Production technology of BDO
There are more than 20 production methods of BDO, but only 5-6 of them are truly industrialized.
The earliest method was the process of producing 1, 4- butanediol from acetylene and formaldehyde successfully developed by German Reppe company in 1930s. Chemical companies such as BASF, ISP and DuPont have always adopted this method and made many improvements, which still occupy the main position until now.
In 1970s, Mitsubishi Chemical Company of Japan successfully developed a process route with butadiene and acetic acid as raw materials, and operated several sets of production facilities in Japan, South Korea and Taiwan Province Province of China.
At the end of 1980s, Davy Company in Britain developed the low-pressure gas-phase hydrogenation process of maleic anhydride for production, while Crockner Company in Japan developed the production method of 1 4 butanediol with propylene oxide as raw material, which was patented, but failed to realize large-scale industrialization.
In 1990s, leander Company successfully developed allyl alcohol process with propylene oxide as raw material, and built a 50,000-ton/year production facility in Texas. In the same period, after three years' efforts, British BP Company and German Lurgi Company successfully developed the "Geminox" process for producing maleic anhydride from n-butane and then 1, 4- butanediol, and successfully applied it to industrial production.
Supplement: abbreviation: BDO
Alias: 1, 4- dihydroxybutane
English name: 1, 4- propanediol; 1, 4- butanediol; 1, 4- dihydroxybutane
Structural formula: hoch2ch2oh
Molecular formula: C4H 10O2.
Colorless oily liquid, flammable and miscible. Soluble in methanol, ethanol and acetone, slightly soluble in ether, boiling point 235℃, melting point 20. 10C, flash point (open cup) 12 10C, relative density (d-420)10/7.
Product use: 1, 4- butanediol is a basic chemical and fine chemical raw material, which is widely used to produce engineering plastics and fibers, such as PBT, elastic fiber, tetrahydrofuran (THF), polytetramethylene glycol ether (PTMEG), UP, solvents, and pharmaceutical and cosmetic industries. 1, 4- butanediol can also be used to produce N- methylpyrrolidone (NMP), adipic acid, acetal, maleic anhydride, 1, 3- butadiene and linear UP chain accelerators.
Packaging, storage and transportation: packaging in aluminum, galvanized iron drums or plastic drums, or storage and transportation in tankers as flammable and toxic substances. Because the melting point is as high as 200C, heating pipes should be installed on the tank car.
1, the design capacity of 4- butanediol production plant is 25,000 tons/year. The plant adopts the improved GAF low-pressure slurry bed butanediol production process, which is the most advanced production route of butanediol by Reppe method in the world. The butanediol plant built by our company has become the most advanced plant in the world. The plant uses calcium carbide and acetylene as raw materials to produce butanediol in a low-pressure slurry bed by Reppe method. At the same time, it fills the blank of this production process in China and becomes the largest production base of 1 4- butanediol in China. The product 1, 4- butanediol has the characteristics of high purity and good quality, which can provide good raw material guarantee for downstream product development. It will promote the adjustment of industrial structure in this field in Shanxi and even the whole country.
1, 4- butanediol is an important organic and fine chemical raw material and the basic raw material for producing engineering plastics and PBT fibers. PBT plastic is one of the five most promising engineering plastics.
1, 4- butanediol is the main raw material for producing tetrahydrofuran, which is an important organic solvent. Polymerized polytetramethylene glycol ether (PTMEG) is the basic raw material for producing high elastic spandex (Lycra fiber). Spandex is mainly used to produce elastic knitwear such as high-grade sportswear and swimsuits.
γ -butyrolactone, the downstream product of 1 4 butanediol, is the raw material for producing 2- pyrrolidone and N- methylpyrrolidone, from which a series of high value-added products such as vinyl pyrrolidone and polyvinylpyrrolidone are derived, which are widely used in the fields of pesticides, medicine, cosmetics and so on.
At present, there are five main raw material routes for industrial production of 1, 4- butanediol:
1, Rapa with acetylene and formaldehyde as raw materials
Ripe method is a classic production method successfully developed by Sid Ripe and others in 1930s. The company is the predecessor of BAsP. In this method, acetylene and formaldehyde are used as raw materials to produce 1, 4- butanediol through two steps of synthesis and hydrogenation. The first step is to generate butynediol from acetylene and formaldehyde, and the second step is to hydrogenate butynediol to generate 1, 4- butanediol. This method is a traditional method to produce 1, 4- butanediol. The earliest copper oxide catalyst with SiO2 _ 2 as the carrier, the acetylene partial pressure in the reactor is as high as 0.5MPa, which is very unsafe to produce. After improvement, copper acetylene catalyst with aluminum silicate as carrier was used, and bismuth was added to inhibit the polymerization reaction, which overcame the shortcomings of the original process, and the reaction temperature was uniform and stable, and the safety was guaranteed. There are two kinds of Reppe processes, namely the classic BASF process and the improved GAF process.
2. Butadiene method
1, 4- butanediol is produced from butadiene. The completed production facilities include butadiene acetoxylation and butadiene chlorination, the former being the main one. Acetoxylation of butadiene was first industrialized in Mitsubishi Chemical Company of Japan on 1970. This method has the advantages of complex production process, high investment, expensive catalyst and large steam consumption during hydrolysis, but it has the advantages of easily available raw materials, high reaction selectivity and easy adjustment of the ratio of 1 4- butanediol to tetrahydrofuran.
3. Cola Li method with propylene oxide as raw material.
Firstly, propylene oxide was isomerized into allyl alcohol, and then hydroformylated into the main product Y- hydroxypropionaldehyde under the action of organic phosphine ligand catalyst, and then 1, 4- butanediol was obtained through extraction, hydrogenation and refining. The process has the characteristics of less investment, simple process, competitiveness of thousands of tons, high utilization value of by-products, recyclable rhodium catalyst, long service life, high yield of 1, low steam consumption, liquid phase reaction of hydroformylation and hydrogenation, easy change of process load, and the output of 1, 4- butanediol can be adjusted according to the market. Japan's Coca-Cola Company developed this process, and Japan's Dasailu Company also built a 65,438+0,000 t/a production plant, but it was not put into production due to the shortage of propylene oxide raw materials in Japan. American Arco Chemical Company co-produced styrene and propylene oxide by Haakon oxidation method, and built a 34,000 t/a 1 4- butanediol plant with cheap propylene oxide, which has been put into production. Therefore, the economy of this process largely depends on the price of propylene oxide.
4, maleic anhydride esterification hydrogenation method
The low-pressure gas-phase hydrogenation process of maleate was successfully developed by David Company in Britain. By adjusting the process conditions, the ratio of BDO, GBL and THF can be changed. In order to design the maximum output of BDO in industrial plants, we can maximize the output of BDO by recycling GBE until GBL is exhausted according to the chemical balance of BDO and GBL. Its advantages are high ester conversion rate, mild reaction conditions, low equipment material requirements, low catalyst price, long service life, low investment and production costs, and wide range of ratio adjustment of 1, 4- butanediol and tetrahydrofuran products.
5.BP/Lurgi geminox process
Developed jointly by BP and Lurgi Company of Germany. This process combines the gas phase oxidation of n-butane to maleic anhydride with maleic anhydride hydrogenation technology. C4 fraction is still used as raw material, and the whole process includes maleic anhydride production, maleic acid hydrogenation and 1, 4- butanediol refining. In this process, BDO can be obtained only by hydrofining without esterification. Shorten the whole process, reduce the number of equipment, and correspondingly reduce capital investment and operation and maintenance costs. The purity requirement of maleic anhydride is relatively low. The process has high selectivity to the catalyst, long service life, no need to replace the catalyst, less by-products, and can almost convert maleic anhydride into BDO. THF and GBL can also be produced by slightly changing the process conditions in hydrogenation, recovery and purification. BP invested more than $654.38 billion in Lima, Ohio to build the first BDO device. The project capacity is 63,000 tons/year, and the plant was put into production in July 2000. BP and Lurgi are cooperating to design a second device, which is expected to save 10-20% compared with Lima device.
Second, technological progress.
1 and BASF process
A new process for producing BDO from butane, which combines the gas phase oxidation method of converting butane from BASP company into maleic anhydride with ester hydrogenation technology from Kvaerner company, will be tested in a demonstration plant with an annual output of 65,438+00 tons of BDO in ludwigshafen. This technology began to develop after BASF reached an agreement with Kvaemer technology company, which included the process that BASF could use maleic anhydride from kvaener company to produce butanediol. The new combined process belongs to BASF company, while the existing esterification and ester hydrogenation processes still belong to Carna company, and the license can continue to be issued to third parties. The combined process eliminates the distillation and refining procedures of maleic anhydride, which can greatly save investment. Maleic anhydride contained in the solvent can be esterified directly without separation. Hydrogen used in hydrogenation gasifies maleate, leaving solvent for recycling. Kvaerner process converts acidic substances into non-acidic chemicals through ester intermediates, which makes it possible to use carbon steel equipment and copper-based catalysts can be used in hydrogenation reactors.
2. Sisas Process
Sisas in Milan also developed the maleic anhydride combined process. It is said that it can greatly save investment and reduce the consumption of raw materials and public works. The deputy general manager of the company said: "The key factors of producing BDO and its derivatives from butane are MA technology, hydrogenation process and economies of scale. We are very close to direct hydrogenation without esterification. " Sisas is known as the lowest-cost producer, and some other processes adopt traditional processes (such as MA esterification), which limits the operation scale or must overcome the difficulties of fluidized bed. At present, the company is looking for a suitable location in Europe or America, and adopting new technology to build a 654.38+ 10,000-ton/year device.
3. Suggestions on the production and development of 1, 4- butanediol in China
At present, only one propargyl aldehyde device and one maleic anhydride device are produced industrially in China. However, the demand for PBT and polyurethane in China is growing rapidly, and the required BDO is heavily dependent on imports. At the same time, the existing n-butane resources in China have not been fully utilized. Therefore, it is necessary to introduce foreign advanced technology or take the form of joint venture and cooperation, pool resources, build 1-2 sets of n-butane-maleic anhydride -BDO combined process with considerable scale and competitiveness, and promote the overall level of maleic anhydride and BDO industry in China. But at the same time, we should also pay attention to the fact that all localities should rely on n-butane resources and not blindly develop. On the basis of the existing maleic anhydride production facilities in China, we can also explore the possibility of technical transformation to realize the separation and refining of maleic anhydride solution to BDO, so as to reduce production costs and enhance market competitiveness.
Worthy of reference:/dangyuan/file/3wandun.doc.
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