20 years of development of China's fluorine chemical industry

Fluorochemicals generally refer to the chemical industry that contains many or a small amount of fluorine atoms in the products and related raw materials and intermediates produced

After more than half a century of development from the earliest fluorine refrigerant and its main basic raw material, anhydrous hydrogen fluoride, the fluorine chemical industry in China has formed a system with more varieties and relatively complete categories, with more than 1,000 enterprises and a production capacity of more than 500 10,000 tons, with annual sales revenue exceeding 60 billion yuan

1.

From the 1920s to the end of the last century, Shanghai's fluorine chemical industry has developed vigorously and has made great contributions to the development of China's fluorine chemical industry

Entering the 21st century, especially during the "Eleventh Five-Year Plan" and "Twelfth Five-Year Plan" period, China's fluorine chemical industry has developed rapidly and achieved remarkable achievements.

2.

3.

Fluorocarbon chemicals: The overall technical level of China's fluorocarbon chemicals has been greatly improved, and the technological gap with foreign countries has also been narrowing

In the past 20 years, China has completed the phase-out of CFCs except for special uses and raw materials, and started the accelerated phase-out process of HCFCs for ODS use.

Fluoropolymers: Fluoropolymers mainly include new materials such as fluororesins, fluororubbers and their products.

While the production of fluoropolymers and supporting monomers in China has been intensively expanded, new breakthroughs have been made in the polymerization process and engineering amplification technology, many new brands have appeared, and product quality has been rapidly improved

Fluorine-containing coatings: Fluorine-containing coatings have achieved considerable development during this period, and domestic fluorine-containing coatings have also become the world's largest producer, and a large proportion of them are exported

Fluorine-containing fine chemicals: China's fluorine fine chemical industry has become the fastest growing and highest value-added segment in the fluorine chemical industry in the past 10 years

Four, a hundred flowers blossom, fruitful

In terms of fluoropolymers, a 10,000-ton tetrafluoroethylene production plant has been built based on self-developed complete sets of technologies; 8 cubic meters of suspension polymerization vessel, 4 cubic meters of dispersion polymerization vessel, and 8 cubic meters of crushing and washing equipment have been successfully applied Industrialized production equipment and production equipment technology have approached the international advanced level
.
The preparation of high-performance polyvinylidene fluoride hollow fiber membrane and its key technology in the application of sewage resources won the second prize of national technology invention; the domestic chlor-alkali ion membrane project won the second prize of national technology invention; research and development of a batch of fluorine-containing materials The application has achieved good results.
The high-performance polyvinylidene fluoride hollow fiber membrane has been researched and applied in sewage recycling.
The domestic chlor-alkali ion membrane, peroxide vulcanized fluorine rubber, and PTFE for biaxially stretched membrane have been developed.
Technologies and products such as PVDF for ethylene and solar back sheet film
.
Breakthroughs have been made in the development of ETFE, PFA and other products, and they are being promoted and applied
.
PFOA substitutes are used in the production of some fluoropolymers
.

In the 1990s, Juhua introduced and absorbed Western AHF, basic fluorine chemical technology, and Russia's 3000t/aPTFE technology, which drove the overall development of China's fluorine chemical industry
.

In 2000, Shanghai Sanaifu Company started the construction of a 1,000-ton/year fluororubber project, which was completed and put into operation in 2002, becoming the largest domestic fluororubber production facility at that time
.

In December 2007, the development and application of key technologies for the industrialization of 1,000 tons of fluorine rubber produced by Shanghai Sanaifu Co.
, Ltd.
won the second prize of Shanghai Science and Technology Progress Award
.

In November 2009, Shanghai Sanaifu Co.
, Ltd.
's 1,000-ton/year polyvinylidene fluoride resin industrialization technology development and industrialization won the second prize of Shanghai Science and Technology Progress Award
.

In 2009, Dongyue Group launched the 863 Program "Perfluorinated Ion Exchange Membrane Materials Research" and the scientific and technological support project "Perfluorinated Ion Exchange Membrane Engineering Technology Research"
.

In 2010, the suspension polytetrafluoroethylene resin FR105 of Shanghai Sanaifu Company was successively included in the 2010 Shanghai and National Key New Product Plans
.

In 2011, Zhonghao Chenguang launched the scientific and technological support program "Key technology development of high-performance special fluororubber industrialization"
.

In 2011, Juhua Group launched the National Science and Technology Support Program "Research and Application of Key Technologies for Continuous Copolymerization of Fluoropolymers"
.

In 2012, Shanghai Sanaifu Co.
, Ltd.
completed the industrialization of 1,000 tons/year of PVDF
.

In 2015, Juhua launched the "Synthesis Research on Green Low Temperature Supercritical Assisted Extrusion Fluorine-containing Membrane Materials"
.

In 2017, Juhua Group carried out "Research on Key Technologies for Industrialization of Fluorine-modified High-Performance Polyimide Composite Materials"
.

Lithium electrolyte and isotope separation, perfluoroether, polyfluoroester and other fine fluorine chemicals have entered the forefront of the world
.

Research and domestic application of HFC series catalysts in Xi’an Institute of Modern History
.

Kaixing developed and demonstrated the polymerization reactor based on JB4732 fatigue stress analysis
.

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.
.
.
.
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The rapid development of fluorine chemical industry has also promoted the construction of a number of fluorine chemical industry parks and the joining of foreign-funded enterprises
.
During this period, more than a dozen economic development bases or parks based on fluorine chemicals have been formed throughout the country, which can be summarized into 6 types
.
First, relying on large-scale "leading" enterprises, supporting the construction of upstream, middle and downstream facilities, such as Zhejiang Quzhou with Juhua Group as the leader, Shandong Dongyue Fluorosilicon Industrial Park with Dongyue Group as the leader
.
The second is a cluster of domestic core companies that drive famous overseas companies, such as Jiangsu Changshu International Fluorochemical Park, with Shanghai Sanaifu Company, DuPont, Daikin, and Arkema as the core
.
The third is the combination of production and circulation.
For example, the fluorosilicon products of Taizhou Yimeilan Chemical Company in Jiangsu are combined with ports and wharves along the Yangtze River
.
The fourth is the relocation and transformation of urban enterprises.
For example, Fuxin, Liaoning, is a coal resource-exhausted city.
In order to re-plan the direction of economic support, fluorination is the focus
.
The fifth is the development of characteristic products.
For example, Dalian, Liaoning focuses on fluorine-containing coatings, and Hubei focuses on fluorine-containing fine chemicals
.
Sixth is the resource development type, such as Ganzhou in Jiangxi, Chenzhou in Hunan, Shangluo in Shaanxi, Pucheng in Fujian and Inner Mongolia, and most of the newly constructed parks belong to this type
.
Among them, the most influential is the International Fluorochemical Park in Haiyu Town, Changshu, Jiangsu, which gathers Shanghai Sanaifu Company, Changshu Sanaifu Zhonghao New Chemical Material Co.
, Ltd.
, Changshu Sanaifu Fluorochemical Co.
, Ltd.
, and Daikin Fluorochemical Industry Co.
, Ltd.
(China) Co.
, Ltd.
, Arkema (Changshu) Fluorochemical Co.
, Ltd.
, DuPont (Changshu) Fluoride Technology Co.
, Ltd.
, Solvay Specialty Polymers (Changshu) Co.
, Ltd.
, Japan Kureha and other companies
.
In the same area, the fluorine chemical product chain is complete and the industrial structure is reasonable.
It is the world's largest fluorine chemical park, reflecting a good industrial agglomeration effect
.

5.
Looking forward to the future, adding new power to the development of China's fluorine chemical industry

After 60 years of development, China's fluorine chemical industry has ushered in many development opportunities: the integration of the global chemical industry is accelerating, and the production capacity of fluorine chemical industry in developed countries is shifting to developing countries; China's fluorine chemical industry has advantages in resources, market and industrial chain; The development of new uses of chemical compounds will form a huge new market; the "ZTE" incident, China really attaches importance to the development of the new material industry, and further exerts the supporting role of fluorine materials in information, modern transportation, and national defense
.
But at the same time, there are also some problems: international advanced companies continue to gather high-end products and terminal applications to implement monopoly and blockade, the rapid development of fluorine chemicals forms strong competition in the middle and low-end markets, PFOA and some short-chain compounds are prohibited or restricted in use, and clean.
The huge pressure of environmental protection and so on
.

In the future, China will truly move from a big country in fluorine industry to a powerful country in fluorine industry.
We need to consider the diversification of raw material routes, high-end industrial structure, industrial equipment automation, intensification of industrial layout, energy conservation and environmental protection, agglomeration of basic fluorine chemicals, and professional back-end products.
To create a new situation in fluorine chemical industry
.

Author of this article: Wu Junyi

This article is selected from: Proceedings of 2019 (20th) Fluorosilicone Coating Industry Annual Conference