Method of isomerization of light paraffin hydrocarbon, c4-c6

 

(57) Abstract:

Usage: petrochemistry. Essence: paraffin hydrocarbons WITH4-C6mixed with hydrogen or hydrogen-containing gas and contacting at elevated temperature and pressure with a catalyst, terrasim 0.2 to 1.0 wt.% platinum or palladium oxide on the media promoted sulfate mass ratio of SO42-:media, equal (0,005-0,1):1. In the catalyst carrier mass ratio of aluminum oxide and zirconium is (0,26-0,03): 1. The technical result is improved stability and selectivity. 1 C.p. f-crystals, 2 tab.

The invention relates to a process for the isomerization of light paraffin hydrocarbons and can be used in the refining and petrochemical industries.

There is a method of isomerization of light paraffin hydrocarbons (U.S. patent N 5494571, 6 C 10 G 35/085, 1996), comprising contacting a mixture of light paraffin hydrocarbons and hydrogen with a catalyst containing metals of platinum, VIII and VII groups on the sulfated metal oxide III or IV groups. The disadvantage of this method is to reduce the degree of isomerization of paraffin hydrocarbons in time and nidularia 1.0 MPa, a molar ratio of H2:n-butane, is equal to 1:1, flow rate of feed 2 h-1catalyst containing 0.3 wt.% Pt, 6.0 wt.% Fe, 5.0 wt. % Mn on the zirconium oxide ZnO2promoted sulfate in the amount of 6 wt.%, conversion of n-butane to isobutane 2 hours was 40%, and after 100 hours 31%, and the selectivity of 68.7 and 58.5%, respectively.

The closest in technical essence is a method for the isomerization of light paraffin hydrocarbons (U.S. patent N 5120898, C 07 C 5/27, 1992 ) in the presence of hydrogen and of a catalyst containing from 0.01 to 10 wt%. platinum or palladium on a mixture of aluminum oxide and Zirconia promoted with sulfate mass ratio (0,001-0,72):1.

The disadvantage of this method is the low stability and selectivity. So, when isomerization of n-pentane containing 50 million-1sulfur, at a temperature of 240oC, a pressure of 1.0 MPa, a molar ratio of H2: n-pentane 1:1, flow rate of feed 2 h-1on the catalyst containing 0.5 wt.% platinum on a mixture of aluminum oxide and zirconium oxide in a mass ratio of 0.30:1 promoted sulfate mass ratio of SO42-: (Al2O3+ ZrO2) = 0,5: 1, the conversion of n-pentane to isopentane Karagaily way isomerization of light paraffin hydrocarbons includes mixing them with hydrogen or hydrogen-containing gas and contacting with the catalyst, containing 0.2 to 1.0 wt.% Pt or Pd on the oxide carrier, promoted by the sulfate mass ratio of SO42-: media, equal (0,005-0,1): 1, and the mass ratio of aluminum oxide and zirconium in the media is (0,26-0,03):1. When the process temperature is 170 - 270oC, a pressure of 0.8 to 3.5 MPa, the molar ratio of H2:hydrocarbons (0,2 - 7):1, and the volumetric feed rate of 0.2 - 5.0 hours-1.

The proposed method provides a stable depth isomerization unbranched paraffin hydrocarbon, C4-C6and high selectivity.

Method of isomerization of light paraffin hydrocarbons is as follows.

As raw materials use hydrotreated or straight-run n-butane, n-pentane or light gasoline fraction which is a mixture of paraffin hydrocarbons, C4-C6.

Feedstock is mixed with hydrogen or hydrogen-rich recycle gas is heated to a temperature of 170 to 270oC and at a pressure of 0.8 to 3.5 MPa, a molar ratio of H2: hydrocarbons (0,2 - 7):1 and flow rate of 0.2 - 5.0 hours-1served in a reactor filled with a catalyst containing 0.2 to 1.0 wt.% Pt or Pd on a medium having a mass ratio of Al22">

When preparing the catalyst carrier maintain a mass balance of oxides of aluminum and zirconium in range (0,26 - 0,03):1, a mass ratio of SO4:(Al2O3+ ZrO2within (0,005 - 0,1):1.

The catalyst is prepared by impregnation of the support platinum or palladium solution, followed by drying and calcining at a temperature of 500oC.

The reaction products analyzed by gas chromatography on a thread, using a capillary column coated with phase OV-1.

Selectivity is determined by the formula

< / BR>
where G is the number of received isopentane, wt.%; g is the number of unreacted raw materials, wt.%.

Method of isomerization of light paraffin hydrocarbons is illustrated by the following examples.

Example N 1

As raw material use n-butane containing 70 million-1sulfur. The process is carried out at pilot plant at a pressure of 1.0 MPa, a temperature of 240oC, molar ratio of H2:n-butane, is equal to 1:1, flow rate of feed 2 h-1catalyst containing 0.5 wt.% Pt on a medium having a ratio of aluminum oxide and zirconium Al2O3:ZrO2=to 0.15:1, and the ratio of SO4

Example N 2

The method is carried out according to example No. 1 with the difference that the pressure is 0.8 MPa, a temperature of 270oC, the volumetric feed rate 5 hour-1, the molar ratio of H2: n-butane 7:1, the content of platinum in the catalyst is 1.0 wt.%, while the ratio in the carrier Al2O3:ZrO2= 0,34:1, SO4:(Al2O3+ ZrO2)=0,005:1.

Conversion of n-butane to isobutane by 2 and 100 hours of operation are presented in table 1.

Example N 3

The method is carried out according to example No. 1 with the difference that as raw materials use of n-pentane containing 50 million-1sulfur, pressure is 3.5 MPa, a temperature of 170oC, the volumetric feed rate of 0.2 h-1, the molar ratio of H2: n-pentane to 0.2:1, as a hydrogenating metal catalyst contains palladium in an amount of 0.2 wt.%, while the ratio in the carrier Al2O3:ZrO2= 0,08:1, SO4:(Al2O3+ ZrO2)-0,1:1.

In the same conditions was carried out isomerisation of n-butane,

Conversion of n-pentane to isopentane and n-butane isobutane through 2 and 100 hours of operation are presented in table No. 1.

Example N 4

The method is carried out according to example No. 1 with the difference that in - hexanol, 2 - cyclopentene, 4 - methylcyclopentene, 1 - cyclohexane, 0.2 to benzene and 0.8 - heptanol, and process temperature 200oC.

The content of isopentane and 2.2 Dimethylbutane - the most high-octane components in the isomerized product in 2 and 100 hours of operation are presented in table 1.

Example N 5

The method is carried out according to example No. 1 with the difference that the ratio of aluminum oxide and zirconium in the catalyst carrier 0,26:1.

Conversion of n-butane to isobutane by 2 and 100 hours of operation are presented in table 1.

Example No. 6 (comparative)

The method is carried out according to example No. 1 with the difference that the ratio of aluminum oxide and zirconium in the catalyst carrier is of 0.38:1.

Conversion of n-butane to isobutane by 2 and 100 hours of operation are presented in table 1.

Example 7 (comparative)

The method is carried out according to example No. 1 with the difference that the ratio of aluminum oxide and zirconium in the catalyst carrier is 0.05:1.

Conversion of n-butane to isobutane by 2 and 100 hours of operation are presented in table 1.

Example No. 8 (comparative)

The method is carried out according to example No. 1 with the difference that the ratio of SOsabutan through 2 and 100 hours of operation are presented in table 1.

Example No. 9 (comparative)

The method is carried out according to example No. 1 with the difference that the ratio of SO4: (Al2O3+ ZrO2in the catalyst carrier is 0.12:1.

Conversion of n-butane to isobutane by 2 and 100 hours of operation are presented in table 1.

Example 10 (comparative)

The method is carried out according to example No. 1 with the difference that the ratio of aluminum oxide and zirconium in the catalyst carrier is of 0.28:1.

Conversion of n-butane to isobutane by 2 and 100 hours of operation are presented in table 1.

Example No. 11 (comparative)

The method is carried out according to example No. 1 with the difference that the ratio of aluminum oxide and zirconium in the catalyst carrier is 0.06:1.

Conversion of n-butane to isobutane by 2 and 100 hours of operation are presented in table 1.

Example # 12 (prototype)

The method is carried out according to example No. 1 except that as the catalyst, a mixture of aluminum oxide and zirconium oxide in a mass ratio of 0.3:1 promoted sulfate mass ratio, SO42-:(Al2O3+ ZrO2) =0,5:1 coated with 0.5 wt.% platinum.

The test results represent the raw material using n-pentane.

The test results presented in table 2.

Example # 14

The method is carried out according to example No. 2 with the difference that is used as raw material n-pentane, and the mass ratio of aluminum oxide and zirconium 0,26:1.

The test results presented in table 2.

Example N 15

The method is carried out according to example No. 3 with the difference that the mass ratio of aluminum oxide and zirconium is 0.03:1.

The test results presented in table 2.

Example # 16 (comparative)

The method is carried out according to example No. 1 with the difference that the mass ratio of aluminum oxide and zirconium in the media is of 0.27:1.

The test results presented in table 2.

Example N 17 (comparative)

The method is carried out according to example No. 1 with the difference that the mass ratio of aluminum oxide and zirconium in the media is 0.02:1.

The test results presented in table 2.

Example N 18 (prototype)

The method is carried out according to example No. 12 with the difference that as raw materials use of n-pentane.

The test results presented in table 2.

The results of isomerization of light and selectivity of isomerization (examples N 13 - 15). But these figures are achievable only in the claimed limits of the ratios of the oxides of aluminum and zirconium in the media. When the change of this ratio (examples 6-9 and 16-17) reduced the conversion and selectivity of isomerization.

1. Method of isomerization of light paraffin hydrocarbons WITH4-C6by mixing with hydrogen or hydrogen-containing gas and contacting at elevated temperature and pressure with a catalyst containing 0.2 to 1.0 wt.% platinum or palladium oxide on the media promoted sulfate mass ratio of SO42-: media, equal (0,005-0,1):1, characterized in that the carrier of the catalyst mass ratio of aluminum oxide and zirconium is (0,26-0,03):1.

2. Method of isomerization of light paraffin hydrocarbons WITH4-C6under item 1, characterized in that the process is carried out at a temperature of 170-270oC, a pressure of 0.8 to 3.5 MPa, a molar ratio of N2:hydrocarbons (0,2-7):1 and flow rate of feed to the catalyst is 0.2 to 5.0 h-1.

 

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FIELD: petrochemical processes.

SUBSTANCE: pentane-into-isopentane isomerization is carried out on platinum catalyst (IP-62) at 370-395°ะก, pressure 2.302.7 MPa, and hydrogen-to-hydrocarbon molar ratio (0.2-0.8):1, preferably 0.5:1.

EFFECT: enhanced process efficiency and reduced power consumption.

3 dwg, 3 ex

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