Sparged anthracene oxidation method gas-phase fixed bed oxidation method: Add refined anthracene into the gasification chamber, heat and vaporize it, and then mix it with air. The ratio of the two is 1: (50~100). The mixed gas enters the oxidation chamber and is oxidized under the catalysis of V2O5 at (389±2) ℃. The product is obtained after thin-wall condensation.
Liquid phase oxidation method: Add the refined anthracene to the reaction kettle after measuring it, then add trichlorobenzene and dissolve it under stirring. Then add nitric acid dropwise, control the reaction temperature to 105-110°C, and eliminate the by-product NO. After reacting for 6-8 hours, the solvent is evaporated under reduced pressure and cooled for crystallization. Get the product. This method severely corrodes the equipment. Phthalic anhydride method: Add phthalic anhydride into the reaction kettle after measuring it, add benzene and heat to melt while stirring. Heating to 370 ~ 470 ℃, the mixed gas passes through the silicon-alumina catalyst for gas phase condensation. Get the product. Carboxyl synthesis method: Add a measured amount of benzene to the reaction kettle, pass CO at 4.88 MPa, and react at 200°C for 4 hours until the CO pressure no longer drops and the reaction ends. processed products.
Basic information on anthraquinone Chinese name: Anthraquinone Chinese synonyms: anthraquinone; 9,10-anthraquinone; 9,10-anthrone; enquinone; 9,10-dihydroanthracene-9,10-dione; 9,10 -Dioxanthracene; 9,10-anthracenedione, 97%; English name: Anthraquinone English synonyms: MORKIT;9,10(9H,10H)-anthracenedione;9,10-Anthracenedione;9,10-anthracenequinone;9, 10-Anthrachinon;9,10-dihydro-9,10-dioxo-anthracen;Anthra-9,10-quinone;Anthracene, 9,10-dihydro-9,10-dioxo- CAS number: 84-65-1 Molecular formula: C14H8O2 Molecular weight: 208.21 EINECS number: 201-549-0 Related categories: Chemical additives; Papermaking chemicals; Chemicals for pulping processes; Intermediates of Dyes and Pigments; Chloroanthraquine, etc.; Anthraquinones; AM to AQCarbonyl Compounds; A; Alphabetic;C13 to C14;Carbonyl Compounds;Ketones;AM to AQPesticides&Metabolites;A-BAlphabetic;Alpha sort;Others;Pesticides;Pesticides&Metabolites Mol file: 84-65-1.mol Anthraquinone Properties Melting point 284-286 °C (lit.) Boiling point 379-381 °C(lit.) Density 1.438 Vapor density 7.16 (vs air) Vapor pressure 1 mm Hg (190 °C) Flash point 365 °F Water solubility <0.1 g/100 mL at 23 ºC Merck 14,687 BRN 390030 Stable. Incompatible with strong oxidizing agents. Combustible. CAS Database 84-65-1 (CAS DataBase Reference) NIST Chemical Substance Information 9,10-Anthraquinone(84-65-1) EPA Chemical Substance Information 9,10- Anthracenedione(84-65-1) Safety Information Dangerous Goods Mark Xi Hazard Class Code 43-36/37/38 Safety Instructions 36/37-37/39-26-24 WGK Germany 1 RTECS No. CB4725000 Toxic Substance Data 84-65- 1(Hazardous Substances Data) MSDS Information Provider Language ACROS English SigmaAldrich English ALFA Chinese ALFA English Anthraquinone Usage and Synthesis Method Chemical Properties Yellow needle crystal. Soluble in ethanol, ether and acetone, insoluble in water. Usage: Used as dye intermediate, papermaking cooking agent and hydrogen peroxide raw material, etc. Usage: Used as papermaking and pulping cooking auxiliary, which can reduce the amount of alkali and shorten the cooking time. Uses Most of anthraquinones are used in dyes, but the amount used as a steaming aid for paper pulp has increased rapidly.
(1) For the production of dyes, anthraquinone is used as raw material. After sulfonation, chlorination, nitration, etc., a wide range of dye intermediates can be obtained, which can be used to produce anthraquinone-based disperse dyes, acid dyes, vat dyes, and reaction dyes. Dyes, etc., forming a dye category with full chromatography and good performance. According to statistics, there are more than 400 varieties of anthraquinone dyes, which occupy a very important position in the field of synthetic dyes. (2) Used as cooking agent for papermaking and pulping. Only a small amount of anthraquinone is added to the alkaline cooking liquid to speed up delignification, shorten cooking time, increase pulp yield, and reduce waste liquid load. . The consumption of anthraquinones as cooking additives is growing rapidly. Anthraquinones have other applications. Anthraquinone compounds can be used to produce high-concentration hydrogen peroxide; in the fertilizer industry, they are used to manufacture the desulfurizing agent anthraquinone disulfonate sodium. Used as dye discharge auxiliary in printing and dyeing industry. Production method Before World War I, the output of anthraquinone was very small, and there was only one production method that used sodium dichromate to oxidize anthracene to anthraquinone. The gas-phase catalytic oxidation method of anthracene was developed in the 1940s. The phthalic anhydride method is widely used in the United States. The naphthoquinone method and the styrene method were also developed. 1. Anthracene gas-phase catalytic oxidation method The anthracene oxidation method uses refined anthracene as the raw material, air as the oxidant, and vanadium pentoxide as the catalyst to perform gas-phase catalytic oxidation. The reactors have two types: fixed bed and sulfurized bed. Most anthraquinone production plants in my country use fixed-bed reactors, using refined anthracene with a content of more than 90%. After melting, hot air at about 300°C is used to bring out the vaporized refined anthracene at a flow rate of 1560 cubic meters/h. After mixing in the hot air duct Through the fixed-bed catalytic oxidation tube reactor, the total yield reaches 80%-85%. Raw material consumption quota: refined anthracene (90%) 1260kg/t. Refined anthracene, the raw material used for oxidized anthraquinone, comes from coal tar distillation and does not contain inorganic ions. In the production process of oxidized anthraquinone, distillation and gas-phase catalytic oxidation are mainly used. There is no waste water and gas, and no chloride ions, sulfate ions, iron ions, etc. are produced. Therefore, oxidized anthraquinone has a competitive advantage in being used as a high-end dye. The disadvantage is that the raw material refined anthracene is restricted by coal tar products. 2. Phthalic anhydride method: Use phthalic anhydride and benzene as raw materials, aluminum trichloride as catalyst, conduct Friedel-Crafts reaction, and then use concentrated sulfuric acid to dehydrate to generate anthraquinone. The phthalic anhydride method is divided into solvent method, ball milling method and gas phase condensation method. Most of our countries use the solvent method, which uses excess benzene as the solvent. The raw materials of this method are easily available and can be made from petroleum. It has the advantages of low reaction temperature, simple equipment, and few side reactions. The disadvantages are serious pollution, aluminum trichloride waste acid water is difficult to treat, and the production cost is high. The phthalic anhydride method is used for the synthesis of anthraquinone in my country. Raw material consumption quota: phthalic anhydride 768kg/t, pure benzene 700kg/t, sulfuric acid (98%) 1364kg/t, aluminum trichloride 1554kg/t, oleum 1000kg/t. 3. The naphthoquinone method uses naphthoquinone and butadiene as raw materials, uses cuprous chloride as the catalyst, performs condensation reaction and dehydrogenation to obtain anthraquinone. Due to the rapid development of petrochemical industry, a large amount of raw materials butadiene and naphthoquinone used in this method are provided. This method has the advantages of low consumption and less three wastes. In Japan and the United States, the naphthoquinone method has reached a considerable scale and has a promising future. Japan's Kawasaki Company uses this method to produce. Our country's scientific research department has conducted a lot of research. Although both small and Chinese styles have been successful, they have not been produced industrially. The disadvantages of this method are that the prices of naphthoquinone and butadiene themselves are relatively high. Due to insufficient research on reaction kinetics, the catalyst performance is poor, bed heating often occurs, and the operating flexibility is low. 4. Styrene method: Styrene is first dimerized, then oxidized to o-benzoyl benzoic acid, and then cyclized to synthesize anthraquinone. The advantages of this method are that the raw materials are easily available, there are no pollution problems caused by the aluminum salt wastewater of the phthalic anhydride method, and the product cost is low. However, the reaction conditions are harsh, the technology is complex, and the equipment requirements are high. It is a new achievement of BASF research in Germany. In addition, Mitsui Chemical Company of Japan obtained a patent for the preparation of anthraquinone using toluene as raw material. Because the process is simple and the raw materials are cheap, it has attracted people's attention. Production method: Refined anthracene oxidation method Gas phase fixed bed oxidation method Add refined anthracene to the gasification chamber, heat and vaporize it, then mix it with air. The ratio of the two is 1: (50~100). The mixed gas enters the oxidation chamber and is oxidized under the catalysis of V2O5 at (389±2) ℃. The product is obtained after thin-wall condensation. Liquid phase oxidation method: Add the refined anthracene to the reaction kettle after measuring it, then add trichlorobenzene and dissolve it under stirring. Then add nitric acid dropwise, control the reaction temperature to 105-110°C, and eliminate the by-product NO. After reacting for 6-8 hours, the solvent is evaporated under reduced pressure and cooled for crystallization. Get the product. This method severely corrodes the equipment.
Phthalic anhydride method: Measure phthalic anhydride and add it to the reaction kettle, add benzene and heat to melt while stirring. Heating to 370 ~ 470 ℃, the mixed gas passes through the silicon-alumina catalyst for gas phase condensation. Get the product. Carboxyl synthesis method: Add a measured amount of benzene to the reaction kettle, pass CO at 4.88 MPa, and react at 200°C for 4 hours until the CO pressure no longer drops and the reaction ends. processed products. Category Pesticide toxicity classification Low toxicity Acute toxicity Oral - mouse LD50: 5000 mg/kg; Oral - rat LDL0: 15000 mg/kg Flammability Hazardous characteristics Combustible at high temperatures and open flames; Combustion produces irritating smoke Storage and transportation characteristics Warehouse ventilation Low temperature drying fire extinguishing agent Dry powder, foam, carbon dioxide, mist water occupational standard STEL 5 mg/cubic meter anthraquinone upstream and downstream product information upstream raw material sulfuric acid-->benzene-->aluminum trichloride-->phthalic anhydride-->sodium dichromate-- >Carbon monoxide-->styrene-->nicotinic acid-->tar-->vanadium pentoxide-->anthracene-->trichlorobenzene-->silicon-aluminum-->refined anthracene-->downstream of anthraquinone oxide Product Hydroperoxide-->1-Aminoanthraquinone-->Benzanthrone-->2-Bromoanthraquinone-->Reduced Green 3-->Disperse Blue 56-->1-Chloroanthraquinone--> Anthrone-->1,5-dinitroanthraquinone-->1,2-dihydroxyanthraquinone-->ethyl n-hexanoate-->Direct light fast green 5GLL-->1-anthraquinone sulfonic acid- ->2,6-Diaminoanthraquinone-->1,8-dinitroanthraquinone-->9,10-dimethylanthracene-->Anthraquinone-1,5-disulfonic acid-->1 ,5-Diaminoanthraquinone-->2-anthraquinonesulfonic acid-->2,3-dimethylanthraquinone-->1,5-dichloroanthraquinone-->1,4,5,8- Tetrachloroanthraquinone