Method of producing benzol

专利摘要:
A stabilized hydrocarbon fraction comprising toluene, xylene, sulfur and olefinic hydrocarbons is converted to benzene by (a) catalytic hydrodesulfuration, (b) hydrodealkylation and (c) catalytic hydrogenation.
公开号:SU1349696A3
申请号:SU833529506
申请日:1983-01-05
公开日:1987-10-30
发明作者:Деррьен Мишель；Козен Жан
申请人:Энститю Франсэ Дю Петроль (Фирма)；
IPC主号:

专利说明:

This invention relates to a process for the preparation of benzene and a stabilized hydrocarbon fraction containing toluene, xylenes, sulfur compounds and olefinic hydrocarbons, and may be used in the petrochemical industry.
The aim of the invention is to increase the yield and purity of benzene by carrying out the process in the following sequence: deep hydrodesulfurization of the raw material, hydrodealkylation, hydrotreating, separation of the hydrotreating product into a benzene fraction and a fraction containing toluene, xylene and sulfur compounds, recycling a fraction containing toluene, xylene and sulfur compounds in the hydrodesulphurisation stage.
Example 1. 100 mach. Cg – C cracking hydrocarbon fractions preliminarily stabilized by hydrogenation to remove acetylene and diolefin hydrocarbons in the vapor phase are mixed with hydrogen and the recycled fraction, o alkyl aromatic hydrocarbons, taken in an amount of 10.6 wt.
 The original stabilized fraction has a composition, wt.%:
Paraffins and cycloparaffins 8, 85
Olefins and cycloolefins7, 90
Benzene34,70
Toluene18,95
Alkylaromatic hydrocarbons
Cg-Cc
Up to 100
Bromine number (g g). 15 Total amount of sulfur, May, millionths (ppm) 500 Thiophene and its homologues, ppm1180 Multiple anhydride number, mg / g 1 The mixture obtained is sent for hydrodesulfurization to a catalyst containing 2.5 wt.% CoO and 14 wt.% MoO per alumina substrate, at T 320 C. P 35 atm, bulk flow rate TLHSV 2 h, the ratio of hydrogen.-raw material E, / EU 2.5 mol / mol.
At the end of the hydrodesulphurisation, the bromine number is 0.1, the content
0
five
0
five
0
five
0
five
0
five
sulfur 0.5 ppm, the color of the wash. sulfuric acid 1.
The hydrodesulphurisation product without separation is sent to the hydrodealkylation reactor.
Hydrodealkylation is carried out at T 705 ° C, P 25 atm, the contact time of the mixture of the feedstock with hydrogen is 30 s and the molar ratio is 5 mol / mol.
The hydrodealkylation product contains 83% by weight of benzene in relation to the total amount of hydrocarbons -. The content of organic sulfur is 7 ppm, including the content of thiophene 4 ppm, the color of the washing acid is 9 as a result of the formation of traces of diolefins and olefins.
The hydrodealkylation product without separation is sent to a hydrogenation reactor containing a catalyst of 0.3 wt.% Pd on alumina. Reaction conditions: T 315 C, P 43 atm, ZHSV 5 h-, Hj / HC 1 mol / mol.
The hydrogenation product is sent to a separation, which is carried out in three successively connected plate columns. A first column of 30 plates allows the C-fraction to be selected at the head end. Temperat
tour is 185 ° C at the top of the column and 220 ° C at its bottom. The pressure is 17 atm. The yield of benzene contained in the product remaining at the bottom is 99.8% by weight. The remaining product is directed to the second column of 60 plates. The temperature at the bottom of this column is 150 ° C, at the top 95 ° C, the pressure is 1.5 atm. The output of benzene from the main product of 99.85 wt.%. The product remaining at the bottom is sent to the third column (20 plates), the temperature at the bottom is 250 ° C, at the top of the column 128 ° C, pressure 1.5 atm; At the top of the column, a fraction C, 0 containing toluene and xylenes is obtained, which is recycled to the hydrodesulfurization reactor. The yield of the benzene fraction is 91.7% by weight with respect to the aromatic hydrocarbons of the initial mixture.
The content of cyclohexane 0.06 May,% (using gas chromatography). Coloring of the wash acid 1. The total amount of sulfur is 4 ppm, including thiophene 0.4 ppm. As can be seen from the above results, a good wash color value of the acid was obtained without tillage, usually carried out after hydrodealkylation.
Example 2 (comparative). Example 1 is repeated, but without returning the fraction,. The output of benzene is equal to only 82.3 wt.%. The purity of benzene has not changed.
When carrying out the process according to a known method without a hydrogenation step and without recirculation, the yield of benzene is equal to 82% by weight, the total sulfur content is 7 ppm, and during recycling the content of organic sulfur (thiophene) is 2.83 ppm.
Example 3 (comparative) .. The process is conducted according to the method of example 1, except that at the stage of hydrogenation using a catalyst, a torus containing 2.5 wt.% CoO and
14 wt.% Moo on alumina. US-
Hydrogenation catches do not change.
The yield of benzene fraction is 91.9% by weight, but the content of cyclohexane is 3% by weight, which indicates that this catalyst is less acceptable than the catalyst of Example 1.
Examples 4-6. The operations of Example 1 are repeated using raw materials of similar composition, and hydrodesulphurisation and hydrodealkylation products are obtained with the same quality indicators.
The hydrodealkylation product is sent without fractionation to the hydrogenation reactor containing a catalyst of 0.3 wt.% Palladium on alumina.
The working conditions for the hydrogenation are shown in table. one .
The hydrogenation product is then divided into the conditions of Example 1 into fractions: gaseous components and hydrocarbons up to Cjj, a benzene fraction J alkylaromatic fractions that are recycled to the hydrodesulfurization stage. .
The results of the analysis of the benzene fraction in examples 4-6 are given in table. 2
The results of the analysis of recycled alkyl aromatic fraction
examples 4-6 are given in
table.3.
Example 7. Example 1 is repeated, but the reaction conditions are changed in the hydrodesulphurisation and hydro5 stages.
0
five
0
Hj / HC
dealkylation. The reaction conditions in the hydrogenation step remain unchanged. Use the same download as in example 1.
At the hydrodesulfurization stage, the pressure is 20 atm, temperature, LHSV 2 hours 2.5 mol / mol. The load is shifted with hydrogen and from 10.6 mach. recycled fraction, Q alkylaromatic hydrocarbons per 100 wt.h. the original fraction Cg-C ,. The catalyst contains 5 to 2.5 wt.% CoO and 14 wt.% Moo on alumina. At the end of hydrodesulfurization, the bromine number is 0.02, the sulfur content is 0.1 ppm, and the color of the washing acid is 0-1. The hydrodesulfurization product without fractionation is directed to hydrodealkylation, which is carried out at a pressure of 50 atm, temperature, reaction time 30 s, 5 molar ratio 5.
The proportions of benzene in the hydrodealkylation product in relation to the total hydrocarbon content are 70% by weight, the content of organic sulfur is 2 ppm, and the color of the wash acid is 7.
The hydrodealkylation product without separation is sent to a hydrogenation reactor, the catalyst of which contains 0.3 wt.% Pd on alumina. Conditions at the hydrogenation stage: pressure 43 atm, temperature 315 ° C, LHSV 5 h, 1 mol / mol.
The hydrogenation product is separated under the conditions of Example 1.
The benzene fraction with a yield of 85% by weight with respect to the aromatic hydrocarbons of the initial load of Cg-Cl has the following characteristics:
Color wash acid 1
General content
sulfur, ppt1
Thiophene content, ppm0,2
Example 8. The process is carried out analogously to Example 1. Conditions during the hydrodesulfurization stage: pressure 50 6api temperature 300 ° C, LHSV2h, 5 H2 / HC 2.5 mol / mol.
The load is mixed with hydrogen and with 10.6 wt. recycled fraction C-j-C, g of alkyl aromatic hydrocarbons per 100 mash. fractions
Sat,
five
The catalyst contains 2.5 May CoO and 14 wt.% MoOj on alumina.
 At the end of the hydrodesulfurization, the bromine number is 0.13, the sulfur content is 0.7 ppb, and the color of the wash acid is 1.
The hydrodesulphurisation product is segregated without hydrodealkylation.
which is carried out at a pressure of 20 atm, temperature, reaction time 30 with a molar ratio Hj / HC of 5 mol / mol.
The proportion of benzene in the hydrodealkylation product in relation to the total hydrocarbon content is 89% by weight, the content of organic sulfur is 10 ppm, and the color of the wash acid is -11.
The hydrodealkylation product without separation is sent to a hydrogenation reactor, the catalyst of which contains 0.3 wt.% Palladium on alumina.
The hydrogenation is carried out at a pressure of 43 atm and a temperature of 315 C, LHSV 5, Hj, / HC 1 mol / mol.
The hydrogenation product is subjected to fractionation under the conditions of Example 1. A benzene fraction is obtained with a yield of 94% by weight with respect to aromatic hydrocarbons of the initial loading of Cfi-C, which has the following characteristics:
Color wash
acids1
Overall (5 contents
sulfur, ppt6
Thiophene content, ppt0.5

权利要求:
Claims (2)
[1]
1. A method of producing benzene from a stabilized hydrocarbon.



fractions containing toluene, xylenes, sulfur-containing compounds and olefinic hydrocarbons, comprising the steps of hydrodesulfurizing the feedstock at 300-350 C and a pressure of 20-50 atm in the presence of a catalyst containing 2.5 wt.% CoO and 14 wt.% MoO, on alumina, hydrodealkylation at 650–750 ° C and pressure of 20–50 atm, separating the reaction mixture to obtain a benzene fraction and a fraction containing toluene and xylenes, and a recycling fraction containing toluene and xylenes, o tl and h ay and with the fact that, in order to increase the yield and purity of benzene, the hydr dealkylation hydrotreated at 250-400 ° C and a pressure of 25-60 atmospheres in the presence of a catalyst containing 0.3 wt.% Pd on alumina, and the fraction containing toluene and xylenes is fed to recycle to step hydrodesulfurization
moreover, at the stage of hydrodesulfurization, the feed rate of the raw material is chosen so as to reduce the sulfur content in the mixture of the stabilized hydrocarbon fraction and the recycled fraction by 99.86-99.98 wt.% and reduce the content of monoolefinic hydrocarbons in this mixture so that the bromine number is Lo 0.02-0.13 mg Vg / 100 g
[2]
2. A method according to claim 1, characterized in that, as a stabilized hydrocarbon fraction, use is made of a gasoline fraction previously subjected to selective hydrogenation to remove acetylenic and diolefinic hydrocarbons containing 500 ppm of sulfur and having a bromine number of 15 g and an AC hydrate of 1 MP / g.
Table 1
Indicators
The output of benzene, wt.%, In relation to the content of aromatic hydrocarbons in the original fraction
Common Sulfur, PTH Tiofen, PTT
Coloring after washing
acid
one
Cyclohexane, RRS
Table 3
 t
Content Example
45. j 6
Ethylbenzene, wt.% 6,56,56,5
Toluene, wt.% 92,092,092,0
Xylene, wt.% 1,51,51,5
Organic sulfur, ppt48827
:. I,
Note: The content of each aromatic compound is expressed in wt.% With respect to the mass of the recycled fraction.
Compiled by G.Gul eva Editor M.Kelemesh Tehred L.Oliyyps Proofreader
Order 5203/58 Circulation 371 Subscription
VNIIPI USSR State Committee
for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
-Production and printing company, Uzhgorod, st. Project, 4
table 2
R
Example 5
five
91.60
one
0.2
one
1600
91.68
3
0.3
1,850

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同族专利:

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公开号 | 公开日

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JPS58121223A|1983-07-19|

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GB2113246A|1983-08-03|

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FR2519336B1|1985-03-15|

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GB8300215D0|1983-02-09|

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FR2519336A1|1983-07-08|

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US4463206A|1984-07-31|

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GB2113246B|1986-02-05|

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RU2640207C1|2017-07-11|2017-12-27|Публичное Акционерное Общество "Нижнекамскнефтехим"|Method for producing benzene from aromatic hydrocarbons c6-c9|US3222410A|1962-02-15|1965-12-07|Universal Oil Prod Co|Dealkylation of unsaturated sulfur-containing alkylaromatic hydrocarbons|

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US3844734A|1972-12-27|1974-10-29|Phillips Petroleum Co|Conversion of hydrocarbon oil to a synthetic natural gas|SA1981B1|1991-03-08|2008-03-26|شيفرون فيليبس كيميكال كمبني ال بي|Hydrocarbon treatment apparatus|

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SA446B1|1993-01-04|2005-10-15|شيفرون ريسيرتش أند تكنولوجي كمبني|hydrodealkylation|

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US5575902A|1994-01-04|1996-11-19|Chevron Chemical Company|Cracking processes|

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US6274113B1|1994-01-04|2001-08-14|Chevron Phillips Chemical Company Lp|Increasing production in hydrocarbon conversion processes|

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US6258256B1|1994-01-04|2001-07-10|Chevron Phillips Chemical Company Lp|Cracking processes|

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US6419986B1|1997-01-10|2002-07-16|Chevron Phillips Chemical Company Ip|Method for removing reactive metal from a reactor system|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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FR8200273A|FR2519336B1|1982-01-07|1982-01-07|

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