids, and observed that some characteristic peaks changed significantly with time, and there was an instantaneous exchange reaction between boron oxide particles. The spectral study on the dilution process of borate concentrated solution confirmed the depolymerization process of borate-oxygen anion. The results of spectral study confirmed the conclusion that ion pairs were formed and borate existed in the form of "tetraborate" in concentrated brine titrated with hydrochloric acid -pH, and confirmed the rationality of explaining the complex kinetic reaction process of magnesium tetraborate supersaturated solution crystallization, which laid a foundation for further study on the structural chemistry of borate solution.
Mr. Gao Shiyang attaches great importance to the development and application of salt lake resources and the research of high-value products while carrying out basic research on salt lake chemistry and application. Absorbing the salt-making technology and experience at home and abroad, the problem of building a soil solar pond and its normal operation in the permafrost region of the plateau has been solved.
The scientific and technological achievements of "solarization technology of brine in Dachaidan Salt Lake" completed in 1965 and registered by the State Science and Technology Commission were adopted in the national key scientific and technological project "pilot test of boric acid and lithium chloride in Dachaidan Salt Lake" during the Seventh Five-Year Plan. After two years of industrial operation, the product quality, output and cost all meet the design requirements.
On the basis of studying the pH/δH titration reaction mechanism of hydrochloric acid-boron-containing concentrated brine, the pilot test and scale-up test of boric acid separation were carried out (15 years earlier than similar work in Chile), and the pilot test with an annual output of 230 tons of boric acid was completed.
The process has the advantages of less equipment, short process, simple operation and low cost. Although the content of lithium in brine is high, the ratio of magnesium to lithium is also large, which is difficult to separate. Through screening, lithium chloride was extracted from boric acid extraction mother liquor by TBP- ferric chloride-kerosene system, and a pilot plant with an annual output of 50 tons of lithium chloride was built. This process is applicable. Aiming at the separation of magnesium and lithium, the quaternary system of hydrogen, lithium, magnesium chloride and water and its secondary system were studied. At different temperatures, gas-liquid-solid three phases are in equilibrium. Complete the process of salting out bischofite and separating lithium salt from magnesium chloride concentrated brine with high lithium content. In view of the utilization of lithium resources in Qinghai Salt Lake, polar solvent ethanol was introduced into alkali metal and/or alkaline earth metal sulfate water system to study its gas-liquid-solid equilibrium, and the process of separating lithium sulfate from TBP extraction lithium chloride stripping solution was completed.
According to the thermal reaction behavior of alum and boric acid, aluminum borate whisker with high value and special purpose was prepared by the high temperature reaction of boric acid and alum, and the industrial production was successfully realized.