On the afternoon of March 17th, at the 2021 China International Petrochemical and Downstream Industry Technology Conference and the 9th International Light Hydrocarbon Comprehensive Utilization Conference established at the Biodegradable Materials Technology Forum, participating experts discussed the preparation, R&D, application and application of a variety of biodegradable materials. Wonderful sharing of industry development trends.
BDO stumbling block: the shortage of calcium carbide raw materials makes it difficult to approve the natural gas law
Ni Ji, Chief Analyst of the Chemical Industry of Orient Securities Research Institute
Ni Ji, chief analyst of the chemical industry of the Orient Securities Research Institute, pointed out that degradable plastics have entered the industry's explosive period, and domestic large-scale PBAT projects are also emerging in an endless stream, with a planned production capacity of about 5 million tons/year. With the expansion of supply and the maturity of technology, the price of PBAT is expected to fall further, and together with PLA, it will become an important material for the development of degradable plastics.
The continuous increase of new PBAT projects indicates that the product has a low technical barrier. Although short-term profitability is good, if it fails to make breakthroughs in modification and products, it will inevitably fall into cost competition in the long run. The degree of integration, scale effect, and cost control will become key indicators to measure its competitiveness.
The main raw materials of PBAT are BDO, adipic acid and PTA, among which a large amount of hydrogen (or synthesis gas) is used in the production process of BDO and adipic acid, including the synthesis of methanol and synthetic ammonia, and the hydrogenation of benzene. Using natural gas to produce BDO to support PBAT, the by-product synthesis gas can just meet the hydrogen consumption of adipic acid. In theory, as long as there is natural gas, benzene and air separation (nitrogen and oxygen provided) at the raw material end, it can be produced in line with PBAT Demand for BDO and adipic acid products. Therefore, the natural gas method BDO has unique advantages.
Figure Matching of raw materials required to produce 1 ton of PBAT
(The figure after the product indicates unit consumption: ton, hydrogen unit: cubic / ton)
However, BDO is subject to the shortage of calcium carbide and the approval of the Natural Gas Law, which may become the threshold to limit the expansion of PBAT.
Biodegradable materials will evolve into biosafety materials
Yang Dongyuan, deputy dean of Yanchangxi University Advanced Technology Research Institute, Shaanxi, and postgraduate tutor of Northwest University
(The following only represents the personal opinions of experts, and does not represent any unit or organization)
Yang Dongyuan, deputy dean of Yanchangxi University Advanced Technology Research Institute in Shaanxi and a graduate student tutor of Northwestern University, pointed out that the cost of preparing degradable monomers by biological methods is still high, the availability of large-scale raw materials is still uncertain, food safety, and three wastes emissions. For example, 2.5 tons of corn can get 1 ton of PLA.
Relatively speaking, the preparation of biodegradable monomers from fossil raw materials has the advantages of low cost of large-scale raw materials, abundant sources and easy availability, low cost, significant scale effect, and concentrated pollution emissions. For example, the cost of PGA produced by the coal-to-ethylene glycol route can be close. PE.
Yang Dongyuan said that future materials will evolve from biodegradable materials to biosafety materials. The future degradable materials will have three characteristics:
One is to be compatible with the human body, moving from biodegradable and environmentally friendly to bioabsorbable;
The second is to integrate into one, from the natural degradation of thousands of years and returning to the hour-level metabolism;
The third is smart materials, moving from the physical and chemical properties of cured materials to adjustable and repairable.
Three directions of degradable plastic modification
Wang Pingli, Senior Engineer, National Engineering Research Center for Engineering Plastics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences
Wang Pingli, a senior engineer at the National Engineering Research Center for Engineering Plastics at the Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, pointed out that the substitution of degradable plastics is an important way to reduce the source of plastic pollution. The modification of degradable plastics has three directions: alloying, cheap and functional.
Currently, the demand structure of degradable plastic products is:
●Film bag daily-use products: the most mainstream product, with mature technology, Hainan will demand 48,000 tons next year;
●Meal box tableware: rapid development of products, technology needs to be improved, Hainan needs 15,000 tons next year;
●Plastic film: products covered by the ban on plastics, the technology is basically mature, and the price is far from market acceptance;
●Express delivery: products covered by the ban on plastics, degradable tapes need to be improved, and companies are trying to reserve and wait and see the market.
The demand structure of degradable plastic resin is:
●PBAT: mainstream basic products;
●PLA: Mainstream basic products;
●PBS: rapid development of basic materials;
●PGA/PPC/PHA/PCL: functional materials.
What kind of polymer materials can be biodegradable
Dai Junming, senior expert and professor-level senior engineer of Sinopec Yizheng Chemical Fiber Co., Ltd.
Dai Junming, a senior expert and professor-level senior engineer at Sinopec Yizheng Chemical Fiber Co., Ltd., pointed out that the degradation of biodegradable polymer materials has biophysical and biochemical effects, as well as other physical and chemical effects, such as hydrolysis, oxidation, etc.; degradation depends on The size and structure of macromolecules, types of microorganisms, temperature, humidity and other environmental factors; the biodegradability of different chemical structures is in order: aliphatic ester bond, peptide bond> carbamate> aliphatic ether bond> methylene Base; polymer materials with large molecular weight, regular molecular arrangement and high hydrophobicity are not conducive to the erosion and growth of microorganisms, and are not conducive to biodegradation; the length of the fragments produced by degradation is proportional to the thickness of the single crystal layer of the polymer material, the smaller the polarity The more susceptible the copolyester is to be degraded by fungi, the degrading effect of bacteria on polymer materials with high a-amino content is very obvious.
At present, the mechanism of biodegradation has not been fully studied.
There are 10 ways to use CO2 as a resource
Dr. Kong Fanzhi, Vice President of Innovation Institute of Oak Holding Group
Dr. Kong Fanzhi, deputy dean of the Innovation Institute of Oak Holding Group, pointed out that there are 10 ways to use CO2 as a resource: ①Use CO2 as a raw material to produce chemicals; ②Use CO2 as a raw material to produce fuel; ③Use microalgae for biotransformation;④ Used as a concrete building material; ⑤ CO2 enhanced oilfield regeneration (CO2-EOR); ⑥ Bioenergy for carbon capture and storage (BECCS); ⑦ Enhanced weathering; ⑧ Forestry technology including afforestation and reforestation; ⑨ Through soil Land management of carbon storage technology; ⑩ Biochar.
Ethylene carbonate (EC) and dimethyl carbonate (DMC) are used as high-boiling polar aprotic solvents in industry as lubricants, electrolyte solvents for lithium-ion batteries, synthetic modules of polymer materials, and copolymers of polycarbonate Synthetic intermediates for monomers and other fine chemicals.
Oak Holding Group has successfully realized the production of ethylene carbonate (EC) and dimethyl carbonate (DMC) from CO2.
Schematic diagram of Oak EC/DMC process flow
The EC/DMC process of Aoke-Process Institute has three breakthrough core technologies:
The first is the hydrogen bond strengthening reaction and chemical immobilization of ionic liquids;
The second is the design of gas-liquid efficient distributed tubular reactor;
The third is the coupling of reactive distillation and energy-saving optimization design of the whole process.
Han Changyu, a researcher at the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, introduced the development and market application of biodegradable materials.
Meng Yuezhong, a distinguished professor of “Pearl River Scholars” of Guangdong Province, a second-level professor of Sun Yat-sen University, and director of Guangdong Key Laboratory of Low-Carbon Chemistry and Process Energy Conservation, introduced a new type of biodegradable carbon dioxide-based semi-aromatic copolymer.
Xu Zhigang, Chairman of Changzhou Ruihua Chemical Engineering Technology Co., Ltd. Maleic anhydride is one of the world's three major acid anhydride raw materials (acetic anhydride, maleic anhydride, phthalic anhydride), and its downstream products have a wide range of development and application prospects, which can be used to synthesize resins. , Coatings, pesticides, lubricant additives, medicine, paper treatment agents, food additives, stabilizers, etc. At present, maleic anhydride production technologies mainly include butane process and benzene process. At present, the production capacity of maleic anhydride in my country is dominated by the traditional benzene process, but with the advancement of the utilization of carbon four resources, the butane process maleic anhydride plant has gradually formed a scale. Ruihua maleic anhydride technology uses n-butane as raw material to produce maleic anhydride by reacting with air. The oxidation reaction is a strongly exothermic reaction, and the heat of reaction needs to be removed during the reaction process, so the maleic anhydride device can output a large amount of steam to the outside. Because of this feature, the maleic anhydride device is suitable for joint installation with some devices with high steam consumption, such as the ethyl styrene styrene device, which can achieve the purpose of steam complementation and improve the economic efficiency of the two devices. Compared with traditional benzene maleic anhydride technology, RHMA technology can completely eliminate benzene's environmental pollution, high maleic anhydride yield, low energy consumption, high steam output, and long operation cycle of the device.
After evaporation, butane is mixed with air and then enters the oxidation reactor. The oxidation reactor is a tubular fixed-bed reaction type, the catalyst is placed in the reaction tube, butane and air react with the catalyst to generate maleic anhydride, and at the same time release a large amount of reaction heat, which is removed by the molten salt on the shell side. After the heated molten salt is used to produce steam, it is returned to the reactor. In the oxidation reactor, the single-pass conversion rate of butane can reach 82-85%, and the weight yield of maleic anhydride is 97-103%.
The reacted gas enters the post-treatment system after two-stage cooling. The post-treatment system of Ruihua maleic anhydride technology adopts a solvent absorption process, and the solvent is dibutyl phthalate. After the reaction gas is absorbed, desorbed, and refined, the product maleic anhydride is obtained with a purity of 99.5%.
Changzhou Ruihua Chemical Engineering Technology Co., Ltd.
Changzhou Ruihua Chemical Engineering Technology Co., Ltd. was established in 2007 and is located in the Science and Education City of Wujin District, Changzhou City. It is a professional company with a number of patented technologies and mainly engaged in engineering and technical services in the petrochemical field. The company was formerly known as Changzhou Ruihua Chemical Engineering Technology Co., Ltd., which completed the share reform in December 2017 and officially changed its name to Changzhou Ruihua Chemical Engineering Technology Co., Ltd. In July 2018, it was officially listed on the New Third Board (Ruihua Technology 872869).
Since the establishment of the company, the business has always maintained rapid growth. It has established good business relationships with well-known large petrochemical companies at home and abroad; and has established a stable cooperative relationship with well-known domestic and foreign chemical companies, engineering companies, patent dealers, various industry associations, large design institutes, and research institutes. As a professional company engaged in engineering and technical services in the petrochemical field, Ruihua Chemical is committed to providing users with comprehensive, systematic and professional engineering services and helping users create more value.
It is Ruihua Chemical's goal to gather first-class talents, establish a first-class technical base, and create a first-class modern enterprise. It is also the development path that Ruihua is taking. In addition, the company attaches great importance to the protection of intellectual property rights, and has applied for and authorized more than 60 patents.