The allocation method of the tertiary olefins c4-c5

 

(57) Abstract:

The inventive mixture of hydrocarbons of varying degrees of saturation, containing tertiary olefins, C4-C5, in contact with aliphatic alcohol C1-C4in the presence of ion exchangers molded catalyst in the apparatus of the reactive distillation type. From the top of the apparatus taken unreacted hydrocarbons, and from the cube - product contact. Alcohol is served on the contacts in such quantity. to its content in the product contact was 10 - 85 % .

The invention relates to the separation of tertiary olefins from mixtures of hydrocarbons of varying degrees of saturation and can be used in industry to obtain monomers for the UK.

There is a method of allocation of tertiary olefins from hydrocarbon fractions by the esterification of these olefins with an alcohol in the presence of trail catalyst with subsequent decomposition obtained ethers on the same catalyst. In the specified way and synthesis, and decomposition of the ester is carried out in once-through reactors. In this reactor the conversion of isoolefine is 70-90% due to thermodynamic limitations of reversible ravnovesie, the working flow in the reactor by circulating water that significantly increases the consumption of the process.

Closest to the present invention is a method of separation of tertiary olefins from mixtures of hydrocarbons of varying degrees of saturation, comprising contacting the olefin with alcohol on ionite catalyst in the apparatus of the reactive distillation type, containing the upper distillation, reactive distillation, and the bottom of the distillation zone. The resulting ether is withdrawn from the apparatus as the cubic product and is sent to the decomposition with the formation of the tertiary olefin. In addition to the ether CBM product synthesis apparatus contains small amounts of alcohol.

In this way through the use of reactive distillation apparatus conversion isoolefine reaches 99-99,5% . Furthermore, the reduced consumption of the process due to the removal of heat of reaction by evaporation of part of the reflux stream.

However, this method has its drawbacks.

When processing the most common in industry4-factions dehydrogenation or pyrolysis with the concentration of isobutylene 40-50% in the reactive distillation apparatus for removal of the cities from the air, and consumption of the process remains high.

Synthesis of ether in a known way with small proportions of alcohol and isoolefine and, as a rule, if not a uniform distribution of alcohol on the cross-section of the catalyst layer, leading to a dry alcohol zones, where quite intensive adverse reactions dimerization of isoolefine and destruction ("sintering") catalyst.

Industrial4-C5fractions contain significant amounts of paraffins, which can be separated by extractive distillation. At low concentrations of alcohol and its effects as a separating agent is negligible.

The main problem solved by the claimed invention is a lower energy process.

Proposed method of allocation of tertiary olefins WITH4-C5of the containing mixtures of hydrocarbons of varying degrees of saturation by contact with an aliphatic alcohol WITH1-C4in the presence of ion exchangers molded catalyst in the apparatus of the reactive distillation type selection from the top of the device unreacted hydrocarbons from the cube - product contact, and alcohol use is oduct, containing in addition to unreacted alcohol formed ether, is sent to the stage of decomposition of the last known methods.

The process can be carried out using ion exchangers molded catalysts such as CU-PPP, KIF, or KIF, the Catalyst KU-PPP is a composition sulfonic cation exchanger (sulfonated copolymer of styrene with divinylbenzene) with polypropylene. Used in the form of granules of cylindrical shape. The diameter of 5-6 mm, a length of 5-10 mm Full static exchange capacity (PSOY) 0.1 n solution of NaOH of 2.0 to 3.7 mEq/g

The catalyst'KEEFE is a sulphonated composition of a copolymer of styrene with divinylbenzene and polyethylene. Used in the form of granules of cylindrical shape with a diameter of 5-6 mm and a length of 5-10 mm PARTICIPATED in the 2.0 to 4.0 mEq/g, solubility in boiling xylene is not more than 8 wt. % .

The catalyst KIF-T is a sulphonated composition of ternary copolymer (styrene, divinylbenzene and a monomer with a functional group) with polyethylene. Used in the form of granules of cylindrical shape with a diameter of 2-6 mm and a length of 3-15 mm participated in the 2.0 to about 4.0 mEq/g, solubility in boiling xylene is not more than 8 wt. % .

The difference of the proposed method in the s in the product contact 10-85% .

At this stage of esterification in the reaction-distillation apparatus creates conditions for implementation there extractive distillation. Due to the presence of a solvent (alcohol) increases the coefficient of relative volatility of the reactants, it is possible to reduce the reflux. Thus, in the present method in the reaction-distillation apparatus combined flow of two processes: synthesis of tert-alkyl Akilova ether and the separation of hydrocarbons by extractive distillation. The excess of alcohol, is heated in the synthesis reactor to 125-150aboutWith, acts as a coolant, absorbing part of the heat of reaction and transferring it into the decomposition reactor, requiring active heat. Due to these factors, the total energy consumption in the process are reduced.

It should be noted that when the alcohol content in a cube less than 10%, the effect as separating agent is small. The alcohol content in Cuba more than 85% , it is impractical because dramatically increase the cost of its circulation.

P R I m e R 1. The selection of isobutylene from hydrocarbon fractions WITH4dehydrogenation of isobutane combination of esterification N.-butanol with extractive rectification N.-butanol.

Vydelenijami of two zones: the upper distillation zone, filled with nozzle efficiency 15 theoretical plates, intended for rectification waste WITH4fractions from N.-butanol, which coreagent and the extractant at the same time, the average reactive distillation zone, filled with ionite molded catalyst KU-PPP, PARTICIPATED in a 3.5 mEq/g in the amount of 0.5 l, intended for etherification of isobutylene N.-butanol and extractive distillation of isobutylene from isobutane, and the lower distillation zone, filled with nozzle efficiency 20 theoretical plates and which is the comprehensive part of the extractive distillation column.

Source faction in the amount of 170 g/h with the composition, wt; % :

Hydrocarbons WITH30,1

Isobutane 52,46

N.-butane 0,50

Isobutylene 46,40

Butene-1 0,12

TRANS-Butene-2 0,14

CIS-Butene-2 0,14

Butadiene 0.04

Hydrocarbons WITH50,10 served between the middle and bottom of the distillation zones.

The source of n-butanol in the amount of 255 g/h is served between middle and upper distillation zone. The ratio of ad-butanol to isobutylene (mol. ) is a 2.45: 1.

The temperature of the top of the column 40aboutWith the temperature in the Central zone 43aboutWith the temperature the top of the column 5,3 ATA, reflux the number is 1.

On top of the column selected in number to 90.4 g/h waste hydrocarbon fraction of the following composition, wt. % :

Hydrocarbons WITH30,18

Isobutane 97,39

N.-butane 0,93

Isobutylene 0,50

Butene-1 0,22

TRANS-Butene-2 0,26

CIS-Butene-2 0,26

Butadiene 0,08

Hydrocarbons WITH50,18

N.-Butanol 0,01

From the cube columns selected in the number 334,7 g/h of reaction SMS the following composition, wt. % :

Isobutylene 2,3

N.-Butylene 0,1

Hydrocarbons WITH548,08

butyl tert-Butyl ether 49,32

The diameters of isobutylene + other

heavy components of 0.20 which is sent on the decomposition of the butyl tert-butyl ether N. butanol and isobutene known methods.

The residual content of isobutene in the hydrocarbon fractions WITH4and 0.5 wt. % the degree of extraction of isobutylene 98,8% , the selectivity of the extraction of isobutylene 99.4% of the cost of power is 2.5 rubles per 1 ton of the original fraction.

P R I m m e R 2. The selection of isobutylene from C4-fractions of pyrolysis combination of esterification N.-butanol with extractive rectification.

The selection is carried out with the setup described in example 1. Effectivenes zone, the catalyst loading in the middle area 1 l

Source faction in the amount of 186 g/h with the composition, wt. % :

Hydrocarbons WITH30,79

Isobutane 5,97

n-butane 19,78

Isobutylene 37,90

Butene-1 20,84

TRANS-Butene-2 8,35

CIS-Butene-2 6,37 served between the middle and lower zones

Source butanol in the amount of 152 g/h is served between middle and upper distillation zone. The ratio of butanol to isolario constitutes 1.63: 1 (mol. ).

The temperature of the top of the column 17aboutWith the temperature in the middle zone 20aboutWith temperatures in the cube column 145aboutWith the pressure of the top of the column 2,3 ATA, reflux number is equal to 1.

On top of the column selected in the amount of 117 g/h waste hydrocarbon fraction of the following composition, wt. %

Hydrocarbons WITH31,27

Isobutane 9,37

N. butane 31,08

Isobutylene 2,45

Butene-1 32.76ˆ

TRANS-Butene-2 to 13.09

CIS - Butene - 2 becomes 9.97

n-Butanol from 0.01 to Cuba columns selected in the number of 221 g/h the reaction mixture of the following composition, wt. % :

n-butane 0,1

Isobutylene 0,2

Butene-1 0,1

The butenes-2 0,1

N. Butanol 28,81

butyl tert-Butyl

ether to 7.59

The diameters of isobutylene+other

heavy components 0.10 coderange of isobutene in the hydrocarbon fractions WITH4-2,45 wt. % , the degree of extraction of isobutylene to 95.3 wt. % selectivity of extraction of isobutylene to 99.7 wt. % cost of power make 3.8 rubles per 1 ton of the original fraction.

P R I m e R 3. The experience carried out at the same installation as in example 1. The amount and composition of the original faction, and butanol are the same as in example 2.

The temperature of the top of the column 45aboutWith temperatures in the Central zone 50aboutWith temperatures in the cube column 165aboutWith the pressure of the top of the column 4,8 ATA, reflux number is equal to 1.

On top of the column selected in number to 114.7 g/h waste hydrocarbon fraction of the following composition, wt. %

Hydrocarbons WITH31,29

Isobutane 9,59

n-butane 31,78

Isobutylene 0,26

Butene-1 33,50

TRANS-Butene-2 13,38

CIS-Butene-2 10,19

N. Butanol From 0.01 to Cuba columns selected in the number 223,3 g/h the reaction mixture of the following composition, wt. %

n-butane 0,1

Isobutylene 0,2

Butane-1 0,1

Butanol 28,12

The butenes-2 0,1

butyl tert-Butyl

ether 70,37

Dimers of isobutylene 0,99

Water of 0.02 which is sent on the decomposition of the butyl tert-butyl ether in n-butanol and isobutene. The residual content of isobutene in the hydrocarbon fractions WITH4

P R I m e R 4. The selection of isobutylene butane-butenova fractions of catalytic cracking combination of esterification N. butanol with extractive rectification, the rectification of the mixture of ether and alcohol from hydrocarbons with subsequent decomposition of the ester to the alcohol and isobutylene.

The selection is carried out with the setup described in example 2.

The source of the hydrocarbon fraction in the amount of 300 g/h with the composition, wt. %

Hydrocarbons WITH30,2

Isobutane 43,0

N. butane 11,0

N. Butylene 36,3

Isobutylene 9,0

Hydrocarbons WITH50,5 served between the middle and lower zones.

Source N. butanol in the amount of 61 g/h is served between middle and upper distillation zone. (The ratio of n-butanol to isobutylene is 1.7: 1 (mol. ).

The temperature of the top of the column 40aboutWith the temperature in the middle zone 43-45aboutWith temperatures in the cube column 160aboutWith the pressure of the top of the column of 4.7 ATA, reflux number is 0.5.

On top of the column selected in the number 272,2 g/h waste hydrocarbon fraction of the following composition, wt. %

Hydrocarbons WITH30,2

Isobutane 47,35

N. butane 12,1

N. the Butenes 39,8

N. butane 0,1

N. the Butenes 0,3

Isobutylene 0,2

Hydrocarbons WITH51,7

N. Butanol 30,7

butyl tert-Butyl

ether 66,8

Dimers of isobutylene + other

heavy components of 0.2 which is directed to the selection of the hydrocarbons in the distillation column efficiency 10 theoretical plates 5 a plate, counting from the bottom.

The temperature of the top of the column 40aboutTemperatures cube columns 130aboutWith the pressure of the top of 2.0 ATA, reflux number is equal to 5.

On top of the column selected in the amount of 2.1 g/h fraction of hydrocarbons WITH4-C5containing as impurities of 0.01 wt. % BC-butanol.

From the cube columns are selected in number to 86.7 g/h fraction containing, by weight. % :

Hydrocarbons WITH4-C50,01

n-Butanol 31,5

Butyl tert-butyl ether 68,29

Dimers of isobutylene+

other heavy components 0,2 decomposition butyl tert-butyl ether is carried out at the installation of continuous operation in a flow reactor with a length of 40 cm, diameter 2.5 cm from percenage glass jacket through which water circulates heated in ultramontane. The reactor is filled with the same molded catalyst as in example 1. The initial mixture is served in d 95aboutAnd atmospheric pressure. Volumetric feed rate fraction butyl tert-butyl ether 0.25 l per 1 l of catalyst in 1 h, the amount of catalyst in 200 ml.

Conversion of butyl tert-butyl ether is 81,0% , the selectivity of conversion to isobutylene of 87.5% , the degree of dimerization of isobutylene and 10.8% .

P R I m e R 5. The selection of isoamylenes from hydrocarbon fractions WITH5dehydrogenation of isopentane blend the esterification of n-butanol with extractive distillation with n-butanol.

The selection is carried out on the continuous steps in the reaction-distillation apparatus with a diameter of 32 mm (material-steel NET) consisting of three zones: the upper and lower rectifying filled with nozzle and having an efficiency of 15 and 20 theoretical plates, respectively, and the average reactive distillation filled with ionite molded catalyst'keefe (PSOY of 3.8 mEq/g) in an amount of 1 l, placed in layers with a nozzle, and having an overall height of 2 m

Source faction in the amount of 165 g/h with the composition, wt. % :

Hydrocarbons WITH40,3

Isopentane 61,9

n-Pentane 3,0

3-Methylbutan-1 0,3

2-Methylbutan-1 10,7

2-Methylbutan-2 22,3

pentadiene.

The source of n-butanol in the number 89,5 g/h, is served at a point located between the middle and upper zones. The ratio of n-butanol to isoamylene is 1,54: 1 (mol. )

The temperature of the top of the column 40aboutWith the temperature of the Central zone 45-55aboutTemperatures cube columns 140-160aboutC. the Pressure of the top of the column of 1.5 ATA. Reflux the number of 1.5.

On top of the column selected in the number 110,8 g/h waste fraction of hydrocarbons of the following composition, wt. % :

Hydrocarbons WITH40,4

Isopentane 91,79

n-Pentane 4,5

3-Methylbutan-1 0,5

2-Methylbutan-1 0,4

2-Methylbutan-2 0,9

n-Pentane 0,7

Pentadiene 0,1

Hydrocarbons WITH60,1

n-Butanol 0,01

From the cube columns selected in the number 143,7 g/h, the reaction mixture of the following composition, wt. % :

Isopentane 0,3

2-methylbutan-2 0,1

Hydrocarbons WITH60,5

n-Butanol 23,8

Butyl-tert-amyl ether 74,8

Dimers of isoamylenes 0,3

heavy 0,2 which is directed to an apparatus for decomposition of the butyl-tert-amyl ether.

The degree of extraction of isoamylenes is to 95.3% , the selectivity for isoamylenes 99,0% of the costs of power are 3.0 rubles per 1 ton of the original fraction.

P R I m e R 6. Selection ISI by distillation with isopropanol.

The selection is carried out on the continuous steps in the reaction-distillation apparatus described in example 5.

Source4faction in the number of 143 g/h with the composition, wt. %

Hydrocarbons WITH30,8

Isobutane 6,0

n-butane 19,6

Isobutylene 37,9

Butene-1 20,8

TRANS-Butene-2 8,3

CIS-Butene-2 6,3

Butadiene-1,3 0,2

Hydrocarbons WITH50,1 serves to point out between the middle and lower zones.

Source isopropanol in the number of 70.2 g/h serves at a point between the middle and upper zones. The ratio of isopropanol to the isobutylene is 1.21: 1 (mol. ).

The temperature of the top of the reactor 65aboutWith the temperature in the middle zone 62-65aboutWith temperatures in the cube 150-155aboutWith the pressure of the top of 7.5 ATA, reflux number of 1.5.

On top of the column selected in the number of 91.6 g/h waste fraction of hydrocarbons of the following composition, wt. % :

Hydrocarbons WITH31,2

Isobutane 9,4

n-butane 30,5

Isobutylene 3,3

Butene-1 32,39

TRANS-Butene-2 12,9

CIS-Butene-2 10,0

Betalen-1,3 3,3

Isopropanol 0,01

From the cube columns are selected in number to 121.6 g/h the reaction mixture of the following composition, wt. % :
ether 85,9

Dimers of isobutylene 0,6

Heavy 0.1 and send forth on the decomposition of the ether.

The degree of extraction of isobutylene is 94,5% , the selectivity to isobutene to 98.4% . Costs of power are 2,9 rubles per 1 ton of the original fraction.

P R I m e R 7. The selection of isobutylene from hydrocarbon fractions WITH4processing the combination of the esterification of n-propanol with extractive distillation with n-propanol.

The selection is carried out with the setup described in example 5.

The source of the hydrocarbon fraction in the number 380,0 g/h with the composition, wt. % :

Hydrocarbons WITH30,2

Isobutane 43,0

n-butane 11,0

n-Butenes 36,3

Isobutylene 9,0

Hydrocarbons WITH50,5 served at a point between the middle and lower zones.

The source of n-propanol in the number of respondents (40.1 g/h is served between middle and upper zones. The ratio of n-propanol to isobutylene is 1.1: 1 (mol. ).

The temperature of the top of the reactor 40aboutWith temperatures in the mid-range 50-55aboutTemperatures cube 147-150aboutWith the pressure of the top of the column of 4.7 ATA, reflux number of 0.7.

The top of the column selected in the number 353,0 g/h waste hydrocarbon fraction SL
Isobutane 2,6

n-Propanol 0,1

From the cube columns selected in the number of 67.1 g/h the reaction mixture of the following composition, wt. % :

n-Butenes 0,6

Hydrocarbons WITH52,8

n-Propanol 19,5

Propanol-tert-butyl

ether 76,8

Dimers of isobutylene+

other serious 0.2 and sent to the decomposition of the formed ether.

The degree of extraction of isobutylene is 73,1% , the selectivity to isobutene to 99.6% . Costs of power are 2,1 rubles per 1 ton of the original fraction.

P R I m e R 8. The selection of isobutylene from hydrocarbon fractions WITH4the combination of the esterification of n-propanol with extractive distillation with n-propanol.

The selection is carried out on the continuous steps in the reaction-distillation apparatus described in example 5.

Source4faction in the number 160,0 g/h with the composition, wt. % :

Isobutane 0,12

n-butane 47,67

Isobutylene 52,14

n-Butylene 0,07 served at a point between the middle and lower zones.

The source of n-propanol in the number 133,3 g/h serves at a point between the middle and upper zones. The ratio of n-propanol to isobutylene is 1,49: 1 (mol. ).

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The pressure of the top 6 ATA. Reflux the number of 1.5.

The top of the reactor is taken in the amount of 77.0 g/h waste hydrocarbon fraction of the following composition, wt. % :

Isobutane 0,26

n-butane 98,95

Isobutylene 0,65

n-Butylene 0,13

n-Propanol 0,01

From the cube reactor are selected in number 216,3 g/h the reaction mixture of the following composition, wt. % :

n-butane 0,05

n-Propanol 21,17

Propyl-tert-butyl

ether 78,23

Dimers of isobutylene 0.55 and sent to the decomposition of the formed ether.

The degree of extraction of isobutylene was 99.4 % , the selectivity to isobutene is to 98.6% . The cost of power is 3.1 rubles per 1 ton of the original fraction.

P R I m e R 9. The selection of isobutylene fraction4-hydrocarbons by a combination of esterification of secondary butyl alcohol by extractive distillation with the same spirit.

The selection is carried out in a column of continuous action, with a diameter of 32 mm, made of steel 12X18H10T, consisting of three zones: the upper and lower rectifying filled with nozzle and having an efficiency of 12 and 18 theoretical plates, respectively, and average - reactive distillation filled with ionite forms the Loy 250 ml.

The initial fraction of pyrolysis gasoline in the amount of 28 g/h with the composition, wt. % :

WITH3-Hydrocarbons 0,8

Isobutane 6,0

n-butane 19,6

Isobutan 37,9

Butene-1 20,8

TRANS-Butene-2 8,3

CIS-Butene-2 6,3

Butadiene-1,3 0,2

WITH5-hydrocarbons 0,1 served between the middle and lower zones.

The original fluorine-butanol in the amount of 17.7 g/h is served between middle and upper zones. The ratio of sec-butanol to isobutylene $ 1.26: 1 (mol. ).

The temperature of the top of the column 38-40aboutWith the temperature in the middle zone 45-50aboutWith temperatures in the cube column 155-160aboutWith the pressure of the top of 4.2 ATA, reflux number of 1.5.

On top of the column select waste fraction in the amount of 17.6 g/h, of the following composition, wt. % :

WITH3-hydrocarbons 1,3

Isobutane 9,5

n-butane 31,3

Isobutane 1,5

Butene-1 32,4

TRANS-Butene-2 12,9

CIS-Butene-2 10,0

Butadiene-1,3 0,3

second-Butanol 0,01

From the cube columns selected reaction mixture in the amount of 28.1 g/h of the following composition, wt. % :

TRANS+CIS-Butenes-2 0,1

WITH5-hydrocarbons 0,1

second-Butanol 15,0

Secondary-butyl-tertiary-

butyl ether 84,2

Dimers of isobutylene+

other heavy 0,6 what fraction after separation of 1.5% , the recovery of 97.5% , the selectivity to 98.4% . Costs of power are 3.0 rubles per 1 ton of the original fraction.

P R I m e R 10. The selection of isobutylene from C4-fraction hydrocarbons dehydrogenation of isobutane combination of esterification of secondary butyl alcohol by extractive distillation with the same spirit.

The selection is carried out in a column of continuous operation with a diameter of 32 mm, made of steel 12X18H10T, consisting of three zones: the upper and lower rectifying filled tip with efficiency 14 and 12 theoretical plates, respectively, and the average reactive distillation filled with ionite molded catalyst'KEEFE (PSOY of 3.8 mEq/g) in an amount of 150 ml, with a height of 200 ml.

Source faction in the amount of 50 g/h with the composition, wt. % :

WITH3-hydrocarbons 0,1

Isobutane 52,5

n-butane 0,5

Isobutan 46,4

Butene-1 0,1

TRANS-Butene-2 0,13

CIS-Butene-2 0,13

Butadiene-1,3 0.04

WITH4-hydrocarbons 0,10 served between the middle and bottom of the distillation zones.

The original secondary butyl alcohol in the amount of 66,4 g/h is served between middle and upper distillation zone. The ratio of sec-butanol to the not 50-55aboutWith temperatures in the cube column 150aboutWith the pressure of the top of 5.7 ATA, reflux number of 1.3.

On top of the column selected in the number of 26.8 g/h waste hydrocarbon fraction of the following composition, wt. % :

WITH3-hydrocarbons 0,19

Isobutane 97,80

n-butane 0,93

Isobutan 0,50

Butene-1 0,19

TRANS-Butene-2 0,05

Butadiene-1,3 0,07

WITH5-Hydrocarbons 0,11

second-Butanol 0,10

From the cube selected columns in the amount of 9.4 g/h the reaction mixture of the following composition, wt. % :

Isobutan 3,35

n-butyn 0,11

WITH5-hydrocarbons 0.02

second-Butanol 45,06

Secondary-butyl-tertiary-

butyl ether 51,23

Dimers of isobutylene+

other heavy 0,22 which is sent to the column for separation of isobutylene decomposition of the ether.

The content of isobutene in the fraction after the division of 0.5% , the recovery of 99.4% , the selectivity to 98.6% . The cost of power at 2.8 rubles per 1 ton of the original fraction.

P R I m e R 11. The selection of isobutylene from hydrocarbon fractions WITH4dehydrogenation of isobutane blend of etherification n-butanol with extractive rectification.

The selection is carried out with the setup described in example 1, effektivnostei zone, the catalyst loading in the middle zone - 1 l

Source faction in the amount of 170 g/h having a composition similar to the composition of the fractions in example 1 served between the middle and bottom of the distillation zones.

Source butanol in the amount of 122 g/h is served between middle and upper distillation zone.

The temperature of the top of the column 40aboutWith the temperature in the middle zone 45-50aboutWith temperatures in the cube column 147aboutWith the pressure of the top of the column 5,3 ATA, reflux number is equal to 1.

On top of the column selected in the number of 91.6 g/h of waste hydrocarbon fraction of the following composition, wt. % :

Hydrocarbons WITH30,18

Isobutane 97,38

n-butane 0,93

Isobutylene 0,50

Butene-1 0,22

TRANS-Butene-2 0,26

CIS-Butene-2 0,26

Butadiene 0,08

Hydrocarbons WITH50,18

n-Butanol 0,01

From the cube columns selected in the number 200,4 g/h the reaction mixture of the following composition, wt. % :

Isobutylene 0.02

n-Butylene 0,10

Hydrocarbons WITH50.02

n-Butanol 10

Butyl tert-butyl

ether 89,85

Dimers of isobutylene+

other components of 0.45 which is sent on the decomposition of the butyl tert-butyl ether in n-butanol and isobutene known the ü extraction of isobutylene 98,1% , the selectivity of the extraction of isobutylene 98.7% , cost of power be 2.3 rubles per 1 ton of the original fraction.

P R I m e R 12. The selection of isobutylene fraction4hydrocarbon catalytic cracking combination of esterification with methanol with extractive rectification.

The selection is carried out on the installation described in example 1, the effectiveness of 15 theoretical plates in the upper distillation zone and 15 theoretical plates in the bottom of the distillation zone. The catalyst loading in the middle zone was 1 l

Source faction in the amount of 300 g/h with the composition, wt. % :

Hydrocarbons WITH30,2

Isobutane 43,0

n-butane 11,0

n-Butylene 36,3

Isobutylene 9,0

Hydrocarbons WITH50,5 Served between the middle and lower zones.

The original methanol in the amount of 277,7 g/h is served between middle and upper zones.

The temperature of the top of the column 40aboutWith temperatures in the mid-range 65-70aboutWith temperatures in the cube column 108aboutWith the pressure of the top of 4,4 ATA, reflux number of 0.5.

On top of the column selected in the number 280,7 g/HR of unreacted hydrocarbons in a mixture with methanol, similar to azeotrope, wt. % :

anal 3,5

Dimethyl ether 0,1

From the cube columns selected in the number of 287 g/h the reaction mixture composition, wt. % :

n-butane 0,1

n-Butenes 0,2

Hydrocarbons WITH50,5

Methanol 85,0

Tert-butyl

ether 14,1

tert-Butanol 0,1

Etc. heavy Less than 0.05 which is sent on the decomposition of methyl tert-butyl ether known methods.

The residual content of isobutene in the hydrocarbon fractions WITH40.1 wt. % , the degree of extraction of isobutylene 99,3% , the selectivity of 99.9% , the cost of power constitute 2,1 rubles per 1 ton of the original fraction.

P R I m e p 13. The selection is carried out with the setup described in example 1, the diameter of the reactor 32 mm, the efficiency zone of the upper, middle and lower, respectively 15, 5, 12 theoretical plates.

Source faction in the number of 180.0 g/h with the composition, wt. % :

Isobutane 10,0

n-Butylene 40,0

Isobutylene 50 Serves between the middle and lower zones.

The original methanol in the amount of 257,1 g/h is served between middle and upper zones.

The temperature of the top of the column 60aboutWith the temperature of the Central zone 65-70aboutWith temperatures in the cube column 121,5aboutC. the Pressure of the top of 6.9 ATA. Reflux: the Ohm, similar to azeotrope, wt. % :

Isobutane 18,3

n-Butylene 73,05

Isobutylene 4,6

Methanol 4,0

Dimethyl ether 0,05

From the cube columns selected in the number 338,9 g/h the reaction mixture composition, wt. % :

n-Butylene 0,08

Methanol 60,3

MTBE 39,6

tert-Butanol 0,02 which is sent on the decomposition of MTBE known methods.

The residual content of isobutene in the fraction of unreacted hydrocarbons44.6 wt. % , the degree of extraction of isobutylene is 95,0 % , the selectivity of 99.9% . The cost of power is 3.6 rubles per 1 ton of the original fraction.

P R I m e R 14 (for comparison). Synthesis of MTBE perform the setup described in example 13.

Source4-fraction, number 192 g/h with the composition, wt. % :

Isobutane 10

1-Butene 25

Isobutan 50

TRANS-2-Butene 9,0

CIS-2-Butene serves 6 between the lower and middle zones, and methanol in the amount of 55 g/h between the upper and middle zones.

The temperature of the top of the reactive distillation apparatus 60aboutWith the temperature of the top of the second zone 62aboutWith the temperature of the bottom of the second zone 69aboutTemperatures cube 120aboutC. Reflux 4.

With the top 4 containing 94,0 % unreacted hydrocarbons and 6.0 % methanol. The content of the isobutylene is 0.5 % in terms of hydrocarbons4.

From the bottom of the reactive distillation apparatus taken in the amount of 142 g/h, CBM product containing hydrocarbons WITH4to 0.01%, MTBE was 98.2 % , of methanol and 0.4 % , trimethylarsine 0.49 % and dimers of isobutylene 0.9 percent .

The degree of extraction of isobutylene 99.5% , dimers of 0.9% . The cost of power - 5,4 rubles per 1 ton of the original fraction.

As seen from the above examples, the use of the proposed method to achieve a high degree of extraction of isobutylene at a lower cost of power compared to the prototype. So, when using as a raw material hydrocarbon fractions WITH4containing isobutylene 50% methanol consumption decreases from 5.4 rubles per 1 ton of the original faction in the prototype (see example 14) to 3.6 rubles per 1 ton of the original faction in the claimed method (see example 13).

(56) Caplets A. N. and other Selection of isobutylene and isoamylenes from hydrocarbon fractions. M : Tsniiteneftehim, 1981, S. 22, 27.

THE ALLOCATION METHOD OF THE TERTIARY OLEFINS C4-C5of the containing mixtures of different hydrocarbons with the th molded catalyst in the apparatus of the reactive distillation type selection from the top of the device unreacted hydrocarbons from the cube and product contact, characterized in that the alcohol is used in an amount to provide its content in the product contact 10 to 85 wt. % .

 

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FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: crude alpha-olefin is heated, raw vinylidene olefins are isomerized in the presence of catalyst and alpha-olefin is separated from isomerized vinylidene olefin by rectification. Separation of alpha-olefin is carried out for at least two successive steps at similar temperatures on top of vat and reducing pressure of rectifying column at each following step. Condensed phase removing from top of the rectifying column at previous step is fed to feeding zone of the following step and the rectifying column at top and vat section is sprayed. For spraying the top section of column the condensed phase removing from the top of rectifying column at the same step is used and for spraying the vat section of column the vat liquid of rectifying column at the same step is used. Separated alpha-olefin is purified additionally from oxygen-containing impurities by adsorption up to polymerization degree of purity. Raw heating, isomerization, separation and adsorption are carried out in atmosphere in inert gas. The unit used for treatment of alpha-olefin includes reactor for isomerization of vinylidene olefins in raw, rectifying column wherein feeding zone is joined with reactor outlet and wherein alpha-olefin of high purity degree is removed from the column top. The unit includes also at least one rectifying column for additional treatment of alpha-olefin of high purity from isomerized vinylidene olefins and adsorption column for separation of oxygen-containing impurities in alpha-olefin of high purity wherein the column inlet is joined with the top outlet of the last rectifying column used for additional treatment of alpha-olefin of high purity and outlet is used for removing alpha-olefin of the polymerization purity degree. Invention provides enhancing quality of the end product.

EFFECT: improved method for treatment.

8 cl, 1 dwg, 1 ex

FIELD: petrochemical processes.

SUBSTANCE: invention relates to treatment of C5-hydrocarbons in order to remove cyclopentadiene impurities, which process may be, in particular, used in rubber production industry when producing hydrocarbon monomers applicable in stereospecific polymerization processes. Treatment of hydrocarbons is accomplished with cyclohexane in presence of organic solvent and alkali catalyst, after which C5-hydrocarbons are separated from reaction products via rectification. Organic solvent is selected from alkylene glycol monoalkyl ethers including their mixtures taken in amounts 0.5 to 5.0 wt % based on C5-hydrocarbons.

EFFECT: increased degree of cyclopentadiene extraction at lower reagent consumption.

8 cl, 1 tbl, 23 ex

FIELD: organic chemistry.

SUBSTANCE: invention refers to enhanced method of propane and/or butanes flow separation from original hydrocarbons containing alkylmercaptan impurities by means of fractional distillation resulted in liquid phase and separated flow from column head at pressure providing that separated flow from column head containing propane and/or butanes has temperature within 50 to 100°C, including (i) addition to specified origin hydrocarbons an amount of oxygen sufficient for mercaptan oxidation, (ii) fractional distillation of produced mixture containing at least one catalyst layer oxidising mercaptans to sulphur compounds with higher boiling temperatures and (iii) separation of sulphur compounds with higher boiling temperatures as portion of distillation liquid phase.

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8 cl, 2 tbl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids. The method includes the following stages: (a) contact in the oxidation reaction zone of the alkane, which contains molecular oxygen gas, not necessarily corresponding to the alkene and not necessarily water in the presence of at least one catalyst, effective with the oxidation of the alkane to the corresponding alkene and carboxylic acid, alkane, oxygen and water; (b) separation in the first separating agent at least part of the first stream of products in a gaseous stream, which includes alkene, alkane and oxygen, and a liquid stream, which includes carboxylic acid; (c) contact of the mentioned gaseous stream with the solution of a salt of metal, capable of selectively chemically absorbing alkene, with the formation of a liquid stream rich in chemically absorbed alkene; (d) isolation from the flow of the solution of salt of the metal. The invention also relates to combined methods of obtaining alkyl-carboxylate or alkenyl-carboxylate (for example vinyl acetate), moreover these methods include oxidising of alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acid, isolation of alkene from the mixture of alkene, alkane and oxygen by absorption using the solution of the salt of metal and extraction of the stream rich in alkene from the solution of the salt from metal for using when obtaining alkyl-carboxylate and alkenyl-carboxylate.

EFFECT: improved method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids.

46 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention is referred to the area of hydrocarbons preparation by catalytical hydrodeoxygenation of products of fast pyrolysis of a biomass and working out of the catalyst for this process. The catalyst of oxygen-organic products hydrodeoxygenation of fast pyrolysis of lignocellulose biomasses, containing either precious metal in amount of no more 5.0 wt % or containing nickel, or copper; either iron, or their combination in a non-sulphide restored shape in amount of not more than 40 wt % and transitive metals in a non-sulphide shape in amount of not more than 40 wt %, carrying agent - the rest, is described. Three variants of the catalyst preparation method, providing application of transition metals on the carrying agent by a method of impregnation of the carrying agent solutions of metal compounds are described, or simultaneous sedimentation of hydroxides or carbonates of transition metals in the presence of the stabilising carrier, or the catalyst is formed by joint alloying/decomposition of crystalline hydrate nitrates of transition metals together with stabilising components of zirconium nitrate type. The process of oxygen-organic products hydrodeoxygenation of a biomass fast pyrolysis is performed using the above described catalyst in one stage at pressure of hydrogen less than 3.0 MPa, temperature 250-320°C.

EFFECT: increase stability in processing processes of oxygen-containing organic raw materials with the low content of sulphur, and also soft conditions of process realisation.

10 cl, 12 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention refers to the method of purification of paraffin hydrocarbons from methanol admixtures. The said purification is carried out in the presence of hydrogen on the catalyst containing one of the metal selected from Ni and Pd applied on the inert carrier at temperature 30-100°C, mole excess hydrogen : methanol in the range (5-50): 1 and volume hydrocarbons feed rate 1-6 hrs.-1.

EFFECT: simplifying and cheapening of the process.

1 cl, 9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of extracting isobutylene from an isobutylene containing fraction through hydration of the isobutylene containing fraction, obtaining a tert-butanol containing fraction and its subsequent dehydration. The method is characterised by that, dehydration is done in two stages. At the first stage, temperature is kept at 90-120°C and pressure at 1-3 kgf/cm2 and concentrated isobutylene and an aqueous solution of tert-butyl and sec-butyl alcohol are extracted, from which concentrated sec-butyl alcohol and an isobutylene containing fraction, which is taken for hydration, are extracted at the second stage. Process at the second stage is carried out at temperature 100-130°C and pressure 2-6 kgf/cm2.

EFFECT: use of the given method allows for extracting isobutylene without butene or butadiene impurities, and reduction of tert-butyl alcohol loss.

1 cl, 1 tbl, 8 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: C10+ fraction of alpha-olefins contaminated with aromatic C9+ compounds is extracted from the main product stream and fed into a conversion reactor where C10+ alpha olefins and aromatic C9+ components react in the presence of a Friedel-Crafts alkylation catalyst to form aromatic C19+ compounds, and the obtained aromatic C19+ compounds are separated from unreacted C10+ alpha olefins in or after the conversion reactor.

EFFECT: method simplifies removal of by-products.

10 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing pure 1-butene from C4 hydrocarbon fractions primarily containing 1-butene, 2-butene, and butane(s) with a 1,3-butadiene and isobutene impurity, involving preparation of a mixture primarily containing 2-butenes via rectification, catalytic isomerisation of 2-butenes into 1-butene and extraction of 1-butene via rectification, characterised by that at least catalysed isomerisation of 1-butene into 2-butene in said fraction is carried out at temperature lower than 120°C, as well as rectification with continuous removal of isobutane, isobutene and 1,3-butadiene in the distillate and obtaining a residual stream primarily containing 2-butene and n-butane, in which rectification conditions are maintained such that concentration of 1,3-butadiene and isobutene with respect to the sum of 2-butene is not higher than standard limits in the desired 1-butene. A large portion of n-butane is separated from the residual stream via extractive rectification with a polar agent and catalysed isomerisation of 2-butenes to 1-butene is carried out at temperature higher than 120°C, while continuously extracting the formed 1-butene via rectification.

EFFECT: high efficiency of the method.

14 cl, 5 ex, 4 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to developing a catalyst and a process for obtaining hydrocarbons via catalytic hydrodeoxygenation of products of processing plant biomass. The invention describes a catalyst for hydrodeoxygenation of organooxygen products of processing plant biomass, which is a complex composite containing transition metals and is a mixed oxide of the following type: where Mi is a transition metal in oxide form, other than nickel or boron, 2≤n≤5, with atomic ratio from 0.01-99, mainly from 7 to 99, and a stabilising additive in amount of not more than 30 wt %. The invention also describes a process for hydrodeoxygenation of organooxygen products of processing plant biomass, which is carried out in a single step at hydrogen pressure 0.5-20 MPa, temperature 250-320°C in the presence of the catalyst described above.

EFFECT: high activity of the disclosed non-sulphided catalysts, which enable to conduct a process for hydro-deoxygenation of oxygen-containing compounds - model compounds of products of processing plant biomass at high substrate/catalyst ratios.

4 cl, 24 ex, 3 tbl

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