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公开(公告)号：US4959337A
公开(公告)日：1990-09-25
申请号：US283709
申请日：1988-12-13
摘要： A wax isomerization catalyst is described which comprises a Group VIII hydrogenation metal component on fluorided alumina or material containing alumina which catalyst possesses a surface nitrogen content N/Al ratio of about 0.01 or less determined by X-ray photoelectron spectroscopy, a bulk fluorine content of between about 2 to 10 wt %, a surface fluorine content defined as the amount of fluorine in a layer extending from the outer surface to a depth of about 1/100 of an inch of less than about 3 wt % provided that the surface fluoride concentration is less than the bulk fluoride concentration and an aluminum fluoride hydroxide hydrate peak height of 60 or less determined as the relative amount of hydrate represented by a peak in the X-ray diffraction pattern at 2.theta.=5.66 .ANG. when a hydrate level of 100 corresponds to the XRD peak height exhibited by a standard material. Also described is a method for producing a slack wax isomerization catalyst said method comprising depositing a Group VIII hydrogenation metal on alumina or material containing alumina extrudate, calcining said metal loaded extrudate, fluoriding said material using an aqueous fluorine source solution having a pH of 3.5 to 4.5 to a bulk fluorine level of about 8 wt % or less followed by heating in an air oxygen containing atmosphere or inert gas from ambient to 350.degree. to 450.degree. C. within 3 hours and holding at the final temperature, if necessary, for a time sufficient to reduce the hydrate and nitrogen contents to the aforesaid levels. Alternatively the catalyst can be made using a fluorine solution of pH less than 3.5 to a bulk fluorine level of about 10 wt % or less followed by heating in air or an oxygen containing atmosphere, or inert atmosphere at about 350.degree. to 450.degree. C.
摘要翻译： 描述了一种蜡异构化催化剂，其包括在氟化氧化铝上的VIII族加氢金属组分或含有氧化铝的材料，该催化剂具有通过X射线光电子能谱测定的表面氮含量N / Al比为约0.01以下，体积氟含量 在约2至10重量％之间，表面氟含量定义为从外表面延伸至约1/100英寸的深度小于约3重量％的层中的氟的量，条件是表面氟化物浓度 小于氟化物浓度，氟化氢氢氧化物水合物峰值高度为60或更小，当水合物水平为100时，在2θ= 5.66时X射线衍射图中由峰值表示的水合物的相对量确定为对应于 到标准材料表现出的XRD峰高。 还描述了一种制备松散蜡异构化催化剂的方法，所述方法包括在氧化铝上沉积VIII族氢化金属或含有氧化铝挤出物的材料，煅烧所述负载有金属的挤出物，使用pH为3.5的含氟氟源溶液氟化所述材料， 4.5至大约8重量％或更少的体积氟水平，然后在3小时内在空气含氧气氛或惰性气体中从室温加热至350℃至450℃，并在必要时保持在最终温度 时间足以将水合物和氮含量降低到上述水平。 或者，催化剂可以使用pH小于3.5的氟溶液至约10重量％或更少的体积氟水平制备，然后在空气或含氧气氛中或在约350-450℃的惰性气氛下加热。
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公开(公告)号：US4900707A
公开(公告)日：1990-02-13
申请号：US283658
申请日：1988-12-13
摘要： An improved wax isomerization catalyst is described which is a hydrogenation metal on halogenated refractory metal oxide support catalyst characterized in that the catalyst is prepared by depositing the hydrogenation metal on the refractory metal oxide support followed by fluoriding using a low pH fluorine source such as aqueous HF. Thereafter the catalyst is crushed to expose inner surfaces, the crushed catalyst being sieved to remove fines, the catalyst charge having an average particle diameter of 1/32 inch and smaller across the longest continuous cross sectional dimension, preferably between 1/64 to 1/32". Alternatively, the catalyst is made by depositing a hydrogenation metal on a refractory metal support, crushing the material to a particle size of 1/32 inch and smaller across the longest continuous cross-sectional dimension and fluoriding said material using acidic fluorine source such as HF. Following sizing the sized catalyst is activated by heating in a hydrogen atmosphere.Isomerization using this "sized" catalyst is marked by the production of an isomerized dewaxed oil product having unexpectedly high VI and superior levels of selective conversion of wax to liquid isomerized product.
摘要翻译： 描述了一种改进的蜡异构化催化剂，其是卤化难熔金属氧化物载体催化剂上的氢化金属，其特征在于通过将氢化金属沉积在难熔金属氧化物载体上然后使用低pH氟源如HF水溶液进行氟化而制备催化剂 。 此后，将催化剂粉碎以暴露内表面，将破碎的催化剂筛分以除去细粒，催化剂装料的平均粒径为最大连续横截面尺寸为1/32英寸且较小，优选为1/64至1 / 32“。 或者，催化剂通过在难熔金属载体上沉积氢化金属制成，通过最长的连续横截面尺寸将材料粉碎至1/32英寸或更小的粒度，并使用酸性氟源如HF氟化所述材料 。 在定尺寸之后，通过在氢气氛中加热来活化大小的催化剂。 使用这种“大小”催化剂的异构化的特征在于生产具有出人意料的高VI的异构化脱蜡油产物和优异的蜡向液体异构化产物的选择性转化。
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3.发明授权
公开(公告)号：US4540481A
公开(公告)日：1985-09-10
申请号：US551594
申请日：1983-11-14
摘要： A process for the preparation of novel highly active, highly selective hydrotreating catalysts. These catalysts are prepared, in bulk or in supported form, by contacting together and decomposing, in the presence of hydrogen, hydrocarbon, and sulfur, a catalyst precursor characterized by the formula B.sub.x [Mo.sub.3 S.sub.z ] where B is an ammonium ion, polyammonium ion, tertiary or quaternary phosphonium ion, or a hydrocarbyl substituted ammonium ion, hydrocarbyl substituted polyammonium ion, or hydrocarbyl substituted tertiary or quaternary phosphonium ion, x is 1 where B is a divalent cationic moiety, or 2 where B is a monovalent cationic moiety, [Mo.sub.3 S.sub.z ] is a divalent anionic moiety wherein z is an integer ranging from about 10 to about 46. A preferred precursor catalyst species is Mo.sub.3 (S.sub.2).sub.6 S.
摘要翻译： 一种制备新型高活性，高选择性加氢处理催化剂的方法。 这些催化剂以体积或负载形式通过在氢，烃和硫的存在下接触并分解，其特征在于式Bx [Mo 3 S z]的催化剂前体，其中B是铵离子，聚铵离子， 叔或季鏻离子或烃基取代的铵离子，烃基取代的多铵离子或烃基取代的叔或鏻离子，x是1，其中B是二价阳离子部分，或2其中B是一价阳离子部分[Mo 3 Sz ]是二价阴离子部分，其中z是约10至约46的整数。优选的前体催化剂种类是Mo 3（S 2）6 S。
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公开(公告)号：US3985684A
公开(公告)日：1976-10-12
申请号：US533331
申请日：1974-12-16
IPC分类号： B01J23/74 , B01J23/85 , B01J35/02 , B01J35/10 , B01J37/00 , C10G45/08 , B01J23/84 , B01J23/16 , B01J23/62 , B01J23/64
CPC分类号： B01J37/0009 , B01J23/74 , B01J23/85 , B01J35/10 , C10G45/08 , B01J35/023 , B01J35/1019 , B01J35/1042 , B01J35/1047 , B01J35/1061 , B01J35/108
摘要： This invention relates to novel catalysts, of two distinct types, useful for the catalytic hydroconversion of the 1050.degree.F.+ hydrocarbon material contained in heavy crudes and residua such that the resulting product will be suitable for further processing in conventional refinery operations allowing maximization of clean liquid products. Catalysts, which include Group VIB and Group VIII metals, preferably in admixture, and preferably including a Group IVA metal, notably germanium, having certain critical ranges of physical characteristics inclusive of large uniform pore sizes, are used for the conversion, these having been shown to possess improved catalytic activity and selectivity for the hydroconversion of the 1050.degree.F.+ materials of the heavy feeds and residua. Novel methods are described for the preparation of such catalysts, as well as for use of such catalysts. One of the catalysts, i.e., one having properties inclusive of a large number of pores in the 100-275A pore size diameter range, is particularly suitable as a first stage catalyst and the other, which has properties inclusive of a large number of pores in the 100-200A pore size diameter, is especially suitable as a second stage catalyst for use in processing the effluent of said first stage.
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5.发明授权Catalyst for the hydroisomerization and hydrocracking of waxes to produce liquid hydrocarbon fuels and process for preparing the catalyst 失效用于蜡的加氢异构化和加氢裂解以产生液体烃燃料的催化剂和用于制备催化剂的方法
公开(公告)号：US4923841A
公开(公告)日：1990-05-08
申请号：US283690
申请日：1988-12-13
摘要： A fluorided platinum-on-alumina catalyst for wax isomerization wherein the platinum is substantially uniformly distributed throughout the catalyst in the form of relatively small crystallites, of the total fluoride present in the catalyst very little is located on the outer surface of the catalyst and a significant concentration of the fluoride within the catalyst is present as aluminum fluoride hydroxide hydrate. The catalyst is prepared by contacting a platinum-on-alumina with a solution having a relatively high concentration of fluoride and drying the fluorided platinum-on-alumina catalyst at temperatures not in excess of 650.degree. F.
摘要翻译： 用于蜡异构化的氟化铂 - 氧化铝催化剂位于催化剂的外表面上，其中铂以催化剂中相对小的微晶的形式基本上均匀分布在催化剂中的总氟化物非常少， 作为氟化氢氢氧化物水合物存在催化剂内氟化物的显着浓度。 通过使氧化铝上的铂与具有较高浓度氟化物的溶液接触并在不超过650°F的温度下干燥氟化铂 - 氧化铝催化剂来制备催化剂。
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6.发明授权Process for the hydroisomerization of was to produce middle distillate products (OP-3403) 失效蜡的加氢异构化方法生产中间馏分产物（OP-3403）
公开(公告)号：US4919786A
公开(公告)日：1990-04-24
申请号：US283681
申请日：1988-12-13
IPC分类号： B01J23/42 , B01J23/88 , B01J27/125 , B01J37/26 , C10G45/60 , C10G45/62 , C10G65/04 , C10G73/38 , C10L1/04 , C10M101/02 , C10N20/00 , C10N20/02
CPC分类号： C10G45/62 , Y10S208/95
摘要： A process for selectively producing middle distillate fuel products from paraffin waxes such as slack wax and Fischer-Tropsch wax by hydroisomerizing the wax to convert 60-95 weight percent per pass of the 700.degree. F..sup.+ fraction contained in said wax. The catalyst employed is a fluorided Group VIII metal-on-alumina catalyst where the fluoride within the catalyst is present predominately as aluminum fluoride hydroxide hydrate. The preferred Group VIII metal is platinum.
摘要翻译： 通过将蜡加氢异构化来选择性地从诸如松散蜡和费托蜡的石蜡中产生中间馏分燃料产物的方法，以使每一次通过所述蜡中所含的700°F +级分的60-95重量％。 所使用的催化剂是氟化的第Ⅷ族金属对氧化铝催化剂，其中催化剂内的氟化物主要作为氟化氢氢氧化物水合物存在。 优选的VIII族金属是铂。
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7.发明授权Process for the production of ultra high octane gasoline, and other fuels from aromatic hydrocrackates 失效用于生产超高辛烷值汽油和其他来自芳族加氢裂化剂的燃料的方法
公开(公告)号：US4828676A
公开(公告)日：1989-05-09
申请号：US129546
申请日：1987-12-07
IPC分类号： C10G65/12
CPC分类号： C10G65/12
摘要： A process for the production of high octane gasoline, or high octane gasoline blending components from a sulfur and nitrogen-containing feed composition of wide boiling range rich in fused multi-ring aromatic hydrocarbons containing two, and three or more rings in the molecule. The feed is first hydrogenated to desulfurize, denitrogenate and saturate one ring of the two-ring molecular species, but insufficient to saturate the second ring of said molecular species. The product, as a feed, is then hydrocracked to crack fused multi-ring aromatic hydrocarbons containing three or more rings to the molecule, and to produce lower molecular weight, lower boiling components. The product of the hydrocracker is then split into blends which include (i) a blend rich in fused two-ring aromatic hydrocarbons and (ii) a blend rich in fused multi-ring aromatic hydrocarbons containing three or more rings to the molecule. Blend (i) is selectively hydrogenated and cracked over a catalyst comprised of elemental iron and one or more alkali or alkaline-earth metals to produce gasoline or gasoline blending components, and blend (ii) is hydrocracked to produce gasoline or gasoline blending components.
摘要翻译： 用于生产高辛烷值汽油或高辛烷值汽油共混组分的方法，该组合物含有大分子中含有两个和三个或更多个环的稠合多环芳烃的宽沸点范围的含硫和含氮进料组合物。 该饲料首先被氢化以脱硫，脱氮并饱和一环的两环分子种类，但不足以饱和所述分子种类的第二环。 然后将作为进料的产物加氢裂化以将含有三个或更多个环的稠合多环芳烃裂解成分子，并产生较低分子量的较低沸点组分。 然后将加氢裂化器的产物分离成共混物，其包括（i）富含稠合的双环芳族烃的共混物和（ii）富含融合的多环芳烃的共混物，其含有三个或更多个环到分子上。 混合物（i）在由元素铁和一种或多种碱金属或碱土金属组成的催化剂上被选择性氢化和裂化，以产生汽油或汽油调和组分，并且将（ii）加氢裂化以产生汽油或汽油调和组分。
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8.发明授权
公开(公告)号：US4542121A
公开(公告)日：1985-09-17
申请号：US570364
申请日：1984-01-13
摘要： A process for the preparation of novel highly active, highly selective hydrotreating catalysts. These catalysts are prepared, in bulk or in supported form, from a catalyst precursor characterized by the formula B.sub.x [Mo.sub.3 S.sub.z ] where B is an ammonium ion, polyammonium ion, tertiary or quaternary phosphonium ion, or a hydrocarbyl substituted ammonium ion, hydrocarbyl substituted polyammonium ion, or hydrocarbyl substituted tertiary or quaternary phosphonium ion, x is 1 where B is a divalent cationic moiety, or 2 where B is a monovalent cationic moiety, [Mo.sub.3 S.sub.z ] is a divalent anionic moiety wherein z is an integer greater than 15. The catalyst precursor is dispersed in an ammonium sulfide or dilute ammonium polysulfide solution and heated to remove sulfur from said catalyst precursor to provide a z value of 15 or less. Carbon is also removed from the catalyst precursor and, where B of the B.sub.x [Mo.sub.3 S.sub.z ] catalyst precursor is a non-carbon containing moiety, the finished catalyst will contain an atomic ratio of C/Mo of less than about 0.05. Decomposition of the catalyst precursor in the presence of hydrogen, hydrocarbon and sulfur forms the highly active hydrotreating catalyst.
摘要翻译： 一种制备新型高活性，高选择性加氢处理催化剂的方法。 这些催化剂以体积或负载形式由特征为式Bx [Mo 3 S z]的催化剂前体制备，其中B是铵离子，聚铵离子，叔或季鏻离子或烃基取代的铵离子，烃基取代的聚铵 离子或烃基取代的叔或季鏻离子，x是1，其中B是二价阳离子部分，或2其中B是一价阳离子部分，[Mo 3 S z]是二价阴离子部分，其中z是大于15的整数。 催化剂前体分散在硫化铵或多硫化铵溶液中并加热以从所述催化剂前体中除去硫以提供15或更小的az值。 碳也从催化剂前体中除去，并且其中Bx [Mo3Sz]催化剂前体的B是不含碳的部分，成品催化剂将含有小于约0.05的C / Mo的原子比。 在氢，烃和硫存在下分解催化剂前体形成高活性加氢处理催化剂。
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公开(公告)号：US5037532A
公开(公告)日：1991-08-06
申请号：US586162
申请日：1990-09-21
摘要： A slurry hydrotreating process is described in which a hydrotreating catalyst of small particle size is contacted with a heavy fossil fuel. High catalyst activity is maintained by circulating the catalyst between a hydrotreating zone and a reactivating zone where the catalyst is hydrogen stripped.
摘要翻译： 描述了一种浆料加氢处理方法，其中小粒径的加氢处理催化剂与重质化石燃料接触。 通过使催化剂在加氢处理区和催化剂被氢汽提的再活化区之间循环来维持高的催化剂活性。
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公开(公告)号：US4952306A
公开(公告)日：1990-08-28
申请号：US411149
申请日：1989-09-22
IPC分类号： B01J27/047 , C10G45/08 , C10G45/16 , C10G45/50 , C10G45/56
摘要： A novel slurry hydrotreating process is described which employs a hydrotreating catalyst of small particle size having a quantity of catalyst sites in excess of those required for reaction and/or adsorption of nitrogen compounds in the petroleum or synfuel feed being treated. The excess catalyst sites can therefore in effect be contacted with a low nitrogen or essentially zero nitrogen feed, allowing rapid hydrogenation of aromatics at low temperatures where equilibrium is favored. In a further aspect of the invention, the catalyst which contains adsorbed nitrogen is activated by high temperature denitrogenation.
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