Crude anthracene is separated from anthracene oil fraction obtained by industrial fractionation of coal tar by crystallization, and then purified by sublimation. High purity anthracene can be used as scintillator of scintillation counter.
2065438+07101The list of carcinogens published by the International Agency for Research on Cancer of the World Health Organization was preliminarily sorted out for reference. Anthracene is in the list of three types of carcinogens.
Chinese name: anthracene English name: anthracene chemical formula: c14h10c6h4 (ch) 2c6h4 molecular weight: 178.22 CAS registration number: 120- 12-7 EINECS registration number: 204. Kloc-0/5(℃) boiling point: 340(℃ molecular weight: 178.2292 g/mol physical property data, toxicology data, ecological data, molecular structure data, computational chemistry data, basic properties, storage method, synthesis method, solvent method, distillation-solvent method, chemical method, emulsion liquid membrane method, regional melting method. Melting point (℃): 2 15 3. Boiling point (℃): 340 4. Relative density (water = 1): 1.24 5. Relative steam density (air = 1): 6. 15 6. Saturation. Mol):-7 156.28。 Critical temperature (℃):596. 1.9. Critical pressure (MPa): 3.03 10. Octanol/water partition coefficient: 4.45 1 1. Flash point (℃):121(cc)12. Ignition temperature (℃): 540 13. Upper explosion limit (%): 5.2 65438. 16. refractive index: 1.5948 17. The solubility parameter (j cm-3) is 0.5:17.80918. Van der Waals area (cm2 mol-1):1.084×1019. Van der Waals volume (cm3 mol (kj mol-1):-7064.321. The standard of crystalline phase claims heat (enthalpy) (kj mol- 1): 126.022. Standard entropy of crystalline phase (j mol- 1 k: 207. 15 23. Free energy of formation (kj mol- 1): 282.8 24. Standard hot melting of crystalline phase (jmol-1k-1): 210.5025. Gas phase standard. : -7 166.0 26. the gas standard claims heat (enthalpy) (kj mol- 1): 227.7 27. Gas standard entropy (jmol-1k-1): 386.0328. : 33 1.4 29. Gas-phase standard hot melt (jmol-1 k-1):182.84 Toxicological data1,* * Sex: mouse percutaneous standard Dreitz test:/kloc-0. 16g/kg； Mice were given LD50: 4900 mg/kg orally; Oral LD:> 17g/kg 3 in mice. Acute toxicity [16] LD50: 430mg/kg (mouse vein) 4. * * * Sex [17] Mouse percutaneous: 1 18μg, mild * *. Ecological data 1. Eco-toxicity [18] LC50: 0.36 mg/L (24 hours) (blackhead fish); 1 1.9 μ g/l (96h) (juvenile sunfish) 2. Biodegradability [19] Aerobic biodegradation (H):1200 ~11040 Anaerobic biodegradation (H): 4800 ~ 44 160 3. Photolysis half-life (h) of non-biodegradable [20] aqueous phase: 0.58 ~1.7 photolysis maximum light absorption wavelength range (nm): 25 1.5 ~ 374.5 photooxidation half-life (h):1/kloc. 1029 (mosquito fish); 4400~9200 (rainbow trout); 759~9 12 (flea); Molecular structure data of 7760 (green algae) 1, molar refractive index: 6 1.93 2, molar volume (cm3/mol): 157.63, isotonic specific volume (90.2k): 4 14.94. Reference value of hydrophobic parameter calculation (XlogP): none. Number of hydrogen bond donors: 0.3. Number of hydrogen bond acceptors: 0.4. Number of rotatable chemical bonds: 0.5. Number of tautomers: 0.7. Heavy atoms. Degree: 154 10. Isotope atomic number: 0 1 1. The determined number of atomic solid centers: 0 12. Number of solid centers of indefinite atoms: 0 13. The determined number of chemical bond solid centers: 0 14. (Pure white with purple fluorescence) The relative densities of anthracene are 1.25(27℃), 1.283(25℃), the melting point is 2 17, the boiling point is 342, and the flash point is196./kloc-0. It is stably used as a luminescent material (for example, in scintillation counters), especially for coating (for example, for absorbing ultraviolet rays). Used to make anthraquinones and dyes. Also used as pesticides, fungicides, gasoline coagulants, etc. The preparation or source of anthracene is obtained in the final stage of coal tar distillation and can be separated from anthracene oil of coal tar. Storage method of anthraquinone 1, a derivative of dangerous label 20 (corrosive products). Storage precautions [25] are stored in a cool and ventilated warehouse. Stay away from fire and heat sources. The storage temperature shall not exceed 30℃ and the relative humidity shall not exceed 80%. The package is sealed. Should be stored separately from oxidant, and should not be mixed. Equipped with corresponding varieties and quantities of fire fighting equipment. The storage area should be equipped with suitable materials to control leakage. 2. The production equipment should be sealed and the production site should be well ventilated. Operators should wear protective equipment and apply some protective ointment to their skin. Packed in sacks lined with plastic bags. 25 kg or 50 kg per bag. Store in a cool, ventilated and dry place. The synthetic methods of producing refined anthracene from crude anthracene mainly include solvent method, distillation method, solvent distillation method, sublimation method, extractive distillation method and so on. Solvent method Solvent method is to use the solubility difference of anthracene, phenanthrene and carbazole in crude anthracene in different solvents to select a suitable solvent to wash and crystallize crude anthracene to prepare refined anthracene. Because the solubility of phenanthrene in many organic solvents is much greater than that of anthracene and carbazole, solvent method generally uses the first solvent to wash crude anthracene to remove phenanthrene, and obtains a binary mixture of anthracene and carbazole to complete the regeneration cycle of mother liquor. The first kind of solvent for removing phenanthrene is mainly benzene solvent, such as benzene, toluene, xylene, heavy benzene or solvent oil. Because the solubility of carbazole in nitrogen-containing solvents and some polar solvents is greater than that of anthracene, such as pyridine, furfural, acetophenone and DMF(N, N- dimethylformamide), the second solvent is selected to wash and crystallize the binary mixture of anthracene and carbazole to prepare refined anthracene, and the filtrate can be recycled to obtain 80-90 wt% carbazole. Generally, after twice washing and crystallization, the purity of anthracene can reach above 89 wt%. Distillation-solvent vacuum distillation and heavy benzene washing crystallization: this coupled continuous method first adopts vacuum distillation, because the boiling points of anthracene and phenanthrene are almost the same, and the boiling points of carbazole are quite different from them. Using this characteristic, the anthracene-phenanthrene mixed fraction was cut by distillation, in which the carbazole content was only about 3%, and then the anthracene-phenanthrene fraction was washed once with benzene solvent to prepare refined anthracene with purity over 90%. Moreover, through vacuum distillation, the content of anthracene in the cut anthracene phenanthrene fraction can reach about 48%, which is obviously higher than that of atmospheric distillation, and the yield of anthracene and phenanthrene is also much higher than that of atmospheric distillation. Compared with the simple solvent method, this method can greatly reduce the amount of solvent and improve the product yield. Vacuum distillation of crude anthracene-acetophenone washing crystallization method: its technological process mainly includes distillation and solvent washing crystallization system: firstly, crude anthracene is heated and melted to 65438 050℃ and fed from the middle of the distillation tower, crude phenanthrene is at the top of the tower, semi-refined anthracene is separated from the 52nd tower plate, containing about 55% anthracene, and crude carbazole is extracted from the third tower plate, containing about 55% carbazole; Then, the semi-refined anthracene and acetophenone at 120℃ were mixed according to the ratio of1:1.5 ~1:2 (w/w), added to a scrubber, and finally sent to a crystallizer for cooling to 60℃ to obtain refined anthracene with a purity of 96%. The process has large production capacity, and can simultaneously separate and purify the three main components in crude anthracene, thus realizing industrialization. Solvent washing crystallization of anthracene oil-refined anthracene-recrystallization method: In this process, refined anthracene or semi-refined anthracene is mixed with solvent according to the ratio of 1:0.5~ 1:0.75 before rectification, and then anthracene is separated from the top of the tower as a part of the product, and then cooled and crystallized to obtain anthracene. Using solvent can reduce energy consumption, increase relative volatility, and then improve refining effect. According to calculation, this separation method only needs a few theoretical trays, which greatly reduces energy consumption and cost. Chemical method Chemical method utilizes the different reactivity of anthracene, phenanthrene, carbazole and some substances in crude anthracene to separate anthracene from other substances, and generally can recover carbazole and phenanthrene. Potassium hydroxide method: the most mature process in chemical method is potassium hydroxide method. N atom is attached to the benzene ring of carbazole molecule, which has strong activity and can react with some inorganic bases. Carbazole in crude anthracene can react with KOH to form salt, and the hydrogen on nitrogen atom of carbazole heterocyclic ring can be replaced by KOH under thermal conditions, and carbazole potassium and water can be obtained by reaction. Sulfuric acid method: Carbazole can react with concentrated sulfuric acid at room temperature to produce carbazole sulfate. Emulsion liquid membrane is a fast, efficient and energy-saving separation technology. The emulsion liquid membrane system is actually a highly dispersed system of oil-in-water (W/O/W) or water-in-oil (O/W/O), which has a large specific mass transfer surface area, thus showing a good mass transfer separation effect. Liquid membrane separation process can realize extraction and back extraction at the same time. Emulsion liquid membrane has the advantages of high efficiency and low energy consumption, and it has developed rapidly in the fields of wastewater treatment and organic matter separation. Zone melting zone melting is a separation technique. When each component is in a molten state, different distribution intervals are used. It is realized by using different concentration distributions between substances in molten state. When the melting zone moves forward, more impurities are concentrated in the solidified part behind it. At the end of the operation, the solidified impurities at the back end are cut off, and after repeated operations, a high degree of purification can be achieved. Composite method This method is characterized by using various chemical unit operations to purify anthracene, including solvent extraction, distillation, chemical reaction, crystallization, sublimation and so on. To produce refined anthracene. There is no substantial technological innovation in this method, but the purity of anthracene can be improved as much as possible and industrial production can be realized through reasonable collocation and mutual supplement of unit operations. The purity of refined anthracene, carbazole and phenanthrene can reach 99%, 96% and 96% respectively. The problem to be solved in the large-scale popularization of this process is how to reduce the cost and pollution as much as possible under the complicated process flow. Application At present, that most widely use of anthracene is to prepare anthraquinone. Anthraquinone is an important basic chemical material and dye intermediate. Various types of anthraquinone dye intermediates can be prepared through various substitution reactions, which greatly opens up the development of dye industry. Anthraquinone is also used in papermaking, preparation of cooking AIDS and production of sodium anthraquinone disulfonate (ADA). Anthraquinone and its derivatives have certain effects on the treatment of tumors, while polychloroanthraquinone has certain applications in pesticides and fungicides. In recent years, it has been found that anthraquinone can accelerate the separation of cellulose from wood, increase the yield of cellulose by 3-5% and shorten the cooking time by 30%, thus opening up a new field with great application prospects for anthraquinone. Anthraquinone has been popularized in Japan, the United States, Canada, Northern Europe and other countries and regions. High purity anthracene (above 99.99%) can be used to prepare single crystal anthracene, which can be used as luminescent material (such as scintillation counter). Anthracene crystal has the highest luminous efficiency among all scintillators, so it is often used as a standard substance to compare the luminous efficiency of other scintillators. Adducts of anthracene and magnesium can be used as special catalysts. Anthracene can also be used as monomer raw materials for many compounds, which has a wide range of applications in chemical industry. Toxicity introduces the ways of health hazards: inhalation, ingestion and percutaneous absorption. Health hazards: Pure products are basically non-toxic. Because industrial products contain impurities such as phenanthrene and carbazole, the toxicity is obviously increased. Because the vapor pressure of this product is very low, the possibility of inhalation poisoning is very small. * * On the skin and mucous membrane; It is easy to cause photosensitive dermatitis. It has been listed as the first batch of substances of very high concern by ECHA. Toxicological data and environmental behavior anthracene toxicity: mild toxicity. Acute toxicity: LD50430mg/kg (intravenous injection in mice), subacute and chronic toxicity: 500mg/kg/ day ×7 days of mice110 died, and physical growth slowed down; After 33 months of oral administration of 6mg/ day, 9/3 1 rat died and no tumor was found. Rats died subcutaneous at 5mg/ week ×4 months, 1/5. * * * Sex: rabbit eyes: 250μg, severe * * *. Rabbit percutaneous: 10mg(24 hours), mild * * *. Carcinogenicity: The lowest oral toxic dose of rats (TDL 0): 18g/kg (78 weeks, intermittent), which is carcinogenic. Migration in the environment Some experiments have proved the biodegradability of polycyclic aromatic hydrocarbons (PAHs). Naphthalene, acenaphthene, acenaphthene and other low molecular weight polycyclic aromatic hydrocarbons can be rapidly degraded in experimental research. When the initial concentration is 5 ~ 10 mg/L, more than 90% of PAHs are biodegraded within 7 days. High molecular weight polycyclic aromatic hydrocarbons such as fluoranthene, benzo (a) anthracene, pyrene, benzo (a) pyrene and anthracene are difficult to biodegrade. Hazard characteristics: flammable in case of open fire and high heat. Can react strongly with oxidant. Combustion (decomposition) products: carbon monoxide, carbon dioxide and carbon. Emergency treatment 1. Emergency treatment of leakage shall isolate the leakage contaminated area and set warning signs around it. It is suggested that emergency personnel wear masks and corresponding work clothes. Don't touch the leakage directly, avoid dust, carefully sweep it up, put it in a bag and transfer it to a safe place. Such as a large number of leaks, collected and recycled or discarded after harmless treatment. Second, protective measures respiratory protection: wear a mask when you may come into contact with poisons. Eye protection: generally no special protection is needed. Protective clothing: wear work clothes. Minimize direct contact. Hand protection: Wear protective gloves. Others: Take a shower and change clothes after work. Maintain good hygiene habits. Third, first aid measures skin contact: take off contaminated clothes and rinse thoroughly with a lot of running water. Eye contact: lift the eyelid immediately and rinse with running water. Inhalation: Leave the site and go to a place with fresh air. Give artificial respiration if necessary. See a doctor. Ingestion: gargle, drink water, and see a doctor if you take it by mistake. Fire extinguishing methods: misty water, carbon dioxide, sand and foam.