Catalyst and method for production of phenol from benzene

 

The invention relates to the field of production of phenol, as well as preparation of catalysts for this process. Method for the production of phenol is that a couple of benzene together with a gas containing hydrogen and oxygen is passed through the solid layer of deposited catalyst. The catalyst contains two active components: a transition metal of group VIII and heteropolysaccharide derived from heteropolyacids composition of HnPMImMII12-mO40where MI- W, Mo, MII- V, Zr, Ti, Fe, n = 3-6, m = 0-6, and/or degradation products of these heteropolyanions. Effect: increase the performance of the process. 2 C. and 7 C.p. f-crystals, 5 PL.

The invention concerns a process for the production of phenol and catalyst for this process. The phenol used as starting product in the manufacture of resins, alkyl phenols, aniline and other compounds.

Currently, the most common method of production of phenol is komorny process that produces an equivalent amount of the target product and acetone, the latter requires finding ways of recycling. Two other processes of production of phenol based on the conversion of benzene in the CHL is acesso is a multi-stage, low selectivity for phenol, corrosion properties of the reaction medium and toxic waste.

The disadvantages of conventional processes are deprived of the means of production of phenol, based on the direct oxidation of benzene with the participation of an environmentally friendly and cheap oxidants.

Known methods of oxidation of benzene to phenol by means of relatively inexpensive oxidant hydrogen peroxide by Fe-Cu-Mo oxide catalysts [S. Cao, M. Huang, K. Li, X. Du. Catalytic behavior of Fe-Cu-Mn oxide/sepiolite for hydroxylation of benzene to phenol. Cuihua Xuebao(1996), 17 (2), 170], P-Mo-V heteropolyacids [X. Lu, N. Mizuno, M. Misono. Oxidation of benzene to phenol with hydrogen peroxide catalyzed by heteropolymolybdovanadophosphoric acids. Nippon Called Kaishi (1998) 23]. Catalysts have been developed for processes using as oxidant nitrous oxide [US Pat. 5110995, C 07 C 37/60, 1992].

The interaction of benzene with the cheapest and therefore the most attractive oxidant oxygen in the gas phase flows at high temperature, more than 600oC. Catalytic gas-phase oxidation with oxygen are mixed oxides, including oxides of Zn, Ag, P, Ti, Zr, Sn, Bi, V [US Pat. 4338471, 1982]. Gas-phase oxidation reactions with oxygen are characterized by low selectivity of the formation of phenol. Attempts to lower the reaction temperature, and in this regard, the systems [US Pat. 5981424, 1999]. Picked up some liquid-phase systems that are more capable of selectively oxidize benzene with oxygen at high pressure in the acetic acid medium in the presence of salts of Pd(II) and lithium nitrate or heteropolyacids [L. C. Passoni, A. T. Cruz, R. Buffon. Diirect selective oxidation of benzene to phenol using molecular oxygen in the presence of palladium and heteropoly acids. J. Molec. Catal., 120 (1997) 117].

Systems that use oxygen together with samostanowienia, are characterized by several positive options: mild reaction conditions, a sufficiently high activity and selectivity to benzene. Known systems using as avastantivirus ascorbic acid [Ohtani T. , Nishyama S., Tsuruya, S., Mitsuo Asai M., Liquid-phase benzene oxidation to phenol with molecular oxygen catalyzed by Cu-zeolites. J. Catal., 155 (1995) 158] , aldehydes [JP 94-48696, 1994; BR 9302551-A, 1995], carbon monoxide [JP 62195340 A2] , aliphatic alcohols [JP 8157404-A] and ammonia [JP Appl. 63-268154, 1988].

The most promising uses sopostavitel the processes are those in which hydroxylation occurs under the action of O2/N2of the mixture. In liquid-phase conditions, the reaction is carried out in an organic solvent or mixture of organic solvent with water in the presence of acid. Catalysts are the platinum metals in combination with halogenide other metals [JP 5-4935, 1993; JP 6-256241, 1994; JP 6-256242, 1994; JP 05004935A2; US Pat. 5426245, 1995; T. Miyake, M. Hamada, Y. Sasaki, M. Oguri. Direct synthesis of phenol by hydroxylation of benzene with oxygen and hydrogen. Appl. Catal. A: General, 131 (1995) 33], Ti-silicalite [JP 5-320082, 1993].

For use in practice of gas-phase processes hydroxylation are more preferable in comparison with the liquid phase, because there is no problem of separation of the products from the solvent and catalyst.

Known gas-phase modification process hydroxylation2/H2with the mixture. In these processes is used bicomponent Pd-Cu catalyst [T. Kitano, Y. Kuroda, M. Mori, S. Ito, K. Sasaki, M. Nitta. Gas phase oxidation of benzene to phenol using Pd-Cu composite catalyst. Part 2. Performance of CuSO4-based catalysts. J. C. S. Perkin Trans., 2 (1993) 981; Kitano T., Warii T., Ohnishi T., Jiang L.-F., Y. Kuroda, A. Kunai, Sasaki K. Gas phase oxidation of benzene to phenol using Pd-Cu composite catalysts. Effect of temperature, feeding gas and catalyst composition. Catal. Lett., 11 (1991); T. Kitano, T. Nakai, M. Nitta, M. Mori, S. Ito, K. Sasaki. Gas phase oxidation of benzene to phenol under the simultaneous feeding of hydrogen and oxygen. 3. Catalyst prepared from Cu(II) phosphate. Bull. Chem. Soc. Jpn., 67 (1994) 2850]. In the latter case, the gas-phase process is conducted in such a way that the catalyst is simultaneously supplied with oxygen, hydrogen and benzene. The reaction is carried out at 200oS. known in the literature of gas-phase systems using O2/H2the oxidant, this system characterizes-atom Pt per hour. This system is chosen as a prototype.

The invention solves the problem of increasing the productivity of the process.

There is a wide field for improvement of methods of direct oxidation of benzene under the action of oxygen, which applies to the gas-phase oxidation reactions under the action of O2+H2mix.

The problem of increasing the performance of the system is solved in this invention by selection of the catalyst composition.

The subject of the invention is a method for the production of phenol by catalytic oxidation of benzene with a mixture of gases2+H2in the gas phase and the catalyst for this process, containing a transition metal of group VIII and polyoxazolines, including heteroalicyclic, their salts and degradation products of heteropolyanions.

Method for the production of phenol is that a couple of benzene together with a gas containing hydrogen and oxygen is passed through the solid layer of deposited catalyst. The catalyst contains two active components: a transition metal of group VIII and heteropolysaccharide derived from heteropolyacids composition of NnRMImMII12-mO40(MI- W, Mo, MII- V to be platinum, palladium, rhodium, iridium and ruthenium. Platinum and palladium are most active.

As precursors of the metals in the catalyst composition can be used various inorganic salts and complexes. For example, in the case of palladium it can be a chloride, nitrate or sulfate, palladium (II), tetraamine palladium(II) chloride. In the case of platinum can be used platinochloride-hydrogen acid, tetrachloroplatinate potassium, tetraammineplatinum.

In the composition of the catalyst are introduced polyoxazolines, which can be heteroalicyclic composition of NnRMImMII12-mO40(MI- W, Mo, MII- V, Zr, Ti, Fe, n = 3-6, m = 0-6), and their salts with inorganic cations such as the cations of cesium, potassium, ammonium, and organic ammonium cations, as well as the products of partial or complete destruction of these heteropolysaccharide, such as mixed oxides.

Both the active component of the catalyst applied to the surface of inert carriers, such as silica gel, aluminosilicates, carbon. Apply the usual application methods, in particular can be used procedures impregnation, adsorption, deposition. Application procedure can be performed once, when this is the first serial processing first solution of the compound of metal of group VIII, then a solution of heteropolysaccharide or in reverse order. In those cases where the composition of the catalyst, you must have salt heteroalicyclic, the corresponding cation is administered together with heteropolyanions in the form of ready-made salt or cation previously administered in the composition of the medium before applying heteroalicyclic.

After drying, the catalyst is subjected to heat treatment at a temperature of 100 to 600oWith either in air or in a stream of nitrogen. Since it is necessary the presence of an element of group VIII in the metallic state, the catalyst is kept in a current of hydrogen or with hydrogen gas at a temperature of 100-300oC. the Finished catalyst contains at least 2 wt.%, preferably 5-40 wt.% polyoxazolines and not less than 0.01 wt.%, preferably 0.05 to 5.0 wt.% metals of group VIII.

The catalytic process is carried out in a flow reactor with a fixed catalyst bed.

In contact with the catalyst, the flow of the reactants contains oxygen and hydrogen, the number of which is 1-10 vol.%. At low concentrations of oxygen and hydrogen, the system shows poor performance. The upper limit of the concentration of oxygen and hydrogen is limited by safety considerations. Aderasa the Ute inert gas.

The concentration of benzene in the gas stream is 1-50 vol.%, preferably 5-30 vol.%. Since the dependence of the number of formed phenol concentration of benzene is positive, the low concentration of benzene causes a low rate of hydroxylation reactions and, as a result, the formation of only small amounts of phenol. On the other hand, when an excess of benzene compared with O2/H2oxidant despite the high reaction rate is not achieved high conversion of benzene.

In addition to the reagents, the composition of the gas stream may be injected water vapor, the concentration of which may range from 0 to 30 vol.%. The presence of water vapor at the same time increases the conversion of benzene and reduces the conversion rate of the oxidizer, which results in a more selective consumption of the oxidant in the process of hydroxylation of benzene.

The source reagents are a mixture gas of oxygen, hydrogen, nitrogen and water vapour, taken as a percentage of O2:H2:N2: C6H6:H2About=(1-10): (1-10):(0-97):(1-50):(0-30).

The process is carried out at a temperature of 150-300oSince, it is preferable interval 180-220oC. Both high and too low tempereau temperature is difficult to remove phenol from the surface of the catalyst. High temperature for adverse reactions because it causes deep oxidation of benzene with the formation of carbon oxides and thereby wastes benzene. The reaction generally proceeds at atmospheric pressure, but may be conducted at elevated pressures.

The volumetric rate of the gas mixture can vary in the range from 30 to 3000 ml/min per g of catalyst.

Method for the production of phenol described in more detail in the examples. Examples 1-31 show high performance catalysts, calculated per 1 g of catalyst or per 1 g-atom of metal of group VIII in the catalyst. These examples also allow you to compare the performance under different catalyst composition, and examples 32-34 - at different process temperature. Examples 34-51 illustrate the high conversion of benzene to phenol and high selectivity of the hydroxylation process for oxidizing agent that, when opredelenni process conditions allows to obtain the catalyst.

Example 1 In 2 ml of water was dissolved 0.4 g of phosphorus molybdenum acid3RMO12O407H2O add 0.7 ml of a solution platinochloride-hydrogen acid containing 0,0048 g of platinum. For the 0.5 mm). The sample is left in air to dry. The dry sample is heated in air in an oven at a temperature of 100oWith and recover in a stream of hydrogen at 300oC. After recovery, the sample is kept in air at a temperature of 50oC. This sample can be stored in air for 10 days. During this period it is used as a catalyst without preoperator. The finished sample, designated as 0,2 Pt-20PMo12/SiO2(400), contains 0.2 wt.% the sycamores and 20 wt.% polyoxazolines.

Glass reactor for carrying out catalytic process is a U-shaped tube, the right side is bent in the form of a coil, and in the bottom left is a glass filter. A portion of the catalyst 0.1 g was placed in the left part of the reactor to the filter. The right part of the reactor connected to a device providing reagents to the reactor, and the left end connected to the trap is lowered into the Dewar vessel at -10oC. the Reactor is placed in an oven whose temperature is 200oC. the Reactor was rinsed for 5 minutes with nitrogen, and then a gaseous mixture of O2:H2:C6H6:N2in the ratio of 5.5:5,5:33:57 with a speed of 160 ml/min for 60 minutes. According to the chromatographic EN is 1. The examples illustrate the effect of platinum content on the activity of the catalytic system. The catalysts are prepared analogously to example 1.

Examples 6-7 performed analogously to example 1 and illustrate the change in the activity of the catalytic system with varying phosphorus-molybdenum heteroalicyclic in the catalyst.

Example 8 the Procedure of preparation of the catalyst is similar to that described in example 1, but as media use silica with a specific surface area of 200 m2/g and a particle diameter of about 0.5 mm of the Finished sample, designated as 0,2 Pt-20PMo12/SiO2(200), contains 0.2 wt.% platinum and 20 wt.% polyoxazolines.

The catalytic process is conducted as described in example 1. 1 hour is formed 210 Ámol phenol (No8 in table.1).

Examples 9-11 are shown in table.1 illustrate the effect of platinum content on the activity of the catalytic system. The catalysts are prepared analogously to example 8.

Example 12 illustrates the possibility of using other media, in addition to the SiO2. In 2 ml of water was dissolved 0.4 g of phosphorus molybdenum acid, H3RMO12O407H2Oh, add 0.7 ml of a solution platinochloride-hydrogen acid containing 0p>/g, a fraction with a particle diameter of 1 mm, the Sample is left in air to dry. The dry sample is heated in air in an oven at a temperature of 100oWith and recover in a stream of hydrogen at 300oC. After recovery, the sample can be stored in air for 10 days. During this period it is used as a catalyst without preoperator. The finished sample 2Pt-20PMo12/C(200), contains 2 wt.% platinum and 20 wt.% polyoxazolines. The catalytic process is conducted as described in example 1. 1 hour is formed 115 Ámol phenol.

Examples 13-20 perform similarly to example 2, but instead of phosphorus molybdenum acid, H3RMO12O407H2About using the same number of other heteropolyacids: N4RMO11VO4013 H2O, H5PMo10V2O409H2O, H6RMO9V3O4014N2O, H3RMO6W6O4013 H2O, H3W12O4015 NM2O, H4PW11VO4010H2O, H6PW9V3O4010Hthe but how 0,2 Pt-20PMo11V/SiO2(400), 0,2 Pt-20PMo10V2/SiO2(400), 0,2 Pt-20PMo9V3/SiO2(400), 0,2 Pt-20PMo6W6/SiO2(400), 0,2 Pt-20PW12/SiO2(400), 0,2 Pt-20PW11V/SiO2(400), 0,2 Pt-20PW9V3/SiO2(400), 0,2 Pt-20PW11Zr/SiO2(400), containing 0.2 wt.% platinum and 20 wt. % polyoxazolines. The number of the resulting phenol is given in table. 1.

Examples 21-23 In 2 ml of water was dissolved 0.4 g of phosphorus molybdenum acid3RMO12O407H2O add 0.7 ml of hydrochloric acid solution of palladium chloride containing 0.0024 g of palladium. The obtained ml solution of 2 g of silica gel (specific surface area 400 m2/g, a fraction with a particle diameter of 0.2-0.5 mm). The sample is left in air to dry. The dry sample is heated in air in an oven at a temperature of 100oWith and recover in a stream of hydrogen at 300oC. the Finished sample, indicated as 0.1 Pd-20PMo12/SiO2(400) contains 0.1 wt.% palladium and 20 wt.% polyoxazolines.

In examples 24 and 25 vary the composition of the catalysts under identical preparation procedure. For samples of 0.5 Pd-20PMo12/SiO2and 0.1 Pd-40PMo12/SiO2take, respectively, 0.4 g and 0.8 g of phosphorus-molybdenum Ki is the process carried out as described in example 1. The amount of phenol produced for 1 hour, are given in table. 1.

Examples 24-26 Catalysts prepared as in examples 13-15, but instead platinochloride-hydrogen acid take the appropriate amount of hydrochloric acid solution of palladium chloride.

Examples 27-31 Catalysts are prepared analogously to example 23, but instead of the hydrochloric acid solution of palladium chloride using solutions containing, respectively, 0,0048 g of iridium in the form of chlorosilane H3Irl6, 0.0024 g of ruthenium in the form of a complex K2Ru(OH)Cl5, 0.0024 g of rhodium in the form of chloride N3[Rhl3(OH)3], 0,0048 g of cobalt as cobalt chloride l2or 0,0048 g of Nickel in the form of Nickel chloride NiC2. After drying at 100oWith samples subjected to recovery in hydrogen flow at 400oC. the Amount of phenol produced in the presence of these catalysts are given in table. 1.

Examples 32-34
These examples, together with example 21 illustrate the effect of reaction temperature on the yield of phenol. In the examples using the catalyst described in example 21. The quantity of phenol is shown in table. 2.

Examples 35-39
The catalysts in examples 35 and 37-39 prepared similarly as described in example 1, using media SiO2the ima is impregnated with an aqueous solution of cesium carbonate and dried at a temperature of 100oC. the Further procedure is carried out as in example 1. The amount of cesium in this sample corresponds to the molar ratio of Cs: PMo12equal to 2.

The catalytic process is carried out in a glass reactor as described in example 1. For experiments take a portion of the catalyst, 1,3 Reactor catalyst is rinsed with a mixture of N2:O2=88:12 for 1 hour at 300oC, then cooled to 200oC. At this temperature, a gas mixture of O2: H2: C6H6: N2= a 9.5 to 9.5:6:75 continuously fed into the reactor with the speed of 136 ml/min Every 30 minutes to carry out the analysis of gases at the outlet from the reactor and collected in a cooled trap condensate. Based on data analysis, calculate the conversion of benzene to phenol, and conversion of oxygen. In table. 3 gives the mean values of these characteristics for a reaction time of 3 hours.

Examples 40-48
In examples 40, 42-45, 48 catalysts are prepared in the same way as described in example 1. The surface used SiO2in each case stated in the title of the catalyst in brackets.

In examples 41 and 46-47 catalysts are prepared similarly to the catalyst in example 36.

The catalytic process is conducted in the same manner as described in examples 35-39. Hitch kataliza
:H2O= 9:9:5:62:15 continuously fed into the reactor with the speed of 147 ml/min for 3 hours. Average values of conversion of benzene to phenol, the conversion of oxygen and selectivity of formation of phenol are shown in table. 4.

Examples 49-51
Used catalyst from example 43. The addition of catalyst is 1.5, the Reactor with the catalyst is rinsed with a mixture of N2:O2:H2O = 74:10:16 for 1 hour at 300oC, then cooled to 200oC. At this temperature, the gas mixture was fed into the reactor with the speed of 147 ml/min In a table. 5 shows the composition of the initial gas mixture fed to the catalyst, and the conversion of benzene to phenol, the conversion of oxygen and selectivity of the formation of phenol, measured at a given composition of the mixture.

Described examples demonstrate the high performance of the catalyst. Other positive characteristics of this method for production of phenol is (1) low cost oxidizer (compared to the often used hydropredict), (2) single-stage process process, (3) the absence of troublesome and harmful and related products, (4) low energy consumption (the process may be conducted at T 200oAnd atmospheric pressure).

2. The catalyst p. 1, characterized in that the metal of group VIII of the Periodic table is a metal selected from the group of cobalt, Nickel, ruthenium, rhodium, palladium, iridium, platinum, or any mixture.

3. The catalyst according to any one of paragraphs.1 and 2, characterized in that the inert carrier is silica, aluminosilicate, carbon.

4. The catalyst according to any one of paragraphs.1-3, characterized in that the content of metal of group VIII is not less than 0.01 wt.%.

5. The catalyst according to any one of paragraphs.1-4, characterized in that the content of polyoxazolines is not less than 2 wt.%.

6. Method for production of phenol by the interaction of benzene with oxygen and hydrogen in the gas phase in the presence of a catalyst, characterized in that the use of the catalyst according to any one of paragraphs.1-5.

7. The method according to p. 6, in which ohodnotenie O2:H2:N2:C6H6:H2O=(1-10):(1-10):(0-97):(1-50):(0-30).

8. The method according to any of paragraphs.6 and 7, characterized in that the interaction of phenol with oxygen and hydrogen is carried out at a temperature of 150-300oC.

9. The method according to any of paragraphs.6 and 8, characterized in that the interaction of reagents with the catalyst is carried out by passing them through a fixed bed of catalyst with a bulk velocity 30-3000 ml/min per 1 g of catalyst.

 

Same patents:

The invention relates to a method of selective oxidation of aromatic compounds (e.g. benzene and its derivatives) in gidroksilirovanii aromatic compounds (for example, into the corresponding phenols)

The invention relates to a method for the synthesis of hydroxylated aromatic compounds by the oxidation of aromatic compounds with hydrogen peroxide in an organic solvent in the presence of synthetic zeolites

The invention relates to a method for production of phenol by direct gas-phase oxidation of benzene with nitrous oxide in the presence of industrial zeolites

-methylstyrene" target="_blank">

The invention relates to an improved method for production of phenol, acetone and-methylstyrene Kukolnik method and relates to the stage of acid decomposition of technical cumene hydroperoxide
The invention relates to pharmaceutical industry

The invention relates to organic synthesis, in particular the production of phenol and Cresols selective direct oxidation of benzene and/or toluene nitrogen oxide in the presence of a heterogeneous catalyst

The invention relates to the production of phenol and acetone by decomposition of technical cumene hydroperoxide (CHP)

The invention relates to a method of selective oxidation of aromatic compounds (e.g. benzene and its derivatives) in gidroksilirovanii aromatic compounds (for example, into the corresponding phenols)

The invention relates to the field of organic synthesis, more specifically to a method for production of phenol and its derivatives by catalytic oxidation of benzene and its derivatives

The invention relates to a method for the synthesis of hydroxylated aromatic compounds by the oxidation of aromatic compounds with hydrogen peroxide in an organic solvent in the presence of synthetic zeolites

The invention relates to a method for production of phenol by direct gas-phase oxidation of benzene with nitrous oxide in the presence of industrial zeolites

The invention relates to organic synthesis, in particular the production of phenol and Cresols selective direct oxidation of benzene and/or toluene nitrogen oxide in the presence of a heterogeneous catalyst

The invention relates to a method for production of phenol and its derivatives by oxidation of benzene and its derivatives nitrogen oxide in the presence of heterogeneous catalysts

The invention relates to the field of organic synthesis, in particular to a method for production of phenol and its derivatives by means of one-step oxidative hydroxylation of benzene or other aromatic compounds with nitrous oxide

The invention relates to a method for obtaining phenol by oxidative decarboxylation in the liquid phase corresponding arylcarbamoyl acid in the presence of a catalyst containing Cu(I)

The invention relates to the field of organic synthesis, more specifically to a method for production of phenol and its derivatives by catalytic partial oxidation of benzene and its derivatives with nitrous oxide

(-=62kcal/mol)where X=H, HE, F, Cl, CH3C2H5or any other radical, the replacement of the hydrogen atom in the benzene molecule

The invention relates to substituted phenols, in particular the joint receiving pyrocatechin and hydroquinone

The invention relates to methods of producing 2,3,5-trimethyl-1,4-benzoquinone (TMH) catalytic oxidation of 2,3,6-trimethylphenol (TMP) oxygen
Up!