Phenol production method

FIELD: chemistry.

SUBSTANCE: invention relates to methods (versions) of producing phenol through hydrodeoxidation of polyhydroxylated benzene derivatives, as well as through selective hydroxylation of benzene where a catalyst based on multi-component metal oxides is used. The methods are distinguished by that the said oxides contain at least one active phase of an oxide which corresponds to a scheelite structure, and crystalline materials which are not scheelite, or an amorphous structure where the crystalline scheelite structure is selected from the following compositions: Bi(1-x/3)V(1-x)wNb(1-x)(1-w)MoO4, Cu(1-z)ZnzW(1-y)MoyO4, where each of w, x, y and z are equal to 0 or 1, and where the crystalline materials which are not scheelite or an amorphous structure are selected from cerium oxide or a mixture of cerium oxide and zirconium oxide.

EFFECT: design of an efficient method of producing phenol through hydroxydeoxidation of polyhydroxylated benzene derivatives.

23 cl, 32 ex, 4 dwg

 

The invention relates to a method for producing phenol by hydrodeoxygenation of bentolila hydrogen or by direct oxidation of benzene.

More specifically, it relates to a method for production of phenol, in which the above-mentioned reaction is carried out in the presence of a catalyst based on multicomponent metal oxides.

Phenol is an intermediate product, which is of great importance and used in many industries, for example in the production of polycarbonates or other phenolic resins, fibers, detergents, antioxidants and many other areas.

On an industrial scale phenol get from cumene through a multistage process that begins with benzene and propylene and leads to joint formation of phenol and acetone. Joint production of acetone may further cause problems with its use, because, as you suggest, the market for this product has been slower than the market phenol.

Therefore, to simplify the existing way of actively doing research in search of alternative business process.

Currently considered research areas offer processes both in liquid and in the gas phase.

For example, in U.S. patents 6573413 and 5110995 described "one-step" method in the gas phase, on the basis of nepo is directly from benzene and nitrous oxide (process Alphox). One of the main problems of this method is related to availability of oxidant. Special receiving nitrous oxide (N2O) as oxidant on the basis of ammonia is actually burdensome, while the possibility of the use of N2O - a byproduct of the production of adipic acid from phenol, apparently, is an important factor in the economic viability of the process Alphox. This, however, requires a strong integration between the two processes, which is inconvenient for an independent promotion in the commodity market.

Research alternative methods of production of phenol, based on the direct oxidation of benzene at high temperatures in the gas phase by means of molecular oxygen or air in the presence of various catalysts oxidation, still did not give acceptable results both in relation to the inherent process safety, and process parameters.

Unfortunately, when used in these processes, the temperature is also significant oxidation of the benzene ring, which leads to the formation of products such as carbon dioxide, carboxylic acids or anhydrides, with a consequent loss of selectivity (U.S. patent 5981424; G.I.Panov of SATTEN 4 (2000), 18-32; J. Plotkin, European Chemical News 25/09-1/10 2000, 59-62).

Another disadvantage of the direct oxidation of the gases in the phase, at the same time serves oxidants (e.g., oxygen and hydrocarbons, is the possibility of hitting the limits of Flammability or explosive limit of the mixture of reagents; often these limits are known only approximately to the conditions of industrial plants in relation to temperature, pressure, geometrical characteristics (P.Arpentier, F.Cavani, F.Trifiro, Technology catalytic oxidation. Vol.2. Safety aspects. The technology of catalytic oxidation, vol. 2, Safety aspects), Ed. Technip, 2001).

Patents EP 0919531 and EP 0958861 describe the selective oxidation of benzene without breaking the benzene ring, carried out in the liquid phase with the use of such oxidizing agents as hydrogen peroxide, in the presence of specific solvents and suitable catalytic systems. These methods, however, do not allow to achieve high levels of performance because they must be implemented at low degrees of conversion of benzene to limit the subsequent oxidation of phenol to by-products (pyrocatechin and hydroquinone).

For example, in patent application WO 03042146 indicated that for every ton of phenol can be obtained simultaneously 111 kg of hydroquinone and pyrocatechin (55/45 mixture), when the degree of conversion of benzene to 12.2% and the selectivity with respect to the phenol 90%. These side products are obtained in such a quantity that the market cannot absorb, and thus the time should utilizability, which leads to an increase of costs for the process.

Another method of producing phenol provides as starting substances bentolila (dioxybenzone); these compounds undergo the process of hydrodeoxygenation hydrogen, conducting the process in the presence of water and catalyst based on elements VIB or VIII group of the Periodic system, as described in European patent application EP 1411038.

Integrated method for production of phenol, described in Italian patent application EP 1424320 A1, in which the reaction by-products is hydroquinone and pyrocatechin is selectively converted into phenol and recyclery streams involved in the process, allows you to completely eliminate the simultaneous formation of by-products, getting productivity growth on phenol.

It is now established that phenol can be obtained based on both polyhydroxylated benzene derivatives (for example, bentolila) by hydroxydeoxyguanosine in the presence of hydrogen and benzene by oxidative hydroxylation (also called direct partial oxidation)is carried out in an environment with a lack of reagents, when working in the presence of certain catalytic compositions.

Carrying out the reaction in an environment with a lack of reagent means that the reaction is carried out with de what isicom molecular oxygen or other oxidizing agents in relation to the stoichiometry of the reactions.

These conditions reach, feeding oxygen or other oxidizing agents in the reaction in smaller quantities in comparison with the stoichiometric quantity per reacts benzene, or not feeding them, as more clearly illustrated below.

Thus, the subject of this invention is a method of producing phenol by hydrodeoxygenation polyhydroxylated benzene derivatives or through the selective hydroxylation of benzene in terms of lack of reagent, characterized in that the reaction is carried out in the presence of a catalyst based on multicomponent metal oxides comprising at least one metal selected from groups VB, VIB, VIII, IB, IV, IVA, VA.

The use of catalysts according to this invention under oxidative hydroxylation of benzene in terms of lack of reagent or hydrodeoxygenation polyhydroxylated benzene derivatives in the presence of hydrogen is even more unexpected, given that the usual catalysts of oxidation and reduction are unable to perform the described reaction, as shown in the comparative examples.

In the case of oxidative hydroxylation in terms of lack of reagent missing to the stoichiometry of oxygen provides the catalyst, which is about the same time changes its composition (stage conversion of benzene to phenol and the recovery phase of the catalyst). In a subsequent phase, the catalyst back to its original state by means of oxygen or other oxidizing compounds (stage a re-oxidation catalyst). Stages of the reaction and re-oxidation is carried out cyclically.

At the stage of oxidation of benzene to phenol using the catalyst in a partially or fully oxidized form, and under the reaction conditions support the lack of oxygen or another oxidizing agent.

In practice, the oxidation reaction of benzene to phenol is carried out in the absence of molecular oxygen or other oxidizing agents or by feeding smaller amounts of oxygen or other oxidizing agents than the amount required by the stoichiometry involved in the reaction of benzene.

From reaction (1)below shows that the catalyst participates in the stoichiometry of the reaction, acting as agent, when it is in the oxidized state (catox) and is able to provide a portion of its oxygen, and subsequently calls for a shift in the recovered state (catred").

To the reaction was catalytic, it is necessary that the recovered catalyst was easily able to get oxygen from the agent-oxidant (such as air, oxygen, N2O and so on)button again to turn on the second stage (2) in a higher degree okelani is, able to initiate a new cycle of oxidation.

The oxidation catalyst in its oxidized form may be the maximum degree of oxidation or intermediate oxidation state that is optimal for reduction to the maximum desired parameters of the reaction (outputs, performance, and so on).

where "Oh" represents one of the above oxidizing agents.

In the field of reactions selective catalytic oxidation is known to conduct the reaction in terms of lack of reagent (hereinafter referred to as "redox technology (RedOx technology)) (Ind. Eng. Chem., 41(6), 1949, p.1227).

This approach was developed for reactions of selective oxidation and oxidative dehydrogenization.

In particular, it is possible to trace the history of RedOx technologies for the reactions of selective oxidation, as described in the introduction to this patent, to engineering concepts that were supposed to work in periodic mode. The most recent development of such technologies are described in G.Emig and M.A.Liauw, Topics in Catalysis, vol.21, Nos. 1-3 (2002), pp.11-24, and P.Silveston, R.R.Hudgins, A.Renken, Catalysis Today 25 (1995) 91-112.

The oxidation of benzene with application of RedOx technologies is carried out in a reactor operating at temperatures in the range from 150 to 700°C., preferably from 200 to 600°C., more is preferably from 250 to 550°C, at a pressure in the range from 0.01 to 10 MPa (from 0.1 to 100 bar), preferably from 0.1 to 3 MPa (from 1 to 30 bar) volumetric velocity, referring to the mass space velocity per hour, WHSV (g feed mixture g of catalyst per hour) in the range from 0.01 to 1000 h-1preferably from 1 to 100 h-1even more preferably from 2 to 50 h-1.

The reaction can be carried out in the presence of a diluent (N2CH4N2O CO2and so on). The catalytic system restore in the regenerator at temperatures above 100°C, restoring, thus, the degree of oxidation, are more useful for the catalyst, and possibly eliminating at least part of the carbon deposits formed during the reaction.

Oxidative environment used in this section, may consist of oxygen, air, suitable mixtures of nitrogen and oxygen, other oxidizing agents, such as, for example, N2O and its mixtures. It is also possible presence of diluents, such as CO2N2About etc.

The oxidation reaction of the organic substrate is preferably carried out outside of the range of explosive gaseous mixture of reagents used for ranges of temperature, pressure and ratio of oxygen/air.

The hydroxylation reaction of benzene according to this invention is preferably carried out in two reactors: one is the La of the reaction, the other for regeneration.

Thus it is possible to separate the hydrocarbon from the oxidizing agent, thus obtaining various advantages compared to oxidation in the gas phase, where both served the substrate and oxidizing agent.

In particular, the separation of the flow of organic matter and flow of oxidant in the reactor allows to provide:

using as oxidizing agent air instead of oxygen without the influence of nitrogen that can interfere with the separation of the product;

higher selectivity, because there is no direct interaction between fed organic substrate and molecular oxygen;

the possibility of more concentrated flows without the risk of explosion due to the separation of a mixture of air/oxidizing gas and hydrocarbons;

the formation of more concentrated product at the outlet of the reactor;

optimizing outputs through appropriate regulation of the reaction conditions (composition and consumption of food, the frequency of re-oxidation catalyst, the oxidation state of the catalyst at the beginning and at the end of the reaction stage).

The process of selective hydroxylation of benzene is usually carried out in several reactors, at least one of which is for the regeneration of the catalyst; in this case, at least one reactor is designed for re is enerali catalyst, which is carried out either by physical movement of the catalyst from the reactor, where the reaction takes place in reactor regeneration, either through the exchange of flows between them.

If using a fluidized bed reactor, the reaction and regeneration can be performed in the same equipment, in accordance with current level of technology.

Reactors with fast motion in the fluidized bed, or reactors of the type of separation columns with flow can be successfully used for hydroxylation at low contact times.

If phenol is obtained by hydrodeoxygenation polyhydroxylated benzene derivatives, such as bentolila, the process is carried out by reaction polyhydroxyalkane a derivative of benzene with hydrogen in the vapor phase at a temperature of 250-500°C., preferably 300-450°C, at pressures of 0.1-10 MPa (1-100 bar), preferably in the range of 0.3 to 5 MPa (3-50 bar), and with a bulk velocity (WHSV mass hourly space velocity, kg bentolila/h/kg of catalyst) of 0.1-10 h-1, preferably 0.5 to 5 h-1.

Water is a normal reaction medium for the reaction, it is actually the optimal solvent for the reactants and products of the reaction and is completely inert towards them both.

Water also has the advantage that it is the possession is t a high heat capacity and consequently, tends to limit the increase in temperature due to the enthalpy of reaction deoxidizing. Finally, water is also particularly economical.

In the process, using hydrodeoxygenation of bentolila can be turned into a phenol with high efficiency and selectivity of 1,2-benzodia (pyrocatechin, hereinafter abbreviated as 1,2-BD), 1,3-benzodia (resorcinol, then 1,3-BD), 1,4-benzodia (hydroquinone, then 1,4-BD), and mixtures thereof.

The reaction is carried out in the vapor phase at a temperature of 250-500°C., preferably 300-450°C, at pressures of 0.1-10 MPa (1-100 bar), preferably in the range of 0.3 to 5 MPa (3-50 bar)and flow rate (WHSV mass hourly space velocity, kg bentolila/h/kg of catalyst) of 0.1-10 h-1, preferably 0.5 to 5 h-1.

Power reactor consists of a solution of bentolila in water with a concentration of 5-60 wt.%, preferably 10-40 wt.%, and hydrogen at a mass ratio with Bentonville 2-50, preferably 5-30.

In a variant implementation of the invention the reaction is carried out inside an adiabatic reactor with a fixed bed containing the catalyst, as described above, which serves stream containing an aqueous solution of benzodia with a concentration in the range 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 bentolila on Tilos in the range from 2:1 to 50:1. Feed stream is vaporized and heated to a temperature in the range from 250 to 500°C and the pressure is maintained within the range from 0.1 to 10 MPa (from 1 to 100 bar). The flow at the exit of the reactor consists of a crude reaction material containing any residual bentolila and the resulting phenol in aqueous solution, and the residual hydrogen, which is then returned to the process.

In another embodiment, the implementation of this invention the reaction is carried out in two or more adiabatic reactors with a fixed layer, connected in series, with the aim of cooling flow at the outlet of the reactor before entering the next reactor, so as to limit the temperature rise in each reactor, for example, supporting its below 40°C. In this form of implementation of both water and feeding a stream of hydrogen can be divided between the individual reactors. The separation is particularly useful because it avoids the use of an intermediate heat exchanger for cooling.

Usually to sustain growth temperature inside each reactor in the range of 40°With only two reactors, which allows to obtain a higher selectivity to phenol.

Figure 1 shows schematically the equipment suitable to implement the method in accordance with the above described configuration.

It is possible to maintain the reactor in which Uchenie several hundred hours in the presence of a catalyst and in the most appropriate operating conditions, when the degree of conversion of bentolila and selectivity for phenol >85%.

If the reactor operates for a longer period of time, the degree of conversion tends to decrease, while the selectivity remains very high. In this situation, the reaction temperature can be gradually increased in the range of 250-500°C, and it is possible to maintain the desired degree of conversion.

The reason for the decline in activity is the deposition of carbonaceous material on the catalyst used in the reaction. It was found that the catalysts suitable for the purposes of this invention, can be subjected to periodic regeneration without any special problems, in accordance with what is known in the technique (temperature 400÷550°C, a pressure of 0.1÷0.3 MPa (1÷3 bar), mixtures of oxygen and nitrogen in the ratio of 0.1÷20%. and bulk velocity 3000÷6000 h-1expressed in liters of gas mixture /HR/liter of catalyst).

The catalytic composition according to this invention on the basis of multicomponent metal oxides containing at least one metal selected from groups VB, VIB, VIII, IB, IIB, IVB, IVA, VA, preferably includes at least one element selected from copper, vanadium, bismuth, molybdenum, niobium, iron, tungsten, zinc, Nickel and mixtures thereof, and may contain antimony and/or phosphorus.

The active phase can be obtained the way the mi, known in the art, including deposition, the use of media or use in any form of mixtures of the oxides or mixed oxides (.Campanati, G, Fornasari, .Vaccari, Basis for heterogeneous catalysts (Fundamentals in the preparation of heterogeneous catalysts), Catalysts Today 77 (2003) 299-314).

The active phase is preferably applied to the carrier (for example, aluminum oxide, silicon dioxide and so on) or formed using a binder and methods known in the art.

The catalyst can suitably be molded, for example, by coating it on a substrate, by compacting (e.g., pelletizing, extrusion and so on) or by drying by spraying, so as to obtain the appropriate forms and sizes catalyst for a specific reaction, in accordance with methods known in the art. If necessary, you can apply additional products, such as lubricants based on graphite or stearic acid, etc. Solid precursor of the active phase can appropriately be formed even before the final firing.

To improve oxidation-reduction, acid-base characteristics and capacity for oxygen catalyst may also include additional metal ions (doping agents), such as, for example: metal ions selected from the group consisting of alkali metal is in the (Na, K) and alkaline earth metals (Mg, CA, Sr), group IVB (preferably Ti, Zr, Hf) and VIIB, of a series of lanthanide (La, CE, Sm, Gd, Dy, Yb) and from the group of noble metals (such as Pt, Pd, Rh, Ru, Ir and mixtures thereof).

The noble metals can be applied to the catalyst by conventional methods, such as impregnation, ion exchange, drying, spraying, etc. using a solution of the compound of the noble metal. Compounds of precious metals, which can be used include salts such as halides, nitrates, acetates and sulfates, or their solutions.

A number of specific examples of metal-containing precursors and their solutions known in the art and readily available on the market include, for example:

Hexachloroplatinum acid, hexachloroplatinic potassium, chloride terminplan, nitrate terminplan, hydroxide terminplan, bis-acetylacetonate, palladium, tetrachloropalladate sodium chloride terminally, rhodium nitrate, trichloride rhodium, trichloride ruthenium, chloropyridin ammonium.

The media treated the predecessor of the noble metal can be subjected to chemical treatment may alternately with heat treatment. Conventional chemical treatment is, for example, recovery of metal previously deposited on a substrate by impregnation connection palladium precursor, solution f is of Miata sodium at 85-95°C, according to the existing level of technology.

The catalysts preferably contain the active phase of oxides essentially in crystalline form.

Especially preferred are multi-component compositions of metal oxides containing at least one crystalline structure, which may correspond to the structure of scheelite.

Especially preferred crystalline structure, which may be associated with scheelite structure having the following General structures:

Bi(1-x/3)V(1-x)wNb(1-x)(1-w)MoxO4

Cu(1-z)ZnzW(1-y)MoyO4

Crystal structure, which may correspond to the structure of scheelite, refers to the phase class AVO4with the structure, isomorphic to the phase present in the mineral scheelite (CaWO4).

Charge of different metal ions a and b may be changed in accordance with characteristics of electroneutrality of the crystal. The General formula ABO4it may, thus, enable triple metal oxide (a+1In+7O4to And+4In+4O4) or multicomponent metal oxides, the charges of the ions which satisfy electroneutrality.

The description relating to crystalline materials such as scheelite can be found in R.W.G.Wickoff "Crystal structure" ("Crystal Structure"), Vol.2, vtoro the publication .VIII A6 and table VIII A5; additional information can be obtained from U.S. patent 3843553 and U.S. patent 3806470 Aykan et al. (DuPont 1974).

Thus, a particular crystalline structure, which may correspond to the structure of scheelite also suggests the inclusion of crystallographic variations obtained by appropriate substitution of CA ions and W in the classical structure. These crystallographic variations include variations in the arrangement of atoms in the unit cell and, therefore, in its entirety.

Application specialists ray diffractometer methods allows to detect the presence of crystalline structures, which may correspond to the structure of scheelite.

More specifically, the presence of such a crystal structure can be identified using the method of x-ray diffraction.

Diffraction spectra associated with these crystal structures may differ from each other either because of the influence of different unit cell volumes, or because of the influence of isomorphic substitutions; sometimes also can be detected by reducing the symmetry of the lattice.

For catalysts mentioned in this patent, used automatic powder diffractometer Philips X'pert θ/2θ geometry of the Bragg - Brentano, using radiation si α λ=1,5416 and power 1.6 kW; used corner is the range is from 5 to 90° (2θ) with a step size of 0.02° (2θ) and the times of detection of 10 seconds per step.

The structure of scheelite can be recognized by x-ray diffraction, using a variety of methods known to experts in this field, in particular, you can use the information contained in the database PDF-2 Powder Diffraction File, the data File by diffraction on powders), published by ICDD (The International Centre for Diffraction Data, international center for diffraction data).

Materials having the structure of scheelite or which may be correlated with it, the type of Bi(1-x/3)V(1-x)wNb(1-x)(1-w)MoxO4can be identified by using the diffraction patterns shown in the reference maps, for example, 14-0688 (BiVO4; x=0, w=1), 85-629 (x=0, w=1), 85-630 (x=0,37, w=1), 85-631 (x=0,55; w=1) and 70-0031 (Bi3(FeO4)MoO4)2).

Materials with scheelite structure, or which may be correlated with it, type Cu(1-z)ZnzW(1-y)MoyO4can be identified using crystallogram contained in the reference maps, for example, 88-0269 (scheelite with the substitution for copper).

It was proved that the presence of other crystalline phases on the basis of oxides gives significant advantages for the production of phenol.

The catalyst may also contain materials with non-scheelite crystal or amorphous structure, resulting, for example, some used predecessors.

The catalyst may also benefits the NGOs to contain materials, also with non-scheelite crystal or amorphous structure, is able to increase the capacity of accumulation structure of oxygen (ENK, the capacity of the accumulation of oxygen), such as the oxides of the lanthanides (LnOx), and, in particular, cerium oxide, or mixtures thereof with other oxides, such as cerium oxide - zirconium oxide.

Typical oxides or mixtures of oxides may be such on the basis of lanthanum, cerium, praseodymium, neodymium, europium, samarium, gadolinium; oxides of lanthanides (lanthanides for brevity denoted by Ln, their oxides LnOxor their mixtures can also be used as a carrier and/or binder.

In accordance with the above, the catalyst may consist not only of oxide materials with the structure of scheelite; examples nasality components can be ions of alkali or alkaline earth metals, noble metals or their compounds in high oxidation States, or mixtures thereof.

Due to the variability of the active phase there are no particular restrictions on the methods of forming the catalyst.

Below, for a better understanding of this invention, and casts implementation options, provides a few illustrative examples, which in no way should be considered as limiting the scope of the invention.

EXAMPLES

Examples of preparation of the catalyst

P is the iMER 1

Catalyst type Bi(1-x/3)V(1-x)wNb(1-x)(1-w)MoxO4

A. 7,22 g metavanadate ammonium [NH4VO3; composition analysis >99.5%pure; MM 116,98; CAS 7803-55-6] was dissolved at 80°C in 450 g of demineralized water and brought to pH 10 by 32% ammonium hydroxide (final weight of a solution of 340 g, due to partial evaporation).

B. and 17.2 g of the pentahydrate of bismuth nitrate [(WMO3)3·5H2About; composition analysis 98%; MM 485,08; CAS 10035-06-0] was dissolved in a solution of 500 g of demineralized water and 5.0 g of 65% nitric acid.

C. 195,4 g of 340 g of solution a was mixed with solution C. the Solvent was evaporated at 80°C under stirring on a magnetic stirrer. The thus obtained solid product was dried in an oven at 120°C for 18 hours, then probalily at 500°C for 4 hours.

The molar ratio of the reactants was such, that:

x=0; w=1 in Bi(1-x/3)V(1-x)wNb(1-x)(1-w)MoxO4

Range of x-ray diffraction thus obtained material was typical peaks linolevaya (Clinosbivanite BiVO4card 14-0688).

Example 2

Catalyst type Bi(1-x/3)V(1-x)wNb(1-x)(1-w)MoxO4

A. 4,74 g of niobium chloride [NbCl4; composition analysis 99.8%, and MM 270,16] placed under stirring on a magnetic stirrer in a beaker containing 50 g of demineralized water. After approximately 5 m the chickpeas whole mixture is brought to pH 8 by 32% solution of ammonium hydroxide. The precipitate was filtered and thoroughly washed with approximately 500 ml of demineralized water. Thus obtained precipitate was dissolved at 90°C in a solution containing 140 g of demineralized water and 16 g of oxalic acid.

B. Prepared in a solution consisting of 5,08 g of tetrahydrate of heptamolybdate ammonium [(NH4)6Mo7O24·4H2O; composition analysis 81,0 83,0% (YPA3); MM 1235,86; CAS 12054-85-2] and 2,055 g metavanadate ammonium (NH4VO3; composition analysis >99.5%pure; MM 116,97; CAS 780305506), dissolved in 400 g of demineralized water at 80°C., brought to pH 10 by 32% ammonium hydroxide solution.

C. the Mixed solution obtained in stages a and b, and added a third solution consisting of 50 g of demineralized water, 7 g of 65% nitric acid and 26,35 g of the pentahydrate of bismuth nitrate [(iN3·5H2About; composition analysis 98%; MM 485,08; CAS 100035-06-0]. The solvent was evaporated at 120°C. under stirring on a magnetic stirrer. The thus obtained solid product was dried in an oven at 120°C for 18 hours and then probalily at 500°C for 4 hours.

The molar ratio of the reactants was such, that:

X=0,45; w=0.5 in Bi(1-x/3)V(1-x)wNb(1-x)(1-w)MoxO4.

Analysis of the thus obtained material by the method of x-ray diffraction showed a crystalline structure, which can be attributed to the structure of the am, correlated with disordered structures scheelite, such as the aforementioned patterns present in the mixed oxides of bismuth, iron, and molybdenum (e.g., Bi3(FeO4)(MoO4)2card 70-0031). X-ray analysis of this material shows the structure of crystals, which can be attributed to such structures scheelite, as mentioned in example 1, example 3 and example 4.

Example 3

Catalyst type Bi(1-x/3)V(1-x)wNb(1-x)(1-w)MoxO4.

Prepared in a solution consisting of 3.0 g of tetrahydrate of heptamolybdate ammonium [(NH4)6Mo7O24·4H2O; composition analysis 81,0÷83,0% (MoO3); MM 1235,86] and 5.38 g of metavanadate ammonium (NH4VO3; composition analysis >99.5%pure; MM 116,97), dissolved at 80°C in 400 g of demineralized water, brought to pH 10 by means of a 32% solution of ammonium hydroxide. Added a solution consisting of 60 g of demineralized water, 6 g of 65% nitric acid and 27,83 g of the pentahydrate of bismuth nitrate [(iN3)3·5H2About; composition analysis 98%; MM 485,07]. The solvent was evaporated at 80°C under stirring on a magnetic stirrer. The thus obtained solid product was dried in an oven at 120°C for 66 hours and then probalily at 500°C for 4 hours.

The molar ratio of the reactants was such, that:

x=0,27; w=1 in Bi(1-x/3)V(1-)w Nb(1-x)(1-w)MoxO4

X-ray diffraction analysis of the thus obtained material showed the structure of crystals, which can be attributed to the structures of scheelite, resembles cards 14-0688 (BiVO4; x=0; w=1); 85-629 (x=0,21; w=1); 85-630 (x=0,37; w=1); 85-631 (x=0,55; w=1).

Example 4

Catalyst type Bi(1-x/3)V(1-x)wNb(1-x)(1-w)MoxO4.

Prepared in a solution consisting of 5,08 g of tetrahydrate of heptamolybdate ammonium [(NH4)6Mo7O24·4H2O; composition analysis 81,0...83,0%(MoO3); MM 1235,85] and 4.11 g of metavanadate ammonium (NH4VO3; composition analysis >99.5%pure; MM 116,97), dissolved at 80°C in 400 g of demineralized water, brought to pH 10 by means of a 32% solution of ammonium hydroxide. Added a solution consisting of 60 g of demineralized water, 6 g of 65% nitric acid and 26,35 g of the pentahydrate of bismuth nitrate [(BiNO3·5H2O; composition analysis 98%; MM 485,07]. The solvent was evaporated at 80°C under stirring on a magnetic stirrer. The thus obtained solid product was dried in an oven at 120°C for 18 hours and then probalily at 500°C for 4 hours.

The molar ratio of the reactants was such, that:

X=0,45; w=1 in Bi(1-x/3)V(1-x)wNb(1-x)(1-w)MoxO4.

X-ray analysis of the thus obtained material showed the structure of crystals, to which e can be attributed to the structures of scheelite, such as the patterns shown in the cards 14-0688 (BiVO4; x=0, w=1), 85-629 (x=0,21, w=1), 85-630 (x=0,37, w=1), 85-631 (x=0,55, w=1).

Example 5

Catalyst type Cu(1-z)ZnzW(1-y)MoyO4.

Prepared in a solution consisting of 60,15 g of the pentahydrate of copper sulfate (CuSO4·5H2O; composition analysis >99%; MM 249,68; CAS 7758-99-8) in 1500 g of demineralized water, and the solution brought to a boil. Added a second solution obtained by dissolving 115 g of dihydrate of sodium tungstate (Na2WO4·2H2O; composition analysis >99%; MM 329,85; CAS 10213-10-2) 1150 g of demineralized water. The suspension was stirred for 5 hours at 50°C and left at room temperature over night. The solid is separated by filtration and washed about 5 liters of demineralized water. The solid is dried in an oven at 120°C for 15 hours and probalily at 600°C for 48 hours.

X-ray analysis of the thus obtained material showed a crystal structure that matches the structure of the substituted scheelite, such as the one shown in the card 88-0263 scheelite, substituted copper - Cu(WO4). In order to limit the formation of phases such as SIO, it is preferable to carry out the deposition with ion deficiency C.

Example 6

Catalyst type Cu(1-z)ZnzW(1-y)MOyO4/LnOx.

The prepared solution, status is ASCII of 24,42 g parabolicamara ammonium [(NH 4)10W12O41·H2O; composition analysis of 99.99%; MM 3050,46; CAS 11120-25-5] and 400 g of demineralized water, with stirring at 70°C. a Second solution obtained by dissolution of 22.4 g of three-hydrate of copper nitrate (cu(MO3)3·3H2O; > 99%; MM 241,60; CAS 10031-43-3) and 8,995 g of uranyl nitrate cerium (CeN3O9·6H2O; 99%; MM 434,22; CAS 10294-41-4) in 150 g of demineralized water. These two solutions were combined and dried by heating to 120°C with stirring. The mixture was dried at 120°C for 15 h and was progulivali at 600°C for 48 hours

X-ray analysis of the thus obtained material shows the structure of crystals, the corresponding substituted scheelite structures, such as shown in the card 88-0269 Cu-substituted scheelite-Cu(WO4).

It should be noted that because of the effects of hydration titer of copper in the predecessor - the nitrate of copper should be considered to be approximately 15% lower than the content of it in a commercial product.

Example 7

Catalyst type Cu(1-z)ZnzW(1-y)MoyO4.

The prepared solution consisting of 9,015 g of the pentahydrate of copper sulfate (CuSO4·5H2O; composition analysis >99%; MM 249,68; CAS 7758-99-8) and 2.18 g of monohydrate zinc sulfate (ZnSO4·H2O; composition analysis >97,5%; MM 179,45; CAS 7446-19-7) in 300 g of water. The mixture is brought to boiling and then added 230 g of 10% solution of tungstate three is in the water (CAS 10213-10-2). The mixture was cooled to 50°C and kept at this temperature for 4 hours. The precipitate was growing over night at room temperature, then it was filtered, washed, dried at 120°C for 15 hours and probalily at 600°C for 48 hours.

For the purposes of this invention as useful examples for comparison were taken of typical catalysts of oxidation and reduction, known in the art.

Example 8 (comparative)

A typical example of oxidation, in particular used in the approach RedOx technologies described R.M.Contractor et al. in Catalysis Today, 1 (1987) 49-58, for the oxidation of butane to maleic anhydride with VPO catalysts. As mentioned above, this process is as described in this patent, one of the RedOx technologies have had the most success on an industrial scale. Here we describe the synthesis of the active phase according to the method similar to that described in the above article.

90 ml of isobutyl alcohol and 60 ml of benzyl alcohol was placed in a glass flask and added 15 g of vanadium pentoxide (V2O5; composition analysis >99,6+%; MM 181,88; CAS 1314-62-1). The mixture was heated in a bath, boiled under reflux for 4 hours at 130°C. and then left overnight at room temperature. Then added 21.8 g of phosphoric acid (H3RHO4; title 85%; CAS 766-38-2) and the mixture was heated to 130°C, boiling with reverse hall is dildocam, within 4 hours. After cooling the product was filtered and dried in air for 15 hours at 120°C. a Portion of the dried sample was probalily at 400°C for 4 hours in air.

As stated in the above article, for optimum catalyst substantially to obtain crystalline phase of (VO)2P2O7through predecessor (VO)2H2O(PO3OH)2these two phases were identified by x-ray diffraction in the calcined sample and in the dried sample, respectively.

Example 9 (comparative)

For the purposes of this invention as a useful example for comparison, we can take commercially available catalyst recovery. You can use catalysts based on copper, deposited on alumina, such as catalyst T-4489, produced and sold by Sud-Chemie Inc., whose description can be found in the technical and commercial literature provided by the manufacturer.

Examples of the PROPERTIES of the CATALYSTS

Hydroxylation of benzene: experiment with catalyst test.

The system testing of the catalyst, which allows for efficient, economical and systematic investigation of optimal reaction conditions for each catalyst is, for the reaction in question, a significant improvement relative to the current state of the art. In this sense, the fundamental task quick comparison of a number of catalysts in a wide range of reaction conditions may have advantages with respect to quantitative accuracy. When testing in conditions of lack of reagent, when the oxidation state of the catalyst is constantly evolving, speed measurements when testing is fundamental to accurately describe the behavior of the catalyst.

Mass spectrometric (MS) method is well known for its ability to rapid analysis and high sensitivity with respect to the identification of by-products, among other things, for samples with a relatively limited number of simultaneously presenting chemical substances.

Commercially available mass spectrometers allow to identify the components when the content is about one part per million (1 ppm) and can achieve (this applies economic models) the limit of detection up to ten parts per billion (10 ppb=0,01 ppm). In addition, when connecting the mass spectrometer with the reactor in which the temperature and flow can be controlled and changed in the course of testing, you can explore a wide range of operating conditions for each catalyst, usually you can after analyzing the price 1÷60 (selected) mass per second; for more complex devices can reach and exceed even 100 wt./apart From these considerations, the mass spectrometer is widely used in cases that require a combined approach in combination with the need to be able to determine low concentrations of the desired product and possible by-products (for example, U.S. patents 6440745, 6316616, 6323366).

Being itself is well adapted to the requirements of this study, mass spectrometer (MS) to allow for rapid and fairly accurate estimate of the selectivity of the catalytic process in terms of maximizing the desired product and minimize by-products.

When used approach for each catalyst can be modified in numerous working conditions (such as temperature, contact time, partial pressure, the oxidation state of the catalyst and so on), and the result can be evaluated in real time during the reaction.

Thus, equipment is defined as TTPC-MS (mass spectrometry in chemical terms, programmable temperature and time).

Hydroxylation of benzene: working procedure for testing of the catalyst.

Except otherwise stated the results refer to tests conducted under standard conditions, as described below.

The reaction is carried out in steam f shall see in a U-shaped reactor with a fixed catalyst bed (material - quartz, total length=320 mm), two branches of which have different inner diameters, to obtain efficient heating of the feed stream, and a fast transfer without re-mixing products to the spectrometer (zone: ⌀int.=4.0 mm, length = 120 mm; the area of the desorption product: ⌀int.=1.2 mm). Near the catalyst reactor is supplied with the external side of the casing with a thin thermocouple (⌀EXT.=0.5 mm) K-type.

The reactor is placed in a tubular oven with electric heating, the temperature at which regulate using the programming device.

Catalyst loading is typically 0.2 g, he has the size 42-80 mesh and is located on the layer of quartz wool.

The first catalyst is kept in a flow of 25 ml/min of inert gas (usually N2in some cases, Not) at 120°C for at least two hours.

At the end of this phase serves an additional stream of N2(usually 25 ml/min, but it can also change during the test), purged through benzene (usually the temperature of the support at 25°C., but this temperature can also be changed during the test to change the partial pressure of benzene).

Under these conditions (25 ml/min, N2passing through benzene at 25°C), using saturation, for each hour of testing serves approximately 0.7 g of benzene, olucha partial pressure of 0.06 and, therefore, the gas volumetric rate 44000 h-1(GHSV: space velocity, expressed in liters of gas passed through the reactor per liter of catalyst per hour), if you count when the reaction temperature of 550°C and take the average bulk density of the catalyst is equal to 1 g/ml), contact time = 0,08 s, mass flow rate = 22 h-1(calculated as described above in relation to the entire feed mixture per gram of catalyst per hour).

Under the described conditions, the signal corresponding atomic mass units 78 (78 AMU), which can be attributed to the molecular ion of benzene supplied without reaction, has in all tests, values of the ion current (I.C.) 3.0 E-7>I.C.>1.5 E-7. With these values of the ion current can be related to the partial pressure of benzene equal to 0.06, corresponding to the concentration of benzene in the gas phase 6 vol.%.

The heated reactor temperature of 120°C to the maximum temperature of the measurement, typically 550°C, occurs at a rate of 11°C/min, and then maintain a constant temperature.

The analysis is performed from the gas phase, continuously, both during heating and isothermal conditions. Because of the reaction in terms of lack of reagent (lack/absence of oxidants in the gas phase), and the reaction rate at a certain temperature contribute to defined the e state of the oxidation catalyst; while the oxidation state of the catalyst surface is especially important to ensure reactivity.

Analysis of the product is carried out at two different sensitivity: scanning from 1 to 80 AMU, the range of the amplifier, the intensity of the ion current (a.b.I.C.) 1E-6 a and scanning from 1 to 180 AMU when a.b.I.C. 1E-9 A. This technique (simultaneous scanning at different sensitivity) should be considered as fundamental to identify products that are not seen in low sensitivity. The described method of analysis allows you to perform a full scan for every minute of analysis.

Thus, a full scan with changing temperature are conducted approximately every 11°C. the test is Then continued in isothermal conditions, registering up to 300 pairs of spectra.

The analysis was carried out under continuous on-line sampling directly from the gas phase, without chromatographic separation.

Line after the reactor is heated to a constant temperature of 120°C. the Residual pressure in the line is controlled by means of the measuring unit Pirani-Penning. The spectrometer MS and end of the line pump with two-stage turbomolecular pump from the spectrometer to a residual pressure 133,3 PA (1 Torr) in the chamber for sampling and about to 8.13×10-4PA (6,1×0 -6Torr) mass spectrometer MS. The measuring instrument is a mass spectrometer model Thermostar supplied by BALZERS. The program processes the data provided by the manufacturer of the device and allows you to track and get up to 63 mass selected within a certain period of time (or up to 300 mass during continuous scanning). Thus, the mass spectrum shows all peaks molecules and fragments of the reaction products and unreacted reagents. Identification of compounds which are of main interest, i.e. benzene (atomic mass units AMU 78, 51, 52, 50, 39, 63, 77), phenol (AMU 94, 66), carbon dioxide (44 AMU, 28) and water (18 AMU, 17) is sufficiently reliable, because the fragments of the molecules do not overlap. What peaks by the method of least squares on the matrix I.C. to identify each individual peak I.C. parts belonging to different connections.

In our case, which should be seen as an exception, the products are appropriately correlated with individual I.C. or a pair of I.C. for Example, phenol recognize and semiquantitative estimate of the I.C. with AMU 94, also it is possible to determine from the value with I.C. AMU 66. Other byproducts of the reaction are maleic anhydride (AMU 26, 54, 28, 98), cyclohexene (AMU 68, 96), dibenzofuran (168, 139, 84) and benzofuran (118, 89).

All these compounds were confirmed by gas, HRO is ecografia with mass spectrometric analysis (GC-MS) medium fractions of the condensate from the carrier gas, coming out of the reactor.

The intensity of each value of the AMU is proportional to the number of the fragment to which it refers, and in the final analysis, if known, the relative intensity of the peaks of the fragments, typical of the product in question, is proportional to the partial pressure/concentration of this product in the analyzed gas phase.

For all the molecules showed that the molecular ion is characterized by a greater intensity, with the exception of maleic anhydride, for which ion with AMU 26 is preferable molecular ion (relative percentage, OS% 98 AMU ≈ 8).

For the considered molecules, except for the already mentioned maleic anhydride, the intensity of the molecular ion can directly correlate (semiquantitative) product concentration in the gas mixture.

However, the determination of the relative concentrations has semiquantitative nature of the uncertainties and discontinuities associated with factors known to current level of technology, such as the efficiency of ionization, the effect of separation in the stream (sampling system tends to enrich the analyzed mixture of heavy products), etc. that are difficult to quantify in this complex gas mixtures for more tochnog the definition.

Regeneration of the catalyst after the experiment to determine the activity of the catalyst is carried out in the same reactor, where the reaction was performed without removing the catalyst. Operating conditions: temperature range from 350 to 550°C., pressure = 0.1 to 0.12 MPa (1-1,2 bar), oxygen concentration = 0.1 to 20% and the gas space velocity = 10000÷50000 h-1. In particular, processing activate a flow of pure nitrogen, which gradually add equal air flow (approximately 1 hour), then the flow of nitrogen is gradually reduced until its termination (approximately 1 hour). Processing continues in a period of time from 1 to 10 hours. At the end of the regeneration processing reactor is washed with nitrogen for 5 minutes at the same temperature, and then cooled by blowing up to 120°C, and then you can start the reaction cycle in terms of lack of reagent, as described above.

It is shown that the tested catalysts are stable for at least twelve cycles of reaction-regeneration.

From the above considerations and information about catalysts should be considered as semi-quantitative, and therefore, in examples 10-20 specified activity, expressed as the value of the ion current (I.C.) for a specific temperature (corresponding to a particular measurement cycle); however, the characteristics of the catalysate is RA assessed by calculating the degree of conversion of benzene and the selectivity of conversion to phenol in accordance with the following formula.

For the degree of conversion of >10%

The difference between the signal intensity of benzene in the presence and in the absence of reaction is significant, and, therefore:

The degree of conversion,%=% = [(I.C. AMU 78 input) to (I.C. AMU 78 output)] / (I.C. AMU 78 at the door)

Output % = Y% = 100 · (I.C. AMU 94) / (I.C. AMU 78 at the door)

Selectivity % = S% = 100 · Y% / C%

where

(I.C. AMU 78 input) = ion current atomic mass of 78 (benzene) in the absence of reaction.

(I.C. AMU 78 output) = ion current atomic mass of 78 (benzene) in the presence of a reaction.

(I.C. AMU 94) = ion current atomic mass 94 (phenol).

For the degree of conversion<10%

The magnitude of the degree of conversion is low and, therefore, cannot be estimated from the difference of the intensities of the characteristics peaks of reagent in the presence and in the absence of a reaction; if in addition to phenol, the only products formed in significant quantities, are products of combustion, the degree of conversion is determined by carbon dioxide:

(C6H6+15/2 O2→6 CO2+3 H2O)

and phenol:

(C6H6+1/2 O26H5(IT)

Thus, typical values of the reactivity assessed as follows:

The degree of conversion%=% = 100 · [(I.C. AMU 94) + (I.C. AMU 44)] / 6] / (I.C. AMU 78 at the door)

where (I.C. AMU 44) = ion current units of atomic mass 44 (obtained carbon dioxide).

Output % the Selectivity % appreciate as in the previous case.

Examples 10-20

The examples were conducted in accordance with the process described above. The estimation of such parameters as the degree of conversion, selectivity and yield, were performed as described in the previous paragraph.

Used working conditions and assess the characteristics of the catalyst are given in tables.

Example 10

Catalyst
Catalyst typeBiVNbMo
Obtaining a catalyst (see)Example 2
Working conditions
Temperature measurement, °C (cycle number)550 (49)
Mass space velocity, WHSV (h-1) (α)22; (3,5)
Characteristics of catalyst
AMU 78 (feed mixture), And (E-10) (β)2600
AMU 94, And (E-10) (χ)0,44
AMU 44, A(E-10) (χ)270
AMU 78, A(E-10) (χ)
Rated output (%)0,02
The estimated degree of conversion (%)2
Estimated selectivity (%)1
Notes:
α = WHSV [g/h of benzene + g/h of N2]/r cat.; [g/h benzene]/g cat.
δ = ion current in the absence of reaction
χ = ion current in the presence of reaction

Example 11

Catalyst
Catalyst typeBiVMo
Obtaining a catalyst (see)Example 3
Working conditions
Temperature measurement, °C (cycle number)550 (80)
Mass space velocity WHSV (h-1) (α)22;(3,5)
Characteristics of catalyst
AMU 78 (feed mixture) And (E-10) (β)2500
AMU 94 And (E-10) (χ) 0,32
AMU 44 And (E-10) (χ)120
AMU 78 And (E-10) (χ)2500
Rated output (%)0,01
The estimated degree of conversion (%)1
Estimated selectivity (%)2
Notes: see notes to example 10

Example 12

Catalyst
Catalyst typeBiVMo
Obtaining a catalyst (see)Example 4
Working conditions
Temperature measurement, °C (cycle number)550(100)
Mass space velocity WHSV (h-1) (α)22; (3,5)
Characteristics of catalyst
AMU 78 (feed mixture) And (E-10) (β)2300
AMU 94 And (E-10) (χ) 0,37
AMA(E-10) (χ)65
AMU 78 And (E-10) (χ)2300
Rated output (%)0,02
The estimated degree of conversion (%)0,5
Estimated selectivity (%)3
Notes: see notes to example 10

Example 13

It shows the influence of changes in flow rate with respect to the tests performed in example 12.

Catalyst
Catalyst typeBiVMo
Obtaining a catalyst (see)Example 4
Working conditions
Temperature measurement, °C (cycle number)550 (70)
Mass space velocity WHSV (h-1) (α)690; (35,0)
Characteristics of catalyst
AMU 78 (feed MES) And (E-10) (β) 2900
AMU 94 And (E-10) (χ)0,28
AMU44A(E-10) (χ)23
AMU 78 And (E-10) (χ)2900
Rated output (%)0,01
The estimated degree of conversion (%)0,1
Estimated selectivity (%)7
Notes: see notes to example 10

Example 14

Catalyst
Catalyst typeCuWO4
Obtaining a catalyst (see)Example 5
Working conditions
Temperature measurement, °C (cycle number)530 (47)
Mass space velocity WHSV (h-1) (α)22;(3,5)
Characteristics of catalyst
AMU 78 (feed mixture And (E-10) (β) 1800
AMU 94 And (E-10) (χ)4,3
AMU44A(E-10) (χ)340
AMU 78 And (E-10) (χ)1700
Rated output (%)0,1
The estimated degree of conversion (%)3
Estimated selectivity (%)3
Notes: see notes to example 10

Example 15

This example shows the stability of the cycles of oxidation-reduction (RedOx cycles). Using the catalyst obtained in Example 5, but subjected to 12 cycles of reaction-regeneration. In the framework of the semi-quantitative analysis was not observed irreversible aging (deterioration) of the catalyst.

Catalyst
Catalyst typeCuWO4after 12 cycles of oxidation-reduction
Obtaining a catalyst (see)Example 5 after 12 cycles of oxidation-reduction
Working conditions
Temperature measurement, °C (cycle number)530 (53)
Mass space velocity WHSV (h-1) (α)22;(3,5)
Characteristics of catalyst
AMU 78 (feed mixture) And (E-10) (β)1900
AMU 94 And (E-10) (χ)2,6
AMU44A(E-10) (χ)115
AMU 78 And (E-10) (χ)1780
Rated output (%)0,14
The estimated degree of conversion (%)1
Estimated selectivity (%)12
Notes: see notes to example 10

Example 16

Catalyst
Catalyst typeCU0,75Znof 0.25WO4
Obtaining a catalyst (see)Example 7
Working conditions
Temperature measurement, °C (cycle number)530 (41)
Mass space velocity WHSV (h-1) (α)22; (3,5)
Characteristics of catalyst
AMU 78 (feed mixture) And (E-10) (β)2250
AMU 94 And (E-10) (χ)2,1
AMU44A (E-10) (χ)148
AMU 78 And (E-10) (χ)2180
Rated output (%)0,09
The estimated degree of conversion (%)1
Estimated selectivity (%)8
Notes: see notes to example 10

Example 17

Catalyst
Catalyst typeCuWO4+CE
Obtaining a catalyst (see)Example 6
Temperature measurement, °C (cycle number)480 (42)
Mass space velocity WHSV (h-1) (α)22; (3,5)
The behavior of the catalyst
AMU 78 (feed mixture) And (E-10) (β)1800
AMU 94 And (E-10) (χ)5,1
AMU44A (E-10) (χ)180
AMU 78 And (E-10) (χ)1650
Rated output (%)0,3
The estimated degree of conversion (%)2
Estimated selectivity (%)15
Notes: see notes to example 10

Figure 2 shows the trend of change of the AMU mass range from 90 to 120 AMU during the measurement cycle when the experiment. Shows the trend of the maximum to obtain a phenol, and this is a typical pattern for carrying out reactions under conditions of lack of reagents.

Example 18

This example shows the stability of the cycles of oxidation recovery. what the objects of study were the catalyst, obtained in example 6, but subjected to one cycle of reaction-regeneration. In the framework of the semi-quantitative analysis was not observed irreversible deterioration of the catalyst.

Also shown is the change of selectivity depending on the oxidation state of the catalyst. Comparison of data obtained at 34-m and 60-m cycles MS analysis, which corresponds to about 30' reactions in the isothermal mode at 407°C. These values can be correlated with a decrease in the average oxidation state of the catalyst.

Catalyst
Catalyst typeCuWO4+CE
Obtaining a catalyst (see)Example 6 after one cycle of oxidation-reduction
Working conditions
Temperature measurement, °C (cycle number)407(34) 407 (60)
Mass space velocity WHSV (h-1) (α)22; (3,5)
Characteristics of catalyst
AMU 78 feed mixture) And (E-10) (β) 19401940
AMU 94 And (E-10) (χ)3,21,9
AMU44A (E-10) (χ)12320
AMU78A (E-10) (χ)17001790
Rated output (%)0,20,1
The estimated degree of conversion (%)10,3
Estimated selectivity (%)1436
Notes: see notes to example 10

Figure 3 shows a tendency to change the values of the masses corresponding to benzene (78 AMU), phenol (AMU 94) and CO2 (44 AMU) during heating and isothermal conditions at 407°Sisenna range of products in isothermal conditions at 407°C indicates the possible existence of a surface, or average, of the state of oxidation of the catalyst, which give optimum for the desired reaction.

Comparative example 19

In this case, assessed the degree of conversion, yield and selectivity for maleic americasales the formula, comparable to the formulas given above:

The degree of conversion%=% = 100·[(I.C. AMU 98) · (1000/81) + (I.C. AMU 94)] + (I.C. AMU 44)/6]/(I.C. AMU 78)

Output % = Y% = 100*(I.C. AMU 98)·(1000/81)/(I.C. AMU 78)

Selectivity % = S% = 100 · Y%/C%

In semi-quantitative assessment of yield and selectivity to maleic anhydride using a multiplication factor equal to 1000/81 as the peak molecules of maleic anhydride is not the most intense and about 8.1% of the most intense peak at AMU 26 (NITS, national Institute of Technology Standards, the Program of search of mass spectra mass spectral library NIST, MS Windows Version 1.6d created 07/27/1998). It is preferable not to use a peak at AMU 26, as it is subject to strong interference from nitrogen (28 AMU), which is used as the carrier gas.

Figure 4 shows the change in mass of maleic anhydride (98 AMU), phenol (AMU 94), CO2(44 AMU) and benzene (78 AMU) during heating and isothermal conditions at 550°C.

Catalyst
Catalyst typeVPO
Obtaining a catalyst (see)Example 8
Working conditions
The temperature of the ISM is of, °C (cycle number)550 (43)
Mass space velocity WHSV (h-1) (α)22;(3,5)
Characteristics of catalyst
AMU 78 (feed mixture) And (E-10) (β)3000
AMU 94 And (E-10) (χ)0,145
AMU 98 And (E-10) (χ)1,29
AMU 44 And (E-10) (χ)130
AMU 78 And (E-10) (χ)2950
Rated output (%)0,005
The estimated degree of conversion (%)1,3
Estimated selectivity (%)0,7
Rated output % of maleic anhydride0,5
Estimated selectivity % maleic anhydride40
Notes: see notes to example 10

This example shows that a typical oxidation catalyst is suitable, in particular, for the redox technologist and (obtaining maleic anhydride), leads to oxidation products, which differ from the desired product (phenol).

Comparative example 20

Catalyst
Catalyst typeCuO-Al2O3(Sud Chemie T)
Obtaining a catalyst (see)Example 9
Working conditions
Temperature measurement, °C (cycle number)400 (25)
Mass space velocity WHSV (h-1) (α)22;(3,5)
Characteristics of catalyst
AMU 78 (feed mixture) And (E-10) (β)2000
AMU94A (E-10) (χ)0,0
AMU 44 And (E-10) (χ)9000
AMU 78 And (E-10) (χ)100
Rated output (%)0
The estimated degree of conversion (%)99
Estimated selectionist the (%) 0
Notes: see notes to example 10

This example shows that a typical hydrogenation catalyst used for the process operating conditions leads to almost complete combustion of organic compounds present.

EXAMPLES of CATALYSTS

Hydrodeoxygenation of benzodia: methods of test catalyst

Described in the examples tested catalysts were performed on laboratory equipment, which can be investigated working conditions in order to optimize the test conditions. Equipment and methods of testing are described below.

The reaction was carried out in the vapor phase and under pressure in a tubular reactor with a fixed catalyst bed (material = stainless steel AISI 316L, length 180 mm, ⌀int.=11.5 mm, located along the axis of the tube for thermocouples With ⌀EXT=3 mm).

The reactor is placed in a tubular oven with electric heating. Catalyst loading is 5.0 g, it has a size of <2 mm, and is located in the reactor between two layers of quartz granules.

The reactor is configured with the stream flowing from the top down. An aqueous solution of bentolila served by using a metering pump of the type used for HPLC, and heated by periduodenal in the upper part of the reactor; then the solution is evaporated and mixed with hydrogen directly in the reactor, in a layer of quartz, which is located before the catalytic Converter, where it reaches the reaction temperature before contact with the catalyst.

The consumption of hydrogen regulate thermal mass flow meter.

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

In the activation phase, the catalyst is heated to reaction temperature in a stream of hydrogen at a pressure and flow rate set for a given experiment, and support under these conditions for 1 hour. Then begin to apply water at the rate established for this experiment, and after 30 minutes the water replaces the solution of bentolila.

The mixture of vapors coming from the regulating pressure valve, condense and collect the raw reaction material. This condensed raw material is usually divided into two phases, organic and aqueous, both of which contain phenol. For analysis by gas chromatography, these two phases are diluted and mixed with a common solvent, typically tert-butyl alcohol, and add the internal standard, usually n-octanol.

Regeneration of the catalyst after the experiment for the determination of catalytic activity carried out in the same reacto is e, used for the reaction without removal of the catalyst. Operating conditions: temperature: 450-550°C, pressure = 0.1-0.3 MPa (1-3 bar), oxygen concentration = 0.1 to 20% and the gas space velocity (GHSV)=3000÷6000 h-1. In particular, the processing begins by passing one of nitrogen, which gradually add equal air flow (approximately 1 hour), then the flow of nitrogen is gradually reduced to zero (approximately 1 hour). Treatment continued for 5 to 10 hours. At the end of the regenerative processing reactor is washed by a stream of nitrogen, and it is possible again to start the reaction hydrodeoxygenation.

HYDRODEOXYGENATION of BENZODIA: CALCULATION of the DEGREE of CONVERSION AND SELECTIVITY

Characteristics of the catalyst is evaluated by calculating the degree of conversion of bentolila and selectivity to phenol according to the following formula:

where:

DB - bentolila

1,2-BD - concentration of 1,2-bentolila

1,4-DB = concentration of 1,4-benzodia

Ref. = input

o. = output

Examples 21-32

The examples were conducted in accordance with the methodology described above.

The adopted operating conditions and characteristics of the catalyst are listed in the following tables.

Example 21

Catalyst
Catalyst typeBiVNbMo
Obtaining a catalyst (see)Example 2
Working conditions
The reaction temperature °C400
Pressure, MPa (bar)2,5 (25)
The solvent feed stream databasewater
1,2-BD in the solution database (wt.%)19,5
1,4-BD in the solution database (wt.%)9,8
The ratio of N2/DB (molar ratio)of 21.2
Mass space velocity WHSV (h-1) (α)2,0
Characteristics of catalyst
The residence time (h) (β)5156
The degree of transformation of bentolila (%) (δ) 100,098,1
The selectivity to phenol (%) (ε)94,0to 91.1
Notes:
DB = bentolila in General
1,2-DB = 1,2-benzodia (pyrocatechin)
1,4-DB = 1,4-benzodia (hydroquinone)
α=mass space velocity WHSV with respect to the power flow bentolila
β, γ = the residence time in the flow, working time in hours from the beginning of testing (β) or since the last regeneration, carried out in this reactor (γ)
δ = the degree of transformation in relation to the amount of 1,2-BD+1,4-DB
ε = the selectivity in relation to the total number of reacted database.

Example 22

Catalyst
Catalyst typeBiVMo
Obtaining a catalyst (see)Example 3
Working conditions
Working conditions as in example 21
Characteristics of catalyst
The residence time (h) (γ) 145
The degree of transformation of bentolila (%) (δ)98,0to 91.6
The selectivity to phenol (%)(ε)89,686,6
Notes: see notes to example 21

Example 23

Catalyst
Catalyst typeBiVO4
Obtaining a catalyst (see)Example 1
Working conditions
The reaction temperature °C400
Pressure, MPa (bar)2,5 (25)
The solvent feed stream databasewater
1,2-BD in the solution database (wt.%)19,3
The ratio of N2/DB (molar ratio)28,0
Mass space velocity WHSV (h-1) (α)1.3
Characteristics of catalyst
The residence time (h) (γ)550
The degree of transformation of bentolila (%) (δ)99,996,0
The selectivity to phenol (%) (ε)89,6for 95.3
Notes: see notes to example 21

Example 24

td align="center" namest="c1" nameend="c2"> water
Catalyst
Catalyst typeBiVO4
Obtaining a catalyst (see)Example 1
Working conditions
The reaction temperature, °C450
Pressure, MPa (bar)2,5 (25)
The solvent feed stream database
1,2-BD in the solution database (wt.%)19,3
The ratio of N2/DB (molar ratio)28,0
Mass space velocity WHSV (h-1) (α)1,3
Characteristics of catalyst
The residence time, (h) (γ)571
The degree of transformation of bentolila (%) (δ)10096,8
The selectivity to phenol (%) (ε)93,098,7
Notes: see notes to Example 21

Example 25

Catalyst
Catalyst typeCuWO4
Obtaining a catalyst (see)Example 5
Working conditions
The reaction temperature °C450
Pressure, MPa (bar)2,5 (25)
The solvent feed stream databasewater
1,2-BD in the solution database (wt.%)19,0
1,4-BD in the solution database (wt.%)the 9.7
The ratio of N2/DB (molar ratio)a 21.5
Mass space velocity WHSV (h-1) (α)0,5
Characteristics of catalyst
The residence time (h) (γ)171
The degree of transformation of bentolila (%) (δ)84,366,9
The selectivity to phenol (%) (ε)82,390,7
Notes: see notes to example 21

Example 26

Catalyst
Catalyst typeCuWO4
Obtaining a catalyst (see)Example 5
Working conditions
The reaction temperature °C450
Pressure, MPa (bar)2,5 (25)
The solvent feed stream databasewater
1,2-BD in the solution database (wt.%)19,0
1,4-BD in the solution database (wt.%)the 9.7
The ratio of N2/DB (molar ratio)11,0
Mass space velocity WHSV (h-1) (α)0,5
Characteristics of catalyst
The residence time, (h) (γ)1
The degree of transformation of bentolila (%) (δ)of 87.3
The selectivity to phenol (%) (ε) 91,2
Notes: see notes to example 21

Example 27

Catalyst
Catalyst typeCu0,75Znof 0.25WO4
Obtaining a catalyst (see)Example 7
Working conditions
Working conditions as in example 25
Characteristics of catalyst
The residence time, (h) (γ)125
The degree of transformation of bentolila (%) (δ)84,962,1
The selectivity to phenol (%) (ε)79,2of 87.0
Notes: see notes to example 21

Example 28

Catalyst
Catalyst type Cu0,75Znof 0.25WO4
Obtaining a catalyst (see)Example 7
Working conditions
Working conditions as in example 26
Characteristics of catalyst
The residence time (h) (γ)1
The degree of transformation of bentolila (%) (δ)89,6
The selectivity to phenol (%) (ε)86,1
Notes: see notes to example 21

Example 29

Catalyst
Catalyst typeCuWO4+CE
Obtaining a catalyst (see)Example 6
Working conditions
The reaction temperature °C450
Pressure, MPa (bar)2,5 25)
The solvent feed stream databasewater
1,2-BD in the solution database (wt.%)19,7
1,4-BD in the solution database (wt.%)10,0
The ratio of N2/DB (molar ratio)21,0
Mass space velocity WHSV (h-1) (α)0,5
Characteristics of catalyst
The residence time (h) (γ)145
The degree of transformation of bentolila (%) (δ)98,596,3
The selectivity to phenol (%) (ε)85,181,5
Notes: see notes to example 21

Example 30

Catalyst
Catalyst typeCuWO4 +CE
Obtaining a catalyst (see)Example 6
Working conditions
Working conditions as in example 25
The behavior of the catalyst
The residence time, (h) (γ)124
The degree of transformation of bentolila (%) (δ)96,897,5
The selectivity to phenol (%) (ε)for 91.392,6
Notes: see notes to example 21

Example 31 (comparative)

Catalyst
Catalyst typeVPO
Obtaining a catalyst (see)Example 8
Working conditions
Working conditions as in example 25
Characteristics of catalyst
The residence time, (h) (γ)121
The degree of transformation of bentolila (%) (δ)1,31,5
The selectivity to phenol (%) (ε)of 58.973,4
Notes: see notes to example 21

This example shows that a typical oxidation catalyst at the operating conditions used in this process has worse characteristics than the characteristics of the obtained catalysts, which is the object of the present invention.

Example 32 (comparative)

Catalyst
Catalyst typeSiO - Al2O3
Obtaining a catalyst (see)Example 9
Working conditions
The reaction temperature °C350
The pressure is PA (bar) 2,5 (25)
The solvent feed stream databasewater
1,2-BD in the solution database (wt.%)18,6
1,4-BD in the solution database (wt.%)9,4
The ratio of N2/DB (molar ratio)22,2
Mass space velocity WHSV (h-1) (α)0,5
Characteristics of catalyst
The residence time (h) (γ)25144
The degree of transformation of bentolila (%) (δ)99,982,5
The selectivity to phenol (%) (ε)48,846,1
Notes: see notes to example 21

This example shows that a typical hydrogenation catalyst under operating conditions used in this process has worse characteristics and, what characteristics obtained with the catalysts, which is the object of the present invention.

1. Method for production of phenol by hydrodeoxygenation polyhydroxylated benzene derivatives in the presence of a catalyst based on multicomponent metal oxides, characterized in that the said oxides comprise at least one active oxide phase, which corresponds to the structure of scheelite, and materials with a crystalline structure which is not a scheelite, or an amorphous structure, where the crystal structure of scheelite are selected from the following structures:
Bi(1-x/3)V(1-x)wNb(1-x)(1-w)MoO4;
Cu(1-z)ZnzW(1-y)MoyO4,
where each of w, x, y, and z ranges from 0 to 1,
and where materials with a crystalline structure which is not a scheelite, or an amorphous structure selected from cerium oxide or a mixture of cerium oxide-zirconium oxide.

2. The method according to claim 1, in which the selective hydrodeoxygenation carried out by the reaction polyhydroxylated derivatives of benzene with hydrogen in the vapor phase at a temperature of 250-500°C., at pressures of 0.1-10 MPa (1-100 bar) mass flow rate (WHSV), calculated with respect to the supplied polyhydroxylated derivative of benzene, 0.1 to 10 h-1.

3. The method according to claim 2, in which hydrodeoxygenation carried out at a temperature OC to 450°C.

4. The method according to claim 2, in which hydrodeoxygenation performed at a pressure of from 0.3 to 5 MPa (3 to 50 bar).

5. The method according to claim 2, in which hydrodeoxygenation carried out at flow rate of 0.5 to 5 h-1.

6. The method according to claim 2, in which hydrodeoxygenation carried out in an adiabatic reactor with a fixed catalyst bed by feeding into the reactor a solution of bentolila in water with a concentration of 5-60 wt.% together with a stream of hydrogen in such quantities that the ratio of the total number of moles of hydrogen and benzodia is from 2:1 to 50:1.

7. The method according to claim 6, in which the solution bentolila in water has a concentration of 10-40 wt.%, and the ratio between the total number of moles of hydrogen and benzodia is from 5:1 to 30:1.

8. The method according to claim 2, in which hydrodeoxygenation carried out in two or more adiabatic reactors with a fixed catalyst bed, connected in series, by separation of the supplied water flow and supplied hydrogen in separate reactors.

9. The method according to claim 1, in which hydrodeoxygenation carried out in the presence of a catalyst based on multicomponent metal oxides containing at least one metal selected from copper, vanadium, bismuth, molybdenum, niobium, iron, tungsten, zinc, Nickel and combinations thereof, possibly containing antimony and/or phosphorus.

10. Ways who according to claim 9, in which the catalyst is supported on a carrier or formed using a binder.

11. The method according to claim 9, in which the catalyst contains the active phase of oxides in crystalline form.

12. Method for production of phenol by the selective hydroxylation of benzene in the presence of a catalyst based on multicomponent metal oxides, characterized in that the said oxides comprise at least one active oxide phase, which corresponds to the structure of scheelite, and materials with a crystalline structure which is not a scheelite, or an amorphous structure in which the crystalline structure of scheelite is selected from the following compounds:
Bi(1-x/3)V(1-x)wNb(1-x)(1-w)MoO4;
Cu(1-z)ZnzW(1-y)MoyO4,
where each of w, x, y, and z ranges from 0 to 1,
and where materials with a crystalline structure which is not a scheelite, or an amorphous structure selected from cerium oxide or a mixture of cerium oxide-zirconium oxide,
and wherein the method is performed by supplying oxygen or other agents oxidizing agents selected from air and N2O, in lower quantities compared with the stoichiometric quantity per reacts benzene or not feeding them, thus missing the stoichiometry of oxygen provides the catalyst, and the fact that it is talization contains the active phase of the oxide in crystalline form.

13. The method according to item 12, in which, at a subsequent stage catalyst regenerate to its original state using oxygen or other connection-oxidant selected from air and N2O.

14. The method according to item 13, in which stages of the reaction and re-oxidation is carried out cyclically.

15. The method according to item 12, in which the selective hydroxylation of benzene is carried out in a reactor operating at temperatures from 150 to 700°C at a pressure of from 0.01 to 10 MPa (from 0.1 to 100 bar) and a mass flow rate (WHSV), calculated with respect to the entire mixture supplied from 0.01 to 1000 h-1.

16. The method according to item 15, in which the selective hydroxylation of benzene is carried out at a temperature of from 200 to 600°C.

17. The method according to clause 16, in which the selective hydroxylation of benzene is carried out at temperatures from 250 to 550°C.

18. The method according to item 15, in which the selective hydroxylation of benzene is carried out at a pressure from 0.1 to 3 MPa (from 1 to 30 bar).

19. The method according to item 15, in which the selective hydroxylation of benzene is carried out at space velocities of from 1 to 100 h-1.

20. The method according to claim 19, in which the selective hydroxylation of benzene is carried out at space velocities of from 2 to 50 h-1.

21. The method according to item 12, in which the selective hydroxylation of benzene is carried out in several reactors, at least one of which is for the reg is erali catalyst, working either through physical transfer of catalyst from the reactor, intended for carrying out the reaction in the reactor, intended for regeneration or by switching threads between reactor intended for the reaction, and the reactor dedicated to regeneration.

22. The method according to item 12, in which the selective hydroxylation of benzene is carried out in one or more than one reactor with a fluidized bed.

23. The method according to item 12, in which the catalyst is supported on a carrier or formed using a binder.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention refers to the analytical chemistry of organic compounds with respect to monoazo dye extraction from water media. The method includes: a) the addition of the crystalline ammonium sulphate to the water solution of monoazo dye E102 and E122 mixture up to its concentration 43 wt %; b) separation by filtering of the monoazo dye E122 segregated due to desalting; c) acetone addition to the filtrate in volume ratio acetone: water solution = 1:10 and d) monoazo dye E102 extraction during 10 min and separation of the water phase. The content of monoazo dye E102 in water phase is determined spectrophotometrically; the rate of extraction (R%) was calculated by formula: R= [(Ainit-Aequil)*100%]/Ainit, where Ainit, Aequil are filtrate optical densities before and after filtration.

EFFECT: invention provides the maximal completeness of the extraction.

1 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to production of phenol, method of extracting phenol from products of splitting cumene hydroperoxide and to a device for extracting phenol from products of splitting cumene. The method of producing phenol involves the following stages: i) oxidation of cumene, obtaining a reaction mixture containing cumene hydroperoxide and unreacted cumene; ii) splitting products obtained from stage i), obtaining a mixture of splitting products containing at least phenol, acetone, hydroxyacetone, unreacted cumene and water; iii) treatment of the mixture of splitting products obtained on stage ii) through distillation, which involves separation of the mixture of splitting products into at least three fractions using a single fractional distillation stage through: putting the mixture of splitting products into a distillation column, removal of the first fraction, containing acetone, from the upper part of the distillation column, removal of the second fraction, containing phenol, from the lower part of the distillation column, and removal of the third fraction, containing at least unreacted cumene, hydroxyacetone and water, in form of an off-stream. The outlet opening of the off-stream is higher the area for putting in the mixture of splitting products into the distillation column, characterised by removal of heat from the distillation column. The section for removing heat is higher than the outlet opening of the off-stream of the third fraction.

EFFECT: increased energy efficiency of methods using old technology, while maintaining quality standards and total output of end products.

25 cl, 6 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: method of producing cumene includes interaction of benzene with acetone and hydrogen with catalytic compound added as containing one or more zeolite in acid form or preferentially acid form, copper and, optionally, one or more element chosen from elements of groups IIIA, VIB, VIIB. Additionally the given invention concerns method of producing phenol with using cumene prepared by the method as described, catalytic compound for production cumene, and also methods of producing catalytic compound for cumene.

EFFECT: application of the methods and catalytic compounds specified above allows simplifying considerably producing phenol from cumene, allowing for simultaneous one-stage reaction for all chemical transformations required to produce high-yield cumene from acetone, benzene and hydrogen with minimum amount of secondary reactions of various reagents, intermediate compounds and products.

69 cl, 16 ex, 2 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: one of method versions is carried out in presence of catalyst with strong acidity in one or several reaction zones with further separation of reaction mixture by means of rectification and possibly partial recycling into reaction zone(s) of one or several components of reaction mixture. Decomposition is carried out in presence of inert easily-boiling solvent, which contains mainly hydrocarbons, whose boiling temperature is lower than 70°C, preferably lower than 40°C, but not lower than minus 1°C, which is partially evaporated directly from reaction zone(s) and partially distilled from obtained reaction mixture, is in liquid state returned to reaction zone(s) with supporting in it (them) temperature from 1 to 70°C, preferably from 10 to 45°C. Second method version is carried out in presence of catalyst with strong acidity in one or several reaction zones with further separation of reaction mixture by means of rectification. Applied is easily-boiling solvent, which after separation from reaction mixture, possibly with part of ketone, is recycled into reaction zone(s), and sulfocationite catalyst in H+ form, resistant in liquid media, containing alkylaromatic hydroperoxides, ketones, phenol and hydrocarbons in large amount, at temperatures up to 70°C, in fine-grain or coarse-grain form, possibly, in form of mass-exchange filling with size from 1.5 to 25 mm.

EFFECT: obtaining phenol and ketones without formation of large amount of by-products and resins and practically without equipment corrosion.

14 cl, 1 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: at first stage by continuous method phenol is obtained by direct benzol oxidation with hydrogen peroxide with ratio of H2O2/benzol from 10 to 70% mol., in three-phase reaction system, which includes first liquid phase, consisting of benzol and organic solvent, second liquid phase, consisting of water, and solid phase, consisting of activated catalyst, which contains titanium silicate TS-1. At second stage phenol and benzol which has not reacted are separated from reaction mixture by fraction distillation. At third stage solvent and by-products, containing dioxybenzols, are separated from mixture, supplied from tail fraction of second stage distillation, by extraction with base obtaining water solution of dioxybenzols. At fourth stage obtained water solution of dioxybenzols is converted into phenol by hydrodeoxygenation with hydrogen in conditions of continuous operation at temperature from 250 to 500°C, pressure 0.1-10 MPa and in presence of catalyst containing element of group VIB or their mixture or element of group VIII of periodic system or their mixture and promoter. At fifth stage obtained by re-cycle at previous stage phenol is supplied to distillation stage.

EFFECT: increase of degree of benzol conversion and selectivity on phenol, elimination of diphenol formation and reduction of solvents quantity.

22 cl, 8 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: cumane hydroperoxide is decomposed in presence of catalyst from processed with acid clay in order to transform cumane hydroperoxide into mass, which after decomposition contains mainly phenol and acetone, and mass reaction after decomposition is carried out in presence of cation catalyst, composed of cation-exchange resin and mercaptane promoter or promoter in form of mercaptoalkane acid in order to transform phenol and acetone in mass after decomposition mainly into diphenol A.

EFFECT: high product output with low admixture formation without necessity of stages of intermediate purification.

10 cl, 3 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: cumane hydroperoxide is decomposed in presence of acid catalyst from sulfated metal in order to transform cumane hydroperoxide into mass, which after decomposition contains mainly phenol and acetone, and mass reaction after decomposition is carried out, preferably without intermediate purification, in presence of cation catalyst, composed of cation-exchange resin and mercaptane promoter or promoter in form of mercaptoalkane acid in order to transform phenol and acetone in mass after decomposition mainly into diphenol A.

EFFECT: high product output with low admixture formation without necessity of stages of intermediate purification.

10 cl, 3 dwg, 6 ex

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

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

The invention relates to a catalyst for the oxidation of phenolic compounds of a number of technological solutions and waste waters containing compound of manganese (II)

The invention relates to the production of phenol/ more specifically to a method for production of phenol/ which may lead to the formation of propylene byproduct of acetone/ and recycling the regenerated propylene as the starting material

FIELD: chemistry.

SUBSTANCE: invention relates to methods (versions) of producing phenol through hydrodeoxidation of polyhydroxylated benzene derivatives, as well as through selective hydroxylation of benzene where a catalyst based on multi-component metal oxides is used. The methods are distinguished by that the said oxides contain at least one active phase of an oxide which corresponds to a scheelite structure, and crystalline materials which are not scheelite, or an amorphous structure where the crystalline scheelite structure is selected from the following compositions: Bi(1-x/3)V(1-x)wNb(1-x)(1-w)MoO4, Cu(1-z)ZnzW(1-y)MoyO4, where each of w, x, y and z are equal to 0 or 1, and where the crystalline materials which are not scheelite or an amorphous structure are selected from cerium oxide or a mixture of cerium oxide and zirconium oxide.

EFFECT: design of an efficient method of producing phenol through hydroxydeoxidation of polyhydroxylated benzene derivatives.

23 cl, 32 ex, 4 dwg

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to new derivatives of glucopyranosyloxybenzylbenzene represented by the formula (I): wherein R1 represents hydrogen atom or hydroxy(lower)alkyl; R2 represents lower alkyl group, lower alkoxy-group and lower alkylthio-group being each group is substituted optionally with hydroxy- or (lower)alkoxy-group, or to its pharmaceutically acceptable salts. Also, invention relates to pharmaceutical composition eliciting hypoglycemic activity and to a method for treatment and prophylaxis of hyperglycemia-associated diseases, such as diabetes mellitus, obesity and others, and to their intermediate compounds. Invention provides preparing new derivatives of glucopyranosyloxybenzylbenzene that elicit the excellent inhibitory activity with respect to human SGLT2.

EFFECT: valuable medicinal properties of compounds.

13 cl, 2 tbl, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to production of phenol via acid catalytic decomposition of cumene hydroperoxide followed by isolation of phenol from decomposition products and purification of phenol to remove trace impurities including acetol. Purification of phenol is accomplished through hetero-azeotropic rectification with water. Acetol is isolated as a part of liquid-phase side stream from semiblind plate located within exhausting section of hetero-azeotropic rectification column. Side stream is supplemented by cumene and used to supply stripping column, from which fraction of acetol/cumene azeotropic mixture is taken as distillate and residue is returned under semiblind plate of hetero-azeotropic rectification column to be further exhausted. From the bottom of the latter, crude phenol is withdrawn and passed to final purification from the rest of reactive trace impurities. Acetol/cumene azeotropic mixture is subjected to heat treatment at 310-350°C, which may be performed in mixtures with high-boiling production waste or in mixtures with bottom product of rectification column for thermal degradation of high-boiling synthesis by-products, which bottom product is recycled via tubular furnace. Above-mentioned semiblind plate, from which side stream is tapped, is disposed in column zone, wherein content of water is minimal and below which contact devices are positioned with efficiency at least 7.5 theoretical plates. Side stream with cumene added to it is passed to the vat of stripping column with efficiency at least 15 theoretical plates.

EFFECT: minimized content of acetol in purified phenol and reduced power consumption.

5 cl, 3 dwg, 6 tbl, 4 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to joint phenol-acetone production via selective decomposition of cumene hydroperoxide. Process is conducted in several in series connected reactors constructed in the form of shell-and-tube heat-exchangers, wherein part of decomposition product is recycled into reaction zone and mixed with feed stream to be decomposed, weight ratio of recycled stream to feed stream being less than 10. Reactors with tubular hydrodynamic characteristic have volumetric heat-exchange surface equal to or larger than 500 m2/m3. Preferably, residual concentration of cumene hydroperoxide is 0.1-0.3 wt % and its residence time in decomposition zone ranges from 0.5 to 10 min.

EFFECT: increased selectivity of decomposition at lesser recycle apparatus volume and reduced investment expenses.

11 cl, 1 dwg, 9 ex

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; 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: 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 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: 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

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