• 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:
    Disclosed is a two-stage process for the production of liquid hydrocarbons from coal. More particularly, disclosed is a two-stage coal liquefaction process wherein subdivided coal is substantially dissolved in a solvent in a first non-catalytic dissolving stage at the temperature in the range 750 DEG to 900 DEG F. In a second stage, the mixture of solvent, dissolved coal and insoluble solids is contacted with a hydrocracking catalyst at a critical temperature below 800 DEG F. The normally liquid portion of the hydrocracker effluent product has a surprisingly low sulfur content of less than 0.1 weight percent, a low nitrogen content of less than 0.5 weight percent, and a high API gravity of at least -3.
    公开号:SU795499A3
    申请号:SU772554598
    申请日:1977-12-15
    公开日:1981-01-07
    发明作者:В.Розентал Джоел；Дж. Далберг Артур
    申请人:Червон Рисерч Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR PRODUCING LIQUID PRODUCTS FROM COAL
    one
    A known method for producing liquid products from coal using solvents, hydrogen and a catalyst.
    The closest to the invention is a method for producing liquid products from coal by dissolving crushed coal in a solvent in the presence of hydrogen at a temperature of 315.6-398.9 ° C, a pressure of 35–350 kg / cm (g,
    The products thus obtained are in contact with a hydrocracking catalyst at a temperature of 427-510 ° C,; a pressure of 35-350 kg / cm.
    During such a process, the yield of the target products is lowered due to the rapid coking of the hydrocracking catalyst, leading to increased gas generation and the termination of the catalyst.
    The aim of the invention is to increase the yield of liquid products by reducing coke formation.
    This goal is achieved by the described method of obtaining liquid products from coal by dissolving crushed coal in a solvent in the presence of hydrogen at: a temperature of 399-482 ° C, a pressure of 35350 kg / cm2, followed by contacting the dissolution products with a hydrocracking catalyst at a temperature below the dissolution temperature and equal to 343-426 Cg pressure 35 350 kg / cm.
    A schematic diagram of the method is shown in the drawing.
    The crushed coal in line 1, along with the solvent supplied in line 2 and being a hydrogen donor, is sent to the mixing zone 3. As a raw material, it is possible to use solid ground coal such as anthracite, bituminous coal, sub-bituminous coal, lignite, and mixtures thereof. Bituminous and sub-bituminous coals are particularly preferred. Usually, the coal is crushed to particles of 100 mesh (0.125 mm or less. However, larger particles can be used.
    Partially hydrogenated aromatic solvents are used as solvents. Examples of such solvents are tetralin (tetrahydronaphthalene), dihydronaphthalene, dihydroalkylnaphthalene, dihydrophenanthrene, dihydroanthracene, dihydrochrycenes, and the like. It is most preferable to use the solvent obtained in the process, for example, a fraction of the boiling fraction, obtained by distilling the hydrocracking product. Ground coal is mixed with. solvent in weight proportions solvent: coal, equal to 1: 2-3: 1, preferably 1: 1-2: 1. The slurry from the mixing zone 3 is fed in line to the dissolution zone 5. In the dissolution zone 5, the suspension is heated to a temperature of 399-482 0, preferably 427-454 s, better; 438-450 s, for a period of time sufficient for a significant dissolution of the coal. In zone 5, at least 50% by weight, preferably more than 70% by weight, preferably more than 90% by weight of coal, based on dry ash-free coal, are dissolved. In this way, a mixture of solvent, dissolved coal and undissolved solid particles is obtained. It is essential that the suspension be heated to at least 399 ° C so as to obtain at least 50% by weight of dissolved coal. In addition, it is important that the coal does not overheat above temperature. , as this leads to thermal cracking, which is a significant yield of liquid products. Hydrogen is introduced into the dissolution zone along line b. The injected hydrogen consists of fresh hydrogen and recycled gas. In addition to the temperature in the dissolution zone, other reaction conditions can vary widely in order to obtain at least 50% dissolution of solid particles. Such reaction conditions in the dissolution zone are: a residence time of 0.01-3 hours, preferably 0.11 hours; pressure is preferably 73.8351 kg / cm, preferably 73 / 8-175.5 KT / CVT hydrogen gas feed rate 3.56 suspensions, preferably 0.53-1.78 m / l suspension. The suspension can pass the dissolving zone from the bottom up, or vice versa. Preferably, the extent of this zone is such that a piston flow regime is realized, in which the process of the proposed method is continuous rather than periodic. The dissolution zone does not contain a catalyst from any external source, although the mineral substances contained in the coal may have some catalytic effect. A mixture of dissolved coal, solvent and undissolved solid particles is fed to the second stage in the reaction zone 7 / containing hydrocracking catalyst. Hydrocracking and cracking processes occur simultaneously in the hydrocracking zone, whereby the high molecular weight compounds are converted to lower molecular weight compounds, the sulfur compounds to hydrogen sulfide, the nitrogen compounds to ammonia and oxygen compounds to water. Preferably, the catalytic reaction zone has a fixed catalyst bed, however it is possible to use a fluidized bed. The mixture of gas, liquid and undissolved solid products preferably passes from bottom to top through the catalytic reaction zone, but can also pass from top to bottom. The catalysts used in the second stage of the process can be any of the well known and industrially available hydrocracking catalysts. The catalyst contains hydrogenating and cracking components. Preferably, the hydrogenating component is applied to a refractory cracking base. As a basis, for example, two or more refractory oxides are used, such as silica-alumina, silica-magnesia, silica-zirconia, alumina-boria, silica-titanium oxide, and silica-zirconia- acid-treated titanium oxide and the like. It is possible to use acidic phosphates of metals, such as aluminum phosphate. Preferred cracking bases are mixtures of silica and alumina. The hydrogenation components are selected from the metals of the VI-B group and the VIII group of their oxides or their mixtures. Cobaltmolybdenum, nickel-molybdenum, or nickel-tungsten catalysts on aluminosilicate supports are particularly effective. In the hydrocracking zone, the temperature is maintained at 343-426 C, more preferably 343-399 seconds. The temperature in the hydrocracking zone is always lower than the temperature in the dissolution zone, preferably at 38-b5s. Other hydrocracking conditions include a pressure of 35-350 MPa, preferably 70-210 cent, better 105-175 MPa; the feed rate of hydrogen is 0.36-3.56 m / l of suspension, preferably 0.53-1.78 m / l of suspension, and the volumetric feed rate of suspension is 0.1-2.0, preferably 0.2-0.5 h. As a rule, at the non-catalytic dissolution stage and the catalytic hydrocracking stage, almost the same pressure is maintained. Preferably, the entire stream leaving the dissolution zone is directed to the hydrocracking zone. However, since in the first stage, amounts of water and light gases () are formed insignificantly, in the second stage, the catalyst is subjected to the action of hydrogen with a reduced partial pressure compared to that which would have been the absence of these substances. Since the increased partial pressures of hydrogen contribute to an increase in the life of the catalyst, in commercial operation it is possible to remove some of the water and light gases before feeding the stream to the hydrocracking stage.
    The product stream leaving the reaction zone 7 through line 8 is divided into a gaseous fraction and a solid-containing fraction discharged through lines 9 and 10, respectively. The gaseous fraction includes light oils boiling below 149-260 ° C, preferably lower, and gaseous components under normal conditions, such as C02. hydrocarbons Cii-C. Preferably, the hydrogen is separated from the other gaseous components and returned, if necessary, to the hydrocracking or dissolving stage. The liquid-solid fraction is fed to the solids separation zone 11, in which it is separated into a solids-lean stream and solids enriched along the line- 13. Undissolved solids are separated using conventional means, for example hydrocyclones, by filtration, centrifugation and sedimentation by gravity or any other combination of these means. Preferably, the undissolved solids are separated by precipitation due to gravity.
    The effluent from the hydrocracking reaction zone has a low viscosity and a low specific gravity (below 1.1012 g / cm). The low specific gravity value allows rapid separation of solids by settling due to gravity. Preferably, the undissolved solids are removed by settling due to the force of gravity at an elevated temperature of 93-427 ° C, preferably 149-204 ° C and at a pressure of 0-350 kg / cm, preferably 0-70 kg / cm. Particularly preferably the selection of solid particles at elevated temperature and pressure. A solids depleted product stream discharged through line 12 is returned to the mixing zone, while a stream enriched in solid particles is directed through line 13 to the second solid particle separation zone 14. Zone 14 may contain distillation, coking in a boil. layer or slag “slow coking, centrifuging, hydrocyclones, filtration, sedimentation or any combination of these methods. Selected solids are removed from zone 14 through line 15. Liquid product is removed through line 16. The liquid product contains almost no solid particles, their content does not exceed 1.0 wt.%.
    The proposed method provides very pure liquid products under normal conditions. Liquids under normal conditions, the products, which are all the fractions of the product boiling above, have a low KIM specific gravity of 1.1012 g / cm, preferably. 1.076 g / cm and more preferably below 1.0366 a low sulfur content of 0.1% by weight of the preferred,
    solid, 02 wt.%, low nitrogen content —CO — 5 wt.%, preferably 40 0.2 wt.%.
    The proposed method provides for the preparation of pure, liquid carbon;
    normal conditions of products used in different areas. It is possible to use the wide fraction of a product as turbine fuel. Narrow fractions of the product are used as gasoline, diesel, jet and other types of fuel.
    Example 1. A slurry containing 33 wt.% Illinois coal and .67 wt.% Recycled oil is successively passed through a first stage, a dissolution zone, and a second stage, a hydrocracking zone. The particle size of the coal is 100 mesh (0.125 mm). The elemental composition in i calculated on dry coal, wt.%: C 64;
    H 4.5; N 1.0; About 12.5; S 4,0; ash
    14.0. The solvent (recycled oil) is a fraction with a boiling point. Hydrogen is introduced in the first stage at a rate
    equal to 1.78 m / l. The residence time of the suspension in the first stage is 1.4 hours, the temperature is 446.5 ° C, the pressure is 168 MPa. The mixture of gases, liquids and solids is then sent to the second stage, where it is contacted with a fixed bed of hydrocracking catalyst consisting of 6.6 wt.% Nickel and 19.2 wt.% Tungsten supported on alumina. At the second stage, the regime is maintained: pressure 168 MPa, temperature 354С, volumetric feed rate of the raw suspension 0.25 h. The effluent is divided into recirculated oil. (Commencement of boiling 204 ° C) and recovered
    lz coal product.
    liquid under normal conditions, i.e. fractions from C4, to have a specific weight of 1.0433 g / cm, contains nitrogen 0.2 wt.%, oxygen 0.69 wt.%; sulfur 0.03 wt.%.
    Below are the outputs of the products after work, for 1300 hours.
    Fraction of output on dry coal, wt.%
    , 2
    C4, 5
    204-371 C39.7
    371-468 "C10,2
    468С11.1
    Unreacted coal6, O Ash. 13.5 NHj, 13.9 Example 2. A slurry containing 25 wt.% Illinois coal with a particle size of 100 mesh (0.125 mm) and less and 75 wt.% Oil obtained from coal (boiling above 204 C) is successively passed through the first stage - the dissolution zone and the second stage - the hydrocracking zone. The operating conditions of the first stage are similar to those of Example 1. The residence time of the suspension, in the first stage, is 0.67 hours. In the second stage, the pressure is maintained at 168 MPa at the initial temperature. After 67 hours, the specific gravity of the product varies from 1.0035 to 1.0679 g / cm. Then the temperature is increased to 446.5 s and the specific gravity of the product decreases to 1.0481 g / cm, but after 65 hours of work it again increases to 1.076 g / cm. At a temperature of 446, the activity of the catalyst drops sharply and the process is further hampered by coking. liquid product yield is reduced.
    Comparison of examples 1 and 2 shows the need to maintain a low temperature at the hydrocracking stage.
    权利要求:
    Claims (2)
    [1]
    1. US patent number 3852183, cl. 208-10, publ. 1974.
    [2]
    2. US patent number 3791957, cl. 208-10, 1974 (prototype).
    类似技术:
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    同族专利:
    公开号 | 公开日
    AU510082B2|1980-06-05|
    AU553120B2|1986-07-03|
    US4330389A|1982-05-18|
    ZA777526B|1978-09-27|
    JPS5382804A|1978-07-21|
    DE2756976C2|1987-04-02|
    AU3206677A|1979-07-05|
    AU7517781A|1983-03-17|
    DE2756976A1|1978-06-29|
    FR2375315B1|1980-12-12|
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    CA1155781A|1983-10-25|
    GB1551177A|1979-08-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB282961A|1926-12-02|1928-01-05|Norman Duxbury|Improvements in, or relating to, doctor mechanism for paper making machines and other machines|
    FR676328A|1928-06-18|1930-02-21|Ig Farbenindustrie Ag|Method for the production of lubricating oils and low-temperature boiling hydrocarbons|
    GB779901A|1954-08-06|1957-07-24|Erwin Bluemner|Improvements relating to the cracking of coal oil mixtures|
    US3488279A|1967-05-29|1970-01-06|Exxon Research Engineering Co|Two-stage conversion of coal to liquid hydrocarbons|
    US3892654A|1974-03-04|1975-07-01|Us Interior|Dual temperature coal solvation process|
    US3884796A|1974-03-04|1975-05-20|Us Interior|Solvent refined coal process with retention of coal minerals|
    US4028221A|1975-06-06|1977-06-07|The Lummus Company|Liquefaction of sub-bituminous and lignitic coal|
    US4057484A|1975-12-15|1977-11-08|John Michael Malek|Process for hydroliquefying coal or like carbonaceous solid materials|
    US4111788A|1976-09-23|1978-09-05|Hydrocarbon Research, Inc.|Staged hydrogenation of low rank coal|
    US4083769A|1976-11-30|1978-04-11|Gulf Research & Development Company|Catalytic process for liquefying coal|
    US4110192A|1976-11-30|1978-08-29|Gulf Research & Development Company|Process for liquefying coal employing a vented dissolver|US4330393A|1979-02-14|1982-05-18|Chevron Research Company|Two-stage coal liquefaction process with petroleum-derived coal solvents|
    US4422922A|1976-12-27|1983-12-27|Chevron Research Company|Coal liquefaction and hydroprocessing of petroleum oils|
    US4379744A|1980-10-06|1983-04-12|Chevron Research Company|Coal liquefaction process|
    US4255248A|1979-09-07|1981-03-10|Chevron Research Company|Two-stage coal liquefaction process with process-derived solvent having a low heptane-insolubiles content|
    US4264429A|1979-10-18|1981-04-28|Chevron Research Company|Two-stage coal liquefaction process with process-derived solvent|
    US4350582A|1979-10-18|1982-09-21|Chevron Research Company|Two-stage coal liquefaction process with process-derived solvent|
    JPS5665085A|1979-10-31|1981-06-02|Mitsui Mining Co Ltd|Liquefaction of coals|
    US4421630A|1981-10-05|1983-12-20|International Coal Refining Company|Process for coal liquefaction in staged dissolvers|
    US4396488A|1981-10-08|1983-08-02|Electric Power Research Institute, Inc.|Process for coal liquefaction employing a superior coal liquefaction process solvent|
    US4537675A|1982-05-13|1985-08-27|In-Situ, Inc.|Upgraded solvents in coal liquefaction processes|
    CA1199293A|1982-06-17|1986-01-14|Chevron Research And Technology Company|Two-stage hydroprocessing of heavy oils with recycleof residua|
    JPS5984978A|1982-11-08|1984-05-16|Mitsubishi Heavy Ind Ltd|Liquefaction of coal|
    CA1238287A|1984-08-04|1988-06-21|Werner Dohler|Process for the production of reformer feed andheating oil or diesel oil from coal|
    US5120429A|1987-07-10|1992-06-09|Lummus Crest Inc.|Co-processing of carbonaceous solids and petroleum oil|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/754,198|US4330389A|1976-12-27|1976-12-27|Coal liquefaction process|
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