公开(公告)号：US4959337A

公开(公告)日：1990-09-25

申请号：US283709

申请日：1988-12-13

Applicant: Ian A. Cody ,  Hamner, deceased Glen P. ,  Willard H. Sawyer ,  Willard H. Sawyer ,  Davis S. Mark

Inventor： Ian A. Cody ,  Hamner, deceased Glen P. ,  Willard H. Sawyer ,  Willard H. Sawyer ,  Davis S. Mark

IPC: B01J23/40 ,  C10G45/62

CPC classification number: C10G45/62 ,  B01J23/40

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US4900707A

公开(公告)日：1990-02-13

申请号：US283658

申请日：1988-12-13

Applicant: Ian A. Cody ,  Glen P. Hamner, deceased ,  Willard H. Sawyer ,  James J. Schorfheide

Inventor： Ian A. Cody ,  Glen P. Hamner, deceased ,  Willard H. Sawyer ,  James J. Schorfheide

IPC: B01J23/40 ,  B01J37/26 ,  C10G45/62

CPC classification number: B01J37/26 ,  B01J23/40 ,  C10G45/62

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US4540481A

公开(公告)日：1985-09-10

申请号：US551594

申请日：1983-11-14

Applicant: Willard H. Sawyer ,  Howard L. Mitchell, III

Inventor： Willard H. Sawyer ,  Howard L. Mitchell, III

IPC: B01J23/28 ,  B01J27/04 ,  C10G45/04 ,  C10G45/08

CPC classification number: C10G49/04 ,  B01J23/28 ,  B01J27/04

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US3985684A

公开(公告)日：1976-10-12

申请号：US533331

申请日：1974-12-16

Applicant: William F. Arey, Jr. ,  Glen P. Hamner ,  Willard H. Sawyer

Inventor： William F. Arey, Jr. ,  Glen P. Hamner ,  Willard H. Sawyer

IPC: B01J23/74 ,  B01J23/85 ,  B01J35/02 ,  B01J35/10 ,  B01J37/00 ,  C10G45/08 ,  B01J23/84 ,  B01J23/16 ,  B01J23/62 ,  B01J23/64

CPC classification number: B01J37/0009 ,  B01J23/74 ,  B01J23/85 ,  B01J35/10 ,  C10G45/08 ,  B01J35/023 ,  B01J35/1019 ,  B01J35/1042 ,  B01J35/1047 ,  B01J35/1061 ,  B01J35/108

Abstract: 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.

公开(公告)号：US5037532A

公开(公告)日：1991-08-06

申请号：US586162

申请日：1990-09-21

Applicant: William E. Winter, Jr. ,  Willard H. Sawyer

Inventor： William E. Winter, Jr. ,  Willard H. Sawyer

IPC: C10G45/46 ,  C10G45/56

CPC classification number: C10G45/56 ,  C10G45/46

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US4952306A

公开(公告)日：1990-08-28

申请号：US411149

申请日：1989-09-22

Applicant: Willard H. Sawyer ,  Roby Bearden, Jr. ,  Russell R. Chianelli ,  William E. Winter, Jr.

Inventor： Willard H. Sawyer ,  Roby Bearden, Jr. ,  Russell R. Chianelli ,  William E. Winter, Jr.

IPC: B01J27/047 ,  C10G45/08 ,  C10G45/16 ,  C10G45/50 ,  C10G45/56

CPC classification number: C10G45/56 ,  C10G45/16

Abstract: 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.

公开(公告)号：US4326947A

公开(公告)日：1982-04-27

申请号：US213921

申请日：1980-12-08

Applicant: Willard H. Sawyer ,  Neville L. Cull

Inventor： Willard H. Sawyer ,  Neville L. Cull

IPC: B01J29/14 ,  B01J29/16 ,  C10G49/08 ,  C10G45/12 ,  C10G47/08

CPC classification number: B01J29/166 ,  B01J29/146 ,  C10G49/08

Abstract: A catalyst is provided which comprises an ultrastable Y-type crystalline aluminosilicate zeolite, an alumina-aluminum fluorophosphate and a hydrogenation component. Hydrocarbon hydroprocessing processes utilizing the catalyst are also provided.

Abstract translation: 提供了一种催化剂，其包括超稳定的Y型结晶硅铝酸盐沸石，氧化铝 - 铝氟磷酸盐和氢化组分。 还提供了利用催化剂的烃加氢处理方法。

公开(公告)号：US4016107A

公开(公告)日：1977-04-05

申请号：US646491

申请日：1976-01-05

Applicant: Willard H. Sawyer ,  Harry E. Robson

Inventor： Willard H. Sawyer ,  Harry E. Robson

IPC: B01J21/04 ,  B01J23/24 ,  B01J23/74 ,  B01J23/85 ,  B01J35/10 ,  B01J37/00 ,  B01J21/06

CPC classification number: B01J21/04 ,  B01J23/24 ,  B01J23/74 ,  B01J23/85 ,  B01J35/10 ,  B01J37/0018 ,  B01J35/1019 ,  B01J35/1042 ,  B01J35/1047 ,  B01J35/1061 ,  Y10S502/507

Abstract: A process for the formation of a catalyst of predetermined pore size distribution and pore volume from an alumina hydrogel formed and obtained by precipitation from a solution containing a hydrous form of alumina in 1-5 wt. % concentration and an anion that is soluble in an alkaline solution and forms an aluminum salt, at pH 8-12, and temperature ranging about 15.degree. F.-120.degree. F., and then extended by contact with a solution of a water-soluble polymer containing 2 to about 24 monomer units from the group consisting of (a) polyethylene glycols, (b) polypropylene glycols, and (c) polyethylene amines sufficient to absorb the polymer and displace water from the pores until the weight ratio of polymer:alumina ranges about 0.5:1 to about 4:1. A metal hydrogenation component, or components, suitably a Group VI-B or Group VIII metal, or both, can be added during the polymer extending step, if desired, by adding a soluble compound, or salt of the desired metal, or metals, to the polymer containing solution. In either event, the polymer is removed by solvent extraction, dried and calcined to form gamma alumina.

Abstract translation: 一种由1-5重量份含有水合氧化铝的溶液沉淀形成并获得的氧化铝水凝胶形成预定孔径分布和孔体积的催化剂的方法。 ％浓度的阴离子和可溶于碱性溶液中并形成铝盐的阴离子，pH为8-12，温度约为15°-120°F，然后通过与水 - 含有（a）聚乙二醇，（b）聚丙二醇和（c）足以吸收聚合物并从孔中移出水直到聚合物的重量比的聚乙烯胺的2至约24个单体单元的可溶性聚合物： 氧化铝的范围为约0.5:1至约4:1。 如果需要，可以在聚合物延伸步骤期间通过加入可溶性化合物或所需金属或金属的盐，加入金属氢化组分或组分，合适地为VI-B族或VIII族金属，或两者， 到含聚合物的溶液。 在任一情况下，通过溶剂萃取除去聚合物，干燥并煅烧形成γ氧化铝。

公开(公告)号：US3993601A

公开(公告)日：1976-11-23

申请号：US533313

申请日：1974-12-16

Applicant: Fred M. Long ,  Willard H. Sawyer

Inventor： Fred M. Long ,  Willard H. Sawyer

IPC: B01J23/74 ,  B01J23/85 ,  B01J35/10 ,  B01J37/00 ,  C10G45/08 ,  B01J21/04 ,  B01J23/10 ,  B01J23/84

CPC classification number: B01J37/0009 ,  B01J23/74 ,  B01J23/85 ,  B01J35/10 ,  C10G45/08 ,  B01J35/1019 ,  B01J35/1042 ,  B01J35/1047 ,  B01J35/1061 ,  B01J35/1085

Abstract: 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 catalyst. 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.

Abstract translation: 本发明涉及两种不同类型的新型催化剂，其可用于重质原油和残余物中所含的1050°F +烃材料的催化加氢转化，使得所得产物将适用于常规精炼操作中的进一步加工，从而使 清洁液体产品。 使用包括VIB族和VIII族金属的催化剂，优选以混合物形式，优选包括具有特定临界范围物理特性（包括大的均匀孔径）的IVA族金属，特别是锗，用于转化，这些已经显示 具有改善催化活性和选择性的1050°F +重料和残渣的材料的加氢转化。 描述了用于制备这种催化剂的新方法，以及使用这种催化剂。 一种催化剂，即在100-275A孔径范围内具有包括大量孔的特性的催化剂，特别适合作为第一级催化剂，另一种具有包括大量孔的性质 100-200A孔径直径，特别适用于用于处理所述第一阶段的流出物的第二阶段催化剂。

公开(公告)号：US3977962A

公开(公告)日：1976-08-31

申请号：US533299

申请日：1974-12-16

Applicant: William F. Arey, Jr. ,  Glen P. Hamner ,  Willard H. Sawyer

Inventor： William F. Arey, Jr. ,  Glen P. Hamner ,  Willard H. Sawyer

IPC: B01J23/74 ,  B01J23/85 ,  B01J35/10 ,  B01J37/00 ,  C10G45/08 ,  C10G13/02 ,  B01J27/04 ,  C10G34/00

CPC classification number: C10G45/08 ,  B01J23/74 ,  B01J23/85 ,  B01J35/10 ,  B01J37/0009 ,  B01J35/1019 ,  B01J35/1042 ,  B01J35/1047 ,  B01J35/1061

Abstract: 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.

Abstract translation: 本发明涉及两种不同类型的新型催化剂，其可用于重质原油和残余物中所含的1050°F +烃材料的催化加氢转化，使得所得产物将适用于常规精炼操作中的进一步加工，从而使 清洁液体产品。 使用包括VIB族和VIII族金属的催化剂，优选以混合物形式，优选包括具有特定临界范围物理特性（包括大的均匀孔径）的IVA族金属，特别是锗，用于转化，这些已经显示 具有改善催化活性和选择性的1050°F +重料和残渣的材料的加氢转化。 描述了用于制备这种催化剂的新方法，以及用于这种催化剂的方法。 一种催化剂，即在100-275A孔径范围内具有包括大量孔的特性的催化剂，特别适合作为第一级催化剂，另一种具有包括大量孔的性质 100-200A孔径直径，特别适用于用于处理所述第一阶段的流出物的第二阶段催化剂。