The method of obtaining aromatic hydrocarbons

 

Usage: petrochemistry. Conduct pre-treatment of the catalyst paraffin hydrocarbons3-C4in mixture with the mercaptan to the amount of mercaptan passing through the catalyst was 0.01 to 0.1 wt.% the weight of the catalyst. Then carry out the contacting of a mixture of paraffin hydrocarbons With2-C5with the catalyst on the basis of high zeolite ZSM-5 at 400-550oWith further separation of the products of the contacting liquid and gaseous products. Perform complete combustion of gaseous products in the presence of the catalyst for complete oxidation of light hydrocarbons and adding to the original paraffin hydrocarbons formed during the combustion of a mixture of carbon dioxide and water vapor. The concentration of mercaptan in a mixture of paraffin hydrocarbons With3-C4support in the range of 0.08 to 0.85 wt. % respectively, the processing of the catalyst is carried out at temperatures 450-520oC. Technical result: the create method of producing aromatic hydrocarbons with greater duration mezhregionalnogo cycle. 1 C.p. f-crystals, 2 tab.

The technical field to which the invention relates Izopet Oronogo raw materials, including associated gas terminal stages of separation.

The prior art method of processing a light hydrocarbon feedstock in the presence of high zeolites. The method consists of passing a mixture of hydrocarbons containing C1With10such as light naphtha, through the catalyst on the basis of high zeolite with additions of si, Zn or CR at 300700o(JP 59-152337, C 07 C 15/00, 1984).

The disadvantage of this method is the formation of compounds of carbon (coke deposits) on the catalyst, which significantly reduces its activity.

A method of obtaining aromatic hydrocarbons by contacting the paraffin hydrocarbons With3With11with the catalyst on the basis of high zeolite ZSM-5 at 380-580oWith, including the separation of the products of the contacting liquid and gaseous products (DE 251710, B 01 F 29/28, 1986).

The process takes place on the catalyst containing the zeolite ZSM-5 (SiO2/Al2O320-100) and the metals of group II (Zn) alone or in combination with metals of group VI (IG) and/or group II (si) in an amount of 0.015% sakartveloshi catalyst and a small length of the working cycle of the process.

Closest to the present invention is a method of obtaining aromatic hydrocarbons (EN 2030376, C 07 C 15/02, 1995).

In the known method, comprising contacting a paraffin hydrocarbons With3With11with the catalyst on the basis of high zeolite ZSM-5 at 380580oWith the separation of the products of the contacting liquid and gaseous products, gaseous products are subjected to complete combustion in the presence of the catalyst for complete oxidation of light hydrocarbons and the resulting mixture of carbon dioxide and water vapor is added to the original paraffin hydrocarbons in the amount of 2.020,0%.

There is a method allows to increase technical and economic indicators of the process of converting light hydrocarbons into aromatic hydrocarbons by increasing the duration mezhregionalnogo cycle of the catalyst (increase stable activity of the catalyst). However, the duration mezhregionalnogo cycle in a known manner by a period of stable activity of the catalyst is insufficient.

Summary of the invention the purpose of this irregularaties cycle. The technical result of the invention is to increase the period of stable activity of the catalyst.

The above technical result is achieved in that in a method of producing aromatic hydrocarbons by contacting the paraffin hydrocarbons with a catalyst based on high zeolite ZSM-5 at 400550oWith, including the separation of the products of the contacting liquid and gaseous products of complete combustion of gaseous products in the presence of the catalyst for complete oxidation of light hydrocarbons and adding to the original paraffin hydrocarbons formed during the combustion of a mixture of carbon dioxide and water vapor, as paraffin hydrocarbons using a mixture With2With5but before applying this mixture of hydrocarbons spend processing catalyst paraffin hydrocarbons3With4mixed with mercaptan, so that the amount of mercaptan passing through the catalyst was 0,010.1 wt.% the weight of the catalyst.

In addition, the content of mercaptan in a mixture with paraffin hydrocarbons3520oC.

The essence of the present invention is illustrated by the following examples.

In examples 1, 2, 3, 4 shows the results of the implementation of the method when it is added to the raw material mixture of carbon dioxide and water vapor, the ratio of carbon dioxide to water 20:1). The number of added gases ranged and ranged 2,0; 5,0; to 12.0 and 20.0 wt.% the number of incoming raw materials.

Example 1. In the process of obtaining aromatic hydrocarbons was used a catalyst containing 57,0% high zeolite ZSM-5 with a ratio of SiO2/Al2O3- 39; Al2About3- 36,4;2About3- 3.5mm; Zn - 3,0 (wt.%).

The catalyst in the amount of 4 kg was placed in a steel reactor and heated in a current of heated air flow 80 l/h to a temperature of 500oC. thereafter, the catalyst was flushed with nitrogen with a flow rate of 80 l/h for 2 hours at a given temperature. Then the flow of nitrogen was stopped, and the reactor was fed a raw material is a mixture of light hydrocarbons, C2C5.

The raw material used a mixture of light hydrocarbons With2-C5the following composition, wt.%: With2- 9,0; C3- 25,0; C4- 62,0; C5to 4.0. The process was carried out at a pace which was burnt to the complete oxidation in the presence of complete oxidation catalyst (a catalyst for complete oxidation was used vanadium catalysts V2About5/Moo3in the form of granules). Side of gaseous products at 550oC, flow rate 250 h-1subjected to full oxidation (weight of catalyst for complete oxidation was 800 g) to form carbon dioxide and water vapor.

Under these conditions, the yield of aromatic hydrocarbons (C6With9) was 61.4%; aliphatic hydrocarbons 3,1%; gases of 28.0% (including hydrogen - 2,5%, methane - 4,0%, With2- 7,5%, With3+C4- 19%, coke - 0,5%).

The catalyst maintains a stable activity in the reaction of conversion of the mixture of light hydrocarbons over 260 hours. Evaluation of the stability of the catalyst was carried out on the yield of aromatic hydrocarbons. The criterion of loss of stability was 30% lower yield of aromatic hydrocarbons.

In examples 2, 3, 4 conditions for the implementation of the method were the same as example 1, except that the amount added to the raw materials of carbon dioxide and water vapor were: in example 2 to 5 wt.%; example 3 - 12 wt.%, example 4 - 20 wt.%.

The results are shown in table 1.

To increase the period of stable operation of the catalyst introduced stage pre-treatment of the catalyst paraffin uglevodorodyonogo mercaptan ranged from 0.01 to 0.1 wt.% the weight of the catalyst.

The results of the method with pretreatment of the catalyst with a mixture of paraffin hydrocarbons With3With4with the addition of mercaptan are shown in table 2. In these experiments after treatment of the catalyst paraffin hydrocarbons3With4with the addition of the mercaptan to the reactor was fed raw light hydrocarbons With2With5with the addition of 12 wt.% carbon dioxide and water vapor from the weight of raw materials).

Example 5. In the process of obtaining aromatic hydrocarbons was used a catalyst containing 57,0% high zeolite ZSM-5 with a ratio of SiO2/Al2About3- 39; Al2About3- 36,4;2About3- 3.5mm; Zn - 3,0 (wt.%). The catalyst in the amount of 4 kg was placed in a steel reactor and heated in a current of heated air flow 80 l/h to a temperature of 500oC. thereafter, the catalyst was flushed with nitrogen with a flow rate of 80 l/h for 2 hours at a given temperature. Then the flow of nitrogen was stopped, and the reactor was fed a mixture of paraffin hydrocarbons With3With4with the addition of the mercaptan with the expectation that after the catalyst was PR is e light hydrocarbons With2C5composition, wt.%: With2- 9,0; C3- 25,0; C4- 62,0; C5to 4.0 with the addition of 12 wt.% the weight of the raw material mixture of carbon dioxide and water vapor.

Examples 5, 6, 7, 8, 9 differ only in the amount of mercaptan passing through the catalyst. In these examples, the concentration of mercaptans in the mixture of paraffin hydrocarbons3With4during pre-treatment of the catalyst was 0.30.4 wt.%.

In examples 10, 11, 12 conditions of the method were the same as example 7 except that when you save the total number of mercaptan passing through the catalyst varied its concentration in the mixture With3With4paraffin hydrocarbons, used for pre-treatment of the catalyst. This was achieved by dilution of a given amount of mercaptan different volumes With3With4paraffins.

Example 9. In the process of obtaining aromatic hydrocarbons was used a catalyst containing 57,0% high zeolite ZSM-5 with a ratio of SiO2/Al2About3- 39; Al2About3- 36,4;2About3oC. thereafter, the catalyst was flushed with nitrogen with a flow rate of 80 l/h for 2 hours at a given temperature. Then the flow of nitrogen was stopped, and the reactor was fed a mixture of paraffin hydrocarbons With3With4with the addition of the mercaptan with the expectation that after the catalyst was omitted 0.08 wt.% mercaptan by weight of the catalyst. The volume passed through the catalyst3With4paraffin was 1600 l, and the concentration of mercaptan to 0.08 wt.%. After that, the feed gas mixture was stopped, and the reactor was fed a raw material is a mixture of light hydrocarbons With2With5composition, wt.%: With2- 9,0; C3- 25,0; C4- 62,0; C5to 4.0 with the addition of 12 wt.% the weight of the raw material mixture of carbon dioxide and water vapor. Under these conditions, the increased duration of the stable operation of the catalyst was 4.4%.

Example 10. The process conditions similar to example 9 except that the amount of a mixture of paraffin hydrocarbons With3C4amounted to 400 l, and the concentration of mercaptan in them - 0.32 wt.%. The increase in the period of stable operation of the catalyst amounted to 8.0%.

Example 11. Usl is the PR paraffin hydrocarbons With3With4amounted to 200 l, and the concentration of mercaptan in them is 0.65 wt.%. The increase of the duration of the stable operation of the catalyst amounted to 2.4%.

Industrial applicability the Present invention can best be applied in the extraction of aromatic hydrocarbons from light hydrocarbons, including petroleum gas terminal stages of separation.

Claims

1. The method of obtaining aromatic hydrocarbons by contacting the paraffin hydrocarbons with a catalyst based on high zeolite ZSM-5 at 400-550oWith, including the separation of the products of the contacting liquid and gaseous products of complete combustion of gaseous products in the presence of the catalyst for complete oxidation of light hydrocarbons and adding to the original paraffin hydrocarbons formed during the combustion of a mixture of carbon dioxide and water vapor, characterized in that the raw material using a mixture of paraffin hydrocarbons With2-C5but before applying this mixture of hydrocarbons spend processing catalyst paraffin hydrocarbons3-C4in compounds is of telesfora.

2. The method according to p. 1, characterized in that the concentration of mercaptan in a mixture of paraffin hydrocarbons With3-C4support in the range of 0.08 to 0.85 wt.% accordingly, processing of the catalyst is carried out at temperatures 450-520oC.

 

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This catalyst has a higher activity
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