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WO2004052833A1 - Procede de preparation d'aniline, de phenol et leurs derives - Google Patents

Procede de preparation d'aniline, de phenol et leurs derives Download PDF

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WO2004052833A1
WO2004052833A1 PCT/CN2003/000134 CN0300134W WO2004052833A1 WO 2004052833 A1 WO2004052833 A1 WO 2004052833A1 CN 0300134 W CN0300134 W CN 0300134W WO 2004052833 A1 WO2004052833 A1 WO 2004052833A1
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metal
aniline
phenol
preparing
derivatives
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Hesheng Zhai
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/02—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings

Definitions

  • the invention belongs to a method for preparing aniline, phenol and its derivatives.
  • Aniline commonly known as Alini oil, is a colorless oily liquid. Aniline is one of the important organic chemical raw materials. The United States, Western Europe, and Japan are the major consumers and regions of aniline in the world, accounting for about 80% of total world consumption. Among these countries and regions, MDI consumption ranks first, accounting for about 80% of total consumption. MDI is one of the raw materials for polyurethane production. Aniline can also be used to prepare rubber additives (about 11% of aniline consumption), dyes and organic pigments
  • aniline can also be used in industrial fields such as pesticides, medicines and special fibers.
  • aniline production processes include reduction of nifediphenone powder, halogenated benzene nitridation, phenol nitridation, and nitrobenzene catalytic hydrogenation.
  • the nitrobenzene iron powder reduction method is the earliest industrial production method and has been basically eliminated; the halogenated benzene ammoniation method is rarely chosen in practice.
  • aniline production mainly uses phenol amination method and nitrobenzene catalytic hydrogenation method.
  • the advantages of the phenol ammoniation method are simple raw materials, cheap catalysts, good product quality, and low three wastes. It is suitable for large-scale continuous production and can co-produce diphenylamine as required, but the cost is higher than the nitrobenzene hydrogenation method. 'At present, only Aristech in the United States uses this method to produce aniline.
  • Nitrobenzene hydrogenation reduction method to prepare aniline is currently the most used method by major manufacturers in the world. According to the characteristics of the reaction, it is divided into two types: gas phase hydrogenation and liquid phase hydrogenation.
  • the liquid-phase hydrogenation yield is high, the production capacity is large, and the side reactions are small, but the solvent recovery of the catalyst is difficult, the operation is complicated, and the equipment cost is high.
  • the gas-phase hydrogenation method is divided into a fixed-bed gas-phase hydrogenation process and a fluidized-bed gas-phase hydrogenation process. Fixed-bed gas-phase catalytic hydrogenation technology is mature, equipment and operation are simple, maintenance costs are low, and production quality is high. The disadvantage is that local overheating is prone to cause side reactions and catalyst deactivation, and the catalyst must be replaced regularly.
  • Fluidized bed gas-phase catalytic hydrogenation better controls the reaction temperature, avoids local overheating, and reduces side reactions. Disadvantages of this process are that the operation is complicated, the catalyst is worn, the reactor structure is complicated, and the catalyst needs to be separated, resulting in high operation maintenance costs.
  • This technology uses Ni / Ni0 / Zr0 2 as "Cataloreactant", which is reduced during the reaction, but can be reoxidized to regenerate.
  • the process has an aniline yield of 12%, but requires pressures as high as 7000 psi, which hinders its commercial prospects.
  • Phenol is an important chemical raw material.
  • phenol is mainly synthesized by sulfonation method, Laxi-Hooker method, chlorobenzene hydrolysis method, cyclohexane method and cumene method at home and abroad.
  • These multi-step synthesis methods have problems such as multiple reaction steps, complicated processes, low overall yield, and severe equipment corrosion. Since the 1960s, various countries have committed to one-step synthesis of benzene The development and research of phenol has achieved certain results.
  • the proposed methods include gas-solid-liquid phase method using N 2 0 as oxidant and Fe-ZSM-5 as catalyst; Ti-Si-Pd as catalyst and 0 2 -3 ⁇ 4 as oxidant; Electrochemical synthesis of 0 2 H 2 fuel cell reaction; gas-solid phase method with Fe-Cu-0 / sepiolite as catalyst, hydrogen peroxide as hydroxylating agent, and PdCl 2 -CuCl 2 / sepiolite as catalyst Liquid-solid phase method for phenol.
  • the purpose of the present invention is to provide a method for preparing aniline, phenol and its derivatives, especially a method for preparing aniline and its derivatives, a method for preparing phenol and its derivatives, and a method for co-producing aniline and phenol and its derivatives. method.
  • the purpose of the present invention is achieved in such a way that the preparation method of aniline, phenol and its derivatives uses a new synthetic aniline, phenol and its derivatives, and a synthetic method for co-production of aniline and phenol and its derivatives.
  • New processes. The process includes the following steps:
  • step 1) the formed bromobenzene or substituted bromobenzene derivative reacts with metal oxide and / or metal hydroxide and ammonia or ammonia water to form aniline and metal bromide or ammonia complex Metal bromide.
  • the brominated benzene and its derivatives obtained in step 1) react with metal oxides and water to form corresponding phenol or phenol derivatives and metal bromides.
  • the bromobenzene and its derivatives are reacted with ammonia or ammonium carbonate or ammonium bicarbonate solution and metal oxides or / and metal hydroxides to form a mixture of aniline or aniline derivatives and phenol or phenol derivatives
  • Metal bromide and ammonia-complexed metal bromide are formed during the reaction.
  • step 2) The ammonia-complexed metal bromide generated in step 2) is decomposed into metal bromide and ammonia under heating conditions to recover ammonia.
  • the metal bromide generated here and the metal bromide generated in step 2) are burned at high temperature in oxygen or air to generate metal oxides and bromine to recover bromine and metal oxides.
  • the net result of the whole process is the synthesis of aniline or aniline derivatives from benzene or benzene derivatives, ammonia, oxygen (or oxygen in the air), and the by-product is water.
  • the by-product is water.
  • benzene or a benzene derivative water, oxygen (or oxygen in the air) are used to synthesize phenol or a phenol derivative.
  • bromine and metal oxides are recycled and are not consumed and there is no environmental pollution.
  • step 1) the conversion rate of benzene per pass in step 1) is more than 30%, the selectivity to bromobenzene is above 97%, and the single pass conversion of bromine reaches 100%.
  • step 2) the conversion rate of bromobenzene is more than 95%, the selectivity of aniline is more than 95%, and the by-product is benzene (return to step 1) for reuse).
  • the recovery rate of Br 2 is more than 99%.
  • the above common benzene and benzene substitutes react with bromine under the action of a catalyst to form a bromination reaction of bromobenzene and a derivative of bromobenzene and HBr, in which hydrogen bromide HBr can be oxidized to recover bromine; Heterogeneous catalytic reactions can also be homogeneous catalytic reactions.
  • the reaction of benzene or a benzene derivative with bromine may be a continuous operation reaction or a batch reaction in a kettle type, and the reaction may be a simultaneous feeding of benzene or a benzene derivative and bromine, or a One after the other, or one reactant is added at a time, and the other reactant is added in batches or continuously.
  • the reaction can be performed between -40 ° C to 55CTC.
  • the preferred operating temperature is -20 ° C to 450 ° C, the best operating temperature is -20 ° C to 300 Torr, the reaction pressure is between 0.1 atmospheres and 300 atmospheres, and the preferred pressure range is between 0.5 atmospheres and 200 atmospheres, preferably Between 0.8 atmospheres and 50 atmospheres.
  • the substituted benzene is selected from the group consisting of chloro, fluoro, Brominated phenyl, fluorenyl, alkenyl, alkynyl, nitro, sulfo, phenol, thiophenol, and aniline.
  • the catalysts are metal oxides, metal chlorides, metal fluorides, metal iodides, metal sulfates, metal phosphates, metal heteropolyacids, BF 3 , metals other than iron powder, and the compounds listed above. Any proportion of the mixture, and the catalyst iron powder is currently used as a commonly used catalyst in the bromination reaction, but no document has been disclosed such as: metal oxide, metal chloride, metal fluoride, metal iodide, metal sulfate , metal phosphates, metal heteropoly acid salt, BF 3, in addition to metal iron, and any of these catalysts the mixture ratio of the compounds.
  • the catalyst may be a homogeneous catalyst or a heterogeneous catalyst.
  • the catalyst may be a supported catalyst or an unsupported catalyst.
  • the supported catalyst contains an active phase of a mixture of one or more metal compounds and a support.
  • the carrier refers to at least one metal compound or non-metal or non-metal selected from the group consisting of Si0 2 , B 2 0 3 , A1, Ge0 2 , Ti0 2 , Zr0 2 , Nb 2 0s, T 0 5 , activated carbon, and the like. Compounds.
  • the active phase of the catalyst is Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Tx, Hf, V, Nb, Ta, Gr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La, Sm, Ce, Tb, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, Gd oxides, fluorides, chlorides, bromides, iodides, oxalates, sulfates, carbonates, silicates, borates, and mixtures thereof or their mixtures with Ru, Rh , Pd, Ir, Pt, Ag, Au and other metal and metal compound mixtures.
  • the bromination reaction of the present invention can use: metal oxide, metal chloride, metal fluoride, metal iodide, metal sulfate, metal phosphate, metal heteropoly acid salt, BF 3 , metal other than iron powder, and These catalysts in any ratio mixture of the above compounds can be carried out using the current general bromination reaction conditions and methods. The results obtained are similar to those of the iron powder catalysts for bromide, and all of them can obtain brominated benzene or brominated groups containing various substituents. benzene.
  • the method for preparing aniline and its derivatives according to the present invention comprises the following steps:
  • step 1) The bromobenzene and derivative formed in step 1) are reacted with N or (N) 2 C0 3 or NH 4 HC0 3 or organic primary or secondary amines and metal oxides and / or metal hydroxides to form aniline or aniline Derivatives that simultaneously form metal bromide, ammonia or amine complexed metal bromide.
  • Step 1) has been described above.
  • Step 2 The reaction of bromobenzene and its derivatives with N3 ⁇ 4 or (N) 2 C0 3 or NH 4 HC0 3 or organic primary or secondary amines with metal oxides and / or metal hydroxides may further help Agents or supported metal oxides react to form aniline or aniline derivatives, while forming metal bromide, ammonia or amine complexed metal bromide.
  • Step 1) The produced product can be separated by distillation to separate the product bromobenzene or bromobenzene substitute, HBr and the reactant benzene or benzene derivative which has not completely reacted; the benzene or benzene derivative is returned to the bromination step for use, HBr It is sent to the bromine regeneration reactor for oxidation and regeneration to bromine, and bromobenzene or bromobenzene derivative is used in step 2) to synthesize aniline or aniline derivative.
  • the reaction in step 2) may be a continuous operation of feeding or a batch operation. The order of feeding may be arbitrarily changed and is not limited to a certain order.
  • Bromobenzene and bromobenzene substitutes can simultaneously react with N or nitrogen derivatives (primary or secondary amines) or (N) m, or NftHC0 3 , and metal oxides and / or metal hydroxides, or It is bromobenzene and its substitutes that react with NH 3 or amine first, and then the reaction mixture with metal oxide.
  • Step 2) Pure bromobenzene and bromobenzene derivatives may be used, or a solution thereof may be used.
  • the ammonia or organic amines are ammonia or organic amines themselves or their carbonates, and other salts which can be decomposed to produce ammonia or amines upon heating.
  • ammonia or at least one organic amine selected from primary and secondary amines can be used, and their solutions can also be used as reactants.
  • the ammonia derivatives refer to all primary amines and secondary amines and organic amine compounds having one hydrogen atom and one hydrogen atom or more on the nitrogen atom.
  • N3 ⁇ 4 can also be replaced by (N) 2 (: 0 3 or N HCCVf3 ⁇ 4) which can be decomposed into N3 ⁇ 4.
  • the metal oxide and metal hydroxide refer to Li, Na, K, Rb, Cs, Mg, Ca, Sr , Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Ws Yb, Mn, Re, Ho, Oxides or / and hydroxides of Sc, Y, La, Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, Gd, and their oxides and / or hydrogen A mixture of oxides.
  • metal oxide It is added to the metal oxide and its role is to make the reaction of bromobenzene and its substitutes with ammonia or amine and the active metal oxide easier, and it is similar to the catalytic effect or the formed metal bromide is oxidized to form metal
  • the oxide process is easier to perform, and those metals, metal salts, metal oxides, and metal hydroxides that are more thorough in the recovery of bromine elemental substances.
  • the specific additives refer to: Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, V, Cr, Mn , Sc, Y, La, Sm, Tb, Ce, Fe, Co, Ni, Cu, Zn, Cd, Tm, Yb, Ru, Pr, Dy, Ho, Nd, Eu, Gd, Ag sulfate, phosphate , Carbonate, fluoride, chloride, bromide, iodide, silicate, borate, aluminosilicate, phosphomolybdate, phosphotungstate, their oxides, hydroxides , And mixtures of the above compounds.
  • the metal additives are Rh, Pd, Ir, Pt, and Au, and mixtures thereof.
  • some metal oxides or carriers can function as active metal oxides, and can also function as carriers to prevent metal oxide and bromide crystal grains from growing. Large to ensure the high activity and reproducibility of the metal oxide active component, they are at least one selected from Ti0 2 , B 2 0 3 , Zr0 2 , Hf0 2 , Nb 2 0 5 , Ta 2 0 5 , Mo0 3 , W0 3 , Si0 2 , Ce0 2 .
  • Load of said metal oxide carrier is selected from Ti0 2, Zr0 2, hops, Nb 2 0 s, Ta 2 0 5, Mo0 3, W0 3, Ce0 2, Si0 2, Ge02, B 2 0 3, AO ⁇ Activated carbon and their mixtures.
  • the reaction temperature is from 50 ° C to 45CTC, preferably 80 ° C to 400 ° C, and most preferably 100 ° C to 350 ° C.
  • the reaction pressure is from 0.1 atmospheres to 400 atmospheres, and a preferred pressure range is from 0.5 atmospheres to 350 atmospheres, and most preferably from 1 atmosphere to 300 atmospheres.
  • Each of the reactants in step 2) reacts according to a chemical reaction measurement coefficient, but the amount of a certain reactant may be appropriately larger.
  • the metal oxides and metal hydroxides are also used in the reaction.
  • a reactant it is a special reactant that participates in the reaction as a catalytic reactant, and the amount is supplied according to the chemical reaction stoichiometric coefficient, not a small amount, it is a reactant with a catalytic effect, that is, it participates in the reaction itself.
  • Metal ammonia or amine complex and other metal compound solid phases are separated by distillation to separate organic products and unreacted reactants.
  • Step 2) The liquid phase generated after the reaction can be used to separate the product aniline and its derivative, the reactant, and water by distillation.
  • Step 2) The generated solid phase can be recovered by heating with water vapor purging N3 ⁇ 4, adsorbed aniline or aniline derivatives, incompletely reacted reactants benzene, benzene derivatives and water; these purged desorbed substances are Combined into a distillation column for separation; the recovered NH 3 can be reused, and the recovered benzene and benzene derivatives can be reused; finally, inorganic compounds remain.
  • Metal oxides and metal hydroxides can be prepared by one of the following methods: 1) Co-precipitation method of metal salts; 2) Thermal decomposition of metal salt mixtures, or immersion of metal salts, including active metal oxidation
  • the precursors of the compounds, hydroxides, and auxiliaries are supported on the carrier, and then dried and thermally decomposed to produce the target oxide or hydroxide.
  • different methods may be used to dry the precursor, and the pyrolysis in high-temperature air or oxygen; these processes include the above-mentioned content, but are not limited to the above-mentioned range.
  • the amount of auxiliary agent in step 2) accounted for 0.01% / of the total weight of the entire reactant. ⁇ 10%.
  • the ratio of the amount of the support to the reactant metal oxide or / and the metal hydroxide is any ratio, that is, 1:99 or 99: 1; the ratio of the amount of the support to the auxiliary agent is arbitrary, that is, 1:99 or 99: 1, preferably 1: 0. 1 ⁇ 10.
  • the method for preparing phenol and its derivatives according to the present invention includes the following steps:
  • Step 1) The formed bromobenzene and its derivative are reacted with water and metal oxide or / and metal hydroxide to form phenol or phenol derivative and metal bromide.
  • Step 1) has been described above.
  • the bromobenzene and its derivatives in step 2) react with water and metal oxides and / or metal hydroxides, and further react with metal oxides, hydroxides and auxiliaries supported by the carrier to generate phenol or phenol derivative Substances and metal bromides.
  • the reaction may be a continuous operation of feeding or a batch operation. The order of feeding may be arbitrarily changed and is not limited to a certain order.
  • Metal oxide in step 2) or / And metal hydroxides refer to Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Zr , Hf, V, Nb, Ta, Cr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La, Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn, Cd, Pr, Nd , Eu, Gd oxides and / or hydroxides, and mixtures thereof, and their mixtures with SiO 2 , B 2 0 3 . Pure bromobenzene, bromobenzene derivatives, or their solutions can be used.
  • the auxiliaries are selected from metal oxides, hydroxides, and salts in 1) and 2), such as carbonates, phosphates, sulfates, chlorides, fluorides, bromides, and iodides of metals. , Ru, Rh, Pd, Ir, Pt, Ag, Au halides, oxides, hydroxides, their salts, and mixtures of the above metal non-metallic compounds, these additives accelerate the derivation of bromobenzene and bromobenzene Hydrolysate; among them auxiliary 1): Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, V, Cr , Mn, Sc, Y, La, Sm, Tb, Ce, Fe, Co, Ni, Cu, Zn, Cd, Tm, Yb, Ru, Pr, Dy, Ho, Nd, Eu, Gd, Ag sulfate, Phosphates
  • some metal oxides or carriers can function as active metal oxides, and can also function as carriers to prevent metal oxide and bromide crystal grains from growing.
  • they are at least one selected from the group consisting of Ti0 2 , B 2 0 3 , Zr0 2 , Hf0 2 , Nb 2 0 5 , Ta 2 0 5 , Mo0 3 , W0 3 ⁇ Si0 2 , Ce0 2 .
  • the carrier is selected from Ti0 2, Zr0 2, hops, Nb 2 0 5, T 0 5, Mo0 3, W0 3, Ce0 2, Si0 2, Sn0 2, Ge0 2, Bi 2 0 3 , A1 2 0 3 , activated carbon, and mixtures thereof.
  • the reaction temperature is from 50 ° C to 450, preferably 80 ° C to 400 ° C, and most preferably 100 ° C to 350 ° C.
  • the reaction pressure is from 0.1 atmospheres to 400 atmospheres, and the preferred pressure range is from 0.5 atmospheres to 350 atmospheres, and most preferably from 1 atmosphere to 300 atmospheres.
  • the reactants in step 2) react according to the chemical reaction measurement coefficient, but the amount of a certain reactant may be appropriately larger.
  • the metal oxide and metal hydroxide also act as reactants in the reaction, but it is a special reactant and participates in the reaction as a catalytic reactant. It is supplied according to the chemical reaction measurement coefficient, not a small amount, and it is a catalytic reagent, that is, it participates in the reaction itself.
  • Step 2) After the reaction, a mixture is obtained, and the unreacted bromobenzene or bromobenzene substitutes, phenol or phenol substitutes, and water are separated by distillation under reduced pressure, and the remainder is a metal bromide and an oxide complex. .
  • Some metal bromides can be oxidized back to metal oxides in air or oxygen.
  • These metal oxides or bromides are called actives; they may also exist as metal hydroxides in the reaction due to reaction with water; these Metals include Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, Dy, V, Cr, Yb, Tm, Mn, Sc, Y, La, Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu, Gd; oxides or hydroxides of these metals play the role of active species in the reaction .
  • Step 2) The resulting mixture can also be separated by spray drying.
  • Inorganic compounds are metal oxides and metal bromides; they are oxidized and regenerated into metal oxides and Br 2 in an oxidation reactor using oxygen or oxygen in the air.
  • Metal oxides and metal hydroxides can be prepared by one of the following methods: They can be prepared by coprecipitation of metal salts, or by thermal decomposition of a mixture of metal salts, or by impregnating metal salts on a carrier and then drying them. Then, it is thermally decomposed to make the target metal oxide or metal hydroxide.
  • the target metal oxide or metal hydroxide In the preparation process of the target metal oxide or metal hydroxide, different methods can be used to dry the precursor, including drying, vacuum drying, and pyrolysis in high-temperature air or oxygen or other special gases; these The process includes the scope of the claims, but is not limited to the scope of the claims. 01% ⁇ 10% ⁇
  • the amount of auxiliary agent in step 2) accounted for 0.01% ⁇ 10% of the total weight of the entire reactant.
  • the ratio of the amount of the support to the reactant metal oxide or / and the metal hydroxide is any ratio, that is, 1:99 or 99: 1; the ratio of the amount of the support to the auxiliary is any ratio, That is 1:99 or 99: 1, preferably 1: 0. 1 ⁇ 10.
  • the method for preparing the co-produced aniline, phenol and its derivatives according to the present invention comprises the following steps:
  • step 2) the bromobenzene and its derivatives generated in step 1) are reacted with ammonia or ammonium carbonate or an aqueous solution of ammonium hydrogen carbonate and a metal oxide or / and a metal hydroxide to form a mixture of aniline or an aniline derivative and phenol or a phenol derivative
  • Metal bromide and nitrogen-complexed metal bromide are generated during the reaction, and metal bromide and ammonia-complexed metal bromide are generated during the reaction.
  • Step 1) has been described above.
  • the bromobenzene and its derivatives in step 2) are reacted with ammonia water or ammonium carbonate or ammonium bicarbonate aqueous solution and metal oxides or metal hydroxides, and further supported by carrier-supported metal oxides, hydroxides and auxiliaries
  • the reaction proceeds to produce a mixture of aniline or an aniline derivative and phenol or a phenol derivative, and a metal bromide and an ammonia complexed metal bromide are formed during the reaction.
  • the reaction in step 2) can be a batch reaction or a continuous reaction, and the feeding and sequence of the reactants can be arbitrarily changed.
  • pure bromobenzene and bromobenzene derivatives may be used, or a solution thereof may be used.
  • Step 2) reaction of ammonia may also be replaced (N) 2 C0 3 or of aqueous NH 4 HC0 3.
  • Step 2) of the ammonia of the reactant wherein the ratio of ammonia to water can be any ratio, and high-concentration ammonia can be formulated under pressure, the ratio can be from 1:99 to 99: 1; the ratio will affect the amine and Phenol ratio;
  • the ammonia concentration can be determined according to the required ratio of aniline or aniline substitute to phenol or phenol substitute.
  • the metal oxide and metal hydroxide refer to Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi , Dy, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La, Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn Or Cd, Pr, Nd, Eu, Gd oxides and / or hydroxides, and mixtures of these oxides and hydroxides.
  • the auxiliaries refer to the sulfates, phosphates, carbonates, fluorides, chlorides, bromides, iodides, silicates, borates, aluminosilicates, and phosphorus molybdenum of the metals listed above. Acid salt, phosphotungstate.
  • the reaction temperature is from 50 ° C to 45 ° C, preferably 8 (TC to 400 ° C, preferably 10CTC to 350 ° C.
  • the reaction pressure is from 0.1 atmosphere to 400 atmospheres, preferably The pressure range is from 0.5 to 350 atmospheres, preferably from 1 to 300 atmospheres.
  • the reactants in step 2) react according to the chemical reaction stoichiometric coefficient, but the amount of a certain reactant may be more appropriate.
  • the metal oxide and metal hydroxide are also reactants in the reaction, but it is a special reactant and is used as Catalytic reactants participate in the reaction, and the amount is supplied according to the chemical reaction measurement coefficient, not a small amount, and it is a reactant with a catalytic effect, that is, it itself participates in the reaction.
  • Step 2) The product contains aniline (or aniline derivative), phenol (or phenol derivative), unreacted bromobenzene (bromobenzene derivative), ammonia, water, and metal compounds and carriers and auxiliary agents (inorganic substances) );
  • the product is spray-evaporated, and the gas phase is organic product, unreacted reactants and water, which can be separated through a fractionation column; the solid phase is metal oxide, metal hydroxide, metal bromide and carrier and auxiliary .
  • Aniline (or aniline derivative), phenol (or phenol derivative), unreacted bromobenzene (bromobenzene derivative), ammonia, water in the product can also be separated by distillation under reduced pressure, leaving inorganic solids Compounds.
  • the remaining inorganic solid compounds will be placed in a regeneration reactor to be oxidized to metal oxides and bromine for recycling in the process.
  • Inorganic solid compounds can also be oxidized and regenerated into metal oxides and bromine with oxygen or air oxygen in an oxidation regeneration reactor.
  • the above-mentioned preparation of "phenol and its derivatives" can be used.
  • the methods described in "Methods" are not limited to the methods described above. 01% ⁇ 10% ⁇
  • the amount of auxiliary agent in step 2) accounted for 0.01% ⁇ 10% of the total weight of the entire reactant.
  • the ratio of the amount of the support to the reactant metal oxide or / and the metal hydroxide is any ratio, that is, 1:99 or 99: 1; the ratio of the amount of the support to the auxiliary agent is arbitrary, that is, 1:99 or 99: 1, preferably 1
  • the present invention is that benzene and benzene containing various substituents are first reacted with bromine to obtain bromobenzene and bromobenzene containing various substituents. Then bromobenzene or bromobenzene containing various substituents is reacted with metal oxide and / or metal hydroxide to form aniline or Aniline derivatives with various substituents. It is also possible to react bromobenzene or bromobenzene containing various substituents with metal oxides and / or metal hydroxides and 0 to form phenol or phenol derivatives containing various substituents.
  • HBr is produced by the reaction, ⁇ ⁇ 1 ⁇ Budapestor / and M (N3 ⁇ 4) r tine, where m and n represent the number.
  • HBr is regenerated to Br 2 by catalytic oxidation with air or oxygen.
  • MBr ⁇ / and M (NH 3 ) m Br n are recovered by thermal decomposition before NH 3 is recovered.
  • the remaining MBr n is regenerated to metal oxides by oxygen or air oxidation.
  • Br 2 which can be recycled for subsequent processes.
  • X 2 represents a substituent such as hydrogen, chlorine, fluorine, bromine, phenyl, fluorenyl, alkenyl, alkynyl, nitro, transverse, phenol, thiophenol, aniline, etc.
  • ⁇ means Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Ge, Sn, Pb, Tm, Sb, Bi, Dy, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Yb, Mn, Re, Ho, Sc, Y, La Sm, Ce, Tb, Fe, Co, Ni, Cu, Zn, Cd, Pr, Nd, Eu , Gel and other metals, x represents the number of 0.
  • the net result is the consumption of benzene or benzene substitutes, ammonia, oxygen to generate aniline or aniline substitutes, water, water and aniline or aniline substitutes can be separated by distillation, where bromine and metal oxides can be recycled Use without environmental pollutants.
  • aniline aniline substitutes, phenol, and phenol substitutes
  • the reaction conditions were mild, and there were no by-products that were difficult to sell on the market (equivalent mols of acetone were produced in traditional phenol synthesis).
  • the raw materials used are low in price, and the traditional process for the synthesis of aniline uses expensive HN0 3 and hydrogen; in the traditional phenol synthesis, propylene is used and 0 2 and 0 are used here.
  • HN0 3 and hydrogen in the traditional phenol synthesis, propylene is used and 0 2 and 0 are used here.
  • the reaction there is no difficult to treat waste liquid.
  • concentrated sulfuric acid is used as a catalyst in the nitrification process, but the nitrification process generates water to dilute the sulfuric acid and cannot continue to function.
  • the present invention Compared with the existing methods for synthesizing aniline, the present invention has very prominent advantages: 1) extremely high benzene conversion rate (>95%); 2) extremely high aniline selectivity (>95%); 3) reaction The temperature is about 100 ° C-200 ⁇ , and the reaction pressure is about 1-80 atm. 4) The entire synthesis route consumes only benzene Nft and 0 2 , and other raw materials used can be recycled. Therefore, the present invention can also be regarded as a special method for synthesizing aniline by direct reaction of benzene, NH 3 and 02 ; 5) The biggest feature of the present invention is that aniline is obtained by reacting bromobenzene with N and metal oxide .
  • This reaction is a completely new one; 6)
  • the entire synthetic route is free of environmental pollution.
  • the invention uses bromobenzene to react with 0 and metal oxide to prepare phenol, which is a completely new reaction system.
  • the raw materials consumed in the entire synthesis route are only benzene, 0, and 0 2. All other raw materials involved can be recycled and reused.
  • the metal oxide can be repeatedly recycled and reused as in Example 5.
  • the metal oxide after seven regenerations is more active than the freshly prepared metal oxide. This indicates that the regeneration of the metal oxide involved in the synthetic route of the present invention is more favorable for the next reaction. That is, the reaction activity of the metal oxide is improved after regeneration.
  • CuO / Ti0 2 to CuO / Ti0 2 / Y 2 0 3 (molar ratio 10: 10: 1) prepared according to Example 2 to (: uO / Ti0 2 / AL0 3 (molar ratio 10: 10: 1)): ⁇ Cu0 ⁇ Y 2 0 3>Ni0> Co 2 0 3> Mn0 2 ⁇ La 2 0 3 ⁇ Bi 2 0 3 ⁇ Ca0 ⁇ Bao ⁇ Zn0 ⁇ Mo 2 0 3 ⁇ Cr 2 0 3 ⁇ Fe 2 0 3 ⁇ MgO
  • the present invention Compared with the existing methods for synthesizing aniline, the present invention has very prominent advantages: 1) extremely high benzene conversion rate (>95%); 2) extremely high aniline selectivity (>95%); 3) reaction The temperature is about 100 ⁇ -200 ⁇ , and the reaction pressure is about 1-80 atm. 4) The entire synthetic route only consumes benzene N and 0 2 , and other raw materials used can be recycled. Therefore, the present invention can also be regarded as a special method for synthesizing aniline by direct reaction of benzene, NH 3 and 02 ; 5) The biggest feature of the present invention is that aniline is prepared by reacting bromobenzene with Mk3 ⁇ 4 metal oxide.
  • This reaction is a completely new one; 6)
  • the entire synthetic route is free of environmental pollution.
  • the invention uses bromobenzene to react with 3 ⁇ 40 and metal oxide to obtain phenol, which is a completely new reaction system.
  • the raw materials consumed in the entire synthesis route are only benzene, 0, and 0 2. All other raw materials involved can be recycled and reused.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention porte sur un procédé de préparation d'aniline, de phénol et de leurs dérivés, ce procédé se caractérisant en ce que l'on met d'abord à réagir un benzène possédant divers substituants avec du brome de façon à obtenir un bromobenzène possédant également divers substituants. Lorsqu'on met ensuite à réagir le bromobenzène ou le bromobenzène possédant divers substituants avec un oxyde métallique et/ou un hydroxyde métallique et de l'ammoniac (ou un amine primaire, ou un amine secondaire), il se forme une aniline ou des dérivés d'aniline possédant divers substituants. Et lorsqu'on met également à réagir le bromobenzène ou le bromobenzène possédant divers substituants avec un oxyde métallique et/ ou un hydroxyde métallique et H2O, il se forme un phénol ou des dérivés de phénol possédant divers substituants. Le résultat de ce processus complet est la synthèse de l'aniline et des dérivés d'aniline par le benzène ou des dérivés de benzène, l'ammoniac et l'oxygène, l'eau étant le produit secondaire. Pour la synthèse des phénols, on utilise le benzène ou des dérivés de benzène, l'eau, l'oxygène afin de synthétiser le phénol ou des dérivés de phénol. Après distillation de l'ammoniac (amine), le bromure métallique et/ou le bromure métallique complexant l'ammoniac, obtenu au cours de la synthèse de l'aniline, des phénols et leurs dérivés, sont reproduits sous forme d'oxyde métallique et/ou d'hydroxyde métallique, le brome étant récupéré. Le brome et les oxyde métalliques sont recyclés en vue d'une autre utilisation et ne sont pas consumés, ce qui évite la pollution de l'environnement. Ce traitement présente des caractéristiques de haute conversion du benzène et une bonne sélectivité.
PCT/CN2003/000134 2002-12-12 2003-02-17 Procede de preparation d'aniline, de phenol et leurs derives Ceased WO2004052833A1 (fr)

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WO2009050366A2 (fr) 2007-09-28 2009-04-23 Centre National De La Recherche Scientifique (C.N.R.S.) Procede de synthese d'arylamines
US7838702B2 (en) 2006-02-24 2010-11-23 Basf Se Direct amination of hydrocarbons
CN112374994A (zh) * 2020-12-08 2021-02-19 衢州学院 一种五氟苯胺的制备方法

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CN101712593B (zh) * 2008-09-29 2013-06-19 微宏动力系统（湖州）有限公司 一种制备苯酚的方法
CN104437459A (zh) * 2014-11-18 2015-03-25 南京理工大学 一种活性炭负载氧化铋、制备及其应用
CN105384603A (zh) * 2015-12-09 2016-03-09 陕西省石油化工研究设计院 一种合成苯酚多氟代化合物的方法
CN108499614B (zh) * 2018-04-28 2021-06-04 西南医科大学附属医院 一种改性镍催化材料制备中枢神经系统用药物中间体的方法
CN109046327A (zh) * 2018-09-14 2018-12-21 宁波中傲环保科技有限公司 一种吸附催化剂
CN109516920B (zh) * 2018-11-20 2021-10-01 浙江工业大学 一种金刚烷胺的合成方法
CN116920863B (zh) * 2023-06-15 2025-11-04 江苏万盛大伟化学有限公司 一种钒镍镁三元催化剂及其制备方法和应用

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EP0549263A2 (fr) * 1991-12-27 1993-06-30 Chemagis Ltd. Procédé de préparation de N-alkyl-3,4-dialkyloxyanilines et leur dérivatives

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7838702B2 (en) 2006-02-24 2010-11-23 Basf Se Direct amination of hydrocarbons
WO2009050366A2 (fr) 2007-09-28 2009-04-23 Centre National De La Recherche Scientifique (C.N.R.S.) Procede de synthese d'arylamines
US8399680B2 (en) 2007-09-28 2013-03-19 Centre National De La Recherche Scientifique (C.N.R.S.) Arylamine synthesis method
CN112374994A (zh) * 2020-12-08 2021-02-19 衢州学院 一种五氟苯胺的制备方法
CN112374994B (zh) * 2020-12-08 2022-07-01 衢州学院 一种五氟苯胺的制备方法

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