• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    In a process for the thermal cracking of hydrocarbons to produce olefins, improvement of recovering hydrocarbons boiling above 200 DEG C. from the thermal cracking stage, preferably removing polymeric components therefrom, catalytically hydrogenating resultant hydrocarbons boiling above 200 DEG C., and recycling resultant hydrogenated hydrocarbons to the thermal cracking stage.
    公开号:SU912043A3
    申请号:SU792729502
    申请日:1979-02-16
    公开日:1982-03-07
    发明作者:Шлибенер Клаус；Юрген Вернике Ганс
    申请人:Линде Аг (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR GETTING HARROW OLEFINS
    The invention relates to the preparation of non-purported compounds, in particular to a process for the preparation of lower olefins, and can be used in the petrochemical industry. A known method for producing lower olefins by hydrogenating a gas oil fraction with hydrogen at elevated temperature and pressure in the presence of a catalyst is based on a mixture of oxides or sulfides of nickel, cobalt, molybdenum and tungsten deposited on alumina or a mixture of silica and alumina, followed by thermal decomposition of the products hydrogenation in the presence of water vapor. The disadvantage of this method is that the continuation of the process is 8-75 hours, which results in only a small yield per unit volume / time, which, in turn, adversely affects the efficiency of the process. The closest to the technical essence and the achieved effect to the proposed method is the production of lower olefins by hydrogenating the gas oil fraction with hydrogen in the presence of a catalyst containing a mixture of two oxides or metal sulfides selected from the group comprising nickel, cobalt, molybdenum and tungsten deposited on a zeolite of the type X or Y with a degree of exchange of sodium ions for ammonium, hydrogen, alkaline earth metals or rare metals, equal to 50-90%, or type X zeolite containing 5-25 wt.% Type A zeolite, with degree exchanging sodium ion for ammonium, hydrogen, alkaline earth metal or rare metals, equal to 50-90% or for type X or Y zeolite, containing 5-25 wt.% silicon dioxide, with a degree of sodium ion exchange for ammonium ions, hydrogen , alkaline earth metals or rare metals, equal to 50-90%, followed by thermal decomposition of hydrogenation products at 700-900C in the presence of water vapor at a weight ratio of water vapor to hydrogenation products equal to 0.25-0.5: 1 U.
    The disadvantages of this method are that all raw materials are subjected to hydrogenation, which is associated with a high consumption of hydrogen. In addition, in the hydrogenation of all the raw materials, hydrocracking reactions take place with the splitting of the low-boiling components of the raw material, which leads to a further 15 in FIG. 1. This increase in the consumption of hydrogen, cht, causes not only high operating costs, but also large investments in the construction of correspondingly executed installations and ultimately leads to a complication of the process technology. The purpose of the invention is to simplify the process technology. This goal is achieved by the fact that in the process of producing lower olefins from a gas oil fraction with a bp. 200-340c, which consists in the fact that the raw material is subjected to thermal cleavage at UOO-EOO C in the presence of water vapor, the raw material is subjected to thermal cleavage, followed by separation from the cleavage products of the polymeric compounds and the fraction with boiling point. 200–750 ° C; the latter is fed to catalytic hydrogenation with hydrogen in the presence of a catalyst containing nickel and tungsten sulfides or cobalt and molybdenum, deposited on Type U zeolite and hydrogenation products are returned to the thermal cleavage stage. The difference of the proposed method lies in the fact that the raw material is thermally decomposed, followed by separation from the polymer decomposition products, and the fraction with boiling point is combined. 200-750 ° C, after nu is fed to catalytic hydrogenation, and hydrogen products are returned to the thermal cleavage stage. The separation of polymeric compounds is carried out by extraction with a non-polar solvent, for example, a light hydrocarbon,
    120434
    The hydrogen required for hydrogenation can be obtained at least partially in the proposed method. In this case, hydrogen can be directly used by thermal cleavage to diis 5 or it can be produced by steam reforming light hydrocarbons formed by thermal cleavage of, for example, methane.
    The proposed method is illustrated by the following examples.
    权利要求:
    Claims (2)
    [1]
    Example 1. The process is carried out according to the technological scheme, the pre-reactor 1, made as a vertical coil, through pipeline 2 serves 1 kg / h of gas oil fraction of the following quality: density of 0.845 g / ml (at), carbon content 86.4 wt.% , the hydrogen content is 13.1 wt.%, the molar ratio of hydrogen to carbon is 1.82, the sulfur content is 0.4 wt.%, the aromatic hydrocarbon content is 29 wt.%, the boiling range is 200-340 ° C, and the pipeline is 3,170 g / Hydrogenation product of the following quality: 88.67 wt.% Carbon, 11.31 wt.% Hydrogen, 0.02 wt.% Sulfur, 12.1 wt.% Paul aromatic hydrocarbons, 6.2 wt.% monoaromatic hydrocarbons, 81.7 wt.% paraffins and naphthenes, boiling range 70-430 C. Thermal splitting is performed with 0.8 kg of water vapor at 850 ° C and pressure of 2 atm for 0.12 s. Pipeline 4 was used to split into node 5 1.170 kg / h of a cleavage product of the following composition, wt.%:, 72 11.86 Sp4; 25.25 Cr. 0.34 12.71 6.31 Sc - hydrocarbons 19 and 28 of pyrolysis gasoline, 19.2 high-boiling fractions and 3.33 other components, from which ethylene and propylene are separated by low-temperature separation. 1 In this case, the high boiling fraction has the following characteristic: 91.24 wt.% Carbon, 7.16 wt.% Hydrogen, 1.6 wt.% Sulfur, molecular weight 520, density 1.20 g / ml (at 15 s) , 17% by weight of coke residue according to Condradson, Pensky-Martens flash point (in a closed crucible), 23.8% by weight of polymer compounds, 0.2% by weight of monoaromatic hydrocarbons and 0.9% by weight of paraffins and naphthenes. By pipeline. 6, this fraction is fed to an extraction column 7, into which polymer compounds are extracted with propane fed through line 8. Propane fed through line 9 serves to compensate for the loss of extractant in column 7. Extraction is carried out at 30 ° C and I5 atm for 1I min using 20% by weight of the propane fraction, | At the extraction stage, 53.2 g of polymeric compounds were separated (softening point 70-80 ° C, density 1.2 g / ml (at)), which were removed from the process via line 10. The extract solution in the extractant through the pipeline 11 serves on the separation by distillation into a column 12. The extract thus separated (171.6 g / h), which has the following characteristics: 91.73 wt.% Z carbon, 7.37 wt.% hydrogen, 0.9 wt.% sulfur, molecular weight 309, density 1.05 g / ml (LI;), 7 wt.% Coondradson coke residue, flash point {Pensky-Martens (in the closed crucible) 47c, bp 200. 750s, 98.5 wt.% Polyaromatic carbon | hydrogens, 1.3 wt.% Paraffins and tenes, 0.1 wt.% Monoaromatic hydrocarbons and 0.1 wt.% Polymeric compounds, through pipeline 13 is fed for hydrogenation in a pump Iy autoclave 14 with a capacity of 1 l. The hydrogenation process is carried out at and 70 atm in the presence of 1.43 g / l of extract / hour of a nickel-tungsten catalyst (9.8% WQs and 3.2% NiO as sulphides) deposited on type V zeolite (Na -O -Ali O 4.8 SiO. In hydrogen form, for 15 minutes One part of the hydrogen required to carry out the hydrogenation process is fed through line 15 and the other part through line 16, which is produced by steam reforming of methane formed at the thermal stage splitting and supplied through the pipeline 17 to the reactor 18. Hydrogenation product of this quality through the pipe Water 3 is fed to the thermal decomposition stage, and through line 19, 0.6 g / h of hydrogen sulfide, 0.3 g / h of C and C hydrocarbons and 0.7 g / h of Ci and C hydrocarbons are removed from the process. Example
    [2]
    2. Example 1 is repeated with the difference that the extraction is carried out at 40 atm for 5 minutes using 5% of the weight of high boiling fraction propane. 53.353 g / h of polymeric compounds are separated (softening point 7080 ° C, density 1.2 g / ml (at 15 s)), which are removed from the process by line 10. After the extractant is separated, the extract (171.6 g / h) containing 0.01 wt.% polymer X compounds, is subjected to hydrogenation at 40 ° C and 100 atm for 14 min in the presence of 1.56 l / l of extract / h of a cobalt-molybdenum catalyst (3.1% CoO and 10% MoOg as sulphides) deposited on zeolite Y in hydrogen form.The hydrogenation product supplied for thermal decomposition (170 g / h) has the following characteristic: 86.45 C.% carbon 13.50 ° C.% hydrogen, 0.05% by weight sulfur, boiling points 60-210 ° C, 5.3% by weight polyaromatic hydrocarbons, 4.4% by weight monoaromatic hydrocarbons and 90.3% by weight % of paraffins and naphthenes. According to pipeline 19, 0.65 g / h of hydrogen sulfide, 0.4 g / h of hydrocarbons C and Cj and 0.55 g / h of hydrocarbons and C) j are removed from the process. The invention The method of producing lower olefins from a gas-oil fraction with a bp. 200340 ° C, including hydrogenation with hydrogen in the presence of a catalyst containing nickel and tungsten sulphides or cobalt and molybdenum, deposited on type Y zeolite, and thermal decomposition of hydrogenation products at 700-900 ° C in the presence of water vapor, characterized in that In order to simplify the process technology, the feedstock is subjected to thermal decomposition followed by separation of the polymer compounds and the batch fraction from the decomposition products. 200-750 0, the last year is for katitic hydration and the hydration products are returned to the thermal splitting stage. Sources of information, rintye taken into account in the examination 1. Published for the Federal Republic of Germany K 216495 J, l. 12 about 19/01, publ. 1972. 2. Patent of the USSR No. 722476, l. C 07 C 11/02, 1977 (prototype).
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    同族专利:
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    BR7901001A|1979-09-25|
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    DE2806854A1|1979-08-23|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2729589A|1952-06-12|1956-01-03|Exxon Research Engineering Co|Deasphalting with propane and butane|
    US2943050A|1957-12-03|1960-06-28|Texaco Inc|Solvent deasphalting|
    US3511771A|1967-07-24|1970-05-12|Exxon Research Engineering Co|Integrated hydrofining,hydrodesulfurization and steam cracking process|
    US3839484A|1970-07-17|1974-10-01|Marathon Oil Co|Pyrolyzing hydrocracked naphthas to produce unsaturated hydrocarbons|
    GB1361671A|1971-01-06|1974-07-30|Bp Chem Int Ltd|Process for the production of gaseous olefins from petroleumdistillate feedstocks|
    US3779895A|1971-12-23|1973-12-18|Texaco Inc|Treatment of heavy petroleum oils|
    GB1383229A|1972-11-08|1975-02-05|Bp Chem Int Ltd|Production of gaseous olefins from petroleum residue feedstocks|
    JPS5742675B2|1973-03-15|1982-09-09|
    US3944481A|1973-11-05|1976-03-16|The Dow Chemical Company|Conversion of crude oil fractions to olefins|
    US3907920A|1974-03-25|1975-09-23|Continental Oil Co|Two-stage hydropyrolysis-cracking process for producing ethylene|
    GB1537822A|1975-01-22|1979-01-04|Shell Int Research|Process for the production of normally gaseous olefins|
    GB1504776A|1975-08-14|1978-03-22|Davy Powergas Ltd|Hydrocracking c3 or higher hydrocarbon feedstock|
    FR2337195B1|1976-01-05|1981-03-06|Inst Francais Du Petrole|
    US4090947A|1976-06-04|1978-05-23|Continental Oil Company|Hydrogen donor diluent cracking process|
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    US4137147A|1976-09-16|1979-01-30|Institut Francais Du Petrole|Process for manufacturing olefinic hydrocarbons with respectively two and three carbon atoms per molecule|
    US4115246A|1977-01-31|1978-09-19|Continental Oil Company|Oil conversion process|
    FR2380337B1|1977-02-11|1983-04-15|Inst Francais Du Petrole|
    FR2390493B1|1977-05-12|1985-04-26|Linde Ag|PROCESS FOR THE PREPARATION OF OLEFINS|JPS623198B2|1981-01-25|1987-01-23|Chiyoda Chem Eng Construct Co|
    US5045174A|1990-03-21|1991-09-03|Exxon Chemical Patents Inc.|Process for the production of heartcut distillate resin precursors|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2806854A|DE2806854C2|1978-02-17|1978-02-17|Process for the thermal cracking of hydrocarbons into olefins|
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