Catalyst for dehydration of cyclohexanol into cyclohexanone, and method of its production

FIELD: process engineering.

SUBSTANCE: invention relates to catalyst for dehydration of cyclohexanol to cyclohexane and to method of its production. Proposed catalyst comprises the following components in wt %: calcium carbonate - 16.4-37.0, graphite - 1.0-3.0, and zinc oxide making the rest. Proposed method comprises preparing reaction mix of previously mentioned composition containing sources of zinc oxide and calcium carbonate, moulding, drying, and calcinating. Note here that said mix comprises the following components in wt %: calcium carbonate - 12.4-29.8, carboxymethylcellulose or methylcellulose - 0.1-1.0, and base zinc carbonate making the rest, while graphite is added into amounts sufficient for production of said catalyst.

EFFECT: higher strength, lower costs, simplified production, reduced harmful effects.

3 cl, 2 tbl, 2 ex

 

The invention relates to a catalyst for the dehydrogenation of cyclohexanol to cyclohexanone, as well as to a method for preparing this catalyst.

From the application DE 1443462 known catalyst for the dehydrogenation of primary and secondary alcohols, mainly composed of zinc oxide. The catalyst may contain as copper compounds, and oxides and hydroxides of alkaline earth metals.

Common symptoms are known and the claimed catalysts are their base is zinc oxide and the use of compounds of alkaline earth metals.

The disadvantages are similar to the complex composition of the catalyst and sophisticated technology of its preparation, low selectivity and a large number of unreacted cyclohexanol using this catalyst.

From (Hoffman N., "AngewandteChemie", 1965, Bd.77, No. 7, S.346-350) known dehydrogenation catalyst containing esters of cyclohexanol. The catalyst consists of zinc oxide with the addition of 6.7% of calcium oxide, 4.5% aluminum oxide and 1.6% of chromium oxide.

In the dehydrogenation at 370°C in the catalyst mixture, which includes 64.3% of cyclohexanol, 28.3% of cyclohexanone, 2.7% of cyclohexylamin esters of mono and dicarboxylic acids, the content of esters decreased to 0.3%. The degree of conversion of cyclohexanol was 80%, and the yield of cyclohexanone per TA the military products 98%.

Common symptoms are known and inventive catalysts is that they are based on zinc oxide and use in the composition of the catalyst compounds of calcium.

Disadvantages described are similar in complex catalyst components and sophisticated technology of its preparation, coupled with the formation of large amounts of toxic wastes, in a low degree of conversion.

Known (caprolactam. Edited Viewindicate and Vnnrysykcg. M.: Khimiya, 1977) catalysts for dehydrogenation of cyclohexanol to cyclohexanone on the basis of zinc oxide, which contain a stabilizing and promoting additives. These include the catalyst brand GIAP-10, which is obtained by decomposition of the basic zinc carbonate at 400°C and subsequent tabletting active zinc oxide with addition of 2% of graphite.

Under optimal conditions (temperature 340÷360°C, the volumetric rate of liquid cyclohexanol 1,0÷1.5 h-1) output of cyclohexanone per unreacted cyclohexanol reaches 98% at conversion degrees 80÷85%. Optimal surface zincating catalyst is 8÷16 m2/year

Common symptoms are known and inventive catalysts is their base is zinc oxide, the use of graphite.

The disadvantage of the catalyst is that when the content of impurities in the cyclohexanol more than the 2% of the activity of the catalyst is markedly reduced, while most of the surface decreases the selectivity of the catalyst.

In patent No. 2181624 (IPC RU7B01J 23/02, B01J 23/06, B01J 27/232, B01J 37/03, C07C 45/00, C07C 49/403, publ. 27.04.2002) described the closest (prototype) a catalyst for the dehydrogenation of cyclic secondary alcohols containing zinc oxide (30÷60 wt.%) and calcium carbonate (40÷70 wt.%) in the modification of calcite.

The catalyst of the prototype has a specific surface according to BET of from 5 to 50, preferably from 10 to 30 m2/g Catalyst possess resistance to failure due to RAM pressure in the range from 500 to 4000 N/cm2primarily from 1000 to 2500 N/cm2and resistance to failure due to lateral pressure (tangent) from 30 to 300 N/cm2preferably from 50 to 200 N/cm2.

Ibid describes closest (prototype) method of preparation of this catalyst, which is carried out by precipitation of sparingly soluble compounds of zinc and calcium base from solutions of water-soluble compounds of zinc and calcium and the subsequent processing, including drying and heat treatment. Drying is carried out at a temperature in the range from 90 to 150°C. the Dried powder calicivirus according to the invention at temperatures in the range from 400 to 475°C (preferably). In the process, calcined powder are pressed together with (preferably) 2 wt.% graphite, assumed the traveler on the total weight.

The process of dehydrogenation of cyclic secondary alcohols in the presence of this catalyst in order to obtain cyclohexanone is carried out at elevated temperature and pressure in the presence of hydrogen. As the cyclic secondary alcohols preferred is the use of cyclohexanol. The preferred load is from 0.6 to 2.0 liters of alcohol per liter of catalyst per hour. The temperature of the gas phase in the reaction zone is recommended to maintain 300÷450°C (preferably). While the transformation of the alcohol was achieved in the range from 65 to 75%.

The technical result of the prototype is to increase the strength of the catalyst and increase the duration of its operation.

The disadvantages of the prototype lies in the sophisticated technology of preparation of the catalyst, coupled with the formation of large amounts of wastewater. Not enough high strength catalyst causes a pretty intense its destruction. A shorter lifetime of the catalyst is associated with the need for a reboot, which reduces technical and economic parameters of the process. When the dehydrogenation of cyclohexanol containing large amounts of impurities, cyclohexanone get with insufficiently high degree of conversion. The low yield of the target product and a large number of unreacted cyclohexanol (ostatic the initial anal) also worsen the techno-economic performance of the process.

The task of the group of inventions is expanding range of inexpensive, efficient with good physico-chemical and consumer properties and simple to manufacture dehydrogenation catalysts containing large amounts of impurities of cyclohexanol, cyclohexanone, and methods of preparing catalysts, the use of which provides high selectivity combined with high activity.

The technical result, which provides an implementation of the claimed group of inventions is to improve the strength and the reduction of the obtained catalyst, the simplification of the method of preparation (no stages of washing, filtering, and other) and the prevention of harmful effects on the environment (drainage and waste-free technology). Implementation of the inventive catalyst in the dehydrogenation of cyclohexanol containing large amounts of impurities can increase the service life of the catalyst, to increase the yield of cyclohexanone, the degree of conversion, selectivity and to reduce the amount of unreacted (residual) cyclohexanol.

The technical result of the catalyst in the dehydrogenation of cyclohexanol to cyclohexanone containing graphite, zinc oxide and calcium carbonate, is due to the fact that the components are contained in the following ratios, wt%:

Calcium carbonate16,4÷37,0
Graphite1,0÷3,0
Zinc oxideRest

When this source of zinc oxide is the reaction mixture, containing basic zinc carbonate, calcium carbonate and the carboxymethylcellulose or methylcellulose, in the following ratio, wt.%:

Calcium carbonate12,4÷29,8
Carboxymethylcellulose
or methylcellulose0,1÷1,0
Basic zinc carbonateRest

Comparative analysis of the prototype (No. 2181624) and the claimed catalyst for the dehydrogenation of cyclohexanol to cyclohexanone shows that the General is content in the catalyst graphite, zinc oxide and calcium carbonate.

A distinctive feature of the claimed catalyst for the dehydrogenation of cyclohexanol to cyclohexanone is that components are contained in the following ratios, wt%:

Calcium carbonate16,4÷37,0
Graphite1,0÷3,0
Zinc oxideRest

When this source of zinc oxide is the reaction mixture, containing basic zinc carbonate, calcium carbonate and the carboxymethylcellulose or methylcellulose in the following ratio, wt.%:

Calcium carbonate12,4÷29,8
Carboxymethylcellulose
or methylcellulose0,1÷1,0
Basic zinc carbonateRest

The technical result of the preparation method of catalyst for the dehydrogenation of cyclohexanol to cyclohexanone, comprising preparing a reaction mixture containing sources of oxides of zinc and carbonate of calcium, molding, drying, calcining, is achieved by first preparing a mixture containing, wt.%:

Calcium carbonate12,4÷29,8
Carboxymethylcellulose
or methylcellulose0,1÷1,0
Basic zinc carbonateRest

The prepared mixture was molded, dried at a temperature of 80÷120°C, calcined at a temperature of 350÷400°C, and then calcined product is pulverized, add to it the graphite, the resulting mass is formed. While graphite is added in amounts providing a catalyst of the following composition, wt.%:

Calcium carbonate16,4÷37,0
Graphite1,0÷3,0
Zinc oxideRest

Comparative analysis of the prototype (No. 2181624) and the proposed method of preparation of the catalyst in the dehydrogenation of cyclohexanol to cyclohexanone shows that total is the preparation of the reaction mixture containing sources of oxides of zinc and carbonate of calcium, molding, drying, calcination.

A distinctive feature of the proposed method for preparation of the catalyst in the dehydrogenation of cyclohexanol to cyclohexanone is that initially preparing a mixture containing, wt.%:

Calcium carbonate12,4÷29,8
Carboxymethylcellulose
or methylcellulose0,1÷1,0
Basic zinc carbonateRest

The prepared mixture was molded, dried at a temperature of 80÷120°C, calcined at a temperature of 350÷400°C, and then calcined product is pulverized, add to it the graphite, the resulting mass is formed. While graphite is added in amounts providing a catalyst of the following composition, wt.%:

Calcium carbonate16,4÷37,0
Graphite1,0÷3,0
Zinc oxideRest

The possibility of implementing the claimed invention and its essence explain the examples below. Physico-chemical characteristics of the catalysts are presented in table 1.

Example 1.

In a mixing machine download 149,2 kg basic zinc carbonate (zingerone carbonate) and 48,8 kg of calcium carbonate, add 2 kg of CMC or MC in the form of previously prepared colloidal solution. A mixture of paramashiva the t for 30 minutes, followed by molding. The resulting extrudates are dried at a temperature of 120°C, and then calcined at 400°C. 155,0 kg obtained after calcination product containing zinc oxide and calcium carbonate, pulverized and mixed with 4.5 kg of graphite, and then form a tabletting method.

Get ready catalyst in the following ratio, wt.%:

Calcium carbonate30,7
Graphite3
Zinc oxideRest

Example 2.

In a mixing machine load 175 kg of basic zinc carbonate (zingerone carbonate) and 24.8 kg of calcium carbonate, add 2 kg of CMC or MC in the form of previously prepared colloidal solution. The mixture is stirred for 30 minutes, followed by molding. The resulting extrudates are dried at a temperature of 120°C, and then calcined at 400°C. 149,4,0 kg obtained after calcination product containing zinc oxide and calcium carbonate, pulverized and mixed with 4.5 kg of graphite, and then form a tabletting method.

Get ready catalyst in the following ratio, wt.%:

Calcium carbonate16,4
Graphite1
Zinc oxideRest

Presented in table 1 data show that the BET surface and the rate of resistance by forming a patented catalyst in all examples is significantly higher than that of the catalyst obtained by the preferred method of the prototype. The proposed catalyst has good teletrauma ability, sufficient hardness (strength). The latter is confirmed by the test results of the inventive catalyst in the dehydrogenation of cyclohexanol to cyclohexanone.

The process of dehydrogenation was carried out without the use of hydrogen and at atmospheric pressure. The feedstock contains 89,838÷92,494 wt.% cyclohexanol, the rest ketone, esters, low-boiling and high-boiling hydrocarbons.

Activity (conversion) of the catalysts was evaluated with a total degree of conversion of cyclohexanol in the products of reaction and the selectivity is the degree of conversion of cyclohexanol to cyclohexanone in %. The composition of the feedstock and reaction products was determined by the chromatographic method. Process performance dehydrogenation presented in table 2.

With postively data analysis table 1 showed, that specific surface area and the proportion of pores with an optimal radius of the catalyst of the prototype is much less than claimed. Resistance by forming a patented catalyst is slightly higher than the known. It can be assumed that the service life of the proposed catalyst is more than known.

The comparative analysis of data of table 2 shows that compared with the prototype implementation of the proposed catalyst allows to obtain higher rates of conversion, selectivity and yield of cyclohexanone, and the remainder of the unreacted anola is considerably less. It is shown that the degree of conversion and selectivity in the implementation of patentable catalyst for change within 88,7÷91,4 and 99,2÷99,3%, respectively. The yield of the target product is 88,800÷90,800 wt.%, and the remainder of the unreacted anola 7,938÷10,197 wt.%. The high activity of the proposed catalyst leads to a deeper transformations of cyclohexanol.

The positive effect from the sale of a group of inventions is provided not additive contribution of each component, and due to the combined (synergistic) effects of these features.

Table 1
Physico-Henichesk what I characteristics of the catalysts
CatalystThe temperature of calcination, °CResistance by forming, MPaSpecific surface area by BET, m2/gThe average radius of the pores, ÅTotal pore volume, cm3/g, less than 800 ÅThe proportion of pores with a radius 40-114 Å (optimal)%
The prototype (the preferred option)4504,313,81440,1016
In example 1 (20% CaO)4504,537,01700,2119
According to example 2 (10% CaO)450a 4.933,01280,2439

Table 2
Technological parameters dehydrogenation on various kata is isatori
The process parametersCatalyst
The prototype (the preferred option)For example 1For example 2
Source anal, wt.%89,83890,11892,494
Process temperature, °C350350350
Space velocity, h-11,01,01,0
Selectivity, %99,099,299,3
Conversion, %85,088,791,4
The output anon, wt.%84,037and 88.890,8
The rest of anola, wt.%13,67510,1977,938

1. The catalyst for the dehydrogenation of cyclohexanol is cyclohexanone, containing graphite, zinc oxide and calcium carbonate, wherein the components are contained in the following ratios, wt%:

Calcium carbonate16,4÷37,0
Graphite1,0÷3,0
Zinc oxiderest

2. The catalyst for the dehydrogenation of cyclohexanol to cyclohexanone according to claim 1, characterized in that the source of the zinc oxide is the reaction mixture, containing basic zinc carbonate, calcium carbonate and the carboxymethylcellulose or methylcellulose in the following ratio, wt.%:

Calcium carbonate12,4÷29,8
Carboxymethylcellulose
or methylcellulose0,1÷1,0
Basic zinc carbonaterest

3. The preparation method of catalyst for the dehydrogenation of cyclohexanol to cyclohexanone containing graphite, zinc oxide and calcium carbonate, comprising preparing a reaction mixture containing sources of oxide the zinc and calcium carbonate, molding, drying, calcining, wherein the first preparing a mixture containing, wt.%:

Calcium carbonate12,4÷29,8
Carboxymethylcellulose
or methylcellulose0,1÷1,0
Basic zinc carbonatethe rest,

and graphite is added in amounts providing
catalyst of the following composition, wt.%:
Calcium carbonate16,4÷37,0
Graphite1,0÷3,0
Zinc oxiderest



 

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2 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing (C60-Ih)[5,6]fullero[2',3':1,9]cyclopropan-1'-yl(cycloalkyl)methanones of general formula (1): n=1; 2; 3, which can be used as components of high-energy fuels, as well as nanomaterials for preparing modern additives for heavily loaded mechanisms and machines and starting substances in production of medicinal agents. The method involves reaction of C60-fullerene with 2-oxo-2-cycloalkyl diazoethanes (N2CHC(O)cycloalkyl) in o-dichlorobenzene (o-DCB) in the presence of a three-component catalyst {Pd(acac)2 : 2PPh3:4Et3Al}, taken in molar ratio C60:2-oxo-2-cycloalkyl diazoethane:Pd(acac)2:PPh3:Et3Al = 0.01:(0.03-0.07):(0.001-0.003):(0.002-0.006):(0.004-0.012), preferably 0.01:0.05:0.002:0.004:0.008, at temperature 80°C for 0.5-1.5 hours.

EFFECT: method enables to obtain desired products with high output.

1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to zeolite-containing catalysts. Described is a zeolite-containing catalyst for converting a straight-run gasoline fraction to a high-octane gasoline component with low benzene content, which contains iron-aluminosilicate with H-ZSM-5 type high-silica zeolite structure with silica modulus SiO2/Al2O3=55, SiO2/Fe2O3=540, in amount of 97.0-99.0 wt % and a modifying component which is at least one of the following: Cu, Zn, Ni, Mo, in amount of 1.0-3.0 wt %; which is introduced into iron-aluminosilicate in form of metal nanopowder; the catalyst is formed during thermal treatment. Described is a method of producing said catalyst, characterised by that the H-ZSM-5 type iron-aluminosilicate with silica modulus SiO2/Al2O3=55, SiO2/Fe2O3=540 is obtained via hydrothermal crystallisation of the reaction mixture at 120-180°C for 1-4 days, which contains sources of silicon oxide, aluminium oxide, iron oxide, alkali metal oxide, hexamethylene diamine and water; with further mixing of the iron-aluminosilicate with nanopowder of metals selected from Cu, Zn, Ni, Mo, obtained by electric blasting the wire of the metal in a medium of argon, followed by mechanochemical treatment, moulding the catalyst mass, drying and calcination. Described is a method of converting a straight-run gasoline fraction to a high-octane gasoline component with low content of benzene in the presence of the catalyst described above at 350-425°C, volume rate of 1.0-2.0 h-1 and pressure 0.1-1.0 MPa.

EFFECT: high activity and selectivity of the catalyst.

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