Presently, there are 3 type of industrial 1,3-PDO production approaches: acrolein hydration technique, ethylene oxide hydroformylation approach and also organic fermentation method Amongst them, the acrolein hydration technique was constructed by Degussa in 1996 with 50,000 heaps/ Annual plant; ethylene oxide hydroformylation method was built by Covering in 1999 with a 72,000-ton/ year industrial plant; biological fermentation approach was built by DuPont in 2006 with a 45,000-ton/ year plant, as well as various other developing Procedures include formaldehyde-acetaldehyde condensation process, ethylene synthesis procedure by Pris reaction, glycerol chemical procedure and also 3-hydroxypropionaldehyde (3-HPA) one-step synthesis procedure. Because the biological fermentation approach has the advantages of light reaction problems, simple operation, much less byproducts, as well as far better option. The benefits of great selectivity, low energy intake, less equipment financial investment, and also environmental kindness have actually ended up being a hot spot in today’s development.
2.1 Acrolein hydration approach.
The process created by Degussa at first utilized an unique ion exchange material driver, as well as included a chelating practical team containing methyleneiminodiacetic acid, as well as the reaction was carried out at 60 ° C. The conversion price of acrolein was 82%, as well as 3-hydroxypropionaldehyde (HPA) selectivity was 80%. After that, 1,3-PDO was gotten by two-stage hydrogenation. When Raney nickel was used as the stimulant, the carbonyl content was minimized from 1000 ppm to below 100 ppm. Degussa transferred the innovation to DuPont in 1998.
2.2 Hydroformylation of ethylene oxide
The procedure created by Shell operates in two actions, first by hydroformylation of ethylene oxide with syngas to HPA, complied with by hydrogenation to 1,3-PDO. The trick to the Covering procedure is using cobalt carbonyl catalysts in the hydroformylation process, and also using numerous ligands (such as diphosphine, trihydrophosphine, arsine, etc) and ingredients (tetrabutylphosphorus acetate, butylpentane, and so on) pyridine, and so on), based on ethylene oxide, the yield of 1,3-PDO can reach 85% to 90%, and also the product pureness can get to 99.6% (mass ratio).
2.3 Biological fermentation approach
The method consists of the option of raw materials, fermentation innovation, removal of bacteria and also healthy proteins, desalination and also rectification.
Along with the target product, the 1,3-PDO fermentation method likewise consists of microbial strains, healthy proteins, nucleic acids, polysaccharides, not natural salts, organic acid salts, glycerol, 2,3-butanediol, water, etc, which is a really intricate procedure. Furthermore, 1,3-PDO is extremely polar, as well as the concentration in the fermentation broth is reduced (concerning 50-110 g/L in one stage), so it is tough to different as well as recover 1,3-PDO from water down service, which likewise restricts organic Approach 1,3 – The essential to PDO manufacturing. In order to address the many problems existing in the whole separation process, it is essential to more optimize the purification process, especially to develop a cost-effective as well as reliable splitting up method, while improving the return and high quality of 1,3-PDO, streamlining the process route, lowering power usage, recycling High value-added by-products in fermentation broth.
Along with organic synthesis of 1,3-PDO, chemical synthesis of 1,3-PDO from glycerol is also worthy of interest. As an example, the research study group of Tohoku University in Japan as well as Daicel have created a procedure for creating 1,3-PFO from glycerol produced by biodiesel. The procedure uses powdered Ir-ReOX/SiO2 stimulant distributed in the reaction remedy, and also the selectivity of 1,3-PDO reaches 60%. The research team likewise confirmed the reaction mechanism for the development of 1,3-PDO using a 2,3-= hydroxypropanol intermediate. The study team additionally enabled the reaction to be carried out in a fixed-bed activator by utilizing an optimized spherical catalyst sustained on silica gel. Continuous operation at laboratory range for more than 300 hrs reveals that the catalyst still maintains high task and also selectivity. Therefore, it can be thought about that the scale-up examination of the industrial path can be carried out, and also the reaction spin-off propanol can likewise be marketed as a solvent. 3 Residential as well as international market supply as well as need and also forecast
In recent years, there have been couple of records of brand-new 1,3-PDO manufacturing plants abroad. The existing manufacturing ability is estimated to be 265,000 tons/year, the largest of which is Shell’s ethylene oxide hydroformylation unit in Geismar, Louisiana, U.S.A., with a production ability of 136,000 tons/year; Degussa’s Weisser, Germany In the Wesseling location, there are 2 sets of acrolein hydration units with a manufacturing capability of 18,000 tons/year as well as 50,000 tons/year respectively. DuPont has a 18,000-ton/ year acrolein hydration device in Germany and also a collection of acrolein hydration units in Tennessee, U.S.A.. The bio-fermentation unit of the firm has a production capability of regarding 60,000 tons/year after expanding its capacity by 30% in 2011. Shell has actually predicted that the need for PTT, the major downstream item of 1,3-PDO, is expected to reach 1 million bunches in the following few years, as well as the needed 1,3-PDO will reach 360,000 lots. Clearly, the existing manufacturing ability can not satisfy the marketplace need.
Currently, my country’s yearly intake of PTT has actually surpassed 30,000 lots, representing about 10% of the world’s total consumption. 90% of PTT intake is straight made use of for spinning as fibers, as well as the continuing to be 10% is utilized for design plastics, of which about two-thirds of fibers are made use of for clothing as well as one-third for carpets. In the following couple of years, the potential market need for PTT in China will certainly be 50,000 to 100,000 tons.