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    • 3. 发明授权
    • Catalytic multi-stage process for hydroconversion and refining hydrocarbon feeds
    • 用于加氢转化和精炼烃进料的催化多阶段方法
    • US06190542B1
    • 2001-02-20
    • US09241505
    • 1999-02-01
    • Alfred G. ComolliLap-Keung Lee
    • Alfred G. ComolliLap-Keung Lee
    • C10G106
    • B01J23/745B01J23/74B01J23/84B01J23/881B01J27/053B01J27/1853B01J27/19B01J35/12B01J37/036C10G1/002C10G1/006C10G1/086C10G1/10C10G47/02C10G47/26C10G49/12C10G65/02C10G65/10
    • A multi-stage catalytic hydrogenation and hydroconversion process for heavy hydrocarbon feed materials such as coal, heavy petroleum fractions, and plastic waste materials. In the process, the feedstock is reacted in a first-stage, back-mixed catalytic reactor with a highly dispersed iron-based catalyst having a powder, gel or liquid form. The reactor effluent is pressure-reduced, vapors and light distillate fractions are removed overhead, and the heavier liquid fraction is fed to a second stage back-mixed catalytic reactor. The first and second stage catalytic reactors are operated at 700-850° F. temperature, 1000-3500 psig hydrogen partial pressure and 20-80 lb./hr per ft3 reactor space velocity. The vapor and light distillates liquid fractions removed from both the first and second stage reactor effluent streams are combined and passed to an in-line, fixed-bed catalytic hydrotreater for heteroatom removal and for producing high quality naphtha and mid-distillate or a full-range distillate product. The remaining separator bottoms liquid fractions are distilled at successive atmospheric and vacuum pressures, low and intermediate-boiling hydrocarbon liquid products are withdrawn, and heavier distillate fractions are recycled and further upgraded to provide additional low-boiling hydrocarbon liquid products. This catalytic multistage hydrogenation process provides improved flexibility for hydroprocessing the various carbonaceous feedstocks and adjusting to desired product structures and for improved economy of operations.
    • 用于重烃原料如煤,重质石油馏分和塑料废料的多阶段催化氢化和加氢转化工艺。 在该方法中,原料在第一级反混合催化反应器中与具有粉末,凝胶或液体形式的高度分散的铁基催化剂反应。 反应器流出物被减压,蒸气和轻馏分馏分顶部除去,较重的液体馏分进料到第二级反混合催化反应器中。 第一级和第二级催化反应器在700-850°F温度,1000-3500psig氢分压和20-80磅/小时/ ft 3反应器空间速度下操作。 蒸汽和轻馏分将从第一和第二阶段反应器中除去的液体馏分进行蒸馏,将流出物流合并,并通入直列固定床催化加氢处理器除去杂质,并生产高质量的石脑油和中间馏分, 范围馏出物。 剩余的分离器底部液体馏分在连续的大气压和真空压力下蒸馏,取出低和中等沸点的烃液体产物,再重馏出馏分,进一步升级以提供另外的低沸点烃液体产物。 这种催化多级氢化方法提供了改进的各种碳质原料的加氢处理和调整到所需产物结构以及改善操作经济性的灵活性。
    • 4. 发明授权
    • Dispersed anion-modified iron oxide catalysts for hydroconversion
processes
    • 用于加氢转化法的分散的阴离子改性的氧化铁催化剂
    • US5866501A
    • 1999-02-02
    • US609759
    • 1996-02-23
    • Vivek R. PradhanAlfred G. ComolliLap-Keung Lee
    • Vivek R. PradhanAlfred G. ComolliLap-Keung Lee
    • B01J23/74B01J23/745B01J23/84B01J23/881B01J27/053B01J27/185B01J27/19B01J35/12C10G1/00C10G1/08C10G1/10C10G47/02C10G47/26C10G49/12C10G65/10B01J27/043C10G1/06
    • B01J27/053B01J23/745B01J23/881B01J27/1853B01J35/12C10G1/002C10G1/006C10G1/086C10G1/10C10G47/02C10G47/26C10G49/12C10G65/10B01J23/74B01J23/84B01J27/19
    • A dispersed fine-sized anion-modified iron oxide slurry catalyst having high surface area exceeding about 100 m.sup.2 /gm and high catalytic activity, and which is useful for hydrogenation and hydroconversion reactions for carbonaceous feed materials is disclosed. The catalyst is synthesized by rapid aqueous precipitation from saturated salt solutions such as ferric alum or ferric sulfate, and is promoted with at least one active metal such as cobalt, molybdenum, nickel, tungsten and combinations thereof. The iron-based dispersed catalysts are modified during their preparation with anionic modifiers such as molybdate (MoO.sub.4.sup.2-), phosphate (PO.sub.4.sup.3-), sulfate (SO.sub.4.sup.2-), or tungstate (WO.sub.4.sup.2-). The resulting catalyst usually has primary particle size smaller than about 50 Angstrom units, and may be used in the form of a gel or wet cake which can be easily mixed with a hydrocarbonaceous feed material such as coal, heavy petroleum fractions, mixed waste plastics or mixtures thereof. Alternatively, the catalyst can be dried and/or calcined so as to be in a fine dry particulate form suitable for adding to the feed material. The invention includes methods for making the catalyst and processes for using the catalyst for hydroprocessing of the carbonaceous feed materials.
    • 公开了一种具有超过约100m 2 / gm的高表面积和高催化活性的分散的细尺寸阴离子改性氧化铁浆料催化剂,其可用于含碳原料的氢化和加氢转化反应。 通过从饱和盐溶液如三价铁或硫酸铁中的快速含水沉淀合成催化剂,并用至少一种活性金属如钴,钼,镍,钨及其组合进行促进。 铁基分散催化剂在制备过程中用钼酸盐(MoO42-),磷酸盐(PO43-),硫酸盐(SO42-)或钨酸盐(WO42-))等阴离子改性剂进行改性。 所得到的催化剂通常具有小于约50埃单位的初级粒度,并且可以以凝胶或湿饼的形式使用,其可以容易地与诸如煤,重质石油馏分,混合废塑料的烃类进料混合,或 其混合物。 或者,可以将催化剂干燥和/或煅烧成适于添加到进料中的细干燥颗粒形式。 本发明包括制备催化剂的方法和使用该催化剂加氢处理含碳原料的方法。
    • 6. 发明授权
    • Catalytic two-stage coal hydrogenation and hydroconversion process
    • 催化两阶段煤炭加氢和加氢转化过程
    • US4842719A
    • 1989-06-27
    • US876307
    • 1986-06-18
    • James B. MacArthurJoseph B. McLeanAlfred G. Comolli
    • James B. MacArthurJoseph B. McLeanAlfred G. Comolli
    • C10G1/00
    • C10G1/006
    • A process for two-stage catalytic hydrogenation and liquefaction of coal to produce increased yields of low-boiling hydrocarbon liquid and gas products. In the process, the particulate coal is slurried with a process-derived liquid solvent and fed at temperature below about 650.degree. F. into a first stage catalytic reaction zone operated at conditions which promote controlled rate liquefaction of the coal, while simultaneously hydrogenating the hydrocarbon recycle oils at conditions favoring hydrogenation reactions. The first stage reactor is maintained at 650.degree.-800.degree. F. temperature, 1000-4000 psig hydrogen partial pressure, and 10-60 lb coal/hr/ft.sup.3 reactor space velocity. The partially hydrogenated material from the first stage reaction zone is passed directly to the close-coupled second stage catalytic reaction zone maintained at a temperature at least about 25.degree. F. higher than for the first stage reactor and within a range of 750.degree.-875.degree. F. temperature for further hydrogenation and thermal hydroconversion reactions. By this process, the coal feed is successively catalytically hydrogenated and hydroconverted at selected conditions, which results in significantly increased yields of desirable low-boiling hydrocarbon liquid products and minimal production of undesirable residuum and unconverted coal and hydrocarbon gases, with use of less energy to obtain the low molecular weight products, while catalyst life is substantially increased.
    • 一种两阶段催化氢化和液化煤的方法,以产生低沸点烃液体和气体产物的产量。 在该过程中,颗粒状煤用工艺衍生的液体溶剂浆化并在低于约650°F的温度下进料到在促进煤的受控速率液化的条件下操作的第一级催化反应区,同时使烃 循环油在有利于氢化反应的条件下。 第一级反应器保持在650-800°F的温度,1000-4000psig的氢气分压和10-60磅煤/小时/立方米的反应器空间速度。 来自第一级反应区的部分氢化的物质直接通入保持在比第一级反应器高至少约25°F的温度的紧耦合的第二级催化反应区,并且在750°-875的范围内 温度进一步氢化和热加氢转化反应。 通过这个过程,煤炭进料在选择的条件下依次进行催化氢化和加氢转化,这导致所需的低沸点烃液体产物的产量显着提高,并且不需要的残渣和未转化的煤和碳氢化合物气体的产生量减少, 获得低分子量产物,而催化剂寿命显着增加。
    • 7. 发明授权
    • Coal liquefaction process utilizing coal/CO.sub.2 slurry feedstream
    • 采用煤/二氧化碳浆料进料流的煤液化过程
    • US4839030A
    • 1989-06-13
    • US199493
    • 1988-05-27
    • Alfred G. ComolliJoseph B. McLean
    • Alfred G. ComolliJoseph B. McLean
    • C10G1/08
    • C10G1/083Y10S208/952
    • A coal hydrogenation and liquefaction process in which particulate coal feed is pressurized to an intermediate pressure of at least 500 psig and slurried with CO.sub.2 liquid to provide a flowable coal/CO.sub.2 slurry feedstream, which is further pressurized to at least 1000 psig and fed into a catalytic reactor. The coal particle size is 50-375 mesh (U.S. Sieve Series) and provides 50-80 W % coal in the coal/CO.sub.2 slurry feedstream. Catalytic reaction conditions are maintained at 650.degree.-850.degree. F. temperature, 1000-4000 psig hydrogen partial pressure and coal feed rate of 10-100 lb coal/hr ft.sup.3 reactor volume to produce hydrocarbon gas and liquid products. The hydrogen and CO.sub.2 are recovered from the reactor effluent gaseous fraction, hydrogen is recycled to the catalytic reactor, and CO.sub.2 is liquefied and recycled to the coal slurrying step. If desired, two catalytic reaction stages close coupled together in series relation can be used. The process advantageously minimizes the recycle and processing of excess hydrocarbon liquid previously needed for slurrying the coal feed to the reactor(s).
    • 煤炭加氢和液化过程,其中颗粒煤进料被加压至至少500psig的中间压力并用CO 2液体浆化以提供可流动的煤/ CO 2浆料进料流,其进一步加压至至少1000psig并进料至 催化反应器。 煤粒度为50-375目(美国筛系列),在煤/二氧化碳浆料进料流中提供50-80%的煤。 催化反应条件保持在650°-850°F的温度,1000-4000psig的氢气分压和10-100lb煤/ hr ft 3反应器体积的煤进料速率,以产生烃气体和液体产物。 从反应器流出气体馏分中回收氢气和二氧化碳,将氢气再循环到催化反应器中,并将二氧化碳液化并再循环至煤浆化步骤。 如果需要,可以使用两个串联连接在一起的催化反应级。 该方法有利地使先前需要的过量碳氢化合物液体的再循环和加工最小化,以使煤进料到反应器中。
    • 8. 发明授权
    • Process for phase separation
    • 相分离方法
    • US4151073A
    • 1979-04-24
    • US956534
    • 1978-10-31
    • Alfred G. Comolli
    • Alfred G. Comolli
    • B01D19/00C10G1/04C10G1/06C10G31/10C10G9/16
    • C10G1/06B01D19/0057C10G1/045C10G31/10
    • This invention provides a continuous process for separating a gaseous phase from a hydrocarbon liquid containing carbonaceous particulates and gases. The liquid is fed to a cylindrical separator, with the gaseous phase being removed therefrom as an overhead product, whereas the hydrocarbon liquid and the particulates are withdrawn as a bottoms product. By feeding the liquid tangentially to the separator and maintaining a particulate-liquid slurry downward velocity of from about 0.01 to about 0.25 fps in the separator, a total solids weight percent in the slurry of from about 0.1 to about 30%, a slurry temperature of from about 550.degree. to about 900.degree. F., a slurry residence time in the separator of from about 30 to about 360 seconds, and a length/diameter ratio for the separator of from about 20/1 to about 50/1, so that the characterization factor, .alpha., defined as ##STR1## DOES NOT EXCEED ABOUT 48 (.degree.R sec.sup.2)/ft, the deposit of carbonaceous materials on the interior surface of the separator may be substantially eliminated.
    • 本发明提供了一种用于从含有碳质颗粒和气体的烃液体中分离气相的连续方法。 将液体进料到圆柱形分离器,其中气相作为塔顶产物从其中除去,而烃液体和颗粒作为塔底产物排出。 通过将液体切向地供给到分离器并且在分离器中保持颗粒状液体浆料向下的速度为约0.01至约0.25fps,浆料中的总固体重量百分比为约0.1至约30%,浆料温度为 约550°至约900°F,在隔板中的淤浆停留时间为约30至约360秒,隔膜的长度/直径比为约20/1至约50/1,使得 表征因子α定义为不超过48(DEG R sec2)/ ft,在分离器内表面上的碳质材料的沉积可以基本上消除。
    • 9. 发明授权
    • Tire recycling method generating carbonous residue
    • 轮胎回收方法产生碳残渣
    • US07795319B1
    • 2010-09-14
    • US12147948
    • 2008-06-27
    • Alfred G. ComolliDavid L. Tanner
    • Alfred G. ComolliDavid L. Tanner
    • C08J11/04
    • C10G1/10
    • A process for making a carbonous residue from scrap tires is disclosed. Tires are digested in an oil product. Steel and glass fibers are separated. A product enhancing additive comprising halogen based organic or inorganic compounds is added. The resulting carbonaceous material is then cured to create the final product. The produced carbonous residue is well suited for capture of mercury. The present invention has the benefits of providing a use for scrap tires that would otherwise require disposal in a landfill, and also produces a product useful for capturing a harmful element, thereby providing multiple environmental and economic benefits.
    • 公开了一种从废轮胎制造碳残余物的方法。 轮胎在油品中消化。 钢和玻璃纤维分离。 加入含有卤素类有机或无机化合物的增产添加剂。 然后将所得碳质材料固化以产生最终产物。 产生的碳残留物非常适合捕获汞。 本发明的优点在于提供另外需要在垃圾填埋场中处理的废旧轮胎的用途,并且还产生用于捕获有害元素的产品,从而提供多种环境和经济效益。
    • 10. 发明授权
    • Catalytic two-stage liquefaction of coal utilizing cascading of used
ebullated-bed catalyst
    • 利用二次沸腾床催化剂的级联催化二阶段液化
    • US4816141A
    • 1989-03-28
    • US109645
    • 1987-10-16
    • Joseph B. McLeanAlfred G. ComolliJames B. MacArthur
    • Joseph B. McLeanAlfred G. ComolliJames B. MacArthur
    • C10G65/10C10G1/00C10G1/06C10G1/08
    • C10G1/006
    • A multi-stage catalytic process for hydrogenation and liquefaction of coal using ebullated-bed catalytic reactors to produce low-boiling hydrocarbon liquid products, in which used catalyst is removed from a lower temperature first stage reactor operating at temperature not exceeding about 800.degree. F. and cascaded forward to a higher temperature second stage reactor for further use therein. Reaction conditions in the first stage reactor are preferably 700.degree.-800.degree. F. temperature, 1000-4000 psig hydrogen partial pressure, and a coal feed rate of 10-90 lb coal/hr per ft.sup.3 catalyst settled volume in the reactor. Useful higher temperature or second stage reaction conditions are 750.degree.-850.degree. F. temperature, and 1000-4000 psig hydrogen partial pressure. The used catalyst withdrawn from the lower temperature of first stage reactor has a catalyst age of 300-3000 lb coal proceses/lb fresh catalyst, and is transferred forward to the higher temperature second stage reactor for further use to catalyst age of 1000-6000 lb coal processed per lb fresh catalyst. If desired, a higher temperature third catalytic reactor can be provided and used catalyst from the second stage reactor cascaded forward into the third reactor for further use therein. Useful catalysts include metal oxides of cobalt, iron, molybdenum, nickel, tin, or tungsten deposited on a base of alumina, magnesia, silica, or titania, with cobalt moly and nickel moly on alumina catalyst being preferred. This process advantageously requires a smaller quantity of fresh catalyst per ton of coal processed to produce the low-boiling hydrocarbon liquid products.
    • 一种用于使用沸腾床催化反应器来加氢和液化煤的多阶段催化方法,用于生产低沸点烃液体产物,其中使用的催化剂在不超过约800°F的温度下操作的较低温度的第一级反应器中除去。 并级联到较高温度的第二级反应器中以便在其中进一步使用。 第一级反应器中的反应条件优选为700-800°F的温度,1000-4000psig的氢分压,以及在反应器中的10-90lb煤/小时/ ft 3催化剂沉降体积的煤进料速率。 有用的较高温度或第二阶段反应条件为750-850°F的温度和1000-4000 psig的氢分压。 从第一阶段反应器的较低温度取出的使用催化剂的催化剂年龄为300-3000磅煤/ lb新鲜催化剂,并转移到较高温度的第二阶段反应器中进一步用于催化剂年龄为1000-6000磅 每磅新鲜催化剂加工煤。 如果需要,可以提供更高温度的第三催化反应器,并将来自第二级反应器的催化剂用于向前进入第三反应器以供其进一步使用。 有用的催化剂包括沉积在氧化铝,氧化镁,二氧化硅或二氧化钛的基体上的钴,铁,钼,镍,锡或钨的金属氧化物,优选钴钼和镍钼氧化铝催化剂。 该方法有利地需要每吨处理生产低沸点烃液体产品的较少量的新鲜催化剂。