Catalyst used for hydrogen peroxide synthesis

FIELD: textile, paper and chemical industries; protection of environment in production of bleachers, biocides and components of oxidizing processes.

SUBSTANCE: proposed catalyst contains one or more metals of platinum group used as active component, one or more polyolefines and activated carbon carrier. It is preferably, that polyolefines have molecular mass above 400 and are selected from ethylene homopolymers and ethylene copolymers with alpha-olefines, propylene homopolymers and propylene copolymers with alpha olefines, butadiene homopolymers and copolymers with styrene and other olefines, isoprene homopolymers and copolymers with other olefines, ethylene-propylene copolymers, ethylene-propylene diolefine three-component copolymers, thermoplastic elastomers obtained from butadiene and/or isoprene and styrene block-copolymers, both hydrogenized and non-hydrogenized. Hydrogen peroxide is produced in presence of said catalyst from hydrogen and oxygen in reaction solvent containing halogenated and/or acid promoter. Proposed catalyst makes it possible to increase degree of conversion and selectivity of process, to obtain aqueous H2O2 solutions at content of acids and/or salts at level of trace amount.

EFFECT: enhanced efficiency.

48 cl, 1 tbl,18 ex

 

The present invention relates to a new catalyst, the method of direct synthesis of hydrogen peroxide (H2O2from hydrogen and oxygen, which use the specified catalyst and to the use of a solution of hydrogen peroxide for oxidation catalyzed by titanium silicalite.

Hydrogen peroxide is commercially important compound widely used as a bleaching agent in the textile and paper industry, as a biocide in the field of environmental protection and oxidative processes in the chemical industry.

Examples of such oxidation processes are processes using titanium silicalite as a catalyst, such as epoxidation of olefins (EP 100119), maximiliane carbonyl compounds (U.S. patent 4794198), the oxidation of ammonia to hydroxylamine (U.S. patent 5320819) and hydroxylation of aromatic hydrocarbons (U.S. patent 4369783).

Industrial production of aqueous solutions of H2O2using a complex two-stage method is already known.

In this method, the solution of anthraquinone, such as butylanthraquinone or ethylanthraquinone, in an organic environment, not miscible with water, first hydronaut, and then oxidized by air with the formation of H2O2, which is then extracted with an aqueous phase.

This is t way, however, has a number of disadvantages arising from the need to work with large volumes of reagents, a large number of required operations, the relatively high cost of reagents and by-products formation.

To overcome these shortcomings, we studied the method of direct synthesis of hydrogen peroxide from H2and O2. Such methods are usually carried out by conducting the reaction between the two gases in a solvent consisting of an aqueous medium or an aqueous-organic medium in the presence of a suitable catalytic system.

Among the ways this type from a technical and economic point of view is quite attractive seem methods, carried out in alcoholic or aqueous-alcoholic medium, for example, in methanol or methanol - water, as described, for example, in U.S. patent 4335092, in international patent application WO 98/16463, in European patent application EP 787681 and, in particular, in European patent application EP 978316 and in Italian patent application MI 2000 A, MI 2000 A and MI 2000 A001881.

In the same, essentially, conditions compared to work in the aquatic environment observed a higher reaction rate and selectivity.

High efficiency of the reaction, in turn, leads to:

i) the possibility of way more safely, far beyond shattered the minute mixtures of N 2-O2without sacrificing technical and economic indices;

ii) the possibility of using very low amounts of promoters (halides and acid) in the reaction medium, which has a beneficial effect on the stability of the catalytic system and the formation of stable solutions of hydrogen peroxide with the concentration of hydrogen peroxide, economically advantageous for the direct use of these solutions in the oxidation processes.

Finally, the concentration of the resulting solutions of hydrogen peroxide is approaching commercial values used as the boiling point and heat of vaporization properly selected alcohol lower than the corresponding constants of water.

These methods are usually carried out in the presence of a catalytic system consisting of a noble metal, particularly platinum group metals or their mixtures, in the form of salts or metals deposited on the media.

Now discovered that it is possible to further improve the way from the point of view of cost and selectivity, using a heterogeneous catalyst consisting of one or more platinum group metals, one or more polyolefins and media.

The use of polyolefins also allows us to improve the mechanical characteristics of the catalyst and facilitates its separation by filtration of the reactions is the TES system.

Thus, the present invention is a heterogeneous catalyst consisting of one or more platinum group metals, one or more polyolefins and media.

The present invention is also a method of producing hydrogen peroxide from hydrogen and oxygen using a specified catalyst. In addition, the present invention is the use of solutions of hydrogen peroxide obtained in the above manner, in the oxidation process catalyzed by titanium silicalite.

The catalyst which can be used for the purposes of the present invention is a heterogeneous catalyst consisting of:

(a) one or more platinum group metals as active components;

(b) one or more polyolefins and

(c) a carrier.

Examples of the platinum group metals are palladium, platinum, ruthenium, rhodium and iridium. The preferred metals are platinum and palladium.

In these palladium catalysts are usually present in amounts of from 0.01 to 4 wt.%, and the platinum in an amount of from 0.001 to 1 wt.%; the atomic ratio of palladium and platinum is in the range from 0.1/of 99.9 to 50/50.

Palladium is preferably present in an amount of from 0.05 to 2 wt.%, and the platinum in the amount of 0.005 to 0.5 wt.%; nuclear zootoxin the e between palladium and platinum is in the range from 1/99 to 30/70.

In addition to palladium and platinum as the active components or promoters may also be other metals such as ruthenium, rhodium, iridium and gold, in concentrations not exceeding the concentration of palladium.

Polyolefins that can be used in the method according to the present invention have a molecular weight above 400, and chosen from:

the homopolymers of ethylene and copolymers of ethylene with alpha-olefins;

the homopolymers of propylene and copolymers of propylene with alpha-olefins;

the homopolymers of butadiene and copolymers with styrene and other olefins;

the homopolymers of isoprene and copolymers with other olefins;

the ethylene/propylene copolymer (EPC);

the ethylene/propylene/diolefines of terpolymer (ternary copolymers) (EPDM);

- thermoplastic elastomers derived from block copolymers of butadiene and/or isoprene and styrene, hydrogenated and negidrirovannah.

The preferred polyolefins are amorphous polyolefins, because they are more soluble and therefore easier dispersing media.

For the purposes of the present invention is especially preferred are rubber and, in General, commercially available butadiene-styrene copolymers (synthetic rubber; GRS, SBR), ethylene-propylene copolymers (EPM, EPR), ethylene-propylene-diene copolymer of the (rubber EPDM, EPDM), styrene-butadiene-styrene copolymers (thermoplastic rubber SBR), isobutylene-isoprene copolymers (butylketone).

Polyolefins that can be used for the purposes of the present invention, can be obtained by any method known in this technical field.

The amount of the polyolefin is in the range from 0.1 to 20 wt.%, preferably from 1 to 10 wt.% by weight of the catalyst.

Typically, the inert carrier may consist of activated carbon, silica, alumina, aluminosilicate, zeolites and other materials well known in the art. For the preparation of the catalyst used for the present invention, it is preferable to use activated charcoal.

Activated charcoal, which can be applied for the purposes of the present invention, are selected from fossil coal or coal natural origin, obtained, for example, from wood, lignite, peat or coconut coir and having a surface area of more than 100 m2/g, preferably more than 300 m2/g; particularly preferred are coals with a surface area exceeding 600 m2/, Preferred activated carbons are activated coals with low ash content.

For this purpose, can also be used from sulphonated activated carbons, the description is given in European patent application EP 978316.

Before deposition of metal or of polyolefins activated carbon may be subjected to processing, such as washing with distilled water or treatment with acids, bases or diluted oxidizing agents, for example acetic acid, chloroethanol (hydrochloric) acid, sodium carbonate or hydrogen peroxide.

The catalyst may be obtained by dispersion of active ingredients in an inert carrier or carrier pre-treated polyolefin, by deposition or impregnation of his predecessors, consisting, for example, from solutions of their salts or soluble complexes, and subsequent reduction to the metallic state by means of thermal and/or chemical treatment with reducing agents, such as hydrogen, sodium formate, sodium citrate, or other preparative methods known in the art.

In accordance with one embodiment of the present invention, the catalyst may be prepared in a sequential and alternate dispersion media predecessors separate metal components of the catalyst, as described and claimed in the patent application IT MI2000-A001219.

The polyolefin is usually dissolved in a suitable solvent, and the resulting solution used for impregnation of the carrier.

Preferably used m todoku dry impregnation, which consists in making a mixture of polyolefins in contact with the carrier in a closed reactor at 100-120°C for 2-3 hours to speed up the deposition of polymer on the surface. After the procedure, the solvent is evaporated at a temperature of 140°C for 3-4 hours.

Examples of solvents suitable for the purposes of the present invention, are selected from paraffins, aromatic hydrocarbons and cycloparaffins. It is preferable to use n-heptane, toluene, decalin, n-decane.

The sequence in which the platinum group metals (a) and the polyolefin (b) is introduced into contact with the carrier in the preparation of the catalyst is not particularly critical.

However, if you use the amount of polyolefin in excess of 5 wt.%, a mixture of polyolefins preferably atomized on the media after the deposition of the metal constituting the active phase.

The catalyst in accordance with the present invention is particularly useful for the method of preparation of hydrogen peroxide from hydrogen and oxygen in the reaction solvent (the solvent for the reaction)containing a halogenated promoter and/or an acid promoter.

The catalyst usually is dispersed in the reaction medium at concentrations in the range from 0.1 to 10 wt.%, preferably from 0.3 to 3 wt.% by weight of the reaction solvent.

The reaction is actuarial consists of one or more alcohols or water-alcohol mixture, to which may be added simple aliphatic ether and/or one or more5-C32of hydrocarbons.

Examples of alcohols suitable for the purposes of the present invention, are selected from alcohols containing from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms.

Among the C1-C4the preferred alcohols are methanol, ethanol, tert-butanol (TB), or a mixture thereof. Especially preferred methanol. Among the preferred compounds, the most preferred mixture of methanol with water.

The number of alcohol (spirits) is in the range from 30 to 99 wt.% by weight of mixtures, preferably from 50 to 98 wt.%.

Aliphatic ethers are selected from ethers having the General formula:

where R and R1- same or different alkyl groups containing from 1 to 6 carbon atoms. In the compounds of formula (I) R is preferably methyl, a R1- tertiary alkyl. Especially preferred methyl tert-butyl ether (MTBE).

The amount of ester used in the solvent mixture depends on the type of alcohol (spirits) and usually is in the range from 0 to 70 wt.%, preferably from 10 to 60 wt.% by weight of the solvent of the reaction.

In accordance with one embodiment of the method according to the present invention, the solvent of reaction which may contain one or more 5-C32of hydrocarbons.

These hydrocarbons are usually chosen from paraffins, cycloparaffins or aromatic compounds.

Examples of paraffin hydrocarbons are preferably selected from linear or branched hydrocarbons having from 5 to 18 carbon atoms.

Examples of these paraffin hydrocarbons are n-hexane, n-heptane, n-octane, n-decane or their branched isomers.

Examples cycloparaffinic paraffin hydrocarbons are cyclohexane, decalin or derivatives thereof, substituted with one or more alkyl group having from 1 to 6 carbon atoms. Typical examples of these compounds are methylcyclohexane, ethylcyclohexane or dimethylcyclohexane.

Aromatic hydrocarbons that are suitable for the purposes of the present invention, preferably selected from hydrocarbons having from 6 to 24 carbon atoms.

Examples of aromatic hydrocarbons are benzene, naphthalene, alkyl benzenes and alkylnaphthalene with one or more linear or branched alkyl groups having from 1 to 18, preferably from 6 to 12 carbon atoms.

Examples of alkyl benzenes are toluene, xylene (ortho-, meta - and para-), ethylbenzene and cumene.

The amount of hydrocarbons used in the reaction depends on the type of alcohol (spirits), and is typically in the interval is from 0 to 20 wt.%, preferably from 0.1 to 10 wt.% by weight of the reaction solvent.

Acid promoter may be any substance capable of generating hydrogen ions (H+in the reaction solvent, and it is usually selected from inorganic acids such as sulfuric, phosphoric, nitric acid, or organic acids such as sulfonic acid. Preferred are sulfuric and phosphoric acids.

The concentration of the acid is usually in the range from 20 to 1000 mg per kg of the reaction solvent, and preferably from 50 to 500 mg per kg of the reaction solvent.

Halogenated promoter may be any substance capable of generating the halide ions in the reaction solvent. Preferred are substances capable of generating bromide ions. These substances are usually selected from Hydrobromic acid and its salts, soluble in the reaction medium, for example, sodium bromide, potassium bromide, ammonium bromide or sodium bromate. Especially preferred Hydrobromic acid, sodium bromide and potassium bromide.

The concentration of the halogenated promoter is typically in the range of from 0.1 to 50 mg per kg of the reaction solvent, and preferably from 1 to 10 mg per kg of the reaction solvent.

Obtaining hydrogen peroxide is carried out by performing the reaction of oxygen with hydrogen is in the reaction solvent in the presence of a catalyst and promoters and in the presence or in the absence of inert gas, selected from nitrogen, helium, argon. The preferred gas is nitrogen.

The molar ratio of N2/O2loading is in the range from 1/1 to 1/100, preferably from 1/2 to 1/15, and the concentration of hydrogen in the gas phase in contact with the solvent of the reaction, it is convenient to maintain a level less than 4.5 mol.%, outside the explosive mixture consisting of H2O2and possibly inert gas.

In accordance with one embodiment of the method according to the present invention the reaction can be conducted using air instead of pure oxygen.

The reaction is usually carried out at a temperature in the range from -5 to 90°S, preferably from 2 to 50°especially preferred temperature is from 20 to 40°and when the total pressure above atmospheric pressure, preferably in the range from 10 to 300 bar (1-30 MPa), particularly preferably the pressure 30-100 bar (3-10 MPa).

The method in accordance with the present invention can be implemented in periodic mode or preferably in a continuous mode, using a reactor suitable for the purposes of the invention and selected from reactors known in the art.

Working in the above conditions, you can get hydrogen peroxide in a safe environment when performance is eacli, usually being in the range from 30 to 200 g of N2O2(expressed as H2O2at 100% concentration) per liter of reaction medium, and the molar selectivity to the formation of H2O2located in the interval from 60 to 90% of the used amount of hydrogen.

Thus obtained solutions of hydrogen peroxide can be used directly for oxidation, which involves N2O2without time-consuming intermediate processing, such as removal of acids or solvents.

Furthermore, the method in accordance with the present invention are suitable for the preparation of aqueous solutions of N2O2having a commercial title, by removing from the reaction medium, for example by distillation, organic components, which can then be returned to the synthesis.

The method in accordance with the present invention allows to make the agents in N2O2with high conversion and selectivity with obtaining aqueous solutions of N2O2that do not contain acids or containing only traces of acids and/or salts.

For a more complete description of the present invention presents the following examples does not limit the present invention.

Example 1

Processing media from activated charcoal

150 g and tipirovanie coal, derived from Maritime pine trees, in powder form (CECA/2S/E) and 1500 ml of distilled water were loaded into a two-liter glass flask equipped with shirt, a refrigerator and a stirrer, heated on an oil bath regulated using a thermostat. After 2 hours at 80°With activated carbon was filtered and washed with distilled water.

Still wet activated carbon is then loaded in two-liter glass flask described above and after adding 1500 ml of a 5% (wt.) hydrochloric acid, the temperature was raised to 80°C. after Approximately 2 hours the mixture was cooled, and the activated carbon was washed on the filter with distilled water to remove the chloride ions. Washed activated charcoal was collected and dried in a drying Cabinet at 120°C for 3 hours.

Example 2 (comparative)

The preparation of the catalyst of Pt-Pd/C (AC2)

(a) 900 ml of distilled water, 2.8 g of Na2CO3and then 80 g of activated carbon prepared in example 1 was loaded into a glass reactor equipped as described in Example 1, the Suspension is kept at room temperature (20-25° (C) under stirring for 10 minutes.

Then for about 10 minutes, was added dropwise a solution of 8 g of Na2PdCl4with the mass concentration of Pd equal to 10%, in 100 ml of distilled water and the resulting suspension in which he had laid down at room temperature for 10 minutes, and then was heated on a water bath for 10 minutes to 90°C. Then added a solution containing from 0.76 g of sodium formate in 100 ml of distilled water, and stirring is continued at 90°within 2 hours.

After cooling to room temperature, the suspension was filtered, the collected catalyst was washed with distilled water to remove chloride ions and dried in a drying Cabinet at 120°C for 3 hours.

(b) thus Obtained catalyst was placed in a two-liter reactor equipped as described above, and were processed using the procedures in paragraph (a), but using a solution 0,404 g H2PtCl6(8 wt.% Pt) instead of the solution of Na2PdCl4.

After drying at 120°received catalyst (NP2), containing 0,97% Pd and 0,038% Pt on charcoal.

Example 3

Preparation of activated carbons, functionalized with sulfonic groups (- SO3H)

80 g of activated carbon, obtained as described in Example 1, was loaded into a two-liter glass reactor equipped with a jacket, a refrigerator and a stirrer, heated on an oil bath regulated using a thermostat, and within 20 minutes there was added dropwise 240 g of 96%H2SO4. After homogenization of the mixture of a light mixing was heated at 140°within 2 hours.

The mixture was cooled decanates temperature and within 10 minutes was added 200 g of crushed ice (distilled water), the mixture was left to cool, added 1000 ml of distilled water, the contents of the reactor were removed and filtered. Thus treated activated carbon was washed until the disappearance of sulfate ions from the wash water.

Elemental analysis showed that the thus treated activated carbon contains 0,38% s

Example 4 (comparative)

The preparation of the catalyst of Pd-Pt/C-SO3H (PR)

Used the procedure described in Example 2, but used as a carrier 8 g of activated carbon functionalized as described in Example 3. Got the catalyst (PR), which, according to elemental analysis, contained 0,039% Pt, 0.98% Of Pd and 0.35% S.

Example 5

The preparation of the catalyst of Pt-Pd/C+2.9% polystyrene

8 g of the catalyst AC2 was loaded into a 200-ml glass vacuum flask, which was purged with nitrogen for 15 minutes to remove air.

0.24 g of polystyrene (PS, the mass-average molecular weight Mw of 120,000) was dissolved in 70°With 100-ml Erlenmeyer flask containing 24 g of toluene. The resulting solution was then added dropwise over 5 minutes, maintaining a stream of nitrogen, the flask containing the catalyst AC2. The flask containing the catalyst, to which was added the polymer attached to the rotary evaporator and slowly heated under reflux until 110°C for 3 hours. Toluene was distilled anabolism vacuum, the catalyst was poured into a 100 ml beaker and dried in a drying Cabinet at 140°C for 3 hours.

Got the catalyst (WP5), which, according to elemental analysis, contained (Pt-Pd/C) + 2,9% PS (being 0.036% Pt, 0,94% Pd).

Example 6

The preparation of the catalyst of Pt-Pd/C-SO3H+3% PS (PR)

Used the procedure described in Example 5, but using the catalyst PR prepared in Example 4.

Got the catalyst (PR), which, according to elemental analysis, contained Pt-Pd/C-SO3H+3% PS (0.035% of Pt, 0,93% Pd and 0.36% S).

Example 7

The preparation of the catalyst of Pt-Pd/C (EPA) (PR)

Used the procedure described in Example 5, but instead of the polystyrene used 0.24 g of ethylene-propylene copolymer with 65% of ethylene and 35% propylene (EPA, ethylene-propylene rubber) with an average molecular weight of 110,000. Got the catalyst (PR), which, according to elemental analysis, contained Pt-Pd/(C+2,9% commissions (being 0.036% Pt, 0,94% Pd).

Example 8

The preparation of the catalyst of Pt-Pd/C-SO3H (EPA) (10% rhodium / platinum)

Used the procedure described in Example 7, but using 8 g of the catalyst PR obtained in Example 4.

Got the catalyst (10% rhodium / platinum), which, according to elemental analysis, contained Pt-Pd/C-SO3H+2,9% commissions (being 0.036% Pt, 0,95% Pd and 0.37% S).

Examples 9-10

There were repeated Examples 5 and 6 using 0.24 g of styrene-butadiene copolymer (SBR, BSC: 75/25) with an average molecular weight of 120,000,instead of With a 2-C3copolymer.

Were, respectively, catalysts (PR and PR), which, according to elemental analysis, contains:

PR: Pt-Pd/(C+2,9% BSC) (being 0.036% Pt, 0,95% Pd).

PR: Pt-Pd/C-SC3H+2,9% BSC) (being 0.036% Pt, 0,94 Pd and 0.36 S).

Examples 11-18

The synthesis of hydrogen peroxide

Used microprotol installation, consisting of a Hastelloy C autoclave with a volume of 400 ml equipped with a thermal control system, magnetic system mixing control system, and control the pressure during the reaction, the filter for the continuous removal of the liquid phase containing the reaction products, the supply system of the mixture of solvent and promoters, in which the reaction occurs, the system supplying gaseous reactants, and a series of instruments of control.

The reaction course was monitored by continuous analysis of the concentrations of hydrogen and oxygen at the inlet and outlet of the reactor.

The concentration of formed H2O2in the liquid stream emerging from the reactor was determined by titration with potassium permanganate. Selectivity for unreacted hydrogen was calculated based on the concentration of H2O2in the liquid stream leaving the reactor, and on the basis of the number of N2coming out of the reactor, steady-state steady-state conditions.

The reactor was loaded with 1.0 g of the catalyst prepared as described in point is imarah 2, 4 and 5-8, and 100 g of a solution of methanol/water (97/3, mass.), containing 6 ppm of HBr (6 mg/kg) and 200 parts per million of H2SO4(200 mg/kg).

In the autoclave without stirring escalate pressure 60 bar gas mixture consisting of 3,6% N2, 11% O2and 85,4% N2. Then he started mixing, bringing the speed up to 800 rpm; pressure is maintained constant stream of the same gas mixture with a flow rate of 916 litres, reduced to standard conditions (NORML), with a simultaneous supply of 400 g/h of a solution of methanol/water, having the above composition and containing 6 ppm of HBr and 200 parts per million of H2SO4.

The temperature inside the reactor was maintained 25°C.

The results obtained after 50 hours of reaction, shown in Table 1.

Table 1
CatalystH2O2, %Selectivity, %
AC2 Pt-Pd/C5,364
PR Pt-Pd/C-SO3Nthe 5.770
WP5 Pt-Pd/C + 3% PS5,673
PR Pt-Pd/C-SO3H + 3% PS5,980
PR Pt-Pd/(C+EPA)5,671
10% rhodium / platinum Pt-Pd/C-SO3H+EPA)6,0 78
PR Pt-Pd/(C+SBR(25-75))5,874
PR Pt-Pd/((C-SO3H+SBR(25-75))5,881

1. The catalyst used for the synthesis of hydrogen peroxide from oxygen and hydrogen, which consists of

(a) one or more platinum group metals as active components;

(b) one or more polyolefins and

(c) a carrier consisting of activated charcoal.

2. The catalyst according to claim 1, in which the metal components of the catalyst is palladium and platinum.

3. The catalyst according to claim 2, in which the amount of palladium is in the range from 0.01 to 4 wt.%, and the amount of platinum is in the range from 0.001 to 1 wt.%, when this atomic ratio of palladium/platinum is in the range from 0.1/of 99.9 to 50/50.

4. The catalyst according to claim 3, in which the amount of palladium is in the range from 0.05 to 2 wt.%, and the amount of platinum is in the range of 0.005 to 0.5 wt.%, when this atomic ratio of palladium/platinum is in the range from 1/99 to 30/70.

5. The catalyst according to claim 2, in which in addition to palladium and platinum as the active components or promoters may also be other metals such as ruthenium, rhodium, iridium and gold, in concentrations not exceeding the concentration of palladium.

6. The catalyst is .1, in polyolefins which have a molecular weight above 400, and selected from the

the homopolymers of ethylene and copolymers of ethylene with alpha-olefins;

the homopolymers of propylene and copolymers of propylene with alpha-olefins;

the homopolymers of butadiene and copolymers with styrene and other olefins;

the homopolymers of isoprene and copolymers with other olefins;

the ethylene-propylene copolymer (EPC);

ethylene-propylene-diolefines ternary copolymers (EPDM);

thermoplastic elastomers derived from copolymers of butadiene and/or isoprene and styrene, hydrogenated and negidrirovannah.

7. The catalyst according to claim 1, in which the amount of the polyolefin is in the range from 0.1 to 20% by weight of the catalyst.

8. The catalyst according to claim 1, in which the activated carbon has a low ash content and surface area of more than 100 m2/year

9. The catalyst according to claim 8, in which the activated carbon has a surface area of more than 300 m2/year

10. The catalyst according to claim 9, in which the activated carbon has a surface area of more than 600 m2/year

11. The catalyst according to claim 1, prepared by dispergirovannom active ingredients in an inert carrier or carrier pre-treated polyolefins using deposition and/or impregnation.

12. The catalyst according to claim 11, prepared after ovately and alternate dispersion of the precursors of the single metal components of the catalyst on an inert carrier or the carrier, the pre-treated polyolefines.

13. A method of producing hydrogen peroxide from hydrogen and oxygen in a reaction solvent containing a halogenated promoter and/or an acid promoter, in the presence of a catalyst according to claims 1-12.

14. The method according to item 13, in which the reaction solvent consists of one or more alcohols or water-alcohol mixture may contain simple aliphatic ether and/or one or more5-C32of hydrocarbons.

15. The method according to 14, in which the alcohol is chosen from alcohols containing from 1 to 6 carbon atoms,

16. The method according to item 15, in which the alcohol is a methanol.

17. The method according to 14, in which the number of alcohol (spirits) is in the range from 30 to 99% by weight of the mixture.

18. The method according to 14, in which simple aliphatic ester selected from esters defined by the General formula (I)

R-O-R1,

where R and R1- same or different alkyl groups containing from 1 to 6 carbon atoms.

19. The method according to p, in which in the compounds of formula (I) R is methyl, and R1- tertiary alkyl.

20. The method according to claim 19, in which a simple ester is a methyl tert-butyl ether (MTBE).

21. The method according to 14, in which the number of simple aliphatic ether having the General formula (I)is in the range from 0 to 70% by weight of the reaction dissolve the El.

22. The method according to 14, in which5-C32hydrocarbons are selected from paraffins, cycloparaffins and aromatic compounds.

23. The method according to item 22, in which the paraffin hydrocarbons are selected from paraffin hydrocarbons having from 5 to 18 carbon atoms.

24. The method according to item 22, in which the aromatic hydrocarbons are selected from aromatic hydrocarbons having from 6 to 24 carbon atoms.

25. The method according to 14, in which the amount of hydrocarbon is in the range from 0 to 20% by weight of the reaction solvent.

26. The method according to item 13, in which the catalyst is used in concentrations in the range of 0.1 to 10% by weight of the reaction solvent.

27. The method according to p, in which the catalyst is used in concentrations in the range of 0.3 to 3% by weight of the reaction solvent.

28. The method according to item 13, in which the acid promoter is selected from substances capable of generating hydrogen ions H+in the reaction solvent.

29. The method according to p, in which the acid promoter is selected from inorganic acids such as sulfuric, phosphoric, nitric acid, or organic acids such as sulfonic acid.

30. The method according to clause 29, in which the acid promoter is a sulfuric acid or phosphoric acid.

31. The method according to item 13, in which the concentration of acid promoter náchod is carried out in the range from 20 to 1000 mg per 1 kg of the reaction solvent.

32. The method according to p, in which the concentration of the acid promoter is in the range from 50 to 500 mg per 1 kg of the reaction solvent.

33. The method according to item 13, in which the halogenated promoter is selected from substances capable of generating the halide ions in the reaction solvent.

34. The method according to p, in which the halogenated promoter is selected from substances capable of generating bromide ions, such as Hydrobromic acid and its salts, soluble in the reaction medium, such as bromides of alkali metals, ammonium bromide or sodium bromate.

35. The method according to clause 34, in which the substance is Hydrobromic acid, sodium bromide and potassium bromide.

36. The method according to item 13, in which the concentration of the halogenated promoter is in the range from 0.1 to 50 mg per 1 kg of the reaction solvent.

37. The method according to p, in which the concentration of the halogenated promoter is in the range from 1 to 10 mg per 1 kg of the reaction solvent.

38. The method according to item 13, in which the reaction is carried out at a temperature in the range from -5 to 90°C.

39. The method according to item 13, in which the reaction is carried out at a total pressure above atmospheric pressure.

40. The method according to § 39, in which the total pressure is in the range from 10 to 300 bar (from 1 to 30 MPa).

41. The method according to item 13, in which the molar ratio of hydrogen/oxygen in zagruzki which is in the range from 1/1 to 1/100.

42. The method according to item 13, in which the reaction is carried out in the presence of an inert gas selected from nitrogen, helium and argon.

43. The method according to § 42, in which the inert gas is nitrogen.

44. The method according to item 13, in which the concentration of hydrogen in the gas phase in contact with the reaction solvent, supported at the level of less than 4.5 mol.%.

45. The method according to item 13, in which the reaction is carried out using air as the oxygen source.

46. The method according to item 13, in which the reaction is carried out in periodic mode or in continuous mode.

47. The method according to item 13, in which the hydrogen peroxide solution is used directly for oxidation of the substrate, selected from olefins, aromatic hydrocarbons, ammonia and carbonyl compounds using titanium silicalite as a catalyst.

48. The method according to item 13, in which the hydrogen peroxide solution is used to produce aqueous solutions of N2About2having a commercial title, by removing from the reaction medium organic components that can be returned in the synthesis.



 

Same patents:

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The invention relates to a method of producing hydrogen peroxide by direct reaction between hydrogen and oxygen in an aqueous medium in the presence of a catalyst

FIELD: waste water treatment.

SUBSTANCE: invention relates to biological waste water treatment methods that can be used at enterprises of power, petroleum processing, petrochemical, chemical, paper-and-pulp, food processing, and other industries as well as for treatment of household sewage. Biocatalytic waste water treatment is performed by oxidation in air tanks or on biofilters in presence of catalytically acting substance and activated sludge. In case of air tanks, catalytically acting substance consists of one (multifunctional) or three (one multifunctional and two selective) heterogeneous catalysts for oxidation of inorganic and/or organic compounds and containing active component: variable-valence metal oxides and/or hydroxides, or spinels, and, additionally, modifying additive, in particular organic bases and/or heteropolyacids, active component being deposited on polymer carrier (polyethylene or polypropylene). Content of active component is 15-20% and that of modifying additive 0.5-20%. For oxidation of organic, sulfur, and nitrogen compounds, multifunctional catalyst is used containing active component consisting of variable-valence metal oxides and hydroxides. For nitrification process (ammonium nitrogen oxidation), selective catalyst is used containing active component consisting of variable-valence metal spinels and oxides. In case of denitrification process (reducing nitrites and nitrates into molecular nitrogen), selective catalyst is used containing active component consisting of variable-valence metal spinels and hydroxides. Oxidation process is accomplished at catalyst-to-water ratio 1:75 at consumption of air not higher than 9.0 m3/m3. Invention also discloses biocatalytic treatment of waste waters via oxidation on biofilters in presence of activated sludge and catalytically acting substance consisting of active component (15-50%): one or several variable-valence metal compounds, flux (50-10%): silicon-containing compound, modifying additive (0.5-20%): carbon-containing material, and carrier: clay.

EFFECT: increased productivity and reduced power consumption on existing treatment plants, reduced investment and operational expenses, and deepened waste water treatment.

8 cl, 5 tbl, 10 ex

The invention relates to the composition of the oligomeric acid catalyst as component of liquid compositions to obtain fenolformaldegidnyh (FF) foams, does not cause corrosion of metal or having a very weak corrosive effect on their surface

The invention relates to the chemical industry, and more specifically to the production of alkylsilanes

The invention relates to a method for linalool, which is an intermediate organic compound used in the pharmaceutical and perfume industry

The invention relates to catalytic chemistry, in particular to catalysts based on Nickel to obtain dimers and oligomers of olefins

The invention relates to the production of ion exchangers molded catalysts used in organic synthesis

The invention relates to the field of petrochemicals, in particular the production of trimers and tetramers of propylene, which are widely used as raw material in the manufacture of additives to oils, plasticizers, flotation agents and other surfactants and synthetic oils

The invention relates to catalysts for the treatment of exhaust gases and can be used to reduce the toxicity of the gases of internal combustion engines, installations for the production and processing of organic and polymeric materials

The invention relates to the field of metal-containing catalysts hydrochlorination of unsaturated compounds

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: preparation of catalyst comprises depositing active components on γ-alumina carrier at stirring, carrier being preliminarily treated with concentrated NaOH solution. Active components are deposited consecutively in three steps. In the first step, preliminarily prepared chitosan in acetic acid solution with KCl solution is deposited for 60-65 min; in the second step, sodium tetrachloropaladate(II) trihydrate Na2PdCl4·3H2O solution is deposited for 60-65 min; and, in the third step, hydrazine hydrate solution as reducing agent is added for 180-240 min. After each step, resulting suspension is filtered off, washed, and dried at 293-303K for 1-2 h in vacuum. Catalyst can be used in chemical industry and in processing of industrial and household wastes.

EFFECT: enhanced nitrate hydrogenation efficiency.

6 cl, 1 dwg, 6 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: palladium-containing hydrogenation catalyst, which can be used to control rate of autocatalytic hydrogenation reactions, is prepared by hydrogen-mediated reduction of bivalent palladium from starting compound into zero-valence palladium and precipitation of reduced zero-valence palladium on carbon material, wherein said starting material is tetraaqua-palladium(II) perchlorate and said carbon material is nano-cluster carbon black. Reduction of palladium from starting compound and precipitation of zero-valence palladium on carbon material are accomplished by separate portions.

EFFECT: increased catalytic activity, enabled catalyst preparation under milder conditions, and reduced preparation cost.

1 dwg, 1 tbl, 12 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of catalyst comprises applying palladium compound onto silica cloth and heat treatment. Palladium compound is applied by circulation of toluene or aqueous palladium acetate solution through fixed carrier bed until palladium content achieved 0.01 to 0.5%. Palladium is introduced into cloth in dozed mode at velocity preferably between 0.1 and 5.9 mg Pd/h per 1 g catalyst. Heat treatment includes drying at temperature not higher than 150oC under nitrogen or in air and calcination in air or nitrogen-hydrogen mixture flow at temperature not higher than 450oC. Original silica cloth can be modified with 0.6 to 6.5% alumina. Palladium is uniformly distributed in silica cloth and has particle size preferably no larger than 15 Å. Invention can be used in treatment of industrial gas emissions and automobile exhaust to remove hydrocarbons.

EFFECT: deepened oxidation of hydrocarbons.

5 cl, 1 tbl, 4 ex

FIELD: supported catalysts.

SUBSTANCE: invention claims a method for preparation of catalyst using precious or group VIII metal, which comprises treatment of carrier and impregnation thereof with salt of indicated metal performed at working pressure and temperature over a period of time equal to or longer than time corresponding most loss of catalyst metal. According to invention, treated carrier is first washed with steam condensate to entirely remove ions or particles of substances constituted reaction mixture, whereupon carrier is dried at 110-130oC to residual moisture no higher than 1%.

EFFECT: achieved additional chemical activation of catalyst, reduced loss of precious metal from surface of carrier, and considerably increased lifetime.

5 cl, 9 ex

FIELD: petrochemical synthesis catalysts.

SUBSTANCE: invention discloses a method for preparation of palladium catalyst comprising impregnation of alumina carrier with palladium chloride solution in presence of aqueous hydrochloric acid, treatment with reducing agent (hydrogen), washing with water, and drying, said carrier being preliminarily decoked exhausted catalyst containing alumina and group I and/or II, and/or VI, and/or VIII metals and subjected to washing with aqueous hydrochloric or nitric acid and then with water. Exhausted ethylene oxide production catalyst or methylphenylcarbinol dehydration catalysts can also be suitably used.

EFFECT: increased selectivity and activity of catalyst.

2 cl, 2 tbl, 21 ex

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to a method for preparing acetic acid by gas-phase oxidation of ethane and/or ethylene with oxygen using catalyst comprising molybdenum and palladium. For realization of method gaseous feeding comprising ethane, ethylene or their mixture and oxygen also are contacted at enhanced temperature with catalyst that comprises elements Mo, Pd, X and Y in combination with oxygen of the formula (I): MoaPdbXcYd wherein X and Y have the following values: X means V and one or some elements optionally taken among the following group: Ta, Te and W; Y means Nb, Ca and Sb and one or some elements optionally taken among the following group: Bi, Cu, Ag, Au, Li, K, Rb, Cs, Mg, Sr, Ba, Zr and Hf; indices a, b, c and d mean gram-atom ratios of corresponding elements wherein a = 1; b = 0.0001-0.01; c = 0.4-1, and d = 0.005-1. Niobium is added to the catalyst structure using niobium ammonium salt. Preferably, niobium ammonium salt is used as the niobium source. The continuance of contact time and composite values of the parent gaseous mixture are so that taken to provide output value by acetic acid to be above 470 kg/(m3 x h). The selectivity of oxidation reaction of ethane and/or ethylene to acetic acid is above 70 mole %. Invention provides enhancing stability and output of catalyst.

EFFECT: improved preparing method.

14 cl, 1 tbl, 6 ex

The invention relates to the production, accompanied by emissions of nitrogen oxides
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