The allocation method of the tertiary olefins c1-c4

 

(57) Abstract:

Usage: the production processes. The inventive mixture of hydrocarbons of varying degrees of unsaturation in contact with alcohol C1-C4in the presence of ion exchangers molded catalyst in the reaction-distillation apparatus when serving alcohol in an amount to provide its content in the bottom product 10 - 85 mage. % , followed by decomposition of the obtained ester contained in the bottom product in a mixture with alcohol, other reactive distillation apparatus having a reaction zone filled with a catalyst, and the top and bottom of the distillation zone in the presence of the same catalyst. Moreover, CBM product from the first apparatus at 100 S served in the second apparatus in the upper distillation zone 5 - 10 plate above the catalyst bed. The result is a greater degree of extraction of the tertiary olefins, reduced power consumption and simplified process technology.

The invention relates to the field of allocation of tertiary olefins from mixtures of hydrocarbons of varying degrees of saturation and can be used in the production of monomers for the UK.

There is a method of allocating tertiary olefinating catalyst with subsequent decomposition of the obtained simple broadcast on the same catalyst. Stage esterification is carried out in a flow reactor. The resulting ether is separated by distillation and is sent to the decomposition of the second flow reactor.

The known method has the following disadvantages.

Low conversion isoolefine (70-90% ) at the stage of synthesis of the ether; low conversion ether (80-90% ) at the stage of its decomposition into alcohol and the tertiary olefin; the need for separation of the reaction mixture after a once-through reactor, which complicates the process flow and increases the consumption of the process, the high cost of allocating and recycling to the synthesis reactor of alcohol, which must be taken in excess to achieve a satisfactory conversion of the tertiary olefin in a continuous reactor.

Closest to the present invention is a method of allocating tert-olefins WITH4-C5from mixtures of hydrocarbons of varying degrees of saturation by contact with alcohol (methanol in the presence of ionite catalyst in the reaction-distillation apparatus to obtain the corresponding methyl-tetelcingo ether in the form of the cubic product and supply it to the second reactive distillation apparatus for the decomposition of the alcohol and tert-olefin on the same catalyst.

In the specified method using the reaction-distillation apparatus can improve the conversion isoolefine aired during the synthesis and tert-alkyl Olkiluoto ether in souletin decomposition, and also to eliminate the stage of separation of the products, resulting in simplified process flow scheme of the process, and reduces energy costs.

However, the method has several disadvantages.

When processing the most common in industry4-factions dehydrogenation or pyrolysis with the concentration of isobutylene 40-50% in the reactive distillation apparatus for the removal of a larger amount released during the synthesis of the ester of heat required to submit significantly more phlegmy than that required for rectification of hydrocarbons4from the air, and the energy intensity of the process remains high.

Synthesis of esters in a known way with small proportions of alcohol and olefin 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 dime the functions 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.

For the stage of decomposition of the ether all the necessary heat is supplied through the external heater due to heat of water vapor, which increases the energy consumption of the process.

During the decomposition of the ether in a reactor reactive distillation type to ensure a sufficiently high temperature in the catalyst layer increases the pressure in the reactor, which leads to an increase of output dialkylamide ether, which is an undesirable impurity in the isobutylene.

The purpose of the invention is to reduce the energy intensity of the process.

Proposed method of allocation of tertiary olefins WITH4-C5from 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 reaction-distillation apparatus to obtain the cubic product containing the corresponding alkyl-tert-alkilany ether and alcohol, and the filing of the cubic product in the second reactive distillation apparatus for the decomposition contained in the alkyl tert-Olkiluoto e is as, providing the content in the bottom product 50-85 wt. % , and the second reactive distillation apparatus having a reaction zone filled with a catalyst, and the top and bottom of the distillation zone, CBM product served with temperature 100-175aboutWith, in the upper distillation zone 5-10 plate above the reaction zone.

The process can be carried out using ion exchangers molded catalysts, such as KU-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 with a diameter of 5-6 mm and 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, the PSOY of 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, decisiveness and a monomer with a functional group) with portformat in boiling xylene is not more than 8 wt. % .

The difference of the proposed method from the prototype is the supply of alcohol for contacting in an amount to provide its content in the bottom product 10-85 wt. % , and submission of the cubic product at the top of the distillation zone of the second reactive distillation apparatus for 5-10 plate above the reaction zone temperature 100-175aboutC.

At this stage the esterification of the alcohol used in the reaction-distillation apparatus in an amount to provide the implementation of extractive distillation. Due to the presence of a solvent (alcohol) increases the coefficient of relative volatility of the reactants, it is possible to reduce reflux a number of means to reduce energy consumption. Thus, in the present method in the reaction-distillation apparatus combined flow of two processes: synthesis of tert-alkyl Olkiluoto ether and the separation of hydrocarbons by extractive distillation.

At the stage of decomposition of the presence in the reaction mixture over a high boiling point component - alcohol can achieve the desired temperature of decomposition without increasing pressure. Energy intensity in the decomposition reactor is reduced by feeding back the heat with alcohol aktivnosti upper distillation zone. The filing of a mixture of alcohol and ether 5-10 plates above catalyst layer provides the temperature of the fluid flowing to the catalyst bed, not above 90aboutWith (at a higher temperature of the catalyst disulfirame and loses activity. In the case of flow on the plate above the tenth significantly increases the height of the upper distillation zone and, consequently, the intensity of the reactor.

P R I m e R 1. The selection of isobutylene from hydrocarbon fractions WITH4dehydrogenation of isobutane.

The selection is carried out on the continuous steps in the reaction-distillation apparatus with a diameter of 32 mm, consisting of three 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'KEEFE, PSOY of 3.8 mEq/g, in the amount of 0.5 l, intended for etherification of isobutylene with n-butanol and extractive distillation of isobutylene from isobutane, and the lower distillation zone, filled with nozzle efficiency 20 the initial fraction in the amount of 170 g/h, having the composition:

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 temperature of the top of the column 40aboutWith temperatures in the Central zone 43aboutWith temperatures in the cube column 146aboutWith the pressure of the top of the column 5,3 ATA, reflux number is equal to 1.

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

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 334,5 g/h the reaction mixture of the following composition:

Isobutylene 2,3

n-Butylene 0,1

Hydrocarbons WITH50.02

n-Butanol 48,08

Butyl tert-butyl ether 49,3

Dimers of isobutylene to 0.2 which is sent at 145aboutWith the decomposition of the butyl tert-butyl ether reactive distillation reactor, similar to that described above. Feeding the mixture to the decomposition assests the 60aboutWith temperatures in the mid-range 90-100aboutWith the pressure of 4.7 ATA, reflux number is equal to 1.

The top of the reactor are selected as the target product isobutilene faction in the number 74,2 g/h having the following composition:

n-Butylene 0,35

Hydrocarbons WITH50.04

Isobutylene 99,60

n-Butanol 0,01

From the cube columns selected in the number 260,4 g/h fraction n-butanol, which after purification from the resulting impurities can be returned to the synthesis.

The residual content of isobutene in the hydrocarbon fractions WITH4- 0.5. % , the degree of extraction of isobutylene in the form of a commercial product is 94% , the concentration of the target product 99,6% .

P R I m m e R 2. The selection of isobutylene butane-butylene fraction of pyrolysis.

The selection is carried out with the setup described in example 1, the effectiveness of 15 theoretical plates in the upper distillation zone, the catalyst loading in the middle zone - 1 l

Source faction in the amount of 186 l/h, having the composition:

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 bottom of the distillation zones.

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:

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 0,1

From the cube selected columns in the amount of 221 g/h the reaction mixture of the following composition:

n-butane 0,1

Isobutylene 0,2

Butene-1 0,1

The butenes-2 0,1

n-Butanol 28,81

Butyl tert-butyl ether 70,59

Dimers of isobutylene 0,10 which is sent at a temperature of 145aboutWith the decomposition of the butyl tert-butyl ether reactive distillation reactor, similar to that described above, on the 7th plate above the catalyst bed.

The temperature of the top of the column 5aboutTemperatures cube 120aboutWith temperatures in the mid-range 90-100aboutWith the pressure to 1.1 ATA, reflux number is equal to 1.

On top of desorber selected as the target product isobutilene fraction of 67 g/h having the following composition:

n-butane 0,12

Isobutylene 99,63

Butene-odorou after purification from the resulting impurities can be returned to the synthesis.

The residual content of isobutene in the hydrocarbon fractions WITH4at 2.45 wt. % , the degree of extraction of isobutylene in the form of a commercial product is 95 % , the concentration of the target product 99,63% .

P R I m e R 3. The selection of isoamylenes from hydrocarbon fractions WITH5dehydrogenation of isopentane.

The selection is carried out on the continuous steps in the reaction-distillation apparatus with a diameter of 32 mm (material - steel 12X18H10T), 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 KIF - T (PSOY 3.8 kg-EQ/g) in an amount of 1 l, placed in layers with a nozzle, and having an overall height of 2 m

Source5the fraction of hydrocarbons in the amount of 165 l/h, having the composition:

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

n-Pentane 0,5

Diene coal. WITH50,5

Hydrocarbons WITH60,5 served at a point between the middle and lower zones.

The source of n-butanol in the number 89,5 g/h, paininator in the middle zone 45-55aboutTemperatures cube 170-175aboutC. 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:

Hydrocarbons WITH40,4

Isopentane 91,79

n-Pentane 4,5

3-Methylbutan-1 0,5

2-Methylbutan-2 0,4

2-Methylbutan-2 0,9

n-Pentane 0,7

Diene coal. WITH50,7

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:

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 sent when 170-175aboutWith the decomposition of the butyl-tert-amyl ether, carried out in a reactive distillation reactor, similar to the synthesis reactor, described in this example, 7 a plate above the catalyst bed.

The temperature of the top of the reactor 40aboutWith, the Central zone 90-100aboutWith Cuba 145-150aboutC.

The pressure of the top of the 1.5 ATA. Reflux 1.

The top of the reactor are selected as the target product isoamylenes faction in the number of 47.7 g/h with the following sea select the number 96,0 g/h recycle n-butanol of the following composition:

Hydrocarbons WITH60,7

n-Butanol 87,4

Butyl-tert-amyl ether 11,3

Dimers of isobutylene 0,4

Heavy 0,2 after purification is returned to the synthesis reactor.

The residual concentration of isoamylenes in isopentanol fractions of 1.8% , the degree of extraction of isoamylenes 88,0% concentration of the target product 99,19% .

P R I m e R 4. The selection of isobutylene from hydrocarbon fractions WITH4pyrolysis.

The selection is carried out with the setup described in example 3.

Source4the fraction of hydrocarbons in the number of 143 g/h has the structure:

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 served between the middle and lower zones.

Source isopropanol in the number of 70.2 g/h is served between middle and upper zones.

The temperature of the top of the column 65aboutWith the temperature in the middle zone 62-65aboutWith temperatures in the cube column 150-155aboutWith the pressure of the top of the column of 7.5.

Reflux the number is 1.5.

On top of the column selected in the number of 91.6 g/h waste fraction WITH4composition:

Uans 12,9

butene-2-CIS 10,9

Butadiene-1,3 0,3

Isopropanol 0,01

From the cube columns are selected in number to 121.6 g/h rectional mixture composition:

TRANS+CIS the Butenes-2 0,1

Hydrocarbons WITH50,1

Isopropanol 13,2

Isopropyl tert-butyl

ether 85,9

Dimers of isobutylene 0,6

Heavy 0,1 which is sent at a temperature of 150-155aboutWith the decomposition of isopropyl-tert-butyl ether reactive distillation reactor, similar to that described above, on the 10th plate above the catalyst bed.

The temperature of the top of the reactor 41aboutWith the temperature in the middle zone 90-100aboutWith temperatures in the cube 150-155aboutWith the pressure of the top of 4.7 MPa. Reflux 1.

The top of the reactor are selected as the target product isobutilene faction in the number 48,0 g/h of the following composition:

Isobutylene 99,79

TRANS+CIS-Butenes-2 0,2

Isopropanol 0,01.

From the cube reactor are selected in number 73,6 g/h recycle isopropanol, having the composition:

Hydrocarbons WITH50,1

Isopropanol 88,3

Isopropyl tert-butyl

ether 7,1

Dimers of isobutene 1,1

Diisopropyl ether 3,1

Water of 0.3 after treatment is returned to the synthesis reactor.

P R I m e R 5. The selection of isobutylene from hydrocarbon fractions WITH4.

The selection is carried out with the setup described in example 3. Source4faction in the number 160,0 g/h, having the composition:

Isobutan 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 temperature of the top of the reactor 55aboutWith temperatures in the mid-range 57-63aboutWith temperatures in the cube 155-160aboutC. 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:

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:

n-butane 0,05

n-Propanol 21,17

Propyl-tert-butyl

ether 78,23

Dimers of isobutylene 0,55 which is sent when the temperature of 155-160aboutWith the decomposition propyl tert-butyl ether reactive distillation R is ktora 45aboutWith the temperature of the Central zone 90-100aboutTemperatures cube 155aboutC. the Pressure of the top 5,0 ATA. Reflux the number of 1.0.

The top of the reactor are selected as the target product isobutilene faction in the number 73,0 g/h of the following composition:

n-butane 0,14

Isobutylene 99,855

n-Propanol 0,005

From the cube reactor are selected in number br143.3 g/h recycle n-propanol having the composition:

n-Propanol 87,22

Propyl-tert-butyl

ether 8,23

Dimers of isobutylene 2,80

DIPROPYLENE ether 1,47

TMK 0,28 after purification is returned to the synthesis reactor.

The residual concentration of isobutylene in the waste WITH4fraction of 0.65% , the degree of extraction of isobutylene 87,4% , the concentration of the target product 99,86% .

P R I m e R 6. The selection of isobutylene from hydrocarbon fractions WITH4.

The selection is carried out with the setup described in example 3 using catalyst KU-FPP (PSOY to 3.5 mEq/g).

The initial fraction of hydrocarbons WITH4in the amount of 120 g/h having the following composition:

Isobutane 0,12

n-butane 47,67

Isobutylene 52,14

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

Source ethanol kolichestvakh 56aboutWith the temperature of the Central zone 65-75aboutTemperatures cube 130aboutC. the Pressure of the top of 6.5 ATA. Reflux 1.

On top of the column selected in the number 59,7 g/h waste hydrocarbon fraction of the following composition:

Isobutane 0,17

n-butane 95,48

Isobutylene 2,18

n-Butylene 0,17

Ethanol 2,00

From the cube columns selected in the number 118,1 g/h the reaction mixture of the following composition:

Isobutane 0,25

Ethanol 10,0

Ethyl tert-butyl

ether 79,33

Dimers of isobutylene 1,87

TMK 8,50

Diethyl ether 0.05 and sent for the decomposition of ethyl tert - butyl ether at a temperature of 130aboutIn reactive distillation reactor, similar to that described above, on the 8th plate above the catalyst bed.

The temperature of the top of the reactor 5aboutWith the temperature of the Central zone 80-85aboutTemperatures cube 105-110aboutC. the Pressure of the top of 1.2 ATA. Reflux 1.

The top of the reactor are selected as the target product isobutilene faction in the number 39,6 g/h of the following composition:

n-butane 0,76

Isobutylene 97,22

Ethanol 2,02

From the cube reactor is taken in the amount of 78.5% of the g/h of reaction product composition:

Isobutylene 0,07

Etano is,99 after purification returned to the synthesis reactor.

The residual concentration of isobutylene in the waste WITH4-fraction of 2.18% , the degree of extraction of isobutylene 61,5% .

Example 7. The selection of isobutylene fraction4-hydrocarbons.

Removing isobutene from the faction perform the installation of continuous action in the reaction-distillation apparatus with a diameter of 32 mm (material - 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 trail molded catalyst'KEEFE (PSOY of 3.8 mEq/g) in an amount of 150 ml, mixed with an inert nozzle, the total height of the layer 250 mm

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 secondary butyl alcohol in the amount of 17.7 g/h is served between middle and upper zones.

The temperature of the top of the column 38-40aboutWith the temperature in the middle zone 45-50about
WITH3-hydrocarbons 1,3

Isobutane 9,5

n-butane to 31.2

Butene-1 33,1

Isobutan 1,5

TRANS-Butene-2 13,1

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 builtrite-

butyl ether 84,2

Dimers of isobutylene to 0.6 which is sent when the temperature of 155-160aboutWith the decomposition of secondary-butyl-tertiary-butyl ether reactive distillation apparatus, which is a column consisting of three zones: the lower distillation, filled with the nozzle and having an efficiency of 22 theoretical plates, medium reactive distillation, filled with a catalyst in the amount of 80 ml, and the upper distillation with the effectiveness of 15 theoretical plates.

Secondary-butyl-tertiary-butyl ether in the amount of 28.1 g/h served in the reactive distillation apparatus 8 a plate above the catalyst bed.

The temperature of the top of the reactor 75-80aboutC.

The temperature in the upper zone 85-95aboutWith the temperature in the cube 100-105aboutWith, Dawley, containing isobutylene, ether, sec-butanol, dimers of isobutylene, which is sent to the partial condenser where it is condensed high boiling products. The isobutene in the gas phase in the amount of 10.3 g/h are selected as the target product of the following composition, wt. % :

Isobutan 97,13

TRANS-CIS-Butenes-2 0,46

Butene-1 0,01

second-Butanol 0,8

Secondary-butyl

tertiary-butyl ether 1,5

Dimers of isobutylene 0,1

From the cube selected columns in the amount of 13.3 g/h recycle second-butanol, having a composition, wt. % :

second-Butanol 99,02

Ether 0,98 which is returned to the synthesis column.

The residual concentration of isobutylene in the waste WITH4-fraction of 1.5 % , the degree of extraction of isobutene 94.6% , concentration of the target product 97,13% .

P R I m e R 8. The selection of isobutylene from C4-fraction hydrocarbons dehydrogenation of isobutane.

Removing isobutene perform the installation of continuous action in the reaction-distillation apparatus with a diameter of 32 mm (material steel 12X18H10T), consisting of three zones: the upper and lower rectifying filled tip with efficiency 14 and 12 theoretical plates, respectively, and the average of reaction is SS="ptx2">

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

WITH5-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 temperature of the top of the column 44aboutWith temperatures in the mid-range 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 98,80

n-butane 0,93

Isobutane 0,40

Butene-1 0,19

TRANS-Butene-2 0,05

CIS-Butene-2 0,05

Butadiene-1,3 0,07

WITH5-hydrocarbons 0,11

second-Butanol 0,10

From the cube columns selected in the number 89,4 g/h the reaction mixture of the following composition, wt. % :

Isobutan 3,35

n-Butenes 0,11

WITH5-hydrocarbons 0.02

second-Butanol 45,06

Sec-butyl tert-butyl

ether 51,23

Dimers of isobutylene 0,22 crtification type, similar to that described above, on the 6th plate above the catalyst bed. The amount of catalyst loaded in the middle zone was 80 ml.

The temperature of the top of the column 35-38aboutWith temperatures in the mid-range 110-120aboutWith temperatures in the cube column 146aboutWith the pressure of the top 4 ATA, reflux number of 0.5.

The bottom of the reactor are selected in number to 66.4 g/h recycle second-butanol, which is returned to the synthesis column.

On top of the column selected as the target product isobutilene faction in the number 23,0 t/h of the following composition: wt. % :

Isobutan 99,47

n-Butenes 0,44

WITH5-hydrocarbons 0,09

The residual concentration of isobutene in the waste WITH4-fraction - 0.5% , and the degree of extraction of isobutene 97,7% , the concentration of the target product 99,47 % .

P R I m e R 9. The selection of isobutylene from hydrocarbon fractions WITH4dehydrogenation of isobutane.

The selection is carried out with the setup described in example 1, the effectiveness of 15 theoretical plates in the upper distillation zone and 15 theoretical plates in the lower distillation zone; catalyst loading in the middle zone - 1 l

Source faction in the amount of 170 t/h with SOS/P> The source of n-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 to 5.3 MPa, reflux number is equal to 1. On top of the column selected in the number of 91.6 g/h waste hydrocarbon fraction of the following composition:

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 from 0.01 to Cuba columns selected in the number 200,4 g/h of reaction mixture of the following composition:

Isobutylene 0.02

n-Butylene 0,10

Hydrocarbons WITH50.02

n-Butanol 10,0

Butyl tert-butyl ether 89,85

Dimers of isobutylene 0,45 which is sent at 147aboutWith the decomposition of the butyl tert-butyl ether reactive distillation reactor, similar to that described above, on the 20th plate above the catalyst bed.

The temperature of the top of the column 40aboutTemperatures cube 160aboutWith the temperature in the middle zone 90-100aboutWith the pressure of 4.7 ATA, reflux number is equal to 1.

Top Rea the composition:

n-Butylene 0,27

Hydrocarbons WITH50.04

Isobutylene 99,70

n-Butanol from 0.01 to Cuba columns selected in the number 125,9 g/h fraction n-butanol, which after purification from the resulting impurities can be returned to the synthesis. The residual content of isobutene in the hydrocarbon fractions of 0.5 wt. % , the degree of extraction of isobutylene in the form of a commercial product 94% , the concentration of the target product of 99.7% .

P R I m e R 10. The selection of isobutylene fraction4hydrocarbon catalytic cracking.

The selection is carried out with the setup 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, having the composition:

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 columns is/h unreacted hydrocarbons in a mixture with methanol, similar to the azeotropic:

Hydrocarbons WITH30,2

Isobutane 45,9

n-butane 11,65

n-Butylene 38,55

Isobutylene 0,1

Methanol 3,5

Dimethyl ether 0,1

From the cube selected columns in the amount of 297 g/h the reaction mixture composition:

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 at a temperature of 100-110abouton the decomposition of methyl tert-butyl ether reactive distillation reactor, similar to that described above. Feeding the mixture to the decomposition carried out on 5-th plate above the catalyst bed.

The temperature of the top of the reactor 40aboutTemperatures cube 110aboutWith the temperature in the middle zone 85-90aboutWith the pressure of the top of 4,6 ATA, reflux 1.

The top of the reactor is taken in the amount of 26.8 g/h isobutilene fraction in a mixture with methanol, similar to azeotrope.

Isobutylene 93,3

n-butane 1,1

n-Butenes 2,2

Dimethyl ether 0,4

Methanol is 3.0 which is sent forth to further purification, followed by distillation.

From the cube reactor-desorber selected in MTBE 0,77

Dimers of isobutene 0,07

Water 0,02 after purification is returned to the synthesis reactor.

The residual concentration of isobutylene in the waste fractions of 0.1% , the degree of extraction of isobutylene 92,6% .

(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-C5from 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 reaction-distillation apparatus to obtain the cubic product containing the corresponding alkyl-creakily ether and alcohol, the supply of the cubic product in the second reactive distillation apparatus for the decomposition of the contained alkyl-tetelcingo ether on tert-olefin and an alcohol in the presence of the same catalyst, characterized in that the alcohol for the probe used in an amount to provide its content in the bottom product 10 to 85 wt. % , and the second reactive distillation apparatus having a reaction zone filled with a catalyst, and the top and bottom of the distillation zone, CBM product is

 

Same patents:
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 IC

FIELD: regeneration of heat and extraction of impurities.

SUBSTANCE: the invention is pertaining to the method of regeneration of heat and extraction of impurities from the area of the heat-producing reaction in the fluidized flow, conducted for conversion into light olefins of oxygenates present in the flow of the oxygenate (oxygen-containing) raw. raw. The offered method includes the new system of a two-stage quick chilling intended for extraction at the first stage of water from the outgoing from the reactor flow and regeneration of heat of this flow for the purpose, at least, of the partial evaporation of the raw flow due to indirect heat-exchange between the oxygenated raw and the flow of the upper product of the first stage or the flow of recirculation of the first stage. The flow of purification being withdrawn from the first stage, contains the large share of impurities and the high-boiling oxygenates. In the second stage besides conduct extraction of water from the products flow containing light olefins, and produce the flow of the purified water, which requires only the minimum evaporation of the water for production of the water flow of the high degree purification. The method allows to concentrate the impurities in a rather small flow and ensures the significant saving of power and money resources at production of a flow of the vaporous raw guided into the area of realization of the heat-exchange reaction in the fluidized flow.

EFFECT: the invention ensures concentration of the impurities in a rather small flow and the significant saving of power and money at production of the flow of the vaporous raw directed into the area of realization of the heat-exchange reaction in the fluidized flow.

19 cl, 3 tbl, 4 dwg, 5 ex

FIELD: petrochemical processes.

SUBSTANCE: narrow-range hydrocarbon stock is fed into reaction-distillation tower at a level located between lower and upper tower parts to perform isomerization and disproportionation of hydrocarbons. Reaction mixture is maintained in vapor-liquid equilibrium state to concentrate lighter reaction products in vapor phase and higher ones in liquid phase by means of controlling temperature profile and in-tower pressure. Higher olefins are withdrawn as bottom product and lighter olefins from the top of tower.

EFFECT: increased yield of desired product.

41 cl, 4 dwg, 5 ex

FIELD: petroleum chemistry.

SUBSTANCE: claimed method includes oligomerization of one or more alpha-olefins with ethylene in presence of metal-containing catalytic system, using one or more bisaryl pyrimidine-MXa complex and/or one or more [bisaryl pyrimidine-MYpLb+]q- complex. Process is carried out at ethylene pressure less than 2.5 MPa.

EFFECT: method for production of target product of increased yield.

10 cl, 1 tbl, 3 dwg, 17 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: catalyst contains following active components: Pd (0.001-1%), Bi (0.001-5%), at least of Ag, Cu, Zn, K, Na, Mg, Ca, Be, Sn, Pb, Cd, Sr, Ba, Ra, Mn, Zr, Mo, and Ge (0.001-10%), and at least one of rare-earth metals deposited on porous inorganic carrier (the balance.). Catalyst is capable of selectively and rapidly hydrogenating strongly unsaturated hydrocarbons such as alkynes. Catalyst is suitable for industrial cracking process and is characterized by favorable long regeneration period, long service time, and low cost.

EFFECT: improved performance characteristics of catalyst at low cost.

23 cl, 5 tbl, 22 ex

FIELD: petroleum chemistry.

SUBSTANCE: 1,3-butadiene is exposed to telomerization with telogene of general formula H-X-Y-H, wherein X represents oxygen, sulfur, nitrogen or phosphorus; Y represents carbon, nitrogen or silicium; and X and Y optionally may have substituents according to valence thereof to form telomer of general formula H2C=CH-CH2-CH2-CH2-CH=CH-CH2-X-Y-H. Said telomer is hydrolyzed to 1-substituted 2-octene of formula H3C-CH-CH2-CH2-CH2-CH=CH-CH2-X-Y-H. Substituted 2-octene is splitted to produce 1-octene.

EFFECT: improved method for production of 1-octene.

28 cl, 4 ex

FIELD: organic chemistry.

SUBSTANCE: claimed method includes a) reaction of carbon monoxide and hydrogen in presence of effective amount of Fischer-Tropsch catalyst; b) separation of at least one hydrocarbon cut containing 95 % of C15+-hydrocarbons from obtained hydrocarbon mixture; c) contacting separated cut with hydrogen in presence of effective amount of hydration catalyst under hydration conditions; d) treatment of hydrated hydrocarbon cut by medium thermal cracking; and e) separation of mixture, including linear C5+-olefins from obtained cracking-product. Method for production of linear alcohols by oxidative synthesis of abovementioned olefins also is disclosed.

EFFECT: improved method for production of linear olefins.

12 cl, 3 tbl, 1 dwg, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: before olefin-containing raw material is brought into contact with isomerization catalyst, one or several components of the raw material are subjected to preliminary treatment coming into contact with preliminary treatment material containing zeolite with pore size at least 0.35 nm. Initial olefin is, in particular, vinylidene olefin of general formula CH2=C(R1)R2, wherein R1 and R2 independently represent alkyl groups having at least 2 carbon atoms so that molecular structure includes at least one allyl hydrogen atom.

EFFECT: increased selectivity.

10 cl, 1 tbl, 11 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: vinylidene olefin-containing starting material is brought into contact with isomerization catalyst consisting of molecule sieve in H form, which contains pore larger than 0.6 nm.

EFFECT: increased selectivity of catalyst.

12 cl, 1 tbl, 11 ex

FIELD: petrochemical processes.

SUBSTANCE: liquid olefin-containing feed stream is brought into contact with activated catalyst composed of basic metal oxides or essentially basic metal oxides under olefin isomerization conditions. Catalyst has original olefin isomerization activity and contains activity affecting admixture in amount not exceeding that which would lead to reduction in catalytic activity with a rate of about 0.075% of hourly conversion loss as measured under 1-butene-to-2-butene isomerization process conditions, said activity affecting admixture being on including sulfur, phosphorus, at least one transition metal, or combination thereof.

EFFECT: increased catalytic activity.

34 cl, 5 dwg, 3 tbl, 2 ex

FIELD: petrochemical processes.

SUBSTANCE: branched olefins from isomerization feedstock in the form of linear olefin/paraffin mixture containing 5 to 50% of linear olefins having 7 to 28 carbon atoms are obtained in the first isomerization stage, wherein carbon backbone of linear olefins in the isomerization feedstock is isomerized when in contact with isomerization catalyst, which is effective to isomerize carbon backbone in linear olefin blend to convert the latter into olefin blend, wherein average number of branches in molecule chain is at least 0.7, followed by second stage, wherein branched and linear molecules are separated, the former being essentially olefinic molecules and the latter olefinic and/or paraffin molecules. Resulting branched olefins are served as starting material for production of alcohols and alkylbenzenes.

EFFECT: enabled olefin branching control.

6 cl, 4 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to producing a catalyst and a process of obtaining hydrocarbons via catalytic hydrodeoxygenation of products of processing plant biomass, including microalgae biomass. Described is a catalyst for hydrodeoxygenation of organooxygen products of processing plant biomass, which is a complex composite containing Ni in a reduced form and other transition metals, wherein the catalyst contains up to 15 wt % P which is in the reduced catalyst in form of phosphides with general formula where: Mi is a transition metal in phosphide 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. Described is a hydrodeoxygenation process, which is carried out in a single step at hydrogen pressure of 0.5-20 MPa, temperature of 250-320°C in the presence of the catalyst.

EFFECT: high catalyst activity.

4 cl, 39 ex, 5 tbl

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.

EFFECT: improved method of propane and/or butanes flow separation from of original hydrocarbons by means of fractional distillation resulted in liquid phase and separated flow.

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

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