Green glycol from renewable resources

Diol technology from renewable resources has become a key project supported by the national “Eleventh Five-Year Plan” for the development of bio-industries, and has received strong support from the National Development and Reform Commission. After two years of promotion, Dacheng Bio-based glycol has been It covers a wide range of China's unsaturated resin industry and is actively promoting the application and breakthrough in the field of chemical fiber.
Dacheng Biochemical Technology Group was founded in 1994 and is headquartered in Hong Kong. It is currently the largest corn deep processing enterprise in Asia. It has eight major series of products and has operations all over the world. In 2007, Dacheng Group perfected the integration of biological and chemical leading technologies through technology accumulation and independent innovation, and successfully built the world's first industrialized production line that uses renewable resources with an annual output of 220,000 tons. In the next five years, the production line will be expanded to a scale of 3 million tons. The product line includes bio-based resin alcohols, propylene glycol and ethylene glycol, which will bring a beautiful experience to the sustainable development of the “post-oil era” chemical industry. It also provides a new choice for the polyester industry's product innovation and industrial upgrading.
China's chemical fiber industry growth confusion
Raw material import dependence is too high
China is the world’s largest producer of chemical fiber. In 2007, the output of chemical fiber was approximately 27 million tons, accounting for 40% of the total amount of global fiber. While over 90% of products in the chemical fiber industry are based on the petroleum industry, raw material costs account for more than 80% of production costs. Due to the serious lag in the development of China's chemical fiber raw materials industry, imports account for about two-thirds of the total demand for chemical fiber raw materials, and the external dependence actually exceeds the steady development of the industry's security cordon.
In 2008, due to the rise in international oil prices and the appreciation of the renminbi, the domestic chemical fiber industry was struggling immediately.
The ups and downs of the chemical fiber industry have brought great investment risks and instability to the healthy development of the entire industrial chain.
Existing oil production is in short supply
According to relevant data, in 2007 China imported about 5 million tons of ethylene glycol, together with domestic 1.57 million tons, apparent consumption reached 6.57 million tons, equivalent to 3.3 million tons of ethylene, or 11.5 million tons of naphtha, The equivalent of 76.65 million tons of crude oil processing. In fact, as an oil-deficit country, if China does not carry out technological innovation, it will be difficult to raise the self-sufficiency ratio of ethylene glycol in the short term, and it will maintain a high level of import dependence in the coming period.
If the underlying chemical raw materials on which the growth of the chemical fiber industry depends are still supported by imported crude oil processing or finished products, according to the existing industrial planning, it is difficult for China's chemical fiber industry to get out of the ups and downs.
Industrial layout before the limit of growth of traditional chemical fiber industry
If raw materials and markets of an industrial chain are outsourced, the primary processing process is in China. If crude oil and its chemical raw materials at source continue to increase in price, the processing costs in various RMB settlements will continue to increase. The US dollar earned on the market will be against the RMB. With constant devaluation, this industry chain will be difficult to sustain. Today, we face the situation in the domestic and foreign business environment.
One of the solutions is to use the global industrial chain as a perspective to extend the source of the domestic industrial chain to the raw material production regions in the Middle East or India, and to participate in the production of basic chemical raw materials through investment, equity participation, or controlling, and ensure a stable source of raw materials; The last part is to increase the added value through cultural promotion, product design and packaging.
The second solution is the sixteen-character principle of “Technological innovation, industrial upgrading, circular economy, and environmental friendliness” put forward by the China Chemical Fiber Industry Association. Through technological innovation, the added value of products will be increased; through industrial upgrading, efficiency will be improved and costs will be reduced. The overall competitiveness; through the development of circular economy and environmentally friendly technology, the "Eleventh Five-Year Plan" for the sustainable development of chemical fiber industry.
Seize the opportunity to meet the arrival of the "BT" era in the 21st century
The era of biotechnology industry is coming
The 21st century will be the era of the biotechnology (BT) industry. With the popularization and application of gene technology and enzymatic technology, compared with non-renewable fossil fuels such as petroleum, coal, and natural gas, renewable woody plants, herbs, seeds, and algae have been produced using biotechnology. Thousands of products such as fuel ethanol, biodiesel, and fine chemicals.
For example, PTT fibers from the United States DuPont Company biological 1,3-propanediol, and the United States Cargill's PLA fiber converted to lactic acid by glucose conversion, etc., has become a hot pursuit of chemical fiber companies. Our country is catching up with the new high ground of science and technology.
National industrial policy provides conditions for technological innovation in the chemical fiber industry
The "Eleventh Five-Year Plan" for the development of bio-industries compiled by the National Development and Reform Commission points out that "according to the requirements of the new industrialization road, we will vigorously develop bio-based products and achieve partial replacement of fossil materials. Accelerate the transformation of traditional industries using biotechnology. Technology to reduce industrial production energy consumption and pollutant emissions.”
The "Eleventh Five-Year Plan for Development of Chemical Fibre Industry" Guideline also included the "Biological Technology Research and Development of Bioprocesses" as a priority in the development of chemical fiber engineering technology, and strived to use biological methods of propylene glycol (PDO) and ethylene glycol (EG). ), butanediol (BG), etc. as the focus, to achieve a breakthrough in industrialization.
Building China's chemical fiber industry chain around bio-based polyols
If only bio-based polyols are used as alternatives to petroleum-based glycols, or if they are viewed as a differentiated product, the thinking of upgrading and developing the existing chemical fiber industry will be greatly limited.
Based on the understanding of bio-chemical science and technology, these bio-based polyols are only a starting point for the development of bio-chemical technology. Through the understanding of the molecular structure of carbohydrates, relevant poly-acids and polyols can be developed in the future, and from Raw materials development and processing, equipment design and manufacturing, product design and processing technology, finished product packaging and application and other aspects to achieve industrial upgrading, will eventually form a closed biochemical fiber industry chain based on petrochemical raw materials.
Various processing technologies of ethylene glycol
With the continuous rise in the price of oil, people are encouraged to start exploring new raw materials, new processes and new methods, and actively develop ethylene glycol products to meet the growing needs of the petrochemical and chemical fiber industries.
Process for producing ethylene glycol using petroleum
There are mainly ethylene oxide direct hydration, ethylene oxide catalytic hydration, ethylene glycol and dimethyl carbonate cogeneration technology and ethylene carbonate hydrolysis synthesis of ethylene glycol and other technologies, mature petrochemical process route is as follows:
Ethylene glycol non-petroleum route
Syngas Direct Synthesis Method Using the CO and H2 in natural gas under the action of rhodium and ruthenium catalysts, ethylene glycol is synthesized directly at high temperature and pressure.
Hydrogen oxalate synthesis method Starting from 2005, the Chinese Academy of Sciences cooperated with Danyang Jinhua Chemical Industry Co., Ltd. to establish a 300t/a ethylene glycol pilot plant and a 10000t/a ethylene glycol industrial plant. In 2007, a 200,000 t/a glycol industrial demonstration unit was built in Tongliao, Inner Mongolia. The core technology is to send appropriately processed lignite into the reactor and pass the gasification agent (air or oxygen + steam) at a certain temperature and pressure to incomplete combustion of the coal, so that the coal can be converted into a certain flow mode. CO and H2 mixed synthesis gas, and then by the gas-phase reaction of CO to produce oxalate, and then hydrogenated from oxalate to generate ethylene glycol.
Glycol technology from renewable resources
In 2005, Dacheng Group first produced glucose with an annual output of 20,000 tons through the production of glucose through fermentation, then converted into sugar alcohol, and then hydrogenated through catalytic cracking. In 2007, it developed an annual output of 200,000. Tons of industrialized demonstration devices. Carbohydrates in nature, whether they are starch-based polysaccharide crops, for example, high yield crops such as corn, wheat, potatoes, sweet potatoes, beet, etc.; or monosaccharides or polysaccharide crops such as sweet sorghum, Jerusalem artichoke and cassava, etc. Can be used as bio-based glycol raw materials. The basic principle is as follows:
Unlike the petroleum-based glycol process route, this technical route does not require the consumption of large amounts of oxygen, emissions of exhaust gas, and waste water. The required raw materials are renewable and rich in resources, and thus are environmentally friendly technologies. Today, the "resin alcohols" named by Dacheng Group (including bio-based propylene glycol, ethylene glycol, and butanediol contents of 60%, 30%, and 10%, respectively) have been widely used in the domestic unsaturated resin industry for reducing. Our country’s dependence on imported polyols has played an important role.
Bio-based Ethylene Glycol Installation Using "Integration of Coal, Electricity, and Chemical Industry"
The entire production facility of Dacheng Group is mainly composed of four parts: a raw material preparation plant, a hydrogen production plant, a hydrogenation catalysis plant, and a separation and purification plant. The energy needed in the production workshop is provided by the thermal power plant. The produced steam is used for hydrogen production and the reactants are distilled to separate and purify the heat medium, and the generated hydrogen is used in hydrogenation catalysis and cracking to realize the construction of “coal, electricity, and chemical integration”.
Due to the recycling of various resources, the production and processing costs are greatly reduced, and the bio-based ethylene glycol has a very strong price competitive advantage, thus becoming a green renewable resource product.
A new PDT polyester from green ethylene glycol
Bio-based glycols can be used directly as raw materials for the polyester industry, and can be esterified with purified terephthalic acid using existing polymerization equipment, and then polycondensed to produce spinning properties and dyeing properties that are better than those of existing polyesters. Excellent novel copolyester fiber, this property is due to bio-based ethylene glycol containing about 2% mass fraction of propylene glycol, butanediol and pentylene glycol and other multi-component glycols. Therefore, we refer to this polyester as "poly-terephthalic acid multi-component glycol ester," which is called "Poly Dihydricalcohols Terephthalate" in English, or PDT (registered trademark).
After more than two years of exploration and research, the R&D institutions jointly formed by Dacheng Group and Donghua University have completed the whole process of industrialization of bio-based glycol from polymerization, spinning, texturing, weaving, dyeing, and garments. Experiments, the experimental results show that: bio-based ethylene glycol due to trace amounts of 1,2-propanediol does not interfere with the polymerization, it is due to the polymerization of terephthalic acid (PTA) and propylene glycol molecules when the introduction of methyl "-CH3" The addition of a certain number of branches to long-chain macromolecules changes the close structure of symmetry between terephthalic acid and ethylene glycol, increases the amorphous structure, and decreases the melting point of the copolymer. Some features that PET does not have. The melting point, spinning temperature, and dyeing temperature of the pellets are about 15~20°C lower than those of petroleum-based polyesters. This is of great significance for energy conservation and consumption reduction of enterprises. Bio-based ethylene glycol contains 2% or more of the other two. Polyols make the obtained fiber physical properties and dyeing properties close to those of PTT fibers; PDT polyesters are very suitable for the production of ultra-fine fibers, deep-stained fibers, and for film or bottle polyester.
The pursuit of a polyester industrial chain built on biomass
With the in-depth development of bio-chemical technology, it has become more and more possible for people to use biomass to develop various petroleum alternative resources. Polylactic acid fiber developed by Cargill of the United States is a typical example. This fiber has properties similar to polypropylene, and Can be completely degraded. There is also a polymer called polybutylene succinate (PBS), in which the raw materials succinic acid and butanediol are both produced by biomass fermentation, and are therefore receiving attention, except that they can be used as plastics. In addition to the toughening agent, it also has a degradable function and has been included in the Beijing Olympic Games as a preferred consumable.
As a result, starch-based crops increasingly function as petroleum-like, through which hydrolyzed starches or monosaccharides are very similar to naphtha. Ethanol obtained by fermentation of hydrolyzed starch has become an important automotive fuel component, and can also be fermented into a variety of dibasic acids; monosaccharides can be cracked to obtain various dihydric alcohols, and polymers obtained by the polymerization of dibasic acids and dihydric alcohols The material will play a role similar to polyester. This biomass-based polyester industrial chain is a dream that can be realized in the future.

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