Method for producing high-octane components from olefins from catalytic cracking

Abstract

The invention relates to the field of petrochemistry, and specifically to a method for synthesizing high-octane oxygen containing components of motor fuel. The objects of the invention consist in variants of a method for synthesizing high-octane oxygen-containing components of motor fuel from olefin-containing gas mixtures via oxidative non-catalytic conversions using nitrous oxide, and the subsequent condensation and hydrogenation of the produced oxygenates using heterogeneous catalysts. The high-octane components according to the proposed method consist in a mixture of carbonyl compounds (ketones, aldehydes, hydroxy ketones, hydroxy aldehydes) C.sub.2-C.sub.9 and/or branched hydrocarbons C.sub.5-C.sub.9 and/or alcohols in different ratios. Depending on the production method variant, the octane number of a mixture of the proposed high-octane components consists in a value between 100 and 130 RON. The technical result consists in broadening the resource base for the production of high-octane gasolines and of a variety of environmentally-friendly high-octane additives.

Claims

1. A method for producing a high-octane component of motor fuels from olefin-containing gas mixtures characterized in that an olefin-containing mixture comprising C2-C4 alkanes and olefins is oxidized with nitrous oxide, followed by an isolation of a product mixture as the high-octane component.

2. The method of claim 1, characterized in that a catalytic cracking gas is used as the olefin-containing mixture.

3. The method of claim 1, characterized in that the method is carried out at a temperature of 300 to 550 C. and a pressure of 1 to 100 atm is maintained.

4. The method of claim 1, characterized in that a volume ratio of the olefin containing mixture to the nitrous oxide is maintained at a level of 2 to 10.

5. A method for producing a high-octane component of motor fuels from olefin containing gas mixtures, characterized in that an olefin-containing gas mixture comprising C2-C4 alkanes and olefins is oxidized with nitrous oxide in a gas phase at the first stage, and then, at the second stage, the products obtained at the first stage are condensed, followed by an isolation of a product mixture as the high-octane component.

6. The method of claim 5, characterized in that a catalytic cracking gas is used as the olefin-containing mixture.

7. The method of claim 5, characterized in that the first stage is carried out at a temperature of 300 to 550 C., and the second stage is carried out at a temperature of 30 to 400 C., a pressure of 1 to 100 atm is maintained at the first stage, and a pressure of 1 to 10 atm is maintained at the second stage.

8. The method of claim 5, characterized in that a volume ratio of the olefin containing mixture to the nitrous oxide is maintained at a level of 2 to 10 at the first stage.

9. The method of claim 5, characterized in that the products of the oxidation of the olefin fraction, before being used as a feedstock at the second stage, are separated into aldehyde and ketone fractions.

10. The method of claim 9, characterized in that the ketone and aldehyde fractions are subjected to the condensation process separately.

11. The method of claim 9, characterized in that the ketone fraction is directly used as a high-octane component, and the aldehyde fraction is subjected to the condensation process.

12. The method of claim 5, characterized in that the products of the oxidation of the olefin fraction, before being used as a feedstock at the second stage, are separated into separate components, followed by using them as a target product and/or using as a feedstock for the condensation process.

13. The method of claim 5, characterized in that the second stage is carried out in a liquid phase by aldol or aldol-crotonic condensation in the presence of any known catalyst.

14. The method of claim 5, characterized in that the second stage is carried out by condensation with methanol in a gas phase in the presence of a copper-containing catalyst at a volume ratio of the product mixture obtained at the first stage to methanol of 1 to 10.

15. The method of claim 14, characterized in that, at the second stage, the condensation of the products obtained at the first stage with methanol is carried out in the presence of at least 0.1 vol. % hydrogen.

16. The method of claim 14, characterized in that, at the second stage, the condensation of the products obtained at the first stage with methanol is carried out in the presence of a catalyst containing 5 to 40 wt % copper on a support.

17. The method of claim 16, characterized in that the catalyst support used at the second stage is Al.sub.2O.sub.3 and/or SiO.sub.2 and/or TiO.sub.2 and/or aluminosilicate and/or silicate or aluminosilicate glass fibers.

18. A method for producing a high-octane component of motor fuels from olefin-containing gas mixtures, characterized in that an olefin-containing mixture comprising C2-C4 alkanes and olefins is oxidized with nitrous oxide in a gas phase at the first stage, and then, at the second stage, the products obtained at the first stage are condensed, and, at the third stage, the mixture of condensed oxygenates obtained at the second stage or the mixture of carbonyl compounds obtained at the first stage are reacted with hydrogen in the presence of a hydrogenation catalyst, followed by an isolation of a mixture of hydrogenated products as the high-octane component.

19. The method of claim 18, characterized in that a catalytic cracking gas is used as the olefin-containing mixture.

20. The method of claim 18, characterized in that the first stage is carried out at a temperature of 300 to 550 C., the second stage is carried out at a temperature of 30 to 400 C., and the third stage is carried out at a temperature of 100 to 400 C.

21. The method of claim 18, characterized in that a pressure of 1 to 100 atm is maintained at the first stage, a pressure of 1 to 10 atm is maintained at the second stage, and a pressure of 1 to 100 atm is maintained at the third stage.

22. The method of claim 18, characterized in that a volume ratio of the olefin-containing gas mixture to the nitrous oxide is 2 to 10 at the first stage.

23. The method of claim 18, characterized in that the products of the oxidation of the olefin fraction, before being used as a feedstock at the second stage, are separated into aldehyde and ketone fractions.

24. The method of claim 18, characterized in that the ketone and aldehyde fractions are subjected to the condensation process separately.

25. The method of claim 18, characterized in that the ketone fraction is directly used as a high-octane component, and the aldehyde fraction is subjected to the condensation process.

26. The method of claim 18, characterized in that the products of the oxidation of the olefin fraction, before being used as a feedstock at the second stage, are separated into separate components, followed by using them as a target product and/or using as a feedstock for the condensation process.

27. The method of claim 18, characterized in that the second stage is carried out in a liquid phase by aldol or aldol-crotonic condensation in the presence of any known catalyst.

28. The method of claim 18, characterized in that the second stage is carried out by condensation with methanol in a gas phase in the presence of a copper-containing catalyst at a volume ratio of the product mixture obtained at the first stage to methanol of 1 to 10.

29. The method of claim 18, characterized in that a volume ratio of the mixture of the condensed products obtained at the second stage to hydrogen of 1 to 10 is maintained at the third stage.

30. The method of claim 18, characterized in that the second stage is carried out in the presence of a catalyst containing 5 to 40 wt % copper on a support, and the third stage is carried out in the presence of a hydrogenation catalyst containing 5 to 40 wt % nickel, and/or 5 to 40 wt % copper, and/or 5 to 40 wt % cobalt, and/or 0.3 to 2 wt % palladium, and/or 0.3 to 2 wt % platinum, and/or 0.3 to 2 wt % gold on a support.

31. The method of claim 30, characterized in that Al.sub.2O.sub.3 and/or SiO.sub.2 and/or TiO.sub.2 and/or aluminosilicate and/or silicate or aluminosilicate glass fibers are used as a catalyst support at the second and third stages.

32. The method of claim 30, characterized in that the third stage is carried out in the presence of a mechanical mixture of a hydrogenation catalyst and an acid catalyst, with H-form zeolite selected from zeolites having FAU, FER, MFI, MEL, BEA, MTT, and TON structures being used as the latter.

Description

(1) The FIGURE illustrates a principal scheme for producing a high-octane component, wherein:

(2) HOC1 is a high-octane component according to embodiment 1;

(3) HOC2 is a high-octane component according to embodiment 2;

(4) HOC3 is a high-octane component according to embodiment 3.

EMBODIMENT 1

Example 1

(5) Butane-butene fraction of the catalytic cracking process having the butene content of 87.4 vol. % and the butane content of 12.1% is mixed with nitrous oxide in a ratio of 9:1. The reaction mixture is passed through a stainless steel reactor having a volume of 25 cm.sup.3 at a pressure of 1 atm, with the temperature of 400 C. being maintained in the reactor. The feed rate of the mixture is 25 cm.sup.3/min (under normal conditions). The results of the experiment are given in Table 1. Here, the reaction temperature (T), nitrous oxide conversion (X.sub.N2O), total olefin conversion (X.sub.R), total ketone and aldehyde productivity (Pr), and total selectivity to carbonyl products (S.sub.), which approaches 100%, are provided. The main product of the reaction is methyl ethyl ketone (MEK), which is formed with a selectivity of 44.8%. Along with MEK, acetone (A) is formed with a selectivity of 17.5%, propanal (PA) is formed with a selectivity of 17.5%, acetaldehyde (AA) is formed with a selectivity of 11.3%, isobutanal (i-BA) is formed with a selectivity of 4.6%, and butyraldehyde (BA) is formed with a selectivity of 4.3%, dimethyl- and ethylcyclopropanes are also formed.

(6) After the unreacted gases are separated, the final mixture of carbonyl compounds and substituted cyclopropanes is used as a high-octane additive. The octane number of the obtained mixture of 5 wt % HOC with gasoline AI-92 (92.1 RON and 83.7 MON (motor octane number)) is 93.6 RON and 85.2 MON with the oxygen content being 1.1 wt %. The content of actual tar is 1.8 mg/100 cm.sup.3. Thus, the blending octane number of the HOC produced according to this example is 122.1 RON and 113.5 MON.

Example 2

(7) The reaction is carried out similarly to Example 1, with the difference being that the reaction temperature is set at 500 C. Table 1 (example 2) shows the results. One can see that the performance of the volume unit of the reactor increases to 1.4 g/l per hour, the total selectivity to carbonyl compounds is 93.8%. The octane number of the obtained mixture of 10 wt % HOC with gasoline AI-92 (92.1 RON and 83.7 MON) is 93.5 RON and 85.2 MON with the oxygen content being 2.2 wt %. The content of actual tar is 2.0 mg/100 cm.sup.3. Thus, the blending octane number of the HOC produced according to this example is 120.1 RON and 109.7 MON.

Example 3

(8) The experiment is carried out in the same manner as in Example 1, with the difference being that the reaction temperature is set at 500 C. Table 1 (example 3) shows the results. One can see that the performance of the volume unit of the reactor increases to 1.4 g/l per hour, the total selectivity to carbonyl compounds is 77.1%. The octane number of the obtained mixture of 10 wt % HOC with gasoline AI-92 (92.1 RON and 83.7 MON) is 93.2 RON and 84.7 MON with the oxygen content being 2.2 wt %. The content of actual tar is 2.7 mg/100 cm.sup.3. Thus, the blending octane number of the HOC obtained in this example is 114.1 RON and 103.7 MON.

Example 4

(9) The experiment is carried out in the same manner as in Example 1, with the difference being that the temperature in the reactor is maintained at 400 C., and the pressure of the reaction mixture is 10 atm. Table 1 (Example 4) shows the results. One can see that an increase in the reactor pressure results in an increase in the reactor performance in what concerns the carbonyl compounds. The octane number of the obtained mixture of 10 wt % HOC with gasoline AI-92 (92.1 RON and 83.7 MON) is 93.7 RON and 85.0 MON with the oxygen content being 2.2 wt %. The content of actual tar is 0.8 mg/100 cm.sup.3. Thus, the blending octane number of the HOC produced according to this example is 124.1 RON and 109.7 MON.

Example 5

(10) The experiment is carried out in the same manner as in Example 1, with the difference being that the temperature in the reactor is maintained at 400 C., and the pressure of the reaction mixture is 70 atm. Table 1 (Example 5) shows the results. One can see that an increase in the reactor pressure results in a substantial increase in the reactor performance in what concerns the carbonyl compounds. The octane number of the obtained mixture of 10 wt % HOC with gasoline AI-92 (92.1 RON and 83.7 MON) is 93.7 RON and 85.2 MON with the oxygen content being 2.2 wt %. The content of actual tar is 0.9 mg/100 cm.sup.3. Thus, the blending octane number of the HOC obtained according to this example is 124.1 RON and 113.7 MON.

Example 6

(11) The experiment is carried out in the same manner as in Example 4, with the difference being that the butane-butene fraction of the catalytic cracking process is mixed with nitrous oxide in a ratio of 7:3. An increase from 10 mol. % to 30 mol. % in the nitrous oxide content in the reaction mixture is accompanied by a more than twofold increase in the reaction volume unit performance with an insignificant decrease in the total selectivity to carbonyl compounds (less than 2%). The octane number of the obtained mixture of 10 wt % HOC with gasoline AI-92 (92.1 RON and 83.7 MON) is 93.6 RON and 85.0 MON with the oxygen content being 2.2 wt %. The content of actual tar is 1.2 mg/100 cm.sup.3. Thus, the blending octane number of the HOC obtained in this example is 122.1 RON and 109.7 MON.

Example 7

(12) Example 7 describes the oxidation of propane-propylene fraction of the catalytic cracking process. The experimental conditions and results are given in Table 1. The main products of the oxidation are carbonyl compounds: acetone (A); acetaldehyde (AA); and propanal (PA). The total selectivity to the carbonyl compounds, depending on the reaction conditions, is 86.7% at 350 C. and 4 atm and 74.6% at productivity of 0.3 g/l.Math.h. The octane number of 10 wt % obtained HOC with gasoline AI-92 (92.1 RON and 83.7 MON) is 94.3 RON and 85.5 MON with the oxygen content being 2.7 wt %. The content of actual tar is 0.8 mg/100 cm.sup.3. Thus, the blending octane number of the produced HOC is 136.1 RON and 119.7 MON.

Example 8

(13) The experiment is carried out in the same manner as in Example 7, with the difference being that the temperature in the reactor is maintained at 450 C., and the pressure of the reaction mixture is 7 atm. Table 1 (Example 8) shows the results. One can see that an increase in the reactor temperature and pressure results in an increase in the reactor performance in what concerns the carbonyl compounds, but is accompanied by a decrease in selectivity. The octane number of 10 wt % obtained HOC with gasoline AI-92 (92.1 RON and 83.7 MON) is 94.0 RON and 85.2 MON with the oxygen content being 2.2 wt %. The content of actual tar is 1.0 mg/100 cm.sup.3. Thus, the blending octane number of the produced HOC is 130.1 RON and 113.7 MON.

EMBODIMENT 2

Example 9

(14) 70 ml/min of the mixture of carbonyl compounds obtained according to embodiment 1 (Example 2) (20 vol. %), methanol (60 vol. %) and argon (20 vol. %/) are passed through a 2.0 cm.sup.3 catalyst bed at a temperature of 250 C. for 10 hours. The catalyst has a composition of 28 wt % CuO and 72 wt % SiO.sub.2. The composition of the reaction mixture is determined by a direct sampling from the vapor-gas flow with a subsequent analysis of organic components in a flame ionization detector and inorganic components in two thermal conductivity detectors. The organic components of the reaction mixture are separated in a capillary column DB-1701. The obtained mixture contains ketones and aldehydes, in particular, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, ethyl isopropyl ketone, methyl isobutyl ketone, propanal, 2-methylpropanal, 2,2-dimethylpropanal, 2-methylbutanal, and 2,2-dimethylbutanal.

(15) Productivity (Pr) for methylated ketones and aldehydes was used as an activity characteristic:
Pr (g methylated ketone or aldehyde/g catalyst per hour)=((N.sub.MKM.sub.MKi)).Math.60/m;
wherein: N.sub.MK is the total flow of the reaction mixture at the reactor outlet, mol/min; M.sub.MKi is the molecular weight of the methylated ketone or aldehyde, g/mol; m is the weight of the catalyst charged to the reactor, g.

(16) Selectivity (S) of formation of the sum of methylated ketones or aldehydes from the starting carbonyl compound is calculated by the formula:
S (%)=100.Math.(N.sub.MKi)/(N.sub.K.sup.0N.sub.K);
wherein: N.sub.MKi is the flow of methylated ketones or aldehydes, mol/min; N.sub.K.sup.0 is the inflow of the mixture of carbonyl compounds, mol/min; N.sub.K is the outflow of the mixture of carbonyl compounds, mol/min.

(17) The time required to reduce the productivity for the sum of methylated carbonyl compounds twofold is used as a parameter characterizing the catalyst operation stability. After the reaction is completed, the obtained mixture of carbonyl compounds, water and methanol is condensed, the unreacted methanol and acetone are distilled from the mixture and used as a HOC after drying. The octane number of 3.9 wt % obtained HOC with gasoline AI-92 (92.6 RON and 84.0 MON) is 93.6 RON and 84.5 MON with the oxygen content being 1.4 wt %. The content of actual tar is 3.1 mg/100 cm.sup.3. Thus, the blending octane number of the produced HOC is 118.3 RON and 96.9 MON.

Example 10

(18) The reaction is carried out in the same manner as in Example 9, with the difference being that a portion of argon is substituted with hydrogen. The starting reaction mixture, as a whole, contains 4 vol. % hydrogen. The results of testing the catalyst are shown in Table 2. One can see that, as compared with Example 9, the catalyst operation time to a twofold decrease in the activity was almost 4 times longer. The final mixture of carbonyl compounds has a similar composition, but, at the same time, the content of alcohol impurities increases. The octane number of 6.6 wt % obtained HOC with gasoline AI-92 (92.6 RON and 84.0 MON) is 93.4 RON and 84.2 MON with the oxygen content being 1.6 wt %. The content of actual tar is 1.2 mg/100 cm.sup.3. Thus, the blending octane number of the produced HOC is 104.7 RON and 87.0 MON.

Example 11

(19) 100 ml of the mixture of carbonyl compounds prepared according to embodiment 1 and having the following composition: 50 mol. % methyl ethyl ketone, 12.8 mol. % acetone, 3.4 mol. % n-butanal, 3.6 mol. % i-butanal, 14.5 mol. % propanal, and 15.7 mol % acetaldehyde, are kept in a flask with a reflux condenser at a temperature of 5 C. with stirring in the presence of 1 g NaOH and 1 ml H.sub.2O for 10 hours. The temperature is then raised stepwise to 22 C. and up to 40 C. and is maintained, in order to carry out aldol condensation reactions, for 1 hour and 3 hours, respectively, at each temperature. After the aqueous phase is separated, the organic fraction is dried by maintaining in the presence of dry calcium chloride at room temperature for 10 hours, followed by filtration and isolation of a mixture of condensed carbonyl compounds. The group composition of the obtained product was determined according to the data of the chromatography-mass spectrometry analysis and is given in Table 3. The octane number of 10 wt % obtained HOC with gasoline AI-92 (92.5 RON and 83.9 MON) is 93.7 RON and 84.7 MON with the oxygen content being 1.1 wt %. The content of actual tar is 193 mg/100 cm.sup.3. Thus, the blending octane number of the produced HOC is 104.5 RON and 84.8 MON.

Example 12

(20) 100 ml of the mixture of carbonyl compounds prepared according to embodiment 1 (Example 2) and having the following composition: 50 mol. % methyl ethyl ketone, 12.8 mol. % acetone, 3.4 mol. % n-butanal, 3.6 mol. % i-butanal, 14.5 mol. % propanal, and 15.7 mol. % acetaldehyde, are kept in a flask with a reflux condenser at a temperature of 20 C. with stirring in the presence of 3 g NaHCO.sub.3 and 5 ml H.sub.2O for 10 hours. The temperature is then raised to 60 and maintained, in order to carry out aldol condensation reactions, for 3 hours. After the aqueous phase is separated, the organic fraction is dried by maintaining in the presence of dry calcium chloride at room temperature for 10 hours, followed by filtration and isolation of a mixture of condensed carbonyl compounds. The group composition of the obtained product was determined according to the data of the chromatography-mass spectrometry analysis and is given in Table 3. The octane number of 10 wt % obtained HOC with gasoline AI-92 (92.6 RON and 84.0 MON) is 93.8 RON and 84.8 MON with the oxygen content being 1.5 wt %. The content of existent gums is 0.4 mg/100 cm.sup.3. Thus, the blending octane number of the produced HOC is 104.6 RON and 92.0 MON.

Example 13

(21) 100 ml of the mixture of carbonyl compounds prepared according to embodiment 1 (Example 4) and having the following composition: 45.6 mol. % methyl ethyl ketone, 11.7 mol. % acetone, 3.1 mol. % n-butanal, 4.3 mol. % i-butanal, 14.0 mol. % propanal, 15.1 mol. % acetaldehyde, 3.2 mol. % dimethylcyclopropane, 3.0 mol. % other products, are kept in a flask with a reflux condenser at a temperature of 5 C. with stirring in the presence of 0.5 g ion-exchange resin Amberlyst 36 and 1 ml H.sub.2O for 5 hours. The temperature is then raised stepwise to 22 C., 50 C. and 7 C. and is maintained, in order to carry out aldol condensation reactions, for 1 hour at each temperature. After the aqueous phase is separated by freezing, the organic fraction is dried over calcium chloride at room temperature for 10 hours, followed by filtration and isolation of a mixture of condensed carbonyl compounds. The group composition of the obtained product was determined according to the data of the chromatography-mass spectrometry and is given in Table 3. The octane number of 6.6 wt % obtained HOC with gasoline AI-92 (92.6 RON and 84.0 MON) is 93.7 RON and 84.6 MON with the oxygen content being 1.3 wt %. The content of actual tar is 1.3 mg/100 cm.sup.3. Thus, the blending octane number of the produced HOC is 103.6 RON and 90.0 MON.

(22) TABLE-US-00001 TABLE 1 Embodiment 1. Gas-phase oxidation of a butane-butylene mixture (BBM) with the butene content of 87.4% vol. % and the butane content of 12.1% (Examples 1 to 6) and a propane-propylene mixture (PPM) with the propylene content of 85 vol. % (Examples 7 to 8) with nitrous oxide. Feedstock mixture: 10 mol. % N.sub.2O, 90 mol. % BBM/PPM; the volume flow rate of the mixture is 25 cm.sup.3/min (under normal conditions). Characteristics of a high-octane component Content of Characteristics of the process for producing a high-octane component Blending actual Selectivity, S, % octane Oxygen tar, P, T, X.sub.N2O, X.sub.R, Pr, Other number content, mg/ No. atm C. % % g/l-h C.sub.5 AA PA i-BA A BA MEK products S.sub..sup.b), % RON MON wt % 100 ml 1 1 400 0.7 0.1 0.1 0.0 11.3 17.5 4.6 17.5 4.3 44.8 0.0 100 122.1 113.7 1.2 1.8 2 500 10.6 1.4 1.8 0.0 7.9 16.0 5.8 13.3 2.3 48.5 6.2 93.8 120.1 109.5 2.2 2.0 3 550 33.5 4.2 4.4 0.0 6.0 13.2 4.6 12.4 1.3 39.5 23.0 77.1 118.1 101.7 2.1 2.7 4 10 400 42.5 5.9 7.4 3.2 15.1 14.0 4.3 11.7 3.1 45.6 3.0 93.8 124.1 109.7 2.4 0.8 5 70 400 98.3 13.7 770.1 5.5 16.3 7.1 2.4 7.8 2.4 39.9 18.5 76.0 124.1 117.7 2.2 0.9 6.sup.a) 10 400 31.0 17.1 16.4 5.6 15.2 14.1 3.9 12.1 2.9 43.9 2.3 92.1 122.1 109.7 2.3 1.2 7.sup.c) 4 350 2.4 0.4 0.3 3.3 37.2 16.8 32.7 10.0 86.7 136.1 119.7 2.7 0.8 8.sup.c) 7 450 74.5 12.5 10.3 6.1 21.3 16.5 36.8 19.2 74.6 130.1 113.7 2.2 1.0 .sup.a)feedstock mixture composition is 30% N.sub.2O + 70% BBM; C.sub.5cyclopropane derivatives; AAacetalaldehyde; PApropanal; i-BAisobutanal; Aacetone; BAbutanal; MEKmethyl ethyl ketone; .sup.b)total selectivity to carbonyl products (S.sub.); .sup.c)gas-phase oxidation of the propane-propylene mixture (PPM).

(23) TABLE-US-00002 TABLE 2 Hydrogen influence on the catalytic properties of copper-containing catalysts in the methylation reaction of a mixture of ketones and aldehydes obtained according to embodiment 1 (temperature of 250 C., feedstock reaction mixture composition: 60% methanol, 20% HOC1, hydrogen as given in the table, the balance being Ar) Characteristics of the process for producing a high-octane component Starting selectivity of the Starting Characteristics of a Hydrogen conversion productivity, Time to high-octane component concentration of the HOC1 kg C.sub.4-C.sub.9 a twofold Content Molar in the mixture to ketones reduction Blending of composition feedstock methylated by kg of the octane Oxygen actual of a Contact mixture, C.sub.4-C.sub.9 catalyst productivity, number content, tar, No. catalyst time, s vol. % products, % per hour h RON MON wt % mg/100 ml 9 0.5CuOAl.sub.2O.sub.3 1.7 0 87 0.98 20 118.3 96.9 1.4 3.1 10 0.5CuOAl.sub.2O.sub.3 1.7 4 81 1.1 80 104.7 87.0 1.6 1.2

EMBODIMENT 3

Example 14

(24) 70 ml/min of the mixture of carbonyl compounds obtained at the second stage of the synthesis of the HOC according to embodiment 2 (10 vol. %) and hydrogen (80 vol. %) in argon (10 vol. %) is passed through a catalyst bed (1 gram) at a temperature of 160 C. for 10 hours. A catalyst of 15 wt % Ni on -Al.sub.2O.sub.3 is used as the catalyst. The reaction mixture composition is determined by a direct sampling from the vapor-gas flow with a subsequent analysis of organic components in a flame ionization detector and inorganic components in two thermal conductivity detectors. The organic components of the reaction mixture are separated in a capillary column DB 1701. The final mixture contains unreacted hydrogen and carbonyl compounds, tertiary, secondary and primary aliphatic alcohols, saturated hydrocarbons of a normal and iso-structure.

(25) Conversion (X.sub.K) of the carbonyl compounds (in percents), taking into account the change in the volume of the reaction mixture, is calculated by the formula:

(26) $\begin{array}{cc}\mathrm{Xk}=100.Math.\frac{C_K^o-.Math.C_K}{C_K^o},& \left(2.2\right)\end{array}$
wherein: C.sup.o.sub.K and C.sub.K are molar fractions of the carbonyl compounds in the starting and final reaction mixtures, respectively; is the coefficient of volume change during the course of the reaction, which is calculated by the formula:
=C.sup.o.sub.Ar/C.sub.Ar (2.3)
where: C.sup.o.sub.Ar is a molar fraction of argon in the starting reaction mixture, %; C.sub.Ar is a molar fraction of argon in the final reaction mixture, relative units.

(27) Catalyst productivity (Pr) for alkanes or alcohols in kg(product)/kg(cat.).Math.h is calculated by the formula:

(28) $\begin{array}{cc}\mathrm{Pr}=\frac{1}{}.Math.\frac{C_{\mathrm{product}}}{100}.Math.\frac{F}{m}.Math.\frac{100.2*3600}{22414},& \left(2.4\right)\end{array}$
wherein: is the coefficient of volume change during the course of the reaction, calculated by the formula (2.3);
C.sub.product is a molar fraction of the product (hydrocarbons or alcohol) in the final reaction mixture, %;
F is the volumetric flow rate of the reaction mixture, cm.sup.3/s;
m is a catalyst weight, g.

(29) Selectivity (S) of the formation of alkanes or alcohols from the mixture of carbonyl compounds (in percents) is calculated by the formula:

(30) $\begin{array}{cc}S=100.Math.\frac{.Math.C_{\mathrm{product}}}{C_{\mathrm{ketone}}-.Math.C_{\mathrm{ketone}}},& \left(2.5\right)\end{array}$
wherein: is the coefficient of volume change as a result of the reaction, calculated by the formula (2.3), relative units;
C.sub.product and C.sub.ketone are molar fractions of the products and the starting carbonyl compounds, respectively, in the reaction mixture at the reactor outlet, %.

(31) The results are given in Table 4.

(32) The composite composition, conversion conditions, conversion of carbonyl compounds, selectivity of conversion of carbonyl compounds to the corresponding alcohols and alkanes, as well as to the by-products of isomerization, demethylation, cracking, and condensation are given here. One can see that the conversion of carbonyl compounds in the presence of a nickel catalyst is 58%. The main product of the conversion with a nickel catalyst is alcohol that is formed with a selectivity of 94 mol. %, followed by by-products that are mainly represented by cracking and condensation products. Alkanes are formed with a selectivity of only 1 mol. %. The octane number of the mixture of 10 wt % HOC with gasoline AI-92 (92.6 RON and 84.0 MON) is 93.5 RON and 85.5 MON with the oxygen content being 1.8 wt %. The content of actual tar is 3.5 mg/100 cm.sup.3. Thus, the blending octane number of the obtained HOC is 110.6 RON and 94.0 MON.

Example 15

(33) The reaction is carried out in the same manner as in Example 14, with the difference being that a composite that is a mechanical mixture of a nickel catalyst (1 g) and a zeolite with a structure (1 g) is charged to the reactor instead of a nickel catalyst. One can see that the replacement of the nickel catalyst by the composite results in an increase in the conversion of the starting carbonyl compounds, wherein a mixture of hydrocarbons of a normal and iso-structure is formed as the main products. The octane number of the mixture of 10 wt % HOC with gasoline AI-92 (92.0 RON and 83.9 MON) is 92.1 RON and 83.7 MON with the oxygen content being 0.1 wt %. The content of actual tar is 1.5 mg/100 cm.sup.3. Thus, the blending octane number of the produced HOC is 95.0 RON and 83.7 MON.

Example 16

(34) The reaction is carried out in the same manner as in Example 15, with the difference being that the process is carried out at a temperature of 200 C. One can see that an increase in the temperature results in a small increase in the conversion, and, at the same time, a significant increase in the formation of alcohols is observed. Thus, the selectivity of the conversion of the mixture of carbonyl compounds to alcohols increases to 24%, and the selectivity of the conversion to hydrocarbons decreases from 94% to 70%. The octane number of the mixture of 10 wt % HOC with gasoline AI-92 (92.0 RON and 83.9 MON) is 92.6 RON and 84.5 MON with the oxygen content being 0.34 wt %. The content of actual tar is 2.1 mg/100 cm.sup.3. Thus, the blending octane number of the obtained HOC is 98.0 RON and 84.6 MON.

Example 17

(35) The reaction is carried out in the same manner as in Example 15, with the difference being that Cu/Al.sub.2O.sub.3 is used as a catalyst. One can see that a copper catalyst is less active, as compared with a nickel catalyst, with respect to the hydrogenation to hydrocarbons. The product is a mixture of alcohols, hydrocarbons and the starting carbonyl compounds. The octane number of the mixture of 10 wt % HOC with gasoline AI-92 (92.0 RON and 83.9 MON) is 93.2 RON and 85.0 MON with the oxygen content being 0.7 wt %. The content of actual tar is 2.4 mg/100 cm.sup.3. Thus, the blending octane number of the produced HOC is 104.0 RON and 85.2 MON.

Example 18

(36) The process is carried out similarly to Example 14, with the difference being that the HOC product obtained according to embodiment 1 is taken as a feedstock mixture of carbonyl compounds, i.e. the product of oxidation of a butane-butylene fraction (BBF) of the catalytic cracking with the following composition: 50 mol. % methyl ethyl ketone, 12.8 mol. % acetone, 3.4 mol. % n-butanal, 3.6 mol. % i-butanal, 14.5 mol. % propanal, and 15.7 mol. % acetaldehyde, and a mixture of 10 vol. % carbonyl compounds with 90 vol. % hydrogen is fed to the reactor. A pressure in the reactor is 10 atm. As a result of hydrogenation, conversion of carbonyl compounds was 100%, and selectivity to alcohols was 95%, hydrocarbons were not formed. The results are given in Table 4. The octane number of the mixture of 10 wt % HOC with gasoline AI-92 (92.6 RON and 84.0 MON) is 94.5 RON and 85.1 MON with the oxygen content being 2.3 wt %. The content of actual tar is 1.0 mg/100 cm.sup.3. Thus, the blending octane number of the obtained HOC is 111.6 RON and 95.0 MON.

Example 19

(37) The process is carried out in the same manner as in Example 18, with the difference being that the temperature in the reactor is maintained at 150 C. As a result of hydrogenation, the total conversion of carbonyl compounds was 90%, and selectivity to alcohols was 95%, hydrocarbons were not formed. The conversion of aldehydes and lower ketones was 100%, and the conversion of methyl ethyl ketone was 80%. The results are given in Table 4. The octane number of the mixture of 10 wt % HOC with a gasoline fraction of the catalytic cracking (92.3 RON and 84.1 MON) is 94.6 RON and 85.2 MON with the oxygen content of 2.4 wt %. The content of actual tar is 1.2 mg/100 cm.sup.3. Thus, the blending octane number of the produced HOC is 112.3 RON and 95.1 MON.

(38) TABLE-US-00003 TABLE 3 Embodiment 2. Production of a HOC by aldol condensation of the mixture of carbonyl compounds prepared according to embodiment 1 with various catalysts. Characteristics of the process for producing a high-octane component Composition of products of aldol condensation of producing Characteristics of the a HOC according to embodiment 2, mol. % high-octane component Paral- Content dehyde of Unsaturated Hydroxy and Unreacted components Blending existent carbonyl carbonyl deriv- of the HOC1.sup.a) octane Oxygen gums T, compounds compounds atives i- number content, mg/ No. C. Catalyst Aldehydes Ketones Aldehydes Ketones thereof AA PA BA BA A MEK RON MON wt % 100 ml 11 40 NaOH 31 31 0 0 0.7 0.2 0.3 1.3 1.0 3.8 9.3 104.5 84.8 1.1 193 12 60 NaHCO.sub.3 2.5 0 19 0 2.5 1.8 4.0 6 6 11 21 104.6 92 1.5 0.4 12 70 Amberlyst 10.4 1.6 6.5 0 0 0.3 4.9 10.0 7.8 0.3 35.8 103.6 90.0 1.3 1.3 .sup.a)AA is acetaldehyde; PA is propanal; BA is butanal; i-BA is isobutanal; A is acetone, MEK is methyl ethyl ketone

(39) TABLE-US-00004 TABLE 4 Embodiment 3. Results of hydrogenation of the high-octane component according to embodiments 1 and 2 over the composite hydrogenation catalyst + dehydration catalyst (weight ratio (hydrogenation catalyst)/(dehydration catalyst) = 1) Characteristics of the process for producing a high-octane component Pr, Characteristics of a kg product high-octane component S, by kg Blending Content of mol. % hydr. cat. octane Oxygen existent T, P, X.sub.k, By- per hour number content, gums, No. Catalyst C. atm mol. % Alcohol Alkane products Alcohol Alkane RON MON wt % mg/100 ml 14 Ni/Al.sub.2O.sub.3 160 1 58 94 1 5 1.02 0.01 110.6 94.0 1.8 3.5 15 Ni/Al.sub.2O.sub.3 160 1 99.5 0 94 6 0 1.54 95.0 83.7 0.1 1.5 16 Composite 200 1 99.99 23.9 70 6.1 0.37 1.08 98.0 84.6 0.34 2.1 Ni/Al.sub.2O.sub.3-MFI 17 Composite 160 1 60 25 67 8 0.39 1.03 104.0 85.2 0.7 2.4 CU/Al.sub.2O.sub.3-MFI 18 Ni/Al.sub.2O.sub.3 160 10 100 95 0 5 1.2 0 111.6 95.0 2.3 1.0 19 Ni/Al.sub.2O.sub.3 150 10 90 95 0 5 1.08 0 112.3 95.1 2.4 1.2