Method of obtaining phenol by hydrodeoxygenation of dioxybenzoles

FIELD: chemistry.

SUBSTANCE: flow of water solution of dioxybenzole with concentration from 5 to 60 wt % with volume rate, expressed in kg of dioxybenzole/hour/kg of catalyst 0.1 - 10 hours-1, and hydrogen flow are supplied to adiabatic reactor with immobile layer of catalyst. Reaction of hydrodeoxygenation in vapour phase working in continuous regime in presence of catalyst is performed. Flow of dioxybenzole water solution and hydrogen flow are supplied in such amount that ratio between total quantity of hydrogen and dioxubenzole moles was within range from 2:1 to 50:1. Reaction is carried out at temperature within range from 250 to 500°C and pressure 0.1-10 MPa. Used catalyst represents catalyst on carrier, containing element of group VIB, or their mixture, or element of group VIII of periodic system, or their mixture and promoter.

EFFECT: invention allows to increase decree of dioxybenzole conversion, selectivity in relation to phenol and process productivity.

21 cl, 27 ex, 1 dwg

 

This invention relates to a method for production of phenol by catalytic hydrodeoxygenation of dioxybenzone.

More specifically, this invention relates to a continuous process for the production of phenol by hydrodeoxygenation of dioxybenzone hydrogen is carried out in aqueous solution in the presence of a catalyst based on elements of group VIB or group VIII of the periodic system.

Phenol is an extremely important industrial intermediate product, which is used, for example, in the production of polycarbonates or other phenolic resins.

Dioxybenzone at low cost can be obtained as derivatives of natural origin or as by-products of industrial chemical processing.

Reaction hydrodeoxygenation described .Furimsky in CATAL. REV.-SCI. ENG., 25(3), 421-458 (1983).

Furimsky gives an overview of the papers published in the field of hydrodeoxygenation, and, in particular, reactions conducted using raw materials used for production of liquid fuels, or model compounds.

Reaction hydrodeoxygenation used mainly for processing of raw materials intended for the production of fuels, the purpose of which is full and exhaustive obezkislorazhivaniya (dioxygenase) initial reagents, because the presence of oxygen in these liquid fuels is undesirable. Content is the oxygen in these source materials can be significant, and it is usually due to the presence of hydroxyl, carbonyl, carboxyl, ether, ketone groups, etc. Among the most widely studied source materials mentioned (C) liquefaction of coal, in which the presence of oxygen mainly due to the presence of phenolic groups.

Among the model compounds used to study reactions obezkislorazhivaniya mentioned o - and p-cresol, naphthol, phenol, o-phenylphenol and other phenols (table 5, 442).

Phenols, due to their structure, to fully obezkislorazhivaniya may require, except for the presence of agent-reducing agent, and also the presence of the catalyst (table 2, s).

Reaction hydrodeoxygenation can be performed in the presence of various catalysts, although it often turns out that a more effective catalysts containing Mo and W in combination with Ni or Co as promoters; for compounds of type phenol it is also shown that suitable catalysts based on Th and Pt (s).

One of the drawbacks observed in the reactions of hydrodeoxygenation is the deactivation of the catalyst due to the presence of water, which is formed by the reaction (s).

Now found a method that is based on the reaction of partial and selective hydrodeoxygenation carried out with hydrogen in the presence of a catalyst based on elements of group VIB or group VIII of the periodic is coy system and allows to convert dioxybenzone in phenol with a high degree of conversion, selectivity and productivity when carrying out the reaction in aqueous solution.

This result is unexpected, as previously water was identified as the agent responsible for the poisoning of the catalyst in the reactions of hydrodeoxygenation.

Moreover, in the considered reactions in which the substrate is exposed obezkislorazhivaniya, consists of dioxybenzone, using water as a solvent has numerous advantages from the point of view of both technology and economy. Water can actually support in the solution of the high concentration of both reactants and products. In addition, water is completely inert towards the reactants and products in the reaction medium. As the solvent for the reaction of water also has the advantage that it has high heat capacity and, therefore, has the property to limit the temperature increase caused by the enthalpy of the reaction of obezkislorazhivaniya. Finally, the water is fairly inexpensive.

In its broadest aspect this invention relates to a method for producing a phenol, which are reaction hydrodeoxygenation in the vapor phase when operating in the continuous mode in the adiabatic reactor feed stream of an aqueous solution of dioxybenzone with a concentration of from 5 to 60 wt%. with a bulk velocity, expression is Noah in kg dioxybenzone/h/kg of catalyst is 0.1 to 10 h -1and the flow of hydrogen in an amount such that the ratio between the total number of moles of hydrogen and dioxybenzone was in the range of from 2:1 to 50:1, at a temperature in the range from 250 to 500°C, a pressure of 0.1-10 MPa, in the presence of a catalyst comprising a catalyst on a carrier containing an element of group VIB, or a mixture or an element of group VIII of the periodic system, or their mixture and the promoter.

Acting in accordance with the method according to this invention, it is possible to obtain a phenol with high efficiency and selectivity of 1,2-dioxybenzone (pyrocatechin, which for brevity denoted in the future 1,2-DB), 1,3-dioxybenzone (resorcinol, then 1,3-DB), 1,4-dioxybenzene (hydroquinone, then 1,4-DB) and mixtures thereof.

Preferably the reaction is carried out in the vapor phase at a temperature of 300-450°C, at a pressure of 0.3 to 5 MPa.

In particular, loading of the reactor consists of a solution of deoxybenzoin in water with a concentration of 10-40 wt%. and the flow of hydrogen in an amount such that the ratio between the total number of moles of hydrogen and dioxybenzone was in the range of from 5:1 to 30:1.

If the catalyst contains elements of group VIB, it can contain as promoters of elements belonging to group VIII, and phosphorus. The elements of group VIB can be used in a mixture, and among them, preferred are molib the Yong and tungsten. Among the promoters of the group VIII preferred are Nickel, cobalt, iron and ruthenium, and can be used in a mixture with each other and with phosphorus.

If the catalyst contains elements of group VIII, it can contain as promoter zinc, rhenium, selenium, tin, germanium and lead. The elements of group VIII can be used in a mixture, and among them, preferred are cobalt, palladium, Nickel and platinum. Promoters can also be mixed with each other.

The active phase is preferably applied to the carrier. The preferred carriers are inorganic oxides selected from the group including aluminum oxide, silicon dioxide, titanium dioxide, crystalline or amorphous aluminosilicates, crystalline spinel having the General formula F2+R23+O4(where F2+can be a Mg, Fe, Zn, Mn, Ni, etc., a R3+can represent Al, Fe, Cr and so on), or mixtures thereof. A typical surface area of these materials is in the range from 1 to 800 m2/g, preferably from 10 to 500 m2/g, pore volume of 0.05-2 cm3/g, preferably from 0.1 to 1.5 cm3/, Catalysts, and carriers must be in a form suitable for use, for example, in a reactor with a fixed bed: for this purpose, suitable extruded products, tablets, spheres with a size in the range from 1 is about 12 mm

For catalysts on the basis of the elements of group VIB specified element is usually present in the medium at a concentration factor of 1 to 50 wt. -%, preferably from 3 to 30 wt%. The promoters of these catalysts are usually present in concentrations of from 0.1 to 100% (atomic) in relation to the element of group VIB, preferably from 1 to 50%. Without establishing any limitations on the possible structures or specify any preferences, examples of such catalysts are Mo, W, CoMo, NiMo, NiW, FeMo, RuMo, CoMoP, NiMoP, CoWMo, CoWMoP.

Before use in the reaction, the catalysts may be treated to modify their chemical characteristics, such as sulfonation with N2S, dimethyl sulfide, dimethyl disulfide, carbon disulfide or other compounds suitable for this purpose.

For catalysts based on group item VIII the specified element is usually present on the carrier at a concentration in the range from 0.05 to 20 wt%, preferably from 0.1 to 10 wt%. The promoters of these catalysts are usually present in concentrations in the range from 0.5 to 200% atomic with respect to the element of group VIII, preferably from 1 to 120%. Not setting any limitations to the possible compositions and not indicating any preference, examples of such catalysts are Pt, Pd, Co, Ni, PtZn, PtRe, PtNi, PtSe, PtSn, PtGe, PdPb, PdSn.

Catalysts, JW is ausina object of the present invention, can be received by way of initial moisture or absorption of the solution.

The first method involves the impregnation of a porous media a certain volume of a solution containing soluble precursors of the active phases equal to the pore volume of the used media. Thus, present in the solution predecessors quantitatively absorbed by the media. In order to achieve the desired loading items, the procedure can be repeated several times, alternating it with the dryer.

The second method involves the absorption by the medium of the precursors of the active phase on the basis of the solution in which the carrier is dispersed.

Among the predecessors, which can be used include tetrahydrate of heptamolybdate ammonium, uranyl nitrate of cobalt, uranyl nitrate Nickel, nonahydrate nitrate of iron, ruthenium chloride, industrial manufactured solutions hexachloroplatinic acid (Pt 7.7 per cent), in accordance with what is known in this technical field.

Impregnated carrier can be subjected to chemical treatment may alternately with heat treatment. Typical chemical processing includes, for example, media recovery, impregnated hexachloroplatinic acid, a solution of sodium formiate at 85-95°C.

The process of obtaining always completes the final stage of heat treatment.

<> In one embodiment of this invention the reaction is carried out in an adiabatic reactor with a fixed catalyst bed containing a catalyst, as described above, which serves stream containing an aqueous solution of deoxybenzoin with concentrations in the range of from 5 to 60 wt. -%, together with a stream of hydrogen in an amount such that the ratio between the total number of moles of hydrogen and dioxybenzone was in the range of from 2:1 to 50:1. This feed stream is transferred into the gaseous state and is heated to a temperature in the range from 250 to 500°and the pressure is maintained within the range from 0.1 to 10 MPa (from 1 to 100 bar). The stream exiting the reactor, consists of the crude reaction product, including, possibly, residual dioxybenzone and phenol obtained in aqueous solution, and the residual hydrogen, which is again sent to the reactor.

In another embodiment of this invention the reaction is carried out in two or more adiabatic reactors with a fixed layer connected in series to cool the stream coming from one of the reactors, before introducing it into the subsequent reactor, thereby limiting the increase in temperature in each reactor, for example, by maintaining it at a level below 40°S. In this embodiment, both water and hydrogen can be submitted separately in each re is ctor. A separate submission is particularly convenient, since it avoids the use of an intermediate heat exchanger for cooling. Two reactors are usually sufficient to maintain the temperature increases in a separate reactor within the desired value.

Conducting the process in such a way as to increase the temperature in each reactor did not exceed 40°receive a higher selectivity to phenol.

See the drawing schematically illustrates the necessary equipment for carrying out the process in accordance with the above described configuration.

In the presence of catalysts and optimal conditions it is possible to maintain the reactor in a period of time, up to several hundred hours, with 100% degree of conversion of dioxybenzone and selectivity with respect to phenol greater than 95%.

With increasing operating time of the reactor, the degree of conversion tends to decrease, while the selectivity remains extremely high. In order to maintain the desired degree of conversion, the reaction temperature can be gradually increased in the range 250-500°C.

The reason for the decline in activity is the deposition of carbonaceous material on the catalyst during its use in the reaction.

Observed that the catalysts that can be used is La the purposes of this invention, can be subjected, without any special problems, periodic regeneration (in accordance with what is known in the art) to remove the above-mentioned deposits by burning to restore the original activity.

Processing for the regeneration can be performed in the same reactor in which the catalyst load for the reaction. Regeneration is usually carried out at a temperature in the range from 400 to 550°and at a pressure in the range from 0.1 to 0.3 MPa (from 1 to 3 bar), a mixture of oxygen and nitrogen in a ratio of from 0.1 to 20% vol. and the bulk gas velocity (GHSV = Gas Hourly Space Velocity, expressed in liters of gas mixture per hour per liter of catalyst) = 3000÷6000 h-1.

The case of continuous processes, it is preferable to have two reaction system, which alternately include in the reaction and regeneration.

The method according to this invention can be successfully used to increase the yield of phenol in the process of direct synthesis of phenol from benzene with hydrogen peroxide in the process that leads to the formation of significant quantities of dioxybenzone (US 06133487 and Italian patent application MI 2001 A 002410).

Provides a few illustrative examples for a better understanding of this invention and for its execution, which, however, in no way should be considered as limiting the scope itself is th invention.

Examples of the preparation of catalysts.

Example 1.

Catalyst type Mo/Al2About3.

50 g of aluminum oxide (spherical alumina 1.0/160 Condea-Sasol, diameter = 1 mm, the pore volume is not less than 0.45 ml/g, surface area = 150-170 m2/g) dried at 120°With during the night. Then, they are impregnated by the method of initial moisture at room temperature with a solution of 3.45 g of heptamolybdate ammonium, dissolved in 23 g of demineralized water. After about 2 hours of aging, the sample is dried at 140°C for 3 hours. Repeat another two cycles of impregnation/drying, and then the sample is annealed at 500°C for 8 hours. The content of molybdenum, calculated based on method of preparation, is Mo=9,6% of the mass.

Example 2.

Catalyst type W/Al2About3.

Apply the same procedure described in Example 1, in which instead of the solution containing molybdenum, used a solution of 1.04 g (pair) of ammonium tungstate dissolved in 26 g of demineralized water, the aging period is 1 hour instead of 2 hours, and instead of two additional cycles of impregnation/drying is carried out only one. The estimated content of tungsten is W=2.9% of the mass.

Example 3.

Catalyst type NDA/Al2About3.

Apply the same procedure described in Example 1, using instead of the solution containing molib the Yong, solution of 1.70 g phospholipases acid (Acros, H3PO40W12·xH2O, MM=2880,17, WO382% min, maximum weight loss at 800°C=17%), dissolved in 26 g of demineralized water; aging 1 hour instead of 2 hours. The estimated content of tungsten and phosphorus-based method of obtaining is W=6,2% wt., P=0,08% of the mass.

Example 4.

Catalyst type SNF/Al2About3.

Getting carried out, as for the catalyst of Example 1, but the solution for impregnation is obtained using 3,45 g heptamolybdate ammonium and 2.67 g of uranyl nitrate of cobalt. Calculated on the basis of the method of obtaining the content of cobalt and molybdenum is SD=2.7% wt., Mo=9,3% of the mass.

Example 5.

Catalyst type CoMoW/Al2About3.

Use the same procedure as for the catalyst of Example 4, but the final, dried but not calcined catalyst impregnated twice more (with a break for drying for 3 hours at 140° (C) a solution consisting of 25 ml of demineralized water and 1.04 g (pair) of ammonium tungstate. The solid is dried at 140°C for 3 hours and then calcined at 500°C for 8 hours. Calculated based on the method of obtaining the content of cobalt, molybdenum and tungsten is With=to 2.6 wt. -%, Mo=9.0 wt%., W=2.4% of mass.

Example 6.

Catalyst type FeMo/Al2/sub> O3.

50 g of aluminum oxide (spherical alumina 1.0/160 Condea-Sasol), dried at 120°With during the night. Then, they are impregnated by the method of initial moisture at room temperature with a solution 3,79 g nonahydrate iron nitrate dissolved in 27 g of demineralized water. After about 1 hour of aging, the sample is dried at 140°C for 3 hours. Then carry out the impregnation solution comprising of 3.45 g heptamolybdate ammonium and 27 g of demineralized water, and the sample is dried at 140°C for 3 hours. Repeat another two cycles of impregnation of Fe/drying and impregnation Mo/drying, and then the sample is annealed at 500°C for 8 hours. Calculated based on the method of obtaining the content of iron and molybdenum is Fe=2.5% wt., Mo=9,3% of the mass.

Example 7.

Catalyst type/Al2About3.

Use the same procedure as described in Example 1, but the solution for impregnation are prepared with 2.67 g of uranyl nitrate of cobalt. Calculated on the basis of the method of obtaining the content of cobalt is From=3,1% of the mass.

Example 8.

The catalyst of the type Pt/Al2About3.

50 g of aluminum oxide (spherical alumina 1.0/160 Condea-Sasol) soaked in 200 ml of demineralized water for 16 hours. After draining the water and washing twice (each time about 100 ml of water) aluminum oxide suspended in the flask Rothorn the second evaporator in 80 ml of an aqueous solution, containing 3.2 g of a solution hexachloroplatinic acid (Pt=7,696%). This mixture is subjected to a slow rotation for 2.5 hours at 30°With, then add a solution consisting of 1.0 g of sodium formate dissolved in 50 g of demineralized water. The solution is heated in the flask of the rotary evaporator at slow rotation, up to 85°C for 90 minutes, drained, filtered and washed with about 5 l of water at 60°C. the Fluid is drained and subjected to drying for 18 hours at 120°C. Calculated based on the method of obtaining the content of platinum relative to the catalyst is Pt=0.5% mass.

Example 9.

Obtaining spinel used as a carrier.

A 5-liter beaker filled with 1500 ml of demineralized water, brought to pH 10 with ammonium hydroxide (32%, Carlo Erba). A second solution consisting of 203,3 g of magnesium chloride and 482,86 g of uranyl chloride aluminum increased to 2 l of demineralized water, is slowly added to the ammonia solution with stirring. When mixing the solution pH is maintained at a value of about 10 by adding the corresponding solutions of ammonium hydroxide. At the end of the addition the mixture was kept under stirring for 2 hours, and the solid residue is subjected to aging in the mother solution for 16 hours, filtered, washed with wash water to neutral pH, dried PR is 120° C for 16 hours. Sludge calcined at 400°C for 16 hours and then at 600°another 16 hours. The resulting oxide is milled and sieved between 18 and 35 mesh.

Catalyst type PtZn on spinel MgAl.

10 g of solids impregnated with a solution consisting of 5 ml chloroplatinic acid (Pt=2 mg/ml), 1 ml of a solution of ZnCl2in water (obtained by dissolving 2.2 g of zinc chloride in 50 ml of demineralized water) and 2.5 ml of demineralized water. The impregnated solid is left to age for 16 hours at room temperature, dried at 120°C for 16 hours and calcined at 500°C for 16 hours. Calculated based on the method of obtaining the content of platinum and zinc is Pt=0.1% wt., Zn=0.2% of the mass.

INDUSTRIALLY PRODUCED CATALYSTS.

For the purposes of this invention it is possible to use catalysts are commercially available and intended for applications other than the present invention.

For example, you can use the Engelhard catalysts ESCAT™ H-60 and ESCAT™ H-50 on the basis of cobalt-molybdenum-phosphorus and Nickel-molybdenum-phosphorus, respectively, deposited on alumina, which are described in the technical literature issued by the manufacturer (Engelhard Italiana S.p.A. - Via Siusi 20-20132 Milan-Italy).

Also, for example, you can apply Akzo Nobel catalysts KF-756 and KF-841-based Koba is TA-molybdenum and Nickel-molybdenum, respectively, which are described in the technical literature issued by the manufacturer (Akzo Nobel Chemicals S.p.A. - Via E.Vismara 80-20020 Arese, MI - Italy).

EXAMPLES OF CHARACTERISTICS OF THE CATALYSTS.

Described in the examples tested the catalytic activity was carried out on experimental laboratory equipment, which you can explore working conditions, ensuring optimal process. This equipment and the test procedure described below.

Test catalyst: equipment and test procedure.

The reaction hydrodeoxygenation of dioxybenzone carried out in the vapor phase in a tubular micro-reactor with a fixed catalyst bed with the following characteristics: material = stainless steel AISI 316L, length 180 mm, ⊘int.=11.5 mm, sheath thermocouple with ⊘EXT.=3 mm, the Reactor is placed in an oven that allows you to bring it to the temperature selected for the reaction.

The catalyst used for testing has a size of <2 mm; if you use a commercially available catalyst produced in industry size, it is pre-reduced to the desired value. Catalyst loading is 5.0 g, and placed in the reactor between two layers of granulated quartz.

The solution dioxybenzone pre-heated before it is loaded into the top of the hour the b reactor, then it is evaporated and mixed with hydrogen directly in the reactor (in the layer of granulated quartz) before bringing into contact with the catalyst. Liquid feed solution dosing pump type HPLC; mass flow rate of hydrogen regulate the control of mass flow rate.

The pressure in the installation regulate by means of the regulating valve located at the outlet of the reactor.

In the activation phase of tests on the activity of the catalyst is heated to reaction temperature in a stream of hydrogen at a pressure and flow rate set for testing, and maintained at these conditions for 1 hour. Then served water and after 30 minutes, begin the actual test of catalytic activity with the beginning of the filing of an aqueous solution of deoxybenzoin.

The mixture of vapours through the pressure regulating valve, condense and samples of the crude reaction product is taken to assess the characteristics of the catalyst.

Samples analyzed by gas chromatography and characterization of the catalyst is evaluated by calculating the degree of conversion of dioxybenzone and selectivity with respect to phenol.

Regeneration of the catalyst after the test on the activity carried out in the same reactor used for the reaction. Operating conditions were as follows: temperature of 450-550°C, a pressure of 0.1-0.3 MPa (1-3 who ar), the oxygen concentration of 0.1-20%, gas space velocity = 3000-6000 h-1. In particular, the processing starts with the flow of one of nitrogen, which gradually (approximately 1 hour) add equal air flow. Then the flow of nitrogen is gradually reduced until, until in the end he does not become equal to zero (approximately 1 hour), and processing continues for 5-10 hours. At the end of the processing reactor is washed by a stream of nitrogen, and can re-start the test of catalytic activity.

In the following tables are examples of catalytic activity of the catalysts based on elements of group VIB of the periodic system (examples 10-23) and elements of group VIII of the periodic system (examples 24-27). The tables use the abbreviations and notes, the values of which are given below.

Abbreviations and references used in the examples:

1,2-DB = 1,2-dioxobenzo

1,4-DB = 1,4-dioxobenzo

DB = dioxybenzone

α = volumetric rate in respect of the filing of dioxybenzone

β = time of transmission of the stream, the operating time in hours since the beginning of the test of catalytic activity

Y = time of transmission of the stream, the time in hours since last regeneration, carried out in the reactor

δ = degree of transformation is related to the amount of 1,2-DB+1,4-DB

ε = selectivity in relation to the total number of exposed pre is the treatment DB.

Example 10
Working conditions
The reaction temperature400
Pressure, MPa (bar)0,3 (3)
The solvent is supplied in DBWater
1,2-DB DB solution (wt. -%)20,0
1,4-DB DB solution (wt. -%)10,0
The ratio of N2/DB (molar)20,5
Space velocity (h-1) (α)0,5
Catalytic properties
Catalyst typeMo/Al2About3
Obtaining a catalyst (see Example)1
Time since start, h (Y)110
The degree of transformation of dioxybenzone (%) (δ)92,532,7
The selectivity to phenol (%) (ε)98,497,6

Example 11
Working conditions
The reaction temperature400
Pressure, MPa (bar)2,5 (25)
The solvent is supplied in DBWater
1,2-DB DB solution (wt. -%)20,0
1,4-DB DB solution (wt. -%)10,0
The ratio of H2/DB (molar)of 21.2
Space velocity (h-1) (α)0,5
Catalytic properties
Catalyst typeMo/Al2About3
Obtaining a catalyst (see Example)1
Time since start, h (β)120
The degree of transformation of dioxybenzone (%) (δ)for 91.335,4
The selectivity to phenol (%) (ε)92,296,9

Example 12
Working conditions
The reaction temperature400
Pressure, MPa (bar)2,5 (25)
The solvent is supplied in DBWater
1,2-DB DB solution (wt. -%)20,0
1,4-DB DB solution (wt. -%)10,0
The ratio of N2/DB (molar)a 21.5
Space velocity (h-1) (α)0,5
Catalytic properties
Catalyst typeW/Al2O3
Obtaining a catalyst (see Example)2
Time since start, h (Y)125
The degree of transformation of dioxybenzone (%) (δ)75,826,0
The selectivity to phenol (%) (ε)81,890,9

Example 13
Working conditions
Working conditions as in example 12
Catalytic properties
Catalyst typeWP/Al2O3
Obtaining a catalyst (see Example)3
Time since start, h (β)10
The degree of transformation of dioxybenzone (%) (δ)17,4
The selectivity to phenol (%) (ε)92,4

Example 14
Working conditions
The reaction temperature400
Pressure, MPa (bar)0,3 (3)
The solvent is supplied in DBWater
1,2-DB DB solution (wt. -%)30,6
1,4-DB DB solution (wt. -%)-
The ratio of H2/DB (molar)20,3
Space velocity (h-1) (α)0,5
Catalytic properties
Catalyst typeCoMoP/Al2O3
Industrially produced catalystEscat H-60
Time since start, h (β)120
The degree of transformation of dioxybenzone (%) (δ)100,073,6
The selectivity to phenol (%) (ε)97,299,2

Example 15
Working conditions
The reaction temperature400
Pressure, MPa (bar)1,8 (18)
The solvent is supplied in DBWater
1,2-DB DB solution (wt. -%)26,9
1,4-DB DB solution (wt. -%)-
The ratio of N2/DB (molar)23,1
Space velocity (h-1) (α)0,5
Catalytic properties
Catalyst typeCoMoP/Al2O3
Industrial catalystEscat H-60
Time since start, h (Y)185
The degree of transformation of dioxybenzone (%) (δ)98,6100,0
The selectivity to phenol (%) (ε)97,999,0

Example 16
Working conditions
The reaction temperature400
Pressure, MPa (bar)0,3 (3)
The solvent is supplied in DBWater
1,2-DB DB solution (wt. -%)15,0
1,4-DB DB solution (wt. -%)8,0
The ratio of N2/DB (molar)26,6
Space velocity (h-1) (δ)0,4
Catalytic properties
Catalyst typeSNF/Al2O3
Obtaining a catalyst (see Example)4
Time since start, h (β)124
The degree of transformation of dioxybenzone (%) (δ)100,094,4
The selectivity to phenol (%) (ε)96,898,3

Example 17
Working conditions
Working the conditions as in example 12
Catalytic properties
Catalyst typeSOMO
Industrial catalystKF-756
Time since start, h (Y)33133151
The degree of transformation of dioxybenzone (%) (δ)100,098,482,5
The selectivity to phenol (%) (ε)94,8to 97.197,9

Example 18
Working conditions
Working conditions as in example 12
Catalytic properties
Catalyst typeAmor/Al2About3
Industrial catalystEscat H-60
Time since start, h (Y)3671116
The degree of transformation of dioxybenzone (%) (δ)100,0100,0100,0
The selectivity to phenol (%) (ε)93,296,997,5
Example 19
Working conditions
Working conditions as in example 11
Catalytic properties
Catalyst typeCoMoW/Al2O3
Obtaining a catalyst (see Example)5
Time since start, h (β)115
The degree of transformation of dioxybenzone (%) (δ)99,999,7
The selectivity to phenol (%) (ε)96,8for 95.2

Example 20
Working conditions
Working conditions as in example 11
Catalytic properties
Catalyst typeFeMo/Al2About3
Obtaining a catalyst (see Example)6
Time since start, h (β)120
The degree of transformation of dioxybenzone (%) (δ)99,2 28,3
The selectivity to phenol (%) (ε)for 95.3of 97.8

Example 21
Working conditions
Working conditions as in example 12
Catalytic properties
Catalyst typeFeMo/Al2About3
Obtaining a catalyst (see Example)6
Time since start, h (Y)24597
The degree of transformation of dioxybenzone (%) (δ)99,999,560,9
The selectivity to phenol (%) (ε)of 97.896,997,9

Example 22
Working conditions
Working conditions as in example 11
Catalytic properties
Catalyst typeNiMo
Industrial catalystKF-841
Time since Zap the ska, h (Y)193187
The degree of transformation of dioxybenzone (%) (δ)99,8100,0100,0
The selectivity to phenol (%) (ε)84,1for 95.395,9

Example 23
Working conditions
Working conditions as in example 11
Catalytic properties
Catalyst typeNiMoP/Al2O3
Industrial catalystEscat H-50
Time since start, h (β)180157
The degree of transformation of dioxybenzone (%) (δ)99,8100,099,7
The selectivity to phenol (%) (ε)93,394,794,5

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Example 24
Working conditions
Working conditions as in example 11
Catalytic properties
Catalyst typeCo/Al2About3
Obtaining a catalyst (see Example)7
Time since start, h (β)120
The degree of transformation of dioxybenzone (%) (δ)69,923,2
The selectivity to phenol (%) (ε)95,488,0

Example 25
Working conditions
The reaction temperature250
Pressure, MPa (bar)2,5 (25)
The solvent is supplied in DBWater
1,2-DB DB solution (wt. -%)20,0
1,4-DB DB solution (wt. -%)10,0
The ratio of N2/DB (molar)6,0
Space velocity (h-1) (α)0,9
Catalytic properties
Catalyst typePt/Al2O3
Obtaining a catalyst (see Note what R) 8
Time since start, h (Y)515
The degree of transformation of dioxybenzone (%) (δ)93,081,0
The selectivity to phenol (%) (ε)19,136,0

Example 26
Working conditions
Working conditions as in example 11
Catalytic properties
Catalyst typePtZn/spinel MgAI
Obtaining a catalyst (see Example)9
Time since start, h (β)148
The degree of transformation of dioxybenzone (%) (δ)99,284,3
The selectivity to phenol (%) (ε)46,6of 37.8

Example 27
Working conditions
The reaction temperature450
Pressure, MPa (bar)2,5 (25)
The solvent is supplied in DB Water
1,2-DB DB solution (wt. -%)19,8
1,4-DB DB solution (wt. -%)10,0
The ratio of N2/DB (molar)6,1
Space velocity (h-1) (α)0,9
Catalytic properties
Catalyst typePtZn/spinel MgAl
Obtaining a catalyst (see Example)9
Time since start, h (Y)37
The degree of transformation of dioxybenzone (%) (δ)81,4
The selectivity to phenol (%) (ε)74,7

1. Method for production of phenol, which are reaction hydrodeoxygenation in the vapor phase when operating in the continuous mode in the adiabatic reactor with a fixed catalyst bed feed stream of an aqueous solution of dioxybenzone with a concentration of from 5 to 60 wt.% with a bulk velocity, expressed in kg of dioxybenzone/h/kg of catalyst is 0.1 to 10 h-1and the flow of hydrogen in an amount such that the ratio between the total number of moles of hydrogen and dioxybenzone was in the range of from 2:1 to 50:1, at a temperature in the range from 250 to 500°C, a pressure of 0.1-10 MPa, in the presence of a catalyst comprising a cat is a lyst on the media, containing an element of group VIB or a mixture or an element of group VIII of the Periodic system or their mixture and the promoter.

2. The method according to claim 1, characterized in that dioxobenzo chosen from the group comprising 1,2-dioxobenzo, 1,3-dioxobenzo, 1,4-dioxybenzene or mixtures thereof.

3. The method according to claim 1 or 2, characterized in that the reaction is carried out in the vapor phase at a temperature of 300-450°and a pressure of 0.3 to 5 MPa.

4. The method according to claim 3, characterized in that the reaction is carried out at flow rate of 0.5-5 h-1.

5. The method according to claim 1, characterized in that the reactor an aqueous solution of deoxybenzoin with a concentration in the range from 10 to 40%, and the flow of hydrogen in an amount such that the ratio between the total number of moles of hydrogen and dioxybenzone was in the range of from 5:1 to 30:1.

6. The method according to claim 1 or 5, characterized in that the feed stream is vaporized and heated to a temperature in the range from 250 to 500°and pressure support when the value in the range from 0.1 to 10 MPa.

7. The method according to claim 1, wherein the element of group VIB is molybdenum or tungsten.

8. The method according to claim 7, wherein the promoter element is selected from the group comprising an element of group VIII, phosphorus or a mixture.

9. The method of claim 8, wherein the element of group VIII selected from the group including Nickel, cobalt, iron and ruthenium.

10. The way is about to claim 1, wherein the element of group VIII is an element selected from the group of cobalt, palladium, Nickel, platinum.

11. The method according to claim 10, characterized in that the catalyst is a member selected from the group comprising an element of group VIII and contains as a promoter element selected from zinc, rhenium, selenium, tin, germanium and lead, or mixtures thereof.

12. The method according to claim 1, characterized in that the medium is selected from the group comprising aluminum oxide, silicon dioxide, titanium dioxide, crystalline or amorphous aluminosilicates, crystalline spinel, or a mixture thereof.

13. The method according to claim 1 or 12, characterized in that the catalyst containing an element of group VIB is present in the carrier at a concentration in the range from 1 to 50 wt.%, and the promoters of these catalysts in concentrations in the range from 0.1 to 100% atomic with respect to the element of group VIB.

14. The method according to item 13, wherein the catalyst containing an element of group VIB is present in the carrier at a concentration in the range from 3 to 30 wt.%, and the promoters of these catalysts in concentrations in the range from 1 to 50% atomic with respect to the element of group VIB.

15. The method according to claim 1 or 12, characterized in that the catalyst containing an element of group VIII is present in the carrier at a concentration in the range from 0.05 to 20 wt.%, and the promoters of these catalysts in concentrations of d is apatone from 0.5 to 200% atomic with respect to the element of group VIII.

16. The method according to item 15, wherein the catalyst containing an element of group VIII is present in the carrier at a concentration in the range from 0.1 to 10 wt.%, and the promoters of these catalysts in concentrations in the range from 1 to 120% atomic with respect to the element of group VIII.

17. The method according to claim 1, characterized in that the reaction is carried out in two or more adiabatic reactors with a fixed catalyst bed, connected in series, by cooling the flow coming from one reactor before it enters the next reactor to limit the temperature rise in each of the reactors is less than 40°C.

18. The method according to 17, characterized in that as the water supply and the supply of hydrogen in separate reactors are separated, and the process is conducted so that the temperature rise in each reactor did not exceed 40°C.

19. The method according to 17, characterized in that the reaction is carried out in two reactors, which alternately switch on the reaction and regeneration.

20. The method according to claim 1, characterized in that the catalyst is subjected to regeneration by burning at a temperature in the range from 400 to 550°and a pressure in the range from 0.1 to 0.3 MPa with a mixture of oxygen and nitrogen in a ratio in the range from 0.1 to 20 vol.% and with a bulk velocity, expressed in liters of gas mixture/h per liter of catalyst component 3000-6000 h-1 .

21. The method according to claim 20, characterized in that the regeneration is carried out in the same reactor in which the catalyst is placed for the reaction.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: process includes resorcinol extraction with organic solvent tributyl phosphate (TBPh). The well-milled hard foamed polyurethane (FPU) will be modified at that with tributyl phosphate in the mass ratio FPU:TBPh = 1:(2.0-2.5), the extraction will be performed prior to establishing the interphase balance with subsequent isolation of organic phase from the water phase.

EFFECT: process enables one to enhance the concentrating coefficient and reduce expenditure of the organic solvent tributyl phosphate.

1 tbl, 2 ex

FIELD: analytical chemistry of organic compounds; in particular quality controlling of alcohol products.

SUBSTANCE: claimed method includes catechol extraction from ground oak wood with organic solvent aqueous solution followed by determination of content thereof, wherein as organic solvent ethanol aqueous solution is used in ethanol/water ratio of 50:50. Then catechols are concentrated into organic phase at pH 2.0-3.0; ammonium sulfate is added in amount of 18-20 % based of probe mass and catechols are determined by extract conductance-measuring titration. Catechol content in aqueous alcohol solution as calculated to quercetine is determined according formula wherein C is catechol concentration in solution, g/dm3; C(PB(NO3)2) is molar concentration of titrant equivalent, g/dm3; V(PB(NO3)2) is titrant volume required for catechol titration, cm3; Mk - molar mass of quercetine, g/mol; Ve - extract volume, cm3; r is equilibrium volume ratio of aqueous and organic phases; R is catechol recovery degree in ethanol/aqueous-salt solution, % (96).

EFFECT: simplified and inexpensive method with increased selectivity, and enhanced applications.

9 ex, 2 tbl, 1 dwg

FIELD: analytical methods.

SUBSTANCE: invention is directed to controlling treated waste waters from varnish-and-paint industry enterprises and discloses a method of separately determining resorcinol and 2,4-dinitroresorcinol involving potentiometric titration in dimethylformamide medium, determination being carried out in aqueous sample preliminarily acidified to pH 2-3 and treated with acetone in presence of ammonium sulfate as salting-out agent in amount 36.5-40.0% of the weight of sample. Organic layer containing resorcinol and 2,4-dinitroresorcinol is then separated, diluted with dimethylformamide at volume ratio 1:5, and titrated with solution of potassium hydroxide in isopropyl alcohol. Content of each of resorcinols is calculated from differential titration curves in according to formula: C = Co100/R wherein C and Co are concentrations of resorcinols in initial aqueous sample and in extract, respectively, mg/dm3, and R degree of recovery of resorcinols in acetone/water-salt solution, %.

EFFECT: enabled selective determination of resorcinol and 2,4-dinitroresorcinol, reduced detection limits (extraction concentration operation), and expanded application area.

2 tbl, 12 ex

FIELD: industrial organic synthesis.

SUBSTANCE: purification of industrial-grade resorcinol mainly comprises removal of phenol by way of disintegrating product at 40-60°C in inert gas or air flow to particle size 0.01-0.1 mm. Depending on pollution and content of phenol in starting resorcinol, disintegration is preceded by extraction of resorcinol with alcohol or ketone, or ether, or water, after which resorcinol is dried in inert gas flow at 20-40°C. Purified product has melting point 110°C and is characterized by phenol level not exceeding 0.001 wt %.

EFFECT: improved quality of product and simplified purification process.

2 cl, 2 ex

The invention relates to organic synthesis, in particular to a method of producing dihydroxybenzene catalytic oxidation of phenol by nitrous oxide in the presence of benzene

The invention relates to the derivatives of resorcinol used to obtain cosmetic preparations

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 an improved method for producing 2,3,5-trimethylhydroquinone - intermediate production of vitamin E.

The invention relates to the synthesis of a derivative of hydroquinone, namely, 2,5-di-(N,N-dimethylaminomethyl)-hydroquinone, which may find application as a colorless treatment of thermo stabilizer rubber stamps SKI-3, representing a synthetic isoprene rubber with a high content of parts of CIS-1,4

FIELD: chemistry.

SUBSTANCE: H-form of ultrastable dealuminated Y-zeolites HUSY with SiO2/Al2O3 ratio within 5 to 120 is used as catalyst. As a rule, zeolites are combined with a binding agent represented by aluminum oxide, silicon oxide or their mix. Usually the catalyst is preliminarily activated by calcination in air at 300-600°C, while the method is implemented at 20-100°C. As a rule, cumol hydroperoxide concentration in the raw mix varies within 3 to 80%, and acetone, cumol, phenol or their mix with various component ratio are used as solvent.

EFFECT: increased process selectivity in relatively mild conditions.

7 cl, 1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: method includes two-stage acid-catalysed decompounding of cumene hydroperoxide in series reactors under heat resulted in simultaneous generation dicumene peroxide in the first stage followed with its decompounding in reaction medium environment in the second stage. Thus any catalytic agent is not used; it is prepared in separate reactor immediately prior to introduce to the first reactor of cumene hydroperoxide decompounding by mixing sulphuric acid with phenol in ratio 2:1 to 1:1000 and keeping produced mixture at temperature 20-80°C within 1-600 minutes.

EFFECT: method allows for considerable yield reduction of hydroxyacetone.

4 cl, 7 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to the method of oxidation of hydrocarbons using oxygen in trifluoroacetic acid and can be used particularly for oxidation of alkanes, cycloalkanes, alkylaromatic hydrocarbons, alkenes, cycloalkenes. The method involves saturation of trifluoroacetic acid with oxygen, after which, the initial hydrocarbon is added to the obtained reaction medium and is kept until depletion of bound oxygen with obtaining the corresponding oxygen containing compound.

EFFECT: invention allows carrying out a process of selective partial catalytic oxidation of hydrocarbons with obtaining different oxygen containing organic compounds without use of high temperature and traditional catalyst systems based on transition metals.

1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the method of obtaining phenol and acetone by acid-catalysable decomposition of hydro-peroxide of cumene in the environment of the reaction products at elevated temperatures in one stage. In this case the process is carried out in the presence of a catalyst, prepared immediately before its introduction into the reactor for the decomposition of hydro-peroxide of cumene by mixing sulfuric acid with phenol at the ratio of from 2:1 till 1:1000 and the waiting time from mixing till putting into the reactor for the decomposition of hydro-peroxide of cumene from 1 to 600 minutes at a temperature from 20 to 80°C. As a rule, sulfuric acid has a concentration of higher than 75% or oleum is used.

EFFECT: it makes it possible to decrease the output of the by-product hydroxyacetone, improves the quality of market-grade phenol and decreases the consumption of sulfuric acid.

2 cl, 4 tbl, 4 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for purifying phenolic flow prepared after distillation of raw acetone in separating decomposition products of cumene hydroperoxide from hydroxyacetone by rectification method. For removal of hydroxyacetone from phenolic flow methods of azeotropic-extractive rectification is used with using a combined separating agent wherein hydrocarbon (cumene and/or α-methylstyrene) is used as one components, and water is used as another component. Method involves feeding a separating agent in common with feeding a column, maintaining the mass ratio of hydrocarbon and water that equal or above the mass ratio of concentrations of hydrocarbon and water in the corresponding azeotropic mixtures, removing hydroxyacetone from column with distillate aqueous flow and feeding organic phase to phlegm wherein this organic phase is depleted with hydroxyacetone. Use of this method provides enhancing selectivity and complete distillation of hydroxyacetone.

EFFECT: improved purifying method.

17 cl, 2 dwg, 13 ex

FIELD: chemical industry; methods of production of the phenols by the catalytic decomposition of the cumene hydroperoxide into phenol and acetone.

SUBSTANCE: the invention is pertaining to production of phenols by the catalytic decomposition of the cumene hydroperoxide into phenol and acetone. The method provides for oxidization of the cumene into the cumene hydroperoxide, catalyzed by the acid decomposition of the cumene hydroperoxide, neutralization of the produced product of the decomposition, maintaining the product in the homogeneous phase before neutralization, which is conducted by means of the aqueous base. The phenol is separated by fractionation of the neutralized product. The aqueous base represents the water solution of the sodium hydroxide or phenoxide. In particular use the regenerated phenoxide, at least, on one phase of the treatment at production of the phenol. It is preferential to add the sodium hydroxide water solution to the reaction product in such a concentration and such amount, that to receive the concentration of sodium phenolate in the homogeneous phase from 0.2 up to 2.5 mass %. The temperature of the homogeneous phase after the add-on of the aqueous base is set within the range of 20°С-150°С, the preferable temperature is within the range of 60°С-120°С. It is preferential, that the reaction product is saturated with the oxygen-containing gas. The technical result of the invention is the decreased quantity of the undesirable impurities in the products of the acid decomposition of the cumene hydroperoxide.

EFFECT: the invention ensures the decreased quantity of the undesirable impurities in the products of the acid decomposition of the cumene hydroperoxide.

13 cl, 4 ex

FIELD: chemical industry; methods of extraction of phenol and biphenols from the homogeneous reactionary mixtures.

SUBSTANCE: the invention is pertaining to the method of extraction of phenol and biphenols from the homogeneous reactionary mixtures of the direct oxidation of benzene by hydrogen peroxide. The method includes delivery of the reactionary mixture containing benzene, water, phenol, the sulfolane and the reaction by-products (biphenols) in еру distillation plant consisting of two or more columns for production of one or more products basically consisting of the azeotropic mixture of benzene with water and phenol, and also the product consisting of sulfolane, phenol and the reaction by-products. The stream including sulfolane is mixed with the water solution of the base and benzene for formation of the salts of the phenols and the subsequent stratification of the mixture, extraction by benzene and separation in the flow column containing benzene and sulfolane, which is returned in the reactor. From the same column separate the stream including sodium phenolates in the water solution, which is treated with the sulfuric acid for extraction of the phenols from their salts. At the stage of the extraction separate the extracting solvent, after distillation of which in the tailings bottom product receive the biphenols water solution. The separated organic solvent recirculates in the system. The technical result of the invention is improvement of the process of separation of phenols and biphenols from the complex azeotropic mixtures containing sulfolane.

EFFECT: the invention ensures the improved process of separation of phenols and biphenols from the complex azeotropic mixtures containing sulfolane.

9 cl, 1 ex, 1 dwg, 1 tbl

FIELD: industrial organic synthesis.

SUBSTANCE: isopropyl alcohol production process comprises hydrogenation of starting acetone including from 0.01 to 10000 ppm benzene in presence of hydrogen and catalyst to give isopropyl alcohol and benzene hydrogenation products, acetone and benzene contained in feedstock being hydrogenated simultaneously. In its second embodiment, isopropyl alcohol production process comprises product separation stage. Process of producing phenol and isopropyl alcohol containing benzene hydrogenation products comprises stages: alkylation of benzene with isopropyl alcohol and/or propylene to form cumene, oxidation of resulting cumene into cumene hydroperoxide, acid cleavage of cumene hydroperoxide to produce phenol and acetone including from 0.01 to 10000 ppm benzene, preferably concentration of produced benzene-polluted acetone, and catalytic hydrogenation of benzene-polluted acetone into isopropyl alcohol containing benzene hydrogenation products, hydrogenation of benzene and acetone proceeding simultaneously.

EFFECT: enhanced process efficiency.

3 cl, 1 dwg, 1 tbl

FIELD: chemical industry; methods of production of phenol and acetone.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the industrial process of production of phenol and acetone by the cumene method. The method is realized by decomposition of the technological cumene hydroperoxide in the in series connected reactors in two stages with formation on the first stage of the dicumylperoxide at the temperature of 40-65°С at presence as the catalytic agent of 0.003-0.015 mass % of the sulfuric acid with its subsequent decomposition on the second stage in the reaction medium at the temperature of 90-140°С. The process is conducted at the excess of phenol in the reaction mixture at the molar ratio of phenol : acetone exceeding 1, preferentially - from 1.01 up to 5. Excess of phenol is formed either by distillation (blowing) of acetone or addition of phenol in the reaction medium. The technical result of the invention is reduction of formation of hydroxyacetone, which one worsens the quality of the commercial phenol.

EFFECT: the invention ensures reduction of formation of hydroxyacetone, which one worsens the quality of the commercial phenol.

5 cl, 4 ex, 8 tbl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to manufacturing phenol by cumene method, in particular, to a step for treatment of final product and preparing phenol of high purity degree. Method for treatment of crude phenol is carried out for two steps. At the first step method involves oxidation of acetol, aldehydes and α-methylstyrene with air oxygen in phenol medium by using a heterogeneous catalyst comprising metals with transient valence. At the second step method involves condensation of oxidation products and non-oxidized products by using a heterogeneous acid catalyst. Separation of compounds in the process of phenol treatment is carried out on the final step of isolation of the commercial product by distillation method. At the first stage metal compounds of by-side subgroups 1 and 6 and metals of 8 group of Periodic system on neutral or acid carrier are used as a catalyst preferably. At the second step alumosilicate contacts based on zeolites of type "X" or "Y", or other zeolites comprising or not comprising promoting and modifying additives are used as a catalyst. Invention provides the high degree of purification of phenol from impurities and the improvement of economy indices of the process.

EFFECT: improved method for phenol treatment.

12 cl, 5 ex

FIELD: chemical industry; non-ferrous metallurgy industry; other industries; methods of production of the catalyst for oxidization of the vanadium oxide particles in the gaseous phase with the definite size distribution.

SUBSTANCE: the invention is pertaining to the method of production of the catalyst for oxidization in the gaseous phase of the vanadium oxide particles with the definite size distribution. The invention describes the method of production of the catalyst for oxidization in the gaseous phase, at which on the fluidized inert carrier they deposit the suspension of TiO2 and V2O5 particles, in which, at least, 90 volumetric % of the particles of V2O5 have the diameter of 20 microns or less and, at least, 95 volumetric % of the particles of V2O5 have the diameter of 30 microns or less. The technical result of the invention is that the certain particle-size distribution allows to achieve the high efficiency of the coating.

EFFECT: the invention allows to achieve the high efficiency of the coating.

6 cl, 2 ex

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