CN1552802A - Cracking assistants with desulfurizing function and preparing method thereof - Google Patents

Cracking assistants with desulfurizing function and preparing method thereof Download PDF

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CN1552802A
CN1552802A CN 03137907 CN03137907A CN1552802A CN 1552802 A CN1552802 A CN 1552802A CN 03137907 CN03137907 CN 03137907 CN 03137907 A CN03137907 A CN 03137907A CN 1552802 A CN1552802 A CN 1552802A
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metal
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zeolite
metals
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CN1234804C (en )
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刘宇键
龙军
朱玉霞
田辉平
陈振宇
郭瑶庆
张久顺
何鸣元
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中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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Abstract

A desulfurizing cracking auxiliary consists of heat-resisting inorganic oxide 2 - 68wt%, clay 30 - 80wt%, metal components 0.1 - 30wt%, and molecular sieves 0 - 40wt%. The metal components are selected from IIIA family but Al, IVA family, VA family, IB family, IIB family, VB family, VIB family, VIIB family and metals of VIIIB family but nobles, one or more. It has higher desulfurizing activity. Catalysts, containing it and cracking auxiliary mixture, will have higher cracking activity.

Description

一种具有脱硫作用的裂化助剂及其制备方法 Cracking method with additives and preparing a desulfurization

技术领域 FIELD

本发明是关于一种助剂及其制备方法,更具体地说是关于一种具有脱硫作用的裂化助剂及其制备方法。 The present invention relates to a method for preparing adjuvant and, more particularly cracking aid and to a method of preparation having the desulfurization.

背景技术 Background technique

近年来,出于环保的考虑,在世界范围内,对燃料油标准的要求不断提高。 In recent years, for environmental reasons, in the world, demand for fuel oil standards continue to improve. 以中国为例,1999年国家质量监督局制定了“车用汽油有害物质控制标准”,按照该标准的要求,成品汽油的硫含量应小于800ppm。 China, for example, the 1999 National Quality Supervision Bureau to develop a "motor gasoline hazardous substances control standards", in accordance with the requirements of the standard, the sulfur content of the finished gasoline should be less than 800ppm. 实际上,成品汽油90%以上的硫来自于FCC汽油,另一方面,具有较高硫含量的中东原油在中国炼厂所占原油中的比重越来越大,因此,降低FCC汽油中的硫含量对生产清洁汽油至关重要。 Indeed, more than 90% of the finished gasoline sulfur from the FCC gasoline, on the other hand, the proportion of Middle East crude oil having a high sulfur content in crude oil in China refineries share increasing, thereby reducing sulfur in gasoline FCC In gasoline is essential for production.

目前,可通过对原料油进行加氢预处理,或对FCC汽油进行加氢后精制来达到降低FCC汽油中硫的目的。 Currently, the feedstock may be by hydrotreating, or post-hydrotreated FCC gasoline to achieve the objective of reducing sulfur in FCC gasoline. 然而,这两种方法投资大,操作费用高,还会使汽油中的烯烃部分加氢,造成辛烷值的损失。 However, both methods of investment, high operating costs, but also the partial hydrogenation of olefins in gasoline, resulting in the loss of octane.

为了降低汽油中烯烃的部分加氢,减少辛烷值的损失,近年来,美国菲利浦石油公司(Phillips Petroleum Company)开发了一系列用于脱除裂化汽油和柴油燃料中硫的吸附剂和脱除裂化汽油和柴油燃料中硫的方法。 To reduce the partial hydrogenation of olefins in gasoline, reduced octane loss, in recent years, U.S. Phillips Petroleum Company (Phillips Petroleum Company) developed a series of adsorbents for the removal of cracked gasoline and diesel fuel sulfur and method for removing cracked gasoline and diesel fuel sulfur.

CN1355727A及其同族专利US6,254,766B1公开了一种用于从裂化汽油和柴油机燃料中脱除硫的吸附剂组合物及从裂化汽油和柴油机燃料流中脱除硫的方法。 CN1355727A and its patent family US6,254,766B1 discloses a method for removal of sulfur from cracked gasoline and diesel fuel in the adsorbent compositions and methods for removing sulfur from cracked gasoline and diesel fuel stream. 该吸附剂组合物由氧化锌、氧化硅、氧化铝和镍组成,所述镍基本上以还原价态存在,其存在的量能在脱硫条件下,从裂化汽油或柴油机燃料中脱除硫。 The sorbent composition of zinc oxide, silicon oxide, aluminum and nickel, said nickel in a substantially reduced valence state is present, can be present in an amount, removal of sulfur from cracked gasoline or diesel fuel under desulfurization conditions. 所述从裂化汽油和柴油机燃料流中脱除硫的方法包括使裂化汽油和柴油机燃料流与所述吸附剂组合物接触,形成裂化汽油或柴油机燃料的脱硫流体和硫化吸附剂,分离出脱硫后的裂化汽油或柴油机燃料。 The method of removal of sulfur from cracked gasoline and diesel fuel stream comprising cracked gasoline and diesel fuel stream with the sorbent composition is contacted to form a desulfurized fluids and sulfurized sorbent cracked gasoline or diesel fuel, separating the desulfurized the cracked gasoline or diesel fuel.

CN1382071A及其同族专利US6,184,176B1公开了一种用于从裂化汽油和柴油机燃料中脱除硫的吸附剂组合物及从裂化汽油和柴油机燃料流中脱除硫的方法。 CN1382071A and its patent family US6,184,176B1 discloses a method for removal of sulfur from cracked gasoline and diesel fuel in the adsorbent compositions and methods for removing sulfur from cracked gasoline and diesel fuel stream. 该吸附剂组合物由氧化锌、氧化硅、氧化铝和钴组成,所述钴基本上以还原价态存在,其存在的量能在脱硫条件下,从裂化汽油或柴油机燃料中脱除硫。 The sorbent composition of zinc oxide, silica, alumina and cobalt, the cobalt valence state to substantially exist, can be present in an amount, removal of sulfur from cracked gasoline or diesel fuel under desulfurization conditions. 所述从裂化汽油和柴油机燃料流中脱除硫的方法包括使裂化汽油和柴油机燃料流与所述吸附剂组合物接触,形成裂化汽油或柴油机燃料的脱硫流体和硫化吸附剂,分离出脱硫后的裂化汽油或柴油机燃料。 The method of removal of sulfur from cracked gasoline and diesel fuel stream comprising cracked gasoline and diesel fuel stream with the sorbent composition is contacted to form a desulfurized fluids and sulfurized sorbent cracked gasoline or diesel fuel, separating the desulfurized the cracked gasoline or diesel fuel.

CN1384770A及其同族专利US6,271,173B1公开了一种用于从裂化汽油和柴油机燃料中脱除硫的吸附剂组合物及从裂化汽油和柴油机燃料流中脱除硫的方法。 CN1384770A and its patent family US6,271,173B1 discloses a method for removal of sulfur from cracked gasoline and diesel fuel in the adsorbent compositions and methods for removing sulfur from cracked gasoline and diesel fuel stream. 该吸附剂组合物由负载于载体组合物上的促进剂金属组成,所述载体组合物由氧化锌、氧化硅、氧化铝和钙化合物组成,所述钙化合物为硫酸钙、铝酸钙、磷酸钙或硅酸钙;所述促进剂金属基本上以还原价态存在,还原价态促进剂金属的量能在脱硫条件下,从裂化汽油或柴油机燃料中脱除硫。 The sorbent composition of promoter metal supported on a carrier consisting of a composition, the carrier composition of zinc oxide, silica, alumina and calcium compounds, the calcium compound is calcium sulfate, calcium aluminate, phosphate or calcium silicate; substantially the promoter metal is present in valence state, the amount of reduced-valence metals capable of promoting, removal of sulfur from cracked gasoline or diesel fuel under desulfurization conditions. 所述从裂化汽油和柴油机燃料流中脱除硫的方法包括使裂化汽油和柴油机燃料流与所述吸附剂组合物接触,形成裂化汽油或柴油机燃料的脱硫流体和硫化吸附剂,分离出脱硫后的裂化汽油或柴油机燃料。 The method of removal of sulfur from cracked gasoline and diesel fuel stream comprising cracked gasoline and diesel fuel stream with the sorbent composition is contacted to form a desulfurized fluids and sulfurized sorbent cracked gasoline or diesel fuel, separating the desulfurized the cracked gasoline or diesel fuel.

CN1382201A及其同族专利US6,338,794B1公开了一种用于从裂化汽油和柴油机燃料中脱除硫的吸附剂组合物及从裂化汽油和柴油机燃料流中脱除硫的方法。 CN1382201A and its patent family US6,338,794B1 discloses a method for removal of sulfur from cracked gasoline and diesel fuel in the adsorbent compositions and methods for removing sulfur from cracked gasoline and diesel fuel stream. 该吸附剂组合物由钛酸锌载体和金属、金属氧化物或金属氧化物前体促进剂组成,所述金属是钴、镍、铁、锰、铜、钼、钨、银、锡、钒或其中任意两种或多种的混合物,所述促进剂金属基本上以还原价态存在,还原价态金属促进剂存在的量能在脱硫条件下,从裂化汽油或柴油机燃料中脱除硫。 The sorbent composition of zinc titanate and a metal support, a metal oxide or metal oxide precursor promoter composition, the metal is cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin, vanadium, or wherein any two or more thereof, the promoter metal in a substantially reduced valence state is present, the presence of the valence state of the metal promoter the amount of energy, removal of sulfur from cracked gasoline or diesel fuel under desulfurization conditions. 所述从裂化汽油和柴油机燃料流中脱除硫的方法包括使裂化汽油和柴油机燃料流与所述吸附剂组合物接触,形成裂化汽油或柴油机燃料的脱硫流体和硫化吸附剂,分离出脱硫后的裂化汽油或柴油机燃料。 The method of removal of sulfur from cracked gasoline and diesel fuel stream comprising cracked gasoline and diesel fuel stream with the sorbent composition is contacted to form a desulfurized fluids and sulfurized sorbent cracked gasoline or diesel fuel, separating the desulfurized the cracked gasoline or diesel fuel.

CN1382199A及其同族专利US6,274,533B1公开了一种用于从裂化汽油和柴油机燃料中脱除硫的吸附剂组合物及从裂化汽油和柴油机燃料流中脱除硫的方法。 CN1382199A and its patent family US6,274,533B1 discloses a method for removal of sulfur from cracked gasoline and diesel fuel in the adsorbent compositions and methods for removing sulfur from cracked gasoline and diesel fuel stream. 该吸附剂组合物由双金属促进剂和颗粒状载体组成,所述双金属促进剂基本上以还原价态存在,其存在的量能在脱硫条件下,从裂化汽油或柴油机燃料中脱除硫。 The sorbent composition of bimetallic promoter and a particulate carrier composed of said bimetallic promoter in a substantially reduced valence state is present, can be present in an amount, removal of sulfur from cracked gasoline or diesel fuel under desulfurization conditions . 所述双金属促进剂选自钴、镍、铁、锰、铜、锌、钼、钨、银、锡、锑或钒的任意两种或多种的混合物。 The dual metal promoter is selected from cobalt, nickel, any two of iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony or vanadium or more thereof. 所述载体由与任何适用的无机和有机载体组合的氧化锌组成。 The carrier consists of zinc oxide, and any combination of suitable inorganic carriers and organic composition. 所述无机载体包括氧化硅、硅胶、氧化铝、粘土、硅酸铝、氧化硅-氧化铝、氧化钛、氧化锆、铝酸锌、钛酸锌、硅酸锌、铝酸钙、硅酸钙、硅酸镁、铝酸镁、钛酸镁、合成沸石和天然沸石。 The inorganic support include silica, silica gel, alumina, clay, aluminum silicate, silica - alumina, titania, zirconia, zinc aluminate, zinc titanate, zinc silicate, calcium aluminate, calcium silicate , magnesium silicate, magnesium aluminate, magnesium titanate, natural zeolites and synthetic zeolites. 所述从裂化汽油和柴油机燃料流中脱除硫的方法包括使裂化汽油和柴油机燃料流与所述吸附剂组合物接触,形成裂化汽油或柴油机燃料的脱硫流体和硫化吸附剂,分离出脱硫后的裂化汽油或柴油机燃料。 The method of removal of sulfur from cracked gasoline and diesel fuel stream comprising cracked gasoline and diesel fuel stream with the sorbent composition is contacted to form a desulfurized fluids and sulfurized sorbent cracked gasoline or diesel fuel, separating the desulfurized the cracked gasoline or diesel fuel.

US6,346,190B1公开了一种用于从裂化汽油和柴油机燃料中脱除硫的吸附剂组合物及从裂化汽油和柴油机燃料流中脱除硫的方法。 US6,346,190B1 discloses a method for removal of sulfur from cracked gasoline and diesel fuel in the adsorbent compositions and methods for removing sulfur from cracked gasoline and diesel fuel stream. 该吸附剂组合物基本上由铁酸锌、镍和一种无机粘结剂组成,所述铁酸锌和镍以还原价态存在,其存在的量能在脱硫条件下,从裂化汽油或柴油机燃料中脱除硫。 The sorbent composition of zinc ferrite, nickel, and consisting essentially of an inorganic binder, and nickel-zinc ferrite in the valence state is present, it can be present in an amount in the desulfurization conditions, from cracked gasoline or diesel removal of sulfur in the fuel. 所述无机粘结剂可以是氧化硅、氧化铝、胶泥、粘土。 The inorganic binder may be silica, alumina, clay, clay. 以所述组合物总量为基准,氧化锌的含量为2-70重量%,氧化铁的含量为3-70重量,所述粘结剂的含量为0.1-30重量%,镍的含量为1-50重量%。 The total amount of the composition, the content of zinc oxide is 2-70 wt%, iron oxide content is 3-70 by weight of the binder content of 0.1 to 30 wt%, a nickel content -50% by weight.

WO 02/18517A1公开了一种用于从裂化汽油和柴油机燃料中脱除硫的吸附剂组合物及从裂化汽油和柴油机燃料流中脱除硫的方法。 WO 02 / 18517A1 discloses a method for removal of sulfur from cracked gasoline and diesel fuel in the adsorbent compositions and methods for removing sulfur from cracked gasoline and diesel fuel stream. 该吸附剂组合物含有一种载体组分、一种抗磨组分和一种促进剂组分,所述促进剂组分基本上以还原价态存在,其存在的量能在脱硫条件下,从裂化汽油或柴油机燃料中脱除硫。 The sorbent composition contains a support component, one component and a promoter component wear, the promoter component is substantially reduced valence state to exist, the amount of energy is present in the desulfurization conditions, removal of sulfur from cracked gasoline or diesel fuel. 所述载体包括氧化锌及任何合适的无机和有机载体。 The carrier comprises zinc oxide, and any suitable inorganic and organic vehicle. 无机载体包括氧化硅、硅胶、氧化铝、硅藻土、膨胀珍珠岩、氧化硅-氧化铝、氧化钛、氧化锆、铝酸锌、钛酸锌、硅酸锌、铝酸镁、钛酸镁、合成沸石、天然沸石及他们的结合。 Inorganic support include silica, silica gel, alumina, diatomaceous earth, perlite, silica - alumina, titania, zirconia, zinc aluminate, zinc titanate, zinc silicate, magnesium aluminate, magnesium titanate , synthetic zeolites, natural zeolites and their binding. 所述抗磨组分选自粘土、高铝水泥、天然水泥波特兰水泥,铝酸钙,硅酸钙,云母及它们的组合。 The wear component is selected from clay, alumina cement, natural cement Portland cement, calcium aluminate, calcium silicate, mica, and combinations thereof. 所述粘土包括斑脱石,钠型斑脱石,经酸洗的斑脱石,硅藻土,陶土,高岭土,蒙脱土,伊利石,埃洛石,锂蒙脱石,海泡石及其混合物。 The clays include bentonite rock, stone sodium type bentonite, nontronite pickled spots, diatomaceous earth, clay, kaolin, montmorillonite, illite, halloysite, hectorite, sepiolite and mixtures thereof. 所述促进剂组分包括钴、镍、铁、锰、铜、锌、钼、钨、银、锡、锑或钒及它们混合物。 The accelerator component comprises cobalt, nickel, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony or vanadium, and mixtures thereof. 所述抗磨组分的含量为1-30重量%,促进剂组分含量为5-50重量%。 The content of the antiwear component is 30% by weight, component content of 5-50% by weight accelerator. 所述载体组分优选含有氧化锌,氧化锌的含量为10-90重量%。 The support component preferably comprising zinc oxide, zinc oxide content of 10-90% by weight. 所述载体组分更优选含有氧化锌、氧化硅和氧化铝,氧化硅的含量为5-85重量%,氧化铝含量为0.1-30重量%。 The more preferred support component comprising zinc oxide, silica and alumina, the silica content of 5-85% by weight, an alumina content of 0.1 to 30 wt%.

上述菲利浦石油公司公开的吸附剂,属于裂化汽油和柴油燃料后精制所用的吸附剂,即它们处理的原料油是裂化汽油和柴油燃料。 Above adsorbent disclosed in Phillips Petroleum Company, it is used after purifying adsorbent cracked gasoline and diesel fuel, i.e., they deal with the feedstock oil is cracked gasoline and diesel fuels. 上述吸附剂中,沸石的含量没有给出,粘土的含量只有0.1-30重量%,这就使得所述吸附剂的比重较大,如果用作助剂,会造成裂化剂与助剂在反应器内混合不够均匀,脱硫效果不理想。 In the above adsorbent, the content of the zeolite is not given, only the content of 0.1-30 wt% of the clay, making a large proportion of the adsorbent, if used as additives, will cause cracking in the reactor with the adjuvants agent mixing not uniform, the desulfurization effect is not ideal.

在FCC提升管内,通过催化裂化的方法,将硫原位脱除是经济上最具有吸引力的技术途径。 Within the FCC riser, by means of catalytic cracking, in situ sulfur removal technology is the most economically attractive way. 为达到这一目的,需要在催化裂化过程中添加具有脱硫功能的助助剂,或者使用具有脱硫功能、含有脱硫组分的助剂。 To achieve this, it is necessary to add the co-additives in the catalytic cracking process having a desulfurization function, or having a desulfurization function, comprising desulfurization aid component.

US6,036,847及其同族专利EP0,798,362A2公开了一种烃类流化催化裂化方法,其中,所述烃类进料在不存在外加氢的条件下,在一个裂化区被裂化,并且包括助剂颗粒的所有颗粒不断在烃类裂化区和一个助剂再生区循环,其中,所有颗粒中含有另外一种颗粒,该颗粒具有比助剂颗粒较低的裂化烃油的活性,所述活性以新鲜颗粒为基准。 US6,036,847 patent family and EP0,798,362A2 discloses a fluid catalytic cracking process of hydrocarbons, wherein the hydrocarbon feed in the absence of the hydrotreatment conditions, is cracked in a cracking zone, and comprising all particles in the builder granules continuously hydrocarbon cracking zone and a regeneration zone aids cycle, wherein all the particles contain another particle, the particles have a lower activity than the builder granules cracking of hydrocarbon oils, the active fresh granules as a reference. 该颗粒基本上由氧化钛和一种非氧化钛的无机氧化物组成。 The titanium oxide particles consist essentially of an inorganic oxide and a non-titanium oxide composition. 所述非氧化钛的无机氧化物含有一种Lewis酸,该Lewis酸选自下列的元素及其化合物组成的一组:镍、铜、锌、银、镉、铟、锡、汞、铊、铅、铋、硼、铝(非氧化铝)和锗,所述Lewis酸负载在氧化铝上。 The non-titanium oxide contains an inorganic Lewis acid, the Lewis acid is selected from a group consisting of elements and their compounds consisting of: nickel, copper, zinc, silver, cadmium, indium, tin, mercury, thallium, lead , bismuth, boron, aluminum (non-alumina) and germanium, the Lewis acid supported on alumina. 由于使用这种含氧化钛的助剂,裂化产物FCC汽油中硫含量得到降低。 The use of this titanium oxide-containing additives, FCC cracked gasoline sulfur content in the product is reduced.

US5,376,608公开了一种具有脱硫作用的助剂组合物,该组合物含有(A)分散在一种无机氧化物基质中的沸石/分子筛,(b)含Lewis酸的氧化铝组分,该氧化铝组分含有1-50重量%的Lewis酸,所述Lewis酸选自负载在氧化铝上的含有镍、铜、锌、银、镉、铟、锡、汞、铊、铅、铋、硼、铝(非氧化铝)和镓的元素和氧化物的一组。 US5,376,608 discloses an adjuvant composition having a desulfurization effect, the composition comprising (A) dispersed in an inorganic oxide matrix zeolite / molecular sieve, (b) a Lewis acid-containing alumina component, which alumina component comprises 1-50% by weight of a Lewis acid, the Lewis acid is selected from supported on alumina containing nickel, copper, zinc, silver, cadmium, indium, tin, mercury, thallium, lead, bismuth, boron , a group of aluminum (non-alumina) and elements and gallium oxide.

WO 99/49001A1公开了一种降低烃类组分中硫含量的组合物,该组合物含有一种类水滑石(hydrotalcite)材料,该材料用一种Lewis酸浸渍过,该组合物中还可以含有一种FCC助剂。 WO 99 / 49001A1 discloses a method for reducing the sulfur content of hydrocarbon components in the composition, the composition comprises a hydrotalcite (hydrotalcite) material which is impregnated with one Lewis acid, the composition may also contain one kind FCC additives. 所述Lewis酸包括过渡金属,特别是锌、铜、镍、钴、铁和锰的元素和化合物。 The Lewis acid comprises a transition metal, in particular zinc, copper, nickel, cobalt, iron and manganese elements and compounds.

WO 01/21733A1公开了一种在热再生助剂存在下,含有有机硫化合物烃类原料的催化裂化方法,所述助剂含有一种降低产物硫的组分,该组分含有一种氧化态大于零的金属组分,所述金属组分包括元素周期表第3周期,VB族,VIIB族,VIII族,IIB族,IVA族的金属化合物或络合物,如钒,锌,铁,钴,锰和镓的金属化合物或络合物。 WO 01 / 21733A1 discloses a thermal regeneration in the presence of auxiliaries, organic sulfur compounds containing a catalytic cracking hydrocarbon feedstock, the adjuvant contains a product sulfur reduction component, the component comprising an oxidized form greater than zero the metal component, the metal component comprises a metal compound or complex of the third cycle of the Periodic Table, VB group, VIIB group, VIII group, IIB group, IVA group, such as vanadium, zinc, iron, cobalt , manganese and gallium metal compounds or complexes. 所述降低产物硫的组分包括孔结构内含有上述金属组分的分子筛,也包括分散在助剂载体任意位置,如多孔氧化物载体中的上述金属组分。 The product sulfur reduction component comprising a molecular sieve containing the metal component within the pore structure, including any position adjuvants dispersed in a carrier, such as the above-described porous metal oxide carrier component.

WO 01/21732A1公开了一种降低裂化石油馏分中硫含量的方法,该方法包括在提高的温度和一种助剂及一种降低产品硫含量的助剂存在下,将石油馏分催化裂化,得到具有较低硫含量的液体裂化产物。 WO 01 / 21732A1 discloses a method of reducing the sulfur content of cracked petroleum fraction, the method comprising at elevated temperature and the presence of an adjuvant and additives for reducing the sulfur content of catalytic cracking of petroleum fractions to give having a low sulfur content of liquid cracking products. 其中,所述降低产品硫含量的助剂含有一种含钒非分子筛载体,所述非分子筛载体可以是有机或无机载体,优选的载体是无定形或次晶无机氧化物,如氧化铝,氧化硅,粘土或它们的混合物。 Wherein said auxiliary reducing the sulfur content of the product contains a non-vanadium-containing molecular sieve support, a non-molecular sieve support may be an organic or inorganic carrier, preferably the carrier is an amorphous or paracrystalline inorganic oxide such as aluminum oxide, silica, clay or mixtures thereof.

CN1281887A公开了一种降低催化裂化石油馏分硫含量的方法,该方法包括在高温和产品脱硫助剂存在下,催化裂化石油原料馏分,制备低硫含量的液态裂化产品。 CN1281887A discloses a method of reducing the sulfur content of catalytic cracking of petroleum fractions, which comprises a high temperature desulfurization products and aids are present, cracking petroleum feedstock distillates, low-sulfur liquid preparation of cracked products. 该脱硫助剂含有一种孔状结构内部含有金属成分的多孔分子筛。 The desulfurization aid comprising a porous internal structure having a pore zeolite containing a metal component. 所述多孔分子筛可以是大孔沸石,即孔口直径至少为0.7纳米的沸石,如Y型沸石、稀土Y型沸石(REY)、超稳Y型沸石(USY)、L沸石、Beta沸石、丝光沸石、ZSM-18沸石。 The porous molecular sieve may be a large pore zeolite, i.e., the aperture diameter of at least 0.7 nm zeolites such as zeolite Y, rare earth Y zeolite (REY), ultrastable zeolite Y (USY), L zeolite, zeolite Beta, mordenite, zeolite, ZSM-18 zeolite. 所述分子筛也可以是中孔沸石,即孔口直径为大于0.56而小于0.7纳米的沸石,如Pentasil沸石、ZSM-5沸石、ZSM-22、ZSM-23沸石、ZSM-35沸石、ZSM-50沸石、ZSM-57沸石、MCM-22沸石、MCM-49沸石、MCM-56沸石。 The molecular sieve may also be a medium pore zeolite, i.e., larger than the orifice diameter of 0.56 and less than 0.7 nm, a zeolite, such as Pentasil zeolites, ZSM-5 zeolite, ZSM-22, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, MCM-56 zeolite. 所述分子筛还可以是非沸石分子筛,如具有不同硅铝比的硅酸盐(如金属硅酸盐metallosilicate。钛硅酸盐titanosilicate)、金属铝酸盐metalloaluminates(如锗铝酸盐Germaniumaluminates)、金属磷酸盐metallophosphates、铝磷酸盐aluminophosphates、金属铝磷酸盐metalloaluminophosphates、金属结合的硅铝磷酸盐metal integrated silicoaluminophosphates(MeAPSO和ELAPSO)、硅铝酸盐silicoaluminophosphates(SAPO)、镓锗酸盐(gallogermanates)及它们的结合。 The molecular sieve may also be a non-zeolitic molecular sieves, silicates such as having different silica to alumina ratio (e.g. metallosilicate metallosilicate. Titanosilicate titanosilicate), metal aluminates metalloaluminates (e.g. germanium aluminates Germaniumaluminates), a metal phosphate salts metallophosphates, aluminophosphates aluminophosphates, metalloaluminophosphates metalloaluminophosphates, metal binding silicoaluminophosphate metal integrated silicoaluminophosphates (MeAPSO and ELAPSO), aluminosilicates silicoaluminophosphates (SAPO), gallium germanate (gallogermanates), and combinations thereof .

CN1261618A公开了一种催化裂化石油馏分的脱硫方法,该方法包括在高温、助剂和产物脱硫助剂的存在下,将含有有机硫化合物的石油原料馏分催化裂化,生产低硫含量的液体裂化产物。 CN1261618A discloses a catalytic cracking desulfurization of petroleum fractions, which comprises a high temperature, the presence of auxiliaries and additives in the desulfurization product, containing the catalytic cracking of petroleum feed fraction of the organic sulfur compound, producing a liquid sulfur content of cracked products . 所述的产物脱硫助剂含有一种多孔分子筛,该分子筛含有第一金属组分和第二金属组分,第一金属组分位于分子筛孔结构内部并且氧化态大于零,第二金属组分包括位于分子筛孔结构内部的至少一种稀土元素。 The product was a porous desulfurizing aid comprising a molecular sieve comprising a first metal component and second metal component, a first metal component located inside the zeolite pore structure and the oxidation state greater than zero, the second metal component comprises located inside the zeolite pore structure is at least one rare earth element. 所述第一种金属组分选自元素周期表第四周期及IIB、VB、IIIA、VIII族的金属,特别是钒、锌、铁、镓。 The first metal component is selected from the fourth period of the Periodic Table and IIB, VB, IIIA, VIII group metals, especially vanadium, zinc, iron, gallium.

上述助剂在制备过程中都经过干燥、焙烧和/或水热处理,没有还原过程,上述助剂中所含的金属组分均以其最高氧化态存在。 In the above-described manufacturing process aids have been drying, calcination and / or hydrothermal treatment, no reduction process, the metal component contained in the above-described additives are present in its highest oxidation state.

本发明的目的是提供一种新的、具有更强的脱硫能力的具有脱硫作用的裂化助剂。 Object of the present invention is to provide a new, more desulfurization capacity cracking additives have a desulfurization effect.

本发明提供的助剂含有一种耐热无机氧化物、粘土和一种金属组分,含或不含分子筛,其中,以助剂总量为基准,耐热无机氧化物的含量为2-68重量%,粘土的含量为大于30至80重量%,分子筛的含量为0-40重量%,以所述最高价态的金属氧化物计,金属组分的含量为0.1-30重量%,所述金属组分以还原价态存在,它选自元素周期表IIIA族非铝金属、IVA族金属、VA族金属、IB族金属、IIB族金属、VB族金属、VIB族金属、VIIB族金属、VIII族非贵金属中的一种或几种。 Aid of the present invention provides a heat-resistant inorganic oxide comprising, clay and one metal component, with or without a molecular sieve, wherein the total amount of auxiliaries, the content of the thermotolerant inorganic oxide is 2-68 % by weight, clay content of greater than 30 to 80 wt%, the content of zeolite is 0-40 wt%, based on the content of the highest valency state metal oxides, the metal component is 0.1-30 wt%, the valence state metal component is present, selected from non-aluminum metal of the Periodic Table group IIIA, IVA metals, VA metals, IB metals, IIB metals, VB metals, VIB metals, VIIB metals, VIII group one or more non-noble metals.

本发明提供的助剂的制备方法包括将含有金属组分化合物、耐热无机氧化物和粘土,含或不含分子筛的组合物与一种含有还原气体的气氛接触,所述接触的温度和接触的时间足以使所述金属组分的平均价态低于其最高氧化态,所述金属选自元素周期表IIIA族非铝金属、IVA族金属、VA族金属、IB族金属、IIB族金属、VB族金属、VIB族金属、VIIB族金属、VIII族非贵金属中的一种或几种,组合物中各组分的含量使最终助剂中含有,以助剂总量计,2-68重量%的耐热无机氧化物,大于30-80重量%的粘土,以最高价态金属的氧化物计,0.1-30重量%的金属组分,0-40重量%的分子筛。 The method of preparation of the present invention to provide aids include compounds containing a metal component, the heat-resistant inorganic oxide and clay, with or without molecular sieve composition with an atmosphere containing a reducing gas, the contact temperature and the contact a time sufficient to allow the average valence state of the metal component is less than its highest oxidation state, the metal is selected from non-aluminum metal group IIIA, IVA metals, VA metals, IB metals, IIB metals of the Periodic Table, group VB metal, a content of each component of group VIB metals, VIIB metals, one or more non-noble metal of group VIII, such that the final composition contain adjuvants, additives to the total count, 2-68 wt. % of the thermotolerant inorganic oxide, greater than 30 to 80 wt% of clay, calculated as the oxide in the highest valence state of the metal, from 0.1 to 30 wt% of metal component, 0-40 wt% of molecular sieve.

与现有技术相比,本发明提供的助剂具有更高的脱硫活性。 Compared with the prior art, the present invention provides adjuvant having a higher desulfurization activity. 例如,采用氧化铝的含量为45.0重量%,高岭土的含量为49.0重量%,以Co2O3计,钴含量为5.0重量%,钴的平均价态为0至+1.5(钴的平均价态为与钴的最高价态的比值为0-0.5),采用不同方法制备的,所述金属组分分布在助剂中或粘土中的本发明提供的助剂与工业牌号为HGY-2000R的工业催化裂化催化剂混合物(混合物中,本发明提供的助剂的含量为5.0重量%,工业催化裂化催化剂的含量为95.0重量%),在反应温度为480℃,重时空速为16小时-1,剂油重量比为6.0的条件下,对硫含量为2.0重量%,馏程为329-550℃的的减压蜡油进行催化裂化,转化率高达70.9-71.8重量%,汽油产物中的硫含量只有603.2-615毫克/升。 For example, the alumina content of 45.0 wt%, the content of kaolin was 49.0 wt%, based on the count Co2O3, 5.0 wt% cobalt content, the cobalt average valence of +1.5 to 0 (average valence state of the cobalt and cobalt the ratio of the highest valence 0 to 0.5), using a different method of preparation, the metal component distribution aids and industrial grade clay in aid of the present invention to provide HGY-2000R or industrial catalytic cracking catalyst the mixture (the mixture, the content of the present invention to provide aids 5.0 wt%, the content of industrial FCC catalyst was 95.0 wt%), at a reaction temperature of 480 deg.] C, a weight hourly space velocity of 16 hr -1, a catalyst to oil weight ratio of under the conditions of 6.0, sulfur content of 2.0 wt%, a distillation range of 329-550 deg.] C in vacuum gas oil catalytic cracking, the conversion rate of up to 70.9-71.8 wt%, sulfur content of gasoline product is only 603.2-615 mg / l. 而采用各组分含量相同,只是钴的价态为其最高价态(+2价)的,不同方法制备的参比助剂与HGY-2000R的催化裂化催化剂混合物,在相同的条件下,对相同的原料油进行催化裂化,转化率只有66.9-67.3重量%,汽油产物中的硫含量高达753.8-765.2毫克/升。 The use of the same content of each component, but its highest valence state cobalt valence (+2), the reference aid of different methods of cracking catalyst mixture HGY-2000R and under the same conditions, catalytic cracking of the same feedstock oil, the conversion rate of only 66.9-67.3 wt%, a sulfur content of up to gasoline product 753.8-765.2 mg / l.

又例如,采用氧化铝的含量为20.2重量%,高岭土的含量为37.0重量%,MOY沸石含量为35.0重量%,以氧化物计,银和钼含量为7.8重量%,银的的平均价态为0(银的平均价态为与银的最高价态的比值为0),钼的平均价态为3.3(钼的平均价态为与钼的最高价态的比值为0.55)的本发明提供的助剂与工业牌号为HGY-2000R的工业催化裂化催化剂混合物(混合物中,本发明提供的助剂的含量为10重量%,工业裂化催化剂的含量为90重量%),在反应温度为520℃,重时空速为16小时-1,剂油重量比为3.5的条件下,对硫含量为2.0重量%,馏程为329-550℃的减压蜡油进行催化裂化,转化率高达76.3重量%,汽油产物中的硫含量只有589.3毫克/升。 As another example, the alumina content of 20.2 wt%, the content of 37.0 wt% kaolin, zeolite content of 35.0 wt% MOY, in terms of oxide, silver and molybdenum content of 7.8 wt%, average valence state of the silver 0 (average valence silver state is the ratio of silver is the highest valence state of 0), the average valence of molybdenum state is 3.3 (average valence of molybdenum state with the ratio of molybdenum highest valency 0.55) of the present invention provides with the aid of a catalyst mixture of industrial grade industrial FCC HGY-2000R (the mixture of the present invention provides the content of 10% by weight auxiliaries, industrial cracking catalyst content of 90 wt%), at a reaction temperature of 520 ℃, weight hourly space velocity of 16 hr -1, a catalyst to oil weight ratio of 3.5 under the condition of 2.0 wt% sulfur content, distillation range of 329-550 ℃ VGO catalytic cracking, the conversion rate as high as 76.3% by weight, the sulfur content in the gasoline product is only 589.3 mg / l. 而采用各组分含量相同,只是银和钼的价态为其最高价态的参比助剂,在相同的条件下,对相同的原料油进行催化裂化,转化率只有72.3重量%,汽油产物中的硫含量高达810.3毫克/升。 The use of the same content of each component, except the valence state of the silver and molybdenum as its highest valency state reference aids, under the same conditions, the same feedstock oil catalytic cracking, the conversion rate of only 72.3% by weight, gasoline product the sulfur content of up to 810.3 mg / liter.

具体实施方式 detailed description

按照本发明提供的助剂,以助剂总量为基准,所述耐热无机氧化物的含量优选为10-60重量%,粘土的含量优选为35-60重量%,分子筛的含量优选为0-30重量%,以所述最高价态的金属氧化物计,金属组分的含量为0.5-20重量%。 According to the present invention provides aid to the total amount of auxiliaries, the content of the heat-resistant inorganic oxide is preferably 10 to 60% by weight, clay content is preferably 35-60 wt%, zeolite content is preferably 0 30% by weight, content of metal oxides to the highest valency state of the metal component is 0.5 to 20 wt%. 优选情况下,以所述助剂的总量为基准,所述粘土和沸石的总含量为35-80重量%,优选为40-75重量%。 Preferably, the total amount of the adjuvant as a reference, the total content of the clays and zeolites are from 35 to 80 wt%, preferably 40-75 wt%.

所述还原价态指所述金属组分的平均价态为零价或高于零价并低于其最高氧化态。 The means the average valence of the metal component in the zero valence state or valence above zero and below its highest oxidation state. 优选情况下,所述金属组分的平均价态与其最高价态的比值为0-0.95,更优选情况下,该比值为0.1-0.7。 Preferably, the ratio of the average valence of the metal components to their highest valency state is from 0 to 0.95, more preferably where the ratio was 0.1 to 0.7.

这里所述金属组分的最高价态是指经充分氧化后,能稳定存在的金属氧化物中所述金属组分的最高氧化态。 Here the highest valency state metal component is the highest oxidation state of the metal oxide after full oxidation, can stably exist in the metal components. 例如,元素周期表IIIA族非铝金属的最高氧化态一般为+3价(如镓);IVA族金属的最高氧化态一般为+4价;VA族金属的最高氧化态一般为+5价;IB族金属的最高氧化态一般为+2价(如铜)或+1价(如银);IIB族金属的最高氧化态一般为+2价;VB族金属的最高氧化态一般为+5价;VIB族金属的最高氧化态一般为+6价;VIIB族金属的最高氧化态一般为+4价(如锰)或+7价(如铼);VIII族非贵金属的最高氧化态一般为+3价(如铁或钴)或+2价(如镍)。 For example, non-aluminum metal highest oxidation state of the Group IIIA of the Periodic Table generally +3 (such as gallium); highest oxidation state Group IVA metal is generally +4; highest oxidation state VA metals generally having a valence; the highest oxidation state of the group IB metal is generally divalent (e.g., copper) or a monovalent (e.g., silver); highest oxidation state group IIB metal is generally divalent; highest oxidation state group VB metals generally having a valence ; highest oxidation state group VIB metal generally +6; VIIB metals highest oxidation state +4 is generally (e.g., manganese), or +7 valency (e.g., rhenium); group VIII non-noble metals generally highest oxidation state + trivalent (e.g., iron or cobalt) or a divalent (e.g., nickel).

测定所述金属组分平均价态的方法如下:精确称取约0.4克助剂,放入TPD/R/O分析测试仪的样品池中,通入氢气含量为5体积%的氢气与氮气的混合气,氢气的流量为20毫升/分钟,将样品池以10℃/分钟的速度,从室温升温至1000℃,对样品池中的助剂进行程序升温还原,分别测定还原前和还原后助剂上金属组分的TPR特征峰,根据以下公式计算金属组分的平均价态: The method of determining the average valence of the metal components as follows: Accurately weigh about 0.4 grams aid, into TPD / R / O cell tester analytical sample, into the hydrogen content of 5% by volume of hydrogen and nitrogen mixed gas, hydrogen gas flow rate was 20 ml / min, the sample cell at a rate of 10 deg.] C / min from room temperature to 1000 ℃, to aid sample cell temperature programmed reduction, were measured before and after co-reducing and reducing wherein the agent TPR peak metal component, the metal component is calculated according to the average valence of the following formula:

βM=βM′-2f(A1-A)/N其中:βM为助剂中金属组分M的平均价态,βM′为助剂中金属组分M的最高价态;A为金属组分M以还原价态存在的助剂中金属组分M的TPR特征峰面积;A1为金属组分M以最高氧化态存在的助剂中金属组分M的TPR特征峰面积;N为助剂中金属组分M的含量(单位为摩尔);f为校正因子,其测定方法如下:精确称取约6.5毫克CuO放入上述TPD/R/O分析测试仪的样品池中,在上述条件下,测定CuO完全被还原的TPR特征峰面积K2,按还原反应的化学计量数计算耗氢量(摩尔)K1,f即为耗氢量与TPR特征峰面积之比,即f=K1/K2,f的单位为摩尔/TPR特征峰面积。 βM = βM'-2f (A1-A) / N where: βM aids highest valency state of the metal component M auxiliaries average valence of the metal component M, βM 'is; A is the metal component M in valence state in the presence of auxiliaries TPR characteristic peak area of ​​the metal component M; M is A1 is a metal component present in the highest oxidation state aids TPR characteristic peak area of ​​the metal component M; N to the metal promoter M content of the component (in moles); F is a correction factor, which is measured as follows: accurately weigh about 6.5 mg of CuO into said TPD / R / O analysis sample cell tester, under the above conditions, the measurement CuO completely reduced TPR characteristic peak area K2, according to the stoichiometry of the reduction reaction the hydrogen consumption is calculated (mol) K1, f is the hydrogen consumption and the peak area ratio of TPR characteristic, i.e., f = K1 / K2, f is in mol / TPR characteristic peak area.

由于每个金属的TPR特征峰的位置不同,因此,即使助剂中含有2种以上金属组分,也可以测定出每个金属组分的TPR特征峰。 Depending on the position of each characteristic peak metal TPR, therefore, even if the auxiliary agent contains two or more metal components can also be measured TPR peaks characteristic of each metal component.

所述金属组分选自元素周期表IIIA族非铝金属、IVA族金属、VA族金属、IB族金属、IIB族金属、VB族金属、VIB族金属、VIIB族金属、VIII族非贵金属中的一种或几种。 The metal component is selected from non-aluminum metal of the Periodic Table Group IIIA, IVA metals, VA metals, IB metals, IIB metals, VB metals, VIB metals, VIIB metals, VIII non-noble metal of group one or several. 所述IIIA族非铝金属包括镓、铟、铊。 The non-Group IIIA metal comprises aluminum, gallium, indium, thallium. 所述IVA族金属包括锗、锡、铅。 The Group IVA metals include germanium, tin, lead. 所述VA族金属包括锑、铋。 The Group VA metals include antimony, bismuth. 所述I B族金属包括铜、银。 The Group I B metals include copper, silver. 所述IIB族金属包括锌、镉。 The Group IIB metals comprise zinc, cadmium. 所述VB族金属包括钒、铌、钽。 The Group VB metals include vanadium, niobium, tantalum. 所述VIB族金属包括铬、钼、钨。 The Group VIB metals include chromium, molybdenum, tungsten. 所述VIIB族金属包括锰、锝、铼。 The Group VIIB metals include manganese, technetium, rhenium. 所述VIII族非贵金属包括铁、钴、镍。 The non-noble Group VIII include iron, cobalt, nickel. 所述金属组分优选为镓、锗、锡、锑、铋、铅、铜、银、锌、镉、钒、钼、钨、锰、铁、钴、镍中的一种或几种,更优选为镓、锡、铜、银、锌、钒、钼、锰、铁、钴中的一种或几种。 The metal component is preferably gallium, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, nickel, one or several, more preferably gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, cobalt, one or several.

所述金属组分可以同时存在于分子筛、耐热无机氧化物和粘土中,也可以存在于分子筛、耐热无机氧化物和粘土的任意两种中,还可以存在于分子筛、耐热无机氧化物和粘土的任意一种中。 The metal component may be present in the molecular sieve, thermotolerant inorganic oxide and clay simultaneously, may also be present in the molecular sieve, any two thermotolerant inorganic oxide and the clay, it may also be present in the molecular sieve, thermotolerant inorganic oxide and any one of the clay.

按照本发明一个具体的实施方案,所述金属组分,特别是当所述金属组分为钒、镍和/或铁时,存在于耐热无机氧化物和/或粘土中。 According to one particular embodiment of the invention, the metal component, particularly when the metal component is a vanadium, nickel and / or iron, present in the heat-resistant inorganic oxide and / or clay.

按照本发明另外一个具体的实施方案,所述金属组分,特别是当所述金属组分为铁时,存在于分子筛中。 According to a further particular embodiment of the invention, the metal component, particularly when the metal component is iron, present in the molecular sieve.

所述耐热无机氧化物选自用作现有催化裂化催化剂基质和粘结剂组分的耐热无机氧化物中的一种或几种,如氧化铝、氧化硅、无定型硅铝、氧化锆、氧化钛、氧化硼、碱土金属氧化物中的一种或几种。 As the heat-resistant inorganic oxide selected from one or more conventional heat-resistant inorganic oxide matrix and binder component of cracking catalyst in such as alumina, silica, amorphous silica-alumina oxide, one or more of zirconium, titanium, boron oxide, an alkaline earth metal oxide. 优选氧化铝、氧化硅、无定型硅铝、氧化锆、氧化钛、氧化镁、氧化钙中的一种或几种。 Preferably, alumina, silica, amorphous silica-alumina, zirconium oxide, titanium oxide, magnesium oxide, calcium oxide, one or several. 这些耐热无机氧化物为本领域技术人员所公知。 The heat-resistant inorganic oxide is known to those skilled in the art.

所述粘土选自用作助剂活性组分的粘土中的一种或几种,如高岭土、多水高岭土、蒙脱土、硅藻土、埃洛石、皂石、累托土、海泡石、凹凸棒石、水滑石、膨润土中的一种或几种。 The clay is selected from one or more clays as adjuvants in the active ingredient, such as kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite one or more stone, attapulgite, hydrotalcite, bentonite. 更优选的粘土为高岭土。 More preferred clay is kaolin. 这些粘土为本领域技术人员所公知。 These clays known to those skilled in the art.

所述分子筛选自用作助剂活性组分的沸石和非沸石分子筛中的一种或几种。 As the molecular sieve is selected from one or more zeolites and non-zeolitic molecular sieves aid of the active ingredient. 这些沸石和分子筛为本领域技术人员所公知。 These zeolites and molecular sieves are known to those skilled in the art.

所述沸石优选为大孔沸石和中孔沸石中的一种或几种。 The zeolite is preferably one or more large pore zeolite and medium pore zeolite. 所述大孔沸石为具有至少0.7纳米环开口的孔状结构的沸石,如八面沸石、L沸石、Beta沸石、Ω沸石、丝光沸石、ZSM-18沸石中的一种或几种,特别是Y型沸石、含磷和/或稀土的Y型沸石、超稳Y沸石、含磷和/或稀土的超稳Y沸石,Beta沸石中的一种或几种。 The large pore zeolite is a zeolite having a pore structure of the ring opening of at least 0.7 nm, such as faujasite, L zeolite, zeolite Beta, [Omega], mordenite, ZSM-18 zeolite is one or more, especially Y type zeolite containing phosphorus and / or rare earth Y zeolite, ultrastable Y zeolite, ultrastable Y zeolite containing phosphorus and / or rare earths, zeolite Beta is one or more.

所述中孔沸石为具有大于0.56纳米小于0.7纳米环开口的孔状结构的沸石,如具有MFI结构的沸石(如ZSM-5沸石),含磷和/或稀土的具有MFI结构的沸石(如含磷和/或稀土ZSM-5沸石,CN1194181A公开的含磷的具有MFI结构的沸石)、ZSM-22沸石、ZSM-23沸石、ZSM-35沸石、ZSM-50沸石、ZSM-57沸石、MCM-22沸石、MCM-49沸石、MCM-56沸石中的一种或几种。 The mesoporous zeolite is greater than 0.56 nanometer pore structure of zeolite is less than 0.7 nanorings opening, such as a zeolite (such as ZSM-5 zeolite) MFI structure, phosphorus and / or rare earth zeolite having an MFI structure (e.g. phosphorus and / or rare earth ZSM-5 zeolite, CN1194181A disclosed a phosphorus-containing zeolite having a MFI structure), ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM -22 zeolite, MCM-49 zeolite, MCM-56 zeolite is one or more.

所述非沸石分子筛指沸石中的铝和/或硅部分或全部被其它元素如磷、钛、镓、锗中的一种或几种取代的分子筛。 The non-zeolitic molecular sieve refers to aluminum in the zeolite and / or silicon is partially or completely other elements such as phosphorus, titanium, gallium, germanium substituted with one or more molecular sieves. 这些分子筛的实例包括具有不同硅铝比的硅酸盐(如金属硅酸盐metallosilicate、钛硅酸盐titanosilicate)、金属铝酸盐metalloaluminates(如锗铝酸盐Germaniumaluminates)、金属磷酸盐metallophosphates、铝磷酸盐aluminophosphates、金属铝磷酸盐metalloaluminophosphates、金属结合的硅铝磷酸盐metal integrated silicoaluminophosphates(MeAPSO和ELAPSO)、硅铝酸盐silicoaluminophosphates(SAPO)、镓锗酸盐(gallogermanates)中的一种或几种。 Examples of these molecular sieves include silicates having different silica to alumina ratio (e.g. metallosilicate metallosilicate, titanosilicate titanosilicate), metal aluminates metalloaluminates (e.g. germanium aluminates Germaniumaluminates), metal phosphate metallophosphates, aluminum phosphate salts aluminophosphates, metalloaluminophosphates metalloaluminophosphates, metal binding silicoaluminophosphate metal integrated silicoaluminophosphates (MeAPSO and ELAPSO), aluminosilicates silicoaluminophosphates (SAPO), gallium germanate (gallogermanates) of one or more. 特别是SAPO-17分子筛、SAPO-34分子筛和SAPO-37分子筛中的一种或几种。 Especially SAPO-17 molecular sieve, SAPO-34 SAPO-37 molecular sieve and one or more molecular sieves.

优选情况下,所述分子筛选自Y型沸石、含磷和/或稀土的Y型沸石、超稳Y沸石、含磷和/或稀土的超稳Y沸石,Beta沸石、具有MFI结构的沸石、含磷和/或稀土的具有MFI结构的沸石中的一种或几种。 Preferably, the molecular sieve selected from zeolite Y, phosphorus and / or rare earth Y zeolite, ultrastable Y zeolite ultrastable Y zeolite containing phosphorus and / or rare earths, zeolite Beta, zeolite having a MFI structure, phosphorus and / or one or more rare earth zeolite having an MFI structure is.

本发明提供的助剂还可以含有稀土金属组分,所述稀土金属组分以金属和/或化合物的形式存在。 Aid of the present invention provides a rare earth metal component may further contain a rare earth metal component is present in the form of metal and / or compounds. 所述稀土金属组分可以同时存在于分子筛、耐热无机氧化物和粘土中,也可以存在于分子筛、耐热无机氧化物和粘土的任意两种中,还可以存在于分子筛、耐热无机氧化物和粘土的任意一种中。 The rare earth metal component may exist within the molecular sieve, thermotolerant inorganic oxide and clay, may also be present in the molecular sieve, any two thermotolerant inorganic oxide and the clay, it may also be present in the molecular sieve, heat resistant inorganic oxide and any one of the clay material. 所述稀土金属选自镧系和锕系稀土金属中的一种或几种,优选为镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥中的一种或几种,更优选为镧、铈、富镧混合稀土金属或富铈混合稀土金属。 The rare earth metal is selected from one or more lanthanide rare earths and actinide series, preferably lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium , lutetium one or more, more preferably lanthanum, cerium, lanthanum-rich mischmetal or cerium-rich misch metal. 以助剂总量为基准,以氧化物计,所述稀土金属组分的含量为0-50重量%,优选为0-15重量%。 Reference to the total amount of additives, on an oxide basis, the content of the rare earth metal component is 0-50 wt%, preferably 0-15 wt%.

本发明提供的助剂还可以含有磷组分,所述磷组分以磷的化合物,如磷的氧化物和/或磷酸盐的形式存在。 The present invention provides adjuvants may also contain a phosphorus component, the phosphorus component, such as the presence of phosphorus compound and / or an oxide of phosphorus in the form phosphate. 所述磷组分可以同时存在于分子筛、耐热无机氧化物和粘土中,也可以存在于分子筛、耐热无机氧化物和粘土的任意两种中,还可以存在于分子筛、耐热无机氧化物和粘土的任意一种中。 The phosphorus component may be present in the molecular sieve, clay thermotolerant inorganic oxide and at the same time, may also be present in the molecular sieve, any two thermotolerant inorganic oxide and the clay, may also be present in the molecular sieve, thermotolerant inorganic oxide and any one of the clay. 以助剂总量为基准,以元素磷计,所述磷组分的含量为0-15重量%,优选为0-8重量%。 Reference to the total amount of additives, as elemental phosphorus, the phosphorus content of the component is 0-15 wt%, preferably 0-8 wt%.

在本发明的实例中,如果稀土组分和/或磷组分是制备助剂时,所用的分子筛本身含有的,所述分子筛的含量是含稀土组分和/或磷组分的分子筛的含量,磷组分和稀土组分的含量不单独计算,也不单独给出。 In the example of the present invention, if the rare earth component and / or phosphorus components are prepared aids, used itself contains molecular sieve, the molecular sieve content of the rare earth component content or molecular sieves and / phosphorus-containing component phosphorus content of rare earth components and components is not calculated separately, not given separately.

按照本发明提供助剂的制备方法,所述含有还原气体的气氛指纯的还原气体或含有还原气体和惰性气体的气氛。 According to the present invention to provide aids production method, the atmosphere containing a reducing gas means a pure gas or a reducing atmosphere containing a reducing gas and an inert gas.

所述纯的还原气体的例子包括氢气、一氧化碳及含有1-5个碳原子的烃类中的一种或几种,优选包括氢气、一氧化碳、甲烷、乙烷、丙烷、丁烷及其各种异构体、戊烷及其各种异构体中的一种或几种。 Examples of the pure reducing gas comprises one or more of hydrogen, carbon monoxide and hydrocarbon containing 1-5 carbon atoms, preferably comprising hydrogen, carbon monoxide, methane, ethane, propane, butane, and various one or more isomers thereof, pentane and the various isomers.

所述惰性气体指不与所述组合物或金属组分化合物发生化学作用的气体,如元素周期表0族气体,氮气、二氧化碳中的一种或几种。 The inert gas refers to a gas without chemical reaction with the components of the composition or compound of a metal, a Group 0 of the Periodic Table such as gas, nitrogen, carbon dioxide, one or several.

所述含有还原气体和惰性气体的气氛的例子包括氢气、一氧化碳、含有1-5个碳原子的烃类中的一种或几种与惰性气体中的一种或几种的混合物,炼油厂中的干气。 Examples of an atmosphere containing a reducing gas and an inert gas comprising hydrogen, carbon monoxide, a mixture of one or more of the one or more hydrocarbons of 1-5 carbon atoms and containing an inert gas, refinery the dry gas.

所述含有还原气体的气氛中,还原气体的浓度没有特别限制,只要所用还原气体的量能将所述金属组分还原即可。 The atmosphere containing reducing gas, the concentration of the reducing gas is not particularly limited, provided that the amount of the reducing gas can be capable of reducing the metal component. 优选情况下,所述含有还原气体的气氛中,还原气体含量至少为10体积%,更优选为50体积%。 Preferably, the atmosphere containing a reducing gas, the reducing gas content is at least 10% by volume, more preferably 50% by volume.

所述接触的温度和接触的时间足以使所述金属组分的平均价态与其最高价态的比值降低至0-0.95,优选为0.1-0.7。 The contact time and temperature sufficient to contact the ratio of the average valence of the metal components to their highest valency state is reduced to 0 to 0.95, preferably 0.1 to 0.7. 一般来说,所述接触的温度可以是100-900℃,优选为400-700℃,接触的时间为0.1秒至10小时,优选为1秒-5小时。 Generally, the contacting temperature may be 100-900 deg.] C, preferably 400-700 deg.] C, the contact time is from 0.1 to 10 seconds, preferably 1 second to 5 hours. 所述接触可以是静态接触,即在一个密闭的容器中,将含有还原气体的气氛与所述组合物接触。 The contact may be static contact, i.e. in a closed container containing a reducing gas atmosphere in contact with the composition. 所述接触也可以是动态接触,即将所述含有还原气体的气氛通过所述组合物的床层。 The contact may also be dynamic contact, i.e. an atmosphere containing the reducing gas through a bed of the composition. 所述接触的压力没有限制,既可以在常压下进行,也可以在高于或低于常压下进行。 The contact pressure is not limited, may be performed at atmospheric pressure, it may be performed at above or below atmospheric pressure. 含有还原气体的气氛的用量为每克助剂每小时不小于5毫升还原气体,优选每克助剂每小时不小于10毫升还原气体,更优选为每克助剂每小时100-2000毫升还原气体。 The amount of reducing gas atmosphere containing additives per hour per gram of the reducing gas is not less than 5 ml, per gram of preferably not less than 10 ml per hour auxiliary reducing gas, more preferably 100-2000 ml per hour per g of the reducing gas aids .

组合物中各组分的含量优选使最终助剂中含有,以助剂总量计,10-60重量%的耐热无机氧化物,35-60重量%的粘土,0-30重量%的分子筛和以最高价态金属的氧化物计,0.5-20重量%的金属组分。 Content of each component in the composition is preferably contained in the final aids, additives to total 10 to 60 weight% of the thermotolerant inorganic oxide, 35-60 wt% of clay, 0-30 wt% of a molecular sieve and oxides to the highest valency of the metal, from 0.5 to 20 wt% of the metal components.

所述含有金属组分化合物、耐热无机氧化物和粘土,含或不含分子筛的组合物可以是现有的含有金属组分的助剂,也可以是在不含金属组分的助剂中引入金属组分化合物后得到的组合物。 The compound containing a metal component, the heat-resistant inorganic oxide and clay, with or without a molecular sieve compositions may be conventional auxiliary component containing a metal, may also be a component of the metal-free additives after the introduction of the metal compound component of the resulting composition.

现有的含有金属组分的助剂的制备方法为本领域技术人员所公知,在这里不再赘述。 Conventional adjuvant preparation containing a metal component of the skilled artisan is well known, here omitted.

在不含金属组分的助剂中引入金属组分化合物的方法也为常规的方法。 The method of introducing auxiliary metal component in the metal-free compound component is also a conventional method. 例如,可以采用下列方法在不含金属组分的助剂中引入金属组分化合物,制备所述含有金属组分化合物、耐热无机氧化物和粘土,含或不含分子筛的组合物。 For example, the following methods may be employed in the introduction of a metal compound component containing no auxiliary metal component in preparing the compound containing a metal component, the heat-resistant inorganic oxide and clay, with or without a molecular sieve composition.

方法之一(1)用含所述金属组分化合物的溶液浸渍耐热无机氧化物、耐热无机氧化物的前身物、粘土和/或分子筛,然后干燥或不干燥;或者将含所述金属组分化合物的溶液与耐热无机氧化物、耐热无机氧化物的前身物、粘土和/或分子筛混合,然后干燥或不干燥;或者将所述金属组分化合物与耐热无机氧化物、耐热无机氧化物的前身物、粘土和/或分子筛进行物理混合;或者将含所述金属组分化合物的溶液与耐热无机氧化物、耐热无机氧化物的前身物、粘土和/或分子筛混合,加入所述金属组分化合物的沉淀剂,将所述金属组分沉积到耐热无机氧化物、耐热无机氧化物的前身物、粘土和/或分子筛中,干燥或不干燥;或者将含所述金属组分化合物的溶液与耐热无机氧化物、耐热无机氧化物的前身物、粘土和/或分子筛混合,将得到的浆液制备成胶体;或者 One method (1) was impregnated with a heat-resistant inorganic oxide, precursors of the heat-resistant inorganic oxide, clay and / or molecular sieve component of the metal-containing compound, and then drying or drying; or the metal-containing , the precursor of the heat-resistant inorganic oxide, and / or mixing the component compounds with the heat-resistant inorganic oxide solution clays and molecular sieves, and then dried or not dried; or the metal compound component and the heat-resistant inorganic oxide, resistant inorganic oxide precursors of heat, clay and / or molecular sieves physically mixed; containing the metal or a solution of compound component heat resistant inorganic oxide, precursors of the heat-resistant inorganic oxide, clay and / or molecular sieves mixing adding a metal compound precipitating agent component, the metal component is deposited into the thermotolerant inorganic oxide, precursors of the heat-resistant inorganic oxide, clay and / or molecular sieve, with or without drying; or containing the, heat-resistant inorganic oxide precursor of clay were mixed with a solution of a metal compound component thermotolerant inorganic oxide and / or molecular sieves, and the resulting slurry was prepared as a colloid; or 不溶于水的所述金属组分化合物与耐热无机氧化物、耐热无机氧化物的前身物、粘土和/或分子筛及去离子水混合,将得到的浆液制备成胶体,干燥或不干燥;(2)将引入所述金属组分化合物的耐热无机氧化物、耐热无机氧化物的前身物、粘土和/或分子筛,或所述混合物,或胶体与去离子水及不含金属组分化合物的耐热无机氧化物、耐热无机氧化物的前身物、粘土和/或分子筛打浆,制备成固含量为10-60重量%,优选为10-50重量%的浆液,干燥得到的浆液,焙烧或不焙烧。 Water-insoluble compound of the metal component and heat-resistant inorganic oxide, precursors of the heat-resistant inorganic oxide, clay and / or molecular sieves and deionized water, and the resulting slurry was prepared as a colloid, with or without drying; (2) introducing the heat-resistant inorganic oxide component of the metal compound, the precursor of the heat-resistant inorganic oxide, clay and / or molecular sieves, or a mixture or gel with deionized water, and metal-free component thermotolerant inorganic oxide compound, the precursor of the heat-resistant inorganic oxide, clay and / or molecular sieves beating, to prepare a solid content of 10 to 60 wt%, preferably 10 to 50% by weight of the slurry, drying the resulting slurry, firing or not firing.

方法之二将耐热无机氧化物和/或耐热无机氧化物的前身物、粘土和去离子水,打浆,制备成固含量为10-60重量%,优选为10-50重量%的浆液,所述浆液中还可以含有分子筛,干燥得到的浆液,焙烧或不焙烧,然后,用含所述金属组分化合物的溶液浸渍干燥后得到的固体,或者将所述金属组分化合物的溶液与干燥后的固体混合,然后,干燥,焙烧或不焙烧。 Two heat-resistant inorganic oxide and / or precursor of the thermotolerant inorganic oxide, clay and deionized water, pulping, method of preparing a solid content of 10 to 60 wt%, preferably 10 to 50% by weight of the slurry, the slurry may further contain a molecular sieve, the resulting slurry was dried, calcination or roasting, and then, is impregnated with a solution containing a solid component of the metal compound obtained after drying, or the solution of the metal compound component and dried after mixing the solids, then drying and baking or roasting.

方法之三将耐热无机氧化物和/或耐热无机氧化物的前身物、粘土、所述金属组分化合物和去离子水打浆,制备成固含量为10-50重量%,优选为20-50重量%的浆液,所述浆液中还可以含有分子筛,干燥得到的浆液,焙烧或不焙烧。 The three methods of heat-resistant inorganic oxide and / or precursor of the thermotolerant inorganic oxide, clay, the metal compound component and a beaten deionized water to prepare a solid content of 10-50% by weight, preferably 20 50% by weight of the slurry, the slurry may further contain a molecular sieve, drying the resultant slurry, calcining or firing.

如果助剂中还含有稀土金属组分和/或磷组分,可以采用上面的方法单独或与引入上述金属组分的同时引入稀土金属组分和/或磷组分,只是用稀土金属化合物和/或磷化合物代替上述金属组分的化合物即可。 If the rare earth metal component also contains additives and / or phosphorus component may be used alone or in combination with the above method while introducing a rare earth metal of the metal component is introduced into the component and / or phosphorus component, and a rare earth metal compound except / or phosphorus compounds in place of the compound to the metal component. 所述稀土金属组分和/或磷组分还可以是市售分子筛本身所带有的(如含稀土和/或磷的Y型沸石或超稳Y沸石)。 The rare earth metal component and / or phosphorus component may also be carried by a commercially available zeolite itself (such as rare earth-containing Y-type zeolite and / or phosphorus, or ultra stable Y zeolite).

其中,所述引入金属组分化合物后的干燥和浆液的干燥方法和条件为本领域技术人员所公知,例如,干燥的方法可以是晾干、烘干、鼓风干燥、喷雾干燥。 Wherein the drying method and conditions, and drying the slurry after the introduction of the metal component compounds are known to those skilled in well-known, for example, the drying process can be dried, drying, blast drying, spray-drying. 浆液的干燥方法优选喷雾干燥的方法。 Spray drying the slurry drying method is preferred. 干燥的温度可以是室温至400℃,优选为100-350℃。 The drying temperature may be from room temperature to 400 ℃, preferably 100-350 ℃. 所述浆液干燥后的焙烧和浸渍金属化合物后的焙烧条件也为本领域技术人员所公知,一般来说,所述浆液干燥后的焙烧和浸渍金属化合物后的焙烧温度均为400-700℃,优选为450-650℃,焙烧时间至少为0.5小时,优选为0.5-100小时,更优选为0.5-10小时。 After firing the slurry after drying and calcining the impregnated metal compounds are also known to those skilled in conditions well known, in general, the firing temperature of the firing after the slurry is dried and impregnated metal compounds are 400-700 deg.] C, preferably 450-650 deg.] C, the calcination time is at least 0.5 hours, preferably 0.5 to 100 hours, more preferably 0.5 to 10 hours.

所述耐热无机氧化物的前身物指在所述裂化催化剂制备过程中,能形成所述耐热无机氧化物的物质中的一种或几种。 The precursor of the thermotolerant inorganic oxide refers to the preparation of the catalyst in the cracking process, one or several substances capable of forming said thermotolerant inorganic oxide in. 如氧化铝的前身物可选自水合氧化铝(如拟薄水铝石)和/或铝溶胶。 The former may be selected from alumina, hydrated alumina (e.g., pseudoboehmite, boehmite) and / or alumina sol. 氧化硅的前身物可选自硅溶胶,硅凝胶和水玻璃中的一种或几种。 Precursor of silicon oxide is selected from silica sol, silica gel and one or more water glass. 无定形硅铝的前身物可选自硅铝溶胶,硅溶胶和铝溶胶的混合物,硅铝凝胶中的一种或几种。 The precursor of amorphous silica-alumina selected from alumina sol, mixture of silica sol and alumina sol, silica-alumina gel is one or more. 其它耐热无机氧化物的前身物可选自其氢氧化物,如锆、钛、碱土金属的氢氧化物、硼酸。 Precursors of other heat-resistant inorganic oxide selected from a hydroxide, such as zirconium, titanium, alkaline earth metal hydroxide, and boric acid.

所述金属组分化合物可以是所述金属的可溶于水的化合物,也可以是难溶于水和/或不溶于水的化合物,如元素周期表IIIA族非铝金属、IVA族金属、VA族金属、IB族金属、IIB族金属、VB族金属、VIB族金属、VIIB族金属、VIII族非贵金属的硝酸盐、氯化物、氢氧化物、氧化物中的一种或几种,特别是镓、锡、铜、银、锌、钒、钼、锰、铁、钴的硝酸盐、氯化物、氢氧化物、氧化物中的一种或几种。 The metal compound component may be water-soluble compound of the metal, may be sparingly soluble in water and / or water-insoluble compounds such as non-aluminum metal of the Periodic Table Group IIIA, IVA metals, VA metals, IB metals, IIB metals, VB metals, VIB metals, VIIB metals, VIII non-noble group nitrates, chlorides, hydroxides, oxides of one or more, especially gallium, tin, copper nitrate, silver, zinc, vanadium, molybdenum, manganese, iron, cobalt, chloride, hydroxide, oxide of one or more.

所述稀土金属化合物可以是稀土金属的可溶于水的化合物,也可以是难溶于水和/或不溶于水的化合物,如稀土金属的氯化物、硝酸盐、氢氧化物、氧化物中的一种或几种。 The rare earth metal compound may be a water-soluble rare earth metal compound, may be sparingly soluble in water and / or water-insoluble compound, such as a rare earth metal chloride, nitrate, hydroxide, oxide one or several.

所述磷化合物可以是所述磷的可溶于水的化合物,也可以是难溶于水和/或不溶于水的化合物,如磷酸、亚磷酸,铵的磷酸盐、碱金属的磷酸盐、磷的氧化物、磷酸铝中的一种或几种。 The phosphorus compound may be a water-soluble phosphorus compound, may be sparingly soluble in water and / or water-insoluble compounds, such as phosphoric acid, phosphorous acid, ammonium phosphate, alkali metal phosphate, phosphorus oxide, aluminum phosphate of one or more.

本发明提供的助剂可作为脱硫助剂,与裂化催化剂混合在一起使用以降低裂化产物,特别是裂化汽油中的硫含量。 Aid of the present invention may be provided as the desulfurization additives, mixed together with the cracking catalyst used to reduce the cracked products, especially cracked gasoline sulfur content. 根据原料油中硫的含量和汽油产品所要求的硫含量,确定裂化催化剂与本发明提供的助剂的催化剂混合物中所含本发明提供的助剂的比例,通常情况下,本发明提供的助剂占催化剂混合物的0.1-50重量%,优选为1-40重量%,更优选为至少1-30重量%,最好是至少1-20重量%。 The sulfur content of the feedstock and the sulfur content of the gasoline products required to determine the proportion of additive of the invention provides a catalyst mixture with the aid of the present invention provides a cracking catalyst contained in, usually, the present invention provides a co- agent comprises 0.1 to 50 wt% of the catalyst mixture, preferably 1-40 wt%, more preferably at least 30% by weight, preferably at least 20% by weight. 此外,本发明提供的助剂还可与其它助剂,如助燃剂、硫转移助剂、辛烷值助剂等一起与现有裂化催化剂混合使用。 Further, the present invention provides additives may also be mixed with other additives, such as oxidant, sulfur transfer additives, and other additives octane cracking catalyst prior to use.

本发明提供的助剂的使用条件为一般烃类裂化过程常规的反应条件,如反应温度为400-700℃,优选为450-600℃,重时空速为10-120小时-1,优选为10-80小时-1,剂油重量比为1-20,优选为3-15。 Conditions of the present invention to provide aid to a conventional reaction conditions are generally a hydrocarbon cracking process, the reaction temperature is 400-700 deg.] C, preferably 450-600 deg.] C, a weight hourly space velocity of 10-120 hr-1, preferably 10 -80 hr -1, a catalyst to oil weight ratio of 1-20, preferably 3-15. 也可以用于深度催化裂化工艺或催化裂解工艺的助剂。 May also be used adjuvants deep catalytic cracking process or a catalytic cracking process.

本发明提供的助剂可与裂化催化剂混合成裂化催化剂混合物,对含硫烃油进行催化裂化。 The present invention provides adjuvants may be mixed with the cracking catalyst mixture into the cracking catalyst, catalytic cracking of a sulfur-containing hydrocarbon oil. 这些烃油选自石油及其各种馏分,如含硫的常压渣油、减压渣油、减压蜡油,常压蜡油,直馏蜡油,丙烷轻/重脱油和焦化蜡油以及经过加氢处理的常压渣油、减压渣油、减压蜡油,常压蜡油中的一种或几种。 These hydrocarbon oil is selected from petroleum and its various fractions, such as sulfur-containing atmospheric residue, vacuum residue, vacuum gas oil, atmospheric gas oil, straight run gas oil, propane, light / heavy coking wax and deoiled hydrotreated oil and atmospheric residue, vacuum residue, one or more vacuum gas oil, atmospheric gas oil is.

下面的实施例将对本发明做进一步说明。 The following examples will further illustrate the present invention.

实例中除非特别说明,所用高岭土为苏州高岭土公司出品,其固含量为76重量%;所用拟薄水铝石为山东淄博501厂出品,其固含量为62重量%;所用铝溶胶为齐鲁催化剂厂出品,其Al2O3含量为21重量%;所用硅溶胶为齐鲁催化剂厂出品,其SiO2含量为27重量%;金属组分的化合物均为化学纯。 Examples Unless otherwise indicated, the kaolin produced by the Suzhou Kaolin Corporation, having a solids content of 76 wt%; as used quasi boehmite is Zibo 501 factory produced, a solids content of 62 wt%; the aluminum sol Qilu Catalyst Factory produced, which Al2O3 content of 21 wt%; silica sol produced by the Qilu catalyst factory, SiO2 content 27% by weight; the metal compound component are chemically pure.

实施例1本实施例说明本发明提供的助剂及其制备方法。 Example 1 This example embodiment described adjuvant and preparation method provided by the invention.

将高岭土、拟薄水铝石、浓度为30重量%的硝酸钴水溶液混合,加入去离子水,混合均匀,在快速搅拌下缓慢加入浓度为36.5体积%的盐酸,调节浆液的pH值至2.0,去离子水的用量使得到的浆液的固含量为25重量%。 Kaolin, pseudoboehmite, boehmite, a concentration of 30 wt% cobalt nitrate aqueous solution were mixed, and deionized water, mixed under rapid stirring was slowly added at a concentration of 36.5 vol% hydrochloric acid, pH adjustment of the slurry to a value 2.0, the amount of deionized water to give a solid content of 25% by weight slurry. 高岭土、拟薄水铝石和硝酸钴水溶液的用量使高岭土干基重量、Al2O3和Co2O3的重量的比值为50.0∶45.0∶5.0。 Kaolin, the amount of boehmite and pseudoboehmite cobalt nitrate aqueous kaolin dry weight, the ratio by weight of Al2O3 and Co2O3 is 50.0:45.0:5.0.

将得到的浆液在150℃的温度下喷雾干燥,在550℃下焙烧1小时。 The resulting slurry at temperature 150 ℃ spray dried, calcined at 550 ℃ at 1 hour. 将得到的催化剂200克装入固定床还原反应器中,在400℃温度下,通入流量为1000毫升/分钟的氢气,使氢气与所述固体接触0.5小时,将反应器的温度降至室温,卸下还原后的固体,得到本发明提供的助剂C1。 200 g of the resultant catalyst was charged in a fixed-bed reduction reactor, at a temperature of 400 ℃, introduced at a flow of 1000 cc / min of hydrogen, the hydrogen in contact with the solid for 0.5 hours the reactor temperature was lowered to room temperature Remove the solid was reduced to give the present invention provides adjuvants C1. 助剂C1的组成及金属组分的种类、分布、平均价态和平均价态与其最高价态的比值列于表1中。 Composition and type of the metal component C1 auxiliaries, distribution, the ratio of its highest valency state Median average valence state of peace state shown in Table 1. 表1中助剂组成由计算得到,金属组分的含量以所述金属组分最高氧化态的氧化物计。 Table 1 auxiliary composition obtained by the calculation, the content of the metal component to the highest oxidation state oxide basis metal component.

实施例2本实施例说明本发明提供的助剂及其制备方法。 EXAMPLE 2 This Example illustrate the present invention and its preparation method aids provided.

按实例1的方法制备助剂,不同的是,所述固体与氢气接触的温度为700℃,接触时间为3小时,得到本发明提供的助剂C2。 Examples of auxiliaries as described in Preparation 1, except that the temperature of the solids contacted with hydrogen gas was 700 deg.] C, contact time of 3 hours to obtain the present invention provides adjuvants C2. 助剂C2的组成及金属组分的种类、分布、平均价态和平均价态与其最高价态的比值列于表1中。 Composition and type of the metal component C2 auxiliaries, distribution, the ratio of its highest valency state Median average valence state of peace state shown in Table 1.

实施例3 Example 3

本实施例说明本发明提供的助剂及其制备方法。 This example illustrates the method of preparation and adjuvants provided herein.

将高岭土、拟薄水铝石和去离子水混合均匀,在快速搅拌下缓慢加入浓度为36.5体积%的盐酸,调节浆液的pH值至2.0,去离子水的加入量使得到的浆液的固含量为25重量%,高岭土、拟薄水铝石的加入量使高岭土和氧化铝的重量比为50.0∶45.0。 Kaolin, quasi boehmite mixed with water and deionized uniform, rapid stirring is slowly added at a concentration of 36.5% by volume of hydrochloric acid, adjusting the pH of the slurry to 2.0, added in an amount of deionized water so that the solid content of the resulting slurry is 25 wt%, the amount of kaolin was added, the quasi boehmite alumina so that the weight ratio of kaolin and 50.0:45.0. 在150℃的温度下喷雾干燥得到的浆液,用浓度为10重量%的硝酸钴水溶液浸渍干燥后的固体,然后在550℃焙烧,硝酸钴水溶液的用量使Co2O3与高岭土和氧化铝的重量比为5.0∶95.0。 At temperature 150 ℃ spray drying the resulting slurry, a concentration of 10 wt% solid was impregnated with an aqueous solution of cobalt nitrate, sulfate, and then the weight Co2O3 kaolin and alumina were calcined at 550 ℃ as an amount, a cobalt nitrate solution 5.0:95.0. 然后在800℃,用100%水蒸气老化6小时。 Then 800 ℃, aged 6 hours with 100% steam. 将老化后的固体200克装入固定床还原反应器中,在400℃温度下,通入流量为1000毫升/分钟的氢气,使氢气与所述固体接触0.5小时,使反应器的温度降至室温,卸下还原后的固体,得到本发明提供的助剂C3。 The temperature after aging 200 g solid fixed-bed reduction reactor was charged, at a temperature of 400 ℃, introduced at a flow of 1000 cc / min of hydrogen, the hydrogen in contact with the solid 0.5 hour, the reactor was reduced to at room temperature, remove the solid was reduced to give the present invention provides adjuvants C3. C3的组成及金属组分的种类、分布、平均价态和平均价态与其最高价态的比值列于表1中。 Species composition and the metal component C3, distribution, the ratio of its highest valency state Median average valence state of peace state shown in Table 1.

实施例4本实施例说明本发明提供的助剂及其制备方法。 Example 4 This example embodiment described adjuvant and preparation method provided by the invention.

用3.19公斤浓度为40重量%的六水合硝酸钴水溶液浸渍3.0公斤(干基重)高岭土,120℃烘干,得到含Co2O39.09重量%的高岭土。 With 3.19 kg of a 40 wt% aqueous solution of cobalt nitrate hexahydrate was immersed 3.0 kg (dry weight) of kaolin, 120 ℃ dried to give% by weight of kaolin-containing Co2O39.09.

按实例1的方法制备助剂,不同的是用含Co2O39.09重量%的高岭土代替实例1所述高岭土,不加硝酸钴,得到本发明提供的助剂C4。 Example 1 was prepared by the method of auxiliaries, except that in place of the Example 1 with kaolin% by weight of kaolin-containing Co2O39.09, without cobalt nitrate, to obtain the present invention provides adjuvants C4. 助剂C4的组成及金属组分的种类、分布、平均价态和平均价态与其最高价态的比值列于表1中。 Adjuvant composition and type of the metal component C4, distribution, the ratio of its highest valency state Median average valence state of peace state shown in Table 1.

对比例1本对比例说明含有最高氧化态金属组分的参比助剂及其制备方法。 Reference Comparative Example 1 Comparative adjuvant and preparation method described containing highest oxidation state of the metal component.

按实例1的方法制备助剂,不同的是,没有在固定床反应器中将固体与氢气接触的过程,得到参比助剂CB1。 Example 1 was prepared by the method of the aid, the difference is not in the process of the solid in the fixed bed reactor in contact with hydrogen, to give a reference aid CB1. CB1的组成列于表1中。 CB1 compositions shown in Table 1.

对比例2本对比例说明含有最高氧化态金属组分的参比助剂及其制备方法。 Comparative Example 2 Reference adjuvant and preparation method highest oxidation state of the metal component contained comparative description.

按实例3的方法制备助剂,不同的是,没有在固定床反应器中将固体与氢气接触的过程,得到参比助剂CB2。 Adjuvants prepared as in Example 3 except that, in the fixed bed reactor is not in the process of solids in contact with hydrogen, to give a reference aid CB2. CB2的组成列于表1中。 The composition of CB2 is shown in Table 1.

表1 Table 1

实施例5本实施例说明本发明提供的助剂及其制备方法。 Example 5 This example embodiment described adjuvant and preparation method provided by the invention.

按实例1的方法制备助剂,不同的是,用浓度为30.0重量%的硝酸锌水溶液代替硝酸钴水溶液,去离子水的加入量使得到的浆液的固含量为20重量%,高岭土、拟薄水铝石、硝酸锌水溶液的加入量使高岭土干基重量、Al2O3和ZnO的重量比为38.0∶50.0∶12.0。 Examples of auxiliaries as described in Preparation 1, except that a concentration of 30.0 wt% aqueous solution of zinc nitrate in place of cobalt nitrate aqueous solution, the amount of deionized water was added so that the slurry had a solids content of 20% by weight, kaolin, pseudoboehmite boehmite, an aqueous solution of zinc nitrate added amounts of kaolin on a dry weight, the weight ratio of Al2O3 and ZnO is 38.0:50.0:12.0. 还原的气氛为氢气含量50体积%和一氧化碳含量50体积%的氢气和一氧化碳的混合气,混合气的流量为2000毫升/分钟,所述固体与混合气接触的温度为800℃,接触时间为3小时,得到本发明提供的助剂C5。 Atmosphere for reducing the content of 50% by volume of hydrogen and carbon monoxide content of 50% by volume of hydrogen and carbon monoxide mixed gas, the mixed gas flow rate of 2000 ml / min, the temperature of the gas mixture in contact with the solid was 800 deg.] C, contact time of 3 hours to obtain the present invention provides adjuvants C5. C5的组成及金属组分的种类、分布、平均价态和平均价态与其最高价态的比值列于表2中。 Composition and type of the metal component C5, the distribution ratio of the average valence states and their median peace highest valency state are listed in Table 2 below.

实施例6本实施例说明本发明提供的助剂及其制备方法。 Example 6 This example embodiment described adjuvant and preparation method provided by the invention.

按实例1的方法制备助剂,不同的是,用浓度为20.0重量%的硝酸铜水溶液代替硝酸钴水溶液,在浆液中还加入了二氧化钛(化学纯),去离子水的加入量使得到的浆液的固含量为20重量%,高岭土、二氧化钛、拟薄水铝石、硝酸铜水溶液的加入量使高岭土干基重量、二氧化钛、Al2O3和CuO的重量比为42.0∶2.4∶48.0∶7.6。 Prepared as in aid of Example 1, except that the 20.0 wt% aqueous copper nitrate solution instead of aqueous cobalt nitrate solution, the slurry is also added to the titanium dioxide (chemically pure) at a concentration of added in an amount of deionized water in the slurry obtained the solids content of 20% by weight, kaolin, titanium dioxide, quasi-boehmite, the amount of copper nitrate aqueous solution was added to the dry weight of kaolin, titanium oxide, Al2O3, and CuO in a weight ratio of 42.0:2.4:48.0:7.6. 还原的气氛为氢气含量50体积%和一氧化碳含量50体积%的氢气和一氧化碳的混合气,混合气的流量为1000毫升/分钟,所述固体与混合气接触的温度为400℃,接触时间为0.5小时,得到本发明提供的助剂C6。 Atmosphere for reducing the content of 50% by volume of hydrogen and carbon monoxide content of 50% by volume of hydrogen and carbon monoxide mixed gas, the mixed gas flow rate of 1000 ml / min, the temperature of the gas mixture in contact with the solid was 400 ℃, a contact time of 0.5 hours to obtain the present invention provides adjuvants C6. C6的组成及金属组分的种类、分布、平均价态和平均价态与其最高价态的比值列于表2中。 Composition and type of the metal component C6, distribution, ratio of the average valence states and their median peace highest valency state are listed in Table 2 below.

实施例7本实施例说明本发明提供的助剂及其制备方法。 Example 7 This Example illustrate the present invention and its preparation method aids provided.

按实例1的方法制备助剂,不同的是,用浓度为20.0重量%的硝酸铁水溶液代替硝酸钴水溶液,用硅溶胶和铝溶胶代替拟薄水铝石,不加盐酸水溶液,高岭土、硅溶胶、铝溶胶和硝酸铁水溶液的加入量使高岭土干基重量、氧化硅、氧化铝和Fe2O3的重量比为45.0∶20.0∶31.8∶3.2。 Examples of auxiliaries as described in Preparation 1, except that 20.0% by weight of an aqueous solution of ferric nitrate in place of cobalt nitrate solution, quasi-boehmite instead of alumina sol and silica sol, without aqueous hydrochloric acid, a concentration of kaolin, silica sol , alumina sol and the added amount of ferric nitrate aqueous solution by weight of dry kaolin, silica, alumina, and the weight ratio of Fe2O3 45.0:20.0:31.8:3.2. 还原的气氛为氢气含量50体积%和一氧化碳含量50体积%的氢气和一氧化碳的混合气,混合气的流量为1200毫升/分钟,所述固体与混合气接触的温度为600℃,接触时间为0.5小时,得到本发明提供的助剂C7。 Atmosphere for reducing the content of 50% by volume of hydrogen and carbon monoxide content of 50% by volume of hydrogen and carbon monoxide mixed gas, the mixed gas flow rate of 1200 ml / min, the temperature of the gas mixture in contact with the solid was 600 ℃, a contact time of 0.5 hours to obtain the present invention provides C7 aid. 助剂C7的组成及金属组分的种类、分布、平均价态和平均价态与其最高价态的比值列于表2中。 Adjuvant composition and type of the metal component of the C7, distribution, the ratio of its highest valence state Median average valence state of peace set forth in Table 2 below.

实施例8本实施例说明本发明提供的助剂及其制备方法。 Example 8 This example embodiment described adjuvant and preparation method provided by the invention.

(1)用3.48公斤浓度为25重量%的钼酸铵((NH4)6Mo7O24·4H2O)水溶液浸渍3.0公斤(干基重)高岭土和0.5公斤(干基重)硅藻土(固含量为85.0重量%,浙江省嵊州市华力硅藻土厂出品)的混合物,120℃烘干,然后再用2.77公斤1.5重量%的硝酸银水溶液浸渍,120℃烘干,600℃焙烧2小时,得到含MoO316.7重量%和Ag2O 0.67重量%的高岭土和硅藻土的混合物。 (1) 3.48 kg of a 25% by weight of ammonium molybdate ((NH4) 6Mo7O24 · 4H2O) impregnating an aqueous solution of 3.0 kg (dry weight) of kaolin and 0.5 kg (dry weight) of diatomaceous earth (a solids content of 85.0 wt. %, Shengzhou Huali plant produced celite) was, 120 ℃ dried and then with 2.77 kg 1.5% by weight of the impregnated silver nitrate aqueous solution, 120 dried deg.] C, 600 deg.] C and calcined for 2 hours to obtain a solution containing MoO316 wt% by weight of a mixture of diatomaceous earth and kaolin and .7% Ag2O 0.67.

(2)将含MoO3和Ag2O的高岭土和硅藻土的混合物、拟薄水铝石和去离子水混合均匀,在快速搅拌下缓慢加入浓度为36.5体积%的盐酸,调节浆液的pH值至1.5,再加入含磷和稀土的HY沸石(工业牌号为MOY,晶胞常数为24.59埃,Na2O含量为1.0重量%,以元素磷计,磷含量为1.2重量%,稀土氧化物含量为8.5重量%,其中,氧化镧含量为4.5重量%,氧化铈含量为1.1重量%,其它稀土氧化物含量为2.9重量%,齐鲁催化剂厂出品),去离子水的加入量使得到的浆液的固含量为25重量%,含MoO3和Ag2O的高岭土和硅藻土的混合物、拟薄水铝石、MOY沸石的加入量使高岭土和硅藻土的干基重量、氧化铝、MOY沸石的干基重量、Ag2O及MoO3的重量比为37.0∶20.2∶35∶0.3∶7.5。 (2) containing a mixture of MoO3 and kaolin and diatomaceous earth of Ag2O, pseudoboehmite and boehmite mixed with deionized water, was slowly added with rapid stirring at a concentration of 36.5% by volume of hydrochloric acid, adjusting the pH of the slurry to 1.5, was added phosphorus and rare earth HY zeolite (MOY grades for industry, a unit cell constant of 24.59 Å, Na2O content of 1.0 wt% in terms of phosphorus, a phosphorus content of 1.2 wt%, rare earth oxide content of 8.5 wt%, wherein the lanthanum oxide content of 4.5 wt%, a cerium oxide content of 1.1 wt%, other rare earth oxide content of 2.9 wt%, produced by Qilu catalyst factory), the amount of deionized water was added so that the slurry had a solids content of 25 wt. %, containing a mixture of diatomaceous earth and kaolin and MoO3 of Ag2O, quasi-boehmite, zeolite is added in an amount so MOY dry weight of kaolin and diatomaceous earth, alumina, zeolite MOY dry weight, MoO3 and Ag2O the weight ratio of 37.0:20.2:35:0.3:7.5. 还原的气氛为氢气含量50体积%的氮气与氢气的混合气,混合气的流量为2500毫升/分钟,所述固体与混合气接触的温度为650℃,接触时间为1小时,得到本发明提供的助剂C8。 Atmosphere for reducing the hydrogen content of 50% by volume of nitrogen and hydrogen mixed gas, the mixed gas flow rate of 2500 ml / min, the temperature of the gas mixture in contact with the solid was 650 ℃, the contact time was 1 hour, to obtain the present invention provides auxiliaries C8. 助剂C8的组成及金属组分的种类、分布、平均价态和平均价态与其最高价态的比值列于表2中。 Composition and type of the metal component auxiliaries C8, distribution, the ratio of its highest valence state Median average valence state of peace set forth in Table 2 below.

对比例3本对比例说明含有最高氧化态金属组分的参比助剂及其制备方法。 Reference Comparative Example 3 Comparative adjuvant and preparation method described containing highest oxidation state of the metal component.

按实例8的方法制备助剂,不同的是,没有在固定床反应器中将固体与氢气和一氧化碳的混合气接触的过程,得到参比助剂CB3。 Example 8 was prepared according to the method of the aid, the difference is not in a fixed bed of solid mixture with hydrogen and carbon monoxide gas in the contact reactor, to obtain the reference aid CB3. CB3的组成列于表2中。 CB3 composition shown in Table 2 below.

表2 Table 2

实施例9本实施例说明本发明提供的助剂及其制备方法。 EXAMPLE 9 This example embodiment described additives and preparation method provided by the invention.

(1)用3.09公斤浓度为20.0重量%的硝酸锰水溶液浸渍3.0公斤(干基重)高岭土,120℃烘干,550℃焙烧2小时,得到含MnO29.09重量%的高岭土。 Impregnating manganese nitrate solution (1) with a concentration of 3.09 kg 3.0 kg 20.0% by weight (dry weight) of kaolin, dried 120 deg.] C, 550 deg.] C and calcined for 2 hours to obtain a wt% of kaolin containing MnO29.09.

(2)将500克NaY(Na2O含量11重%,硅铝比为5.6,长岭催化剂厂生产)与10升0.15摩尔/升的氯化铵水溶液在60℃下交换1小时,过滤后的滤饼在550℃焙烧2小时。 (2) 500 grams of NaY (Na2O content of 11 weight% silica to alumina ratio of 5.6, Changling Catalyst Plant) and 10 liters of 0.15 mol / l aqueous ammonium chloride exchanged for 1 hour at 60 ℃, filtered by filtration cake was calcined at 550 ℃ 2 hours. 将其再按上述步骤交换和焙烧两次,得到氧化钠含量为0.3重量%的HY沸石。 Its exchange and calcination as the above steps twice, to obtain a sodium oxide content of 0.3% by weight of HY zeolite.

(3)按实例8中(2)的方法制备助剂,不同的是,用本实例(1)得到的含MnO2的高岭土代替实例8所述含MoO3和Ag2O的高岭土和硅藻土的混合物,用本实例(2)得到的HY型沸石代替MOY沸石;含MnO2的高岭土、拟薄水铝石、HY沸石的用量使高岭土干基重量、Al2O3、HY沸石干基重量和MnO2的重量的比值为50.0∶40.0∶5.0∶5.0。 (3) in Example 8, (2) a method for preparing additives, the difference is obtained by the present example (1) in place of kaolin-containing mixture of MnO2 and Ag2O MoO3 containing kaolin and diatomaceous earth of Example 8, with the present example (2) obtained HY-type zeolite instead of MOY zeolite; kaolin-containing MnO2, to be boehmite, the amount of HY zeolite kaolin dry basis weight, a ratio by weight of Al2O3, HY zeolite dry weight and MnO2 was 50.0:40.0:5.0:5.0. 还原的气氛为氢气含量80体积%和丙烷含量20体积%的氢气和丙烷的混合气,混合气的流量为1500毫升/分钟,所述固体与混合气接触的温度为500℃,接触时间为1小时,得到本发明提供的助剂C9。 Reducing the hydrogen content of the atmosphere and propane content of 80% by volume of hydrogen and 20 vol% propane mixed gas, the mixed gas flow rate of 1500 ml / min, the temperature of the gas mixture in contact with the solid was 500 ℃, a contact time of 1 hours to obtain the present invention provides adjuvants C9. 助剂C9的组成及金属组分的种类、分布、平均价态和平均价态与其最高价态的比值列于表3中。 Composition and type of the metal component C9 auxiliaries, distribution, the ratio of median average valence state of peace in its highest valency state shown in Table 3.

实施例10本实施例说明本发明提供的助剂及其制备方法。 Example 10 This example embodiment described adjuvant and preparation method provided by the invention.

在搅拌下,用3.86公斤浓度为5.0重量%的偏钒酸铵(NH4VO3)水溶液浸渍3.0公斤(干基重)高岭土和0.225公斤氧化镁的混合物,120℃烘干得到的浆液,550℃焙烧2小时,得到含MgO 6.67重量%,V2O54.44重量%的高岭土。 Under stirring, with 3.86 kg of a 5.0 wt% ammonium metavanadate (NH4VO3) impregnating an aqueous solution of 3.0 kg (dry weight) of kaolin and a mixture of 0.225 kg of magnesium oxide, 120 deg.] C and drying the resulting slurry, 550 ℃ calcined 2 hours, to give%, V2O54.44% by weight of kaolin-containing MgO 6.67 wt.

按实例8中(2)的方法制备助剂,不同的是用上述含MgO和V2O5的高岭土代替实例8所述含MoO3和Ag2O的高岭土和硅藻土的混合物,用超稳Y沸石(工业牌号为DASY,晶胞常数为24.45埃,Na2O含量为1.0重量%,齐鲁催化剂厂出品)代替MOY沸石;含MgO和V2O5的高岭土、拟薄水铝石、DASY沸石的用量使高岭土的干基重量、氧化镁、Al2O3、DASY沸石干基重量和V2O5的重量的比值为40.0∶3.0∶45.0∶10.0∶2.0;所述固体与氢气接触的温度为550℃,氢气的流量为1000毫升/分钟,接触时间为1小时,得到本发明提供的助剂C10。 In Example 8, (2) a method for preparing additives, except that instead of MoO3 and containing a mixture of kaolin and diatomaceous earth Ag2O described in Example 8 above kaolin containing MgO and V2O5, and ultra stable Y zeolite (Industrial Grade DASY is, the unit cell constant of 24.45 Å, Na2O content of 1.0 wt%, produced by Qilu catalyst factory) was used instead of zeolite MOY; MgO-containing V2O5 and kaolin, to be boehmite, so that the amount of DASY zeolite dry weight of kaolin, MgO, Al2O3, DASY zeolite and a dry weight ratio of the weight of V2O5 40.0:3.0:45.0:10.0:2.0; temperature of the solids contacted with hydrogen gas was 550 deg.] C, hydrogen gas flow rate of 1000 ml / min, the contact time 1 hour, to give C10 adjuvants provided herein. 助剂C10的组成及金属组分的种类、分布、平均价态和平均价态与其最高价态的比值列于表3中。 Composition and type of the metal component of the aid-C10, the distribution ratio of the average valence states and their median peace highest valency state are shown in Table 3.

实施例11本实施例说明本发明提供的助剂及其制备方法。 EXAMPLE 11 This example embodiment described adjuvant and preparation method provided by the invention.

用3.42公斤浓度为25重量%的氯化镓水溶液浸渍3.0公斤(干基重)高岭土和0.86公斤(干基重)拟薄水铝石的混合物,120℃烘干,600℃焙烧2小时,得到含Ga2O310.53重量%的高岭土和氧化铝的混合物。 With 3.42 kg of a 25 wt% aqueous solution of gallium chloride was immersed 3.0 kg (dry weight) of kaolin and 0.86 kg (dry weight) mixture of boehmite and pseudoboehmite, 120 ℃ dried, calcined 600 deg.] C for 2 hours to give Ga2O310.53 wt% mixture of kaolin and alumina containing.

将含Ga2O3的高岭土和拟薄水铝石的混合物、硅溶胶、铝溶胶与去离子水混合均匀,用DASY沸石和含磷和稀土的具有MFI结构的沸石(工业牌号为ZRP-1,以元素磷计,磷含量为2.0重量%,稀土氧化物含量为1.0重量%,其中,氧化镧含量为0.53重量%,氧化铈含量为0.13重量%,其它稀土氧化物含量为0.34重量%,Na2O含量小于0.1重量%,SiO2与Al2O3的摩尔比为60,齐鲁催化剂厂出品),混合均匀,去离子水的用量使得到的浆液的固含量为25重量%,含Ga2O3的高岭土和拟薄水铝石的混合物、硅溶胶、铝溶胶、超稳Y沸石和ZSM-5沸石的用量使高岭土干基重量、氧化铝、氧化硅、超稳分子筛干基重量、ZRP-1沸石干基重量和Ga2O3的重量的比值为35.0∶30.0∶9.7∶15.0∶5.0∶5.3。 The mixture was Ga2O3 containing kaolin and a quasi boehmite, silica sol, alumina sol and deionized water mixed with zeolite (industrial designation ZRP-1 having a MFI structure and DASY zeolite containing phosphorus and rare earth, elemental phosphorus, a phosphorus content of 2.0 wt%, rare earth oxide content of 1.0 wt%, wherein lanthanum oxide content of 0.53 wt%, cerium oxide content was 0.13 wt%, the content of other rare earth oxides of 0.34 wt% of Na2O content of less than 0.1 wt%, SiO2 with a molar ratio of Al2O3 was 60, Qilu catalyst factory produced), mixed, the solid content amount of deionized water the resulting slurry was 25 wt%, including Ga2O3 kaolin and pseudo boehmite in the mixture, silica sol, alumina sol, the amount of ultrastable Y zeolite and ZSM-5 zeolite dry weight of kaolin, alumina, silica, ultra-stable molecular sieve dry weight, the weight of the zeolite ZRP-1 and the dry weight of Ga2O3 ratio of 35.0:30.0:9.7:15.0:5.0:5.3. 将得到的浆液在150℃的温度下喷雾干燥,在550℃下焙烧2小时,然后在800℃,用100%水蒸气老化6小时。 The resulting slurry at temperature 150 ℃ spray-dried, calcined at 550 ℃ 2 hours and then at 800 deg.] C, aged with 100% steam for 6 hours. 将得到的固体200克装入固定床还原反应器中,在600℃温度下,通入流量为3000毫升/分钟的氢气,使氢气与所述固体接触2小时,使反应器的温度降至室温,卸下还原后的固体,得到本发明提供的助剂C11。 The temperature of the resulting solid was 200 g was charged in a fixed-bed reduction reactor, at a temperature of 600 ℃, introduced at a flow of 3,000 ml / min hydrogen, the hydrogen and the solid was contacted for 2 hours, the reactor was lowered to room temperature Remove the solid was reduced to give the C11 adjuvants provided herein. 助剂C11的组成及金属组分的种类、分布、平均价态和平均价态与其最高价态的比值列于表3中。 Composition and type of the metal component of the aid C11, the distribution ratio of the average valence states and their median peace highest valency state are shown in Table 3.

实施例12本实施例说明本发明提供的助剂及其制备方法。 Example 12 This Example illustrate the present invention and its preparation method aids provided.

将5.39公斤浓度为4.0重量%的氯化亚锡SnCl2水溶液、1.46公斤(干基重)硅溶胶和3.0公斤(干基重)高岭土混合均匀,120℃烘干,550℃焙烧3小时,得到含SnO23.7重量%的高岭土和氧化硅的混合物。 The 5.39 kg of 4.0 wt% stannous chloride SnCl2 in an aqueous solution, 1.46 kg (dry weight basis) of silica sol and 3.0 kg (dry weight) of kaolin mixed, dried 120 deg.] C, 550 deg.] C calcined for 3 hours to obtain a solution containing SnO23.7% by weight of a mixture of kaolin and silica.

将含SnO2的高岭土和氧化硅的混合物、铝溶胶与去离子水混合均匀,再加入DASY和ZRP-1沸石,混合均匀,去离子水的用量使得到的浆液的固含量为25重量%,含SnO2的高岭土和氧化硅的混合物、铝溶胶、DASY沸石和ZRP-1沸石的用量使高岭土干基重量、氧化铝、氧化硅、DASY沸石干基重量、ZRP-1沸石干基重量和SnO2的重量的比值为35.0∶30.0∶17.0∶11.0∶5.0∶2.0。 The mixture containing SnO2 kaolin and silicon oxide, alumina sol and deionized water were mixed uniformly, added DASY and ZRP-1 zeolites, mixed, the solid content amount of deionized water The resulting slurry was 25 wt%, containing a mixture of kaolin and silicon oxide of SnO2, alumina sol, and the amount of DASY zeolite ZRP-1 zeolite dry weight of kaolin, alumina, silica, a dry weight DASY zeolite, ZRP-1 zeolite dry weight and the weight of SnO2 the ratio 35.0:30.0:17.0:11.0:5.0:2.0. 将得到的浆液在150℃的温度下喷雾干燥,在550℃下焙烧2小时,然后在800℃,用100%水蒸气老化8小时。 The resulting slurry at temperature 150 ℃ spray-dried, calcined at 550 ℃ 2 hours and then at 800 deg.] C, aged with 100% steam for 8 hours. 将得到的固体200克装入固定床还原反应器中,在650℃温度下,通入流量为1000毫升/分钟的氢气,使氢气与所述固体接触1小时,使反应器的温度降至室温,卸下还原后的固体,得到本发明提供的助剂C12。 The temperature of the resulting solid was 200 g was charged in a fixed-bed reduction reactor, at a temperature of 650 ℃, introduced at a flow of 1000 cc / min of hydrogen, the hydrogen in contact with the solid one hour, the reactor was lowered to room temperature Remove the solid was reduced to give the C12 adjuvants provided herein. 助剂C12的组成及金属组分的种类、分布、平均价态和平均价态与其最高价态的比值列于表3中。 Composition and type of the metal component C12 auxiliaries, distribution, the ratio of its highest valency state Median average valence state of peace state shown in Table 3.

表3 table 3

实例13-24下面的实例说明本发明提供的助剂的催化性能。 Examples 13-24 The following examples illustrate the catalytic performance of the aid provided by the present invention.

分别将本发明提供的助剂C1-C12与经过800℃,100%水蒸气老化处理8小时的HGY-2000R工业催化裂化催化剂(活性组分为超稳Y和稀土Y沸石,齐鲁催化剂厂出品)混合,得到催化剂混合物。 The aid of the present invention are provided with C1-C12 through 800 ℃, 100% steam-aging HGY-2000R 8 hours industrial FCC catalyst (active component is rare earth Y and ultrastable Y zeolite, produced by Qilu Catalyst Factory) mixed to obtain a catalyst mixture. 在小型固定床反应装置上,分别采用上述得到的催化剂混合物,对表4所列的馏程为329-550℃的含硫减压蜡油进行催化裂化,催化剂装量4.0克。 In a small fixed bed reactor, were obtained using the catalyst mixture, listed in Table 4 of distillation range of 329-550 deg.] C in a sulfur-containing vacuum gas oil catalytic cracking, loading capacity of the catalyst 4.0 g. 催化剂混合物中本发明提供的助剂的种类和含量,反应条件和反应结果列于表5-7中。 The kind and content of the catalyst mixture of the present invention to provide aids, reaction conditions and reaction results are shown in Table 5-7. 裂化产物中硫含量测定方法采用气相色谱-原子发射光谱法,在HP 6890GC-G2350A AED气相色谱-原子发射光谱仪上测定。 Cracked product sulfur content determination by gas chromatography - atomic emission spectrometry, the HP 6890GC-G2350A AED Gas Chromatography - atomic emission spectrometer.

其中,剂油比指催化剂混合物与所述原料油的重量比。 Wherein oil ratio refers to the weight ratio of the catalyst mixture with the feedstock oil.

对比例4-6下面的对比例说明参比助剂的催化性能。 Comparative Example 4-6 Comparative catalytic performance following description reference aid.

按实例13的方法对相同的原料油进行催化裂化,不同的是所用催化剂混合物分别为CB1、CB2、CB3与经过800℃,100%水蒸气老化处理8小时的HGY-2000R的催化剂混合物,催化剂混合物中参比助剂的种类和含量,反应条件和反应结果列于表5中。 The method of Example 13 by catalytic cracking of the same feedstock oil, except that the catalyst mixture CB1, CB2, CB3 and after 800 ℃, 100% steam aged catalyst mixture HGY-2000R of 8 hours, the catalyst mixture used were the kind and content of the reference aid, reaction conditions and reaction results are shown in table 5.

表4 Table 4

表5 table 5

表5的结果说明,催化剂混合物中均含有助剂5.0重量%,与采用含参比助剂的催化剂混合物时相比,采用含有本发明提供的助剂的催化剂混合物时,烃油转化率显著提高,汽油产物中的硫含量显著下降。 The results described in Table 5, the catalyst mixture contain adjuvants 5.0%, compared with the case using a catalyst mixture containing a reference aid, using a mixture containing the catalyst of the present invention provides aid, a hydrocarbon oil conversion increases significantly , the sulfur content of the gasoline product is significantly decreased. 这说明本发明提供的助剂不仅具有更强的脱硫性能,而且含有本发明提供的助剂的催化剂混合物的裂化活性也有显著提高。 This indicates that the present invention provides not only aids having greater desulfurization performance, and contains a mixture of cracking activity of the catalyst of the present invention to provide aids also significantly improved.

表6 Table 6

从对比实例20和对比例6的结果,可以看出,与含有金属组分为最高氧化态的,金属组分的种类和含量均相同的参比助剂的催化剂混合物相比,含有本发明提供的助剂的催化剂混合物具有更高的裂化活性和脱硫活性。 From the results of Comparative Example 20 and Comparative Example 6, it can be seen, compared with the metal component of the highest oxidation state, the catalyst comprising a mixture of type and content of metal components have the same reference aid, comprising the present invention provides auxiliary catalyst mixture having a higher cracking activity and the desulfurization activity.

表7 Table 7

实例25-27下面的实例说明本发明提供的助剂的催化性能。 Examples 25-27 The following examples illustrate the catalytic performance of the present invention to provide aids.

分别将本发明提供的助剂C8、C10、C11与经过800℃,100%水蒸气老化处理8小时的CR022工业催化裂化催化剂(活性组分为Y型沸石和具有MFI结构的沸石,齐鲁催化剂厂出品)混合,得到催化剂混合物。 The additives of the present invention are provided C8, C10, C11 and after 800 ℃, 100% steam-aging CR022 8 hours industrial FCC catalyst (active component and a Y zeolite having a MFI structure zeolite, Qilu Catalyst Factory produced) were mixed to give a catalyst mixture. 在小型固定床反应装置上对表4所示常压渣油含量为20重量%和减压蜡油含量为80重量%的混合油进行催化裂化,催化剂混合物装量为90克,反应条件和反应结果列于表8中。 In a small fixed bed reactor of atmospheric residue content shown in Table 4 and 20% by weight VGO content of 80% by weight of the mixed oil catalytic cracking, the catalyst mixture was charged in an amount of 90 g, the reaction conditions and the results are shown in table 8.

对比例5下面的实例说明只用经过800℃,100%水蒸气老化处理8小时的工业催化剂CR022的情况。 Comparative Example 5 Example of the following description only after 800 ℃, 100% steam aging of 8 hours of commercial catalysts CR022.

按实例25的方法催化裂化相同的原料油,不同的是,所用催化剂是CR022,反应结果列于表8中。 The method of Example 25 by the same catalytic cracking feed oil except that the catalyst used is CR022, the reaction results are shown in Table 8.

表8 Table 8

表8的结果表明,采用含有本发明提供的助剂的催化剂混合物时,烃油转化率比不含助剂的催化剂显著提高,汽油产物中的硫含量显著下降。 The results in Table 8 show that, when using the catalyst mixture contains the additive of the invention provides a hydrocarbon oil conversion was significantly higher than the catalyst-free additives, gasoline sulfur content in the product decreased significantly. 这再一次说明本发明提供的助剂不仅具有更强的脱硫性能,而且含有本发明提供的助剂的催化剂混合物的裂化活性也得到显著提高。 This shows once again the present invention provides not only aids having greater desulfurization performance, and cracking activity of the catalyst containing the additives of the present invention also provides a mixture significantly improved.

Claims (28)

  1. 1.一种具有脱硫作用的裂化助剂,该助剂含有一种耐热无机氧化物、粘土和一种金属组分,含或不含分子筛,其特征在于,以助剂总量为基准,耐热无机氧化物的含量为2-68重量%,粘土的含量为大于30至80重量%,分子筛的含量为0-40重量%,以所述最高价态的金属氧化物计,金属组分的含量为0.1-30重量%,所述金属组分以还原价态存在,它选自元素周期表IIIA族非铝金属、IVA族金属、VA族金属、IB族金属、IIB族金属、VB族金属、VIB族金属、VIIB族金属、VIII族非贵金属中的一种或几种。 An adjuvant having cracking desulfurization, which aid comprises a heat-resistant inorganic oxide, clay and one metal component, with or without a molecular sieve, characterized in that, with reference to the total amount of additives, content of the thermotolerant inorganic oxide is 2-68% by weight, clay content of greater than 30 to 80 wt%, the content of zeolite is 0-40 wt%, to the highest valency state metal oxides, metal components an amount of 0.1-30 wt%, the metal component is present in valence state, selected from non-aluminum metal of the Periodic Table group IIIA, IVA metals, VA metals, IB metals, IIB metals, VB group metal, VIB metals, VIIB metals, VIII group one or more non-noble metals.
  2. 2.根据权利要求1所述的助剂,其特征在于,以助剂总量为基准,所述耐热无机氧化物的含量为10-60重量%,粘土的含量为35-60重量%,分子筛的含量为0-30重量%,以所述最高价态的金属氧化物计,金属组分的含量为0.5-20重量%。 2. The adjuvant according to claim 1, wherein the total amount of auxiliaries, the content of the heat-resistant inorganic oxide is 10 to 60% by weight, clay content of 35-60% by weight, content of 0-30% by weight of the molecular sieve content of the metal oxides to the highest valency state of the metal component is 0.5 to 20 wt%.
  3. 3.根据权利要求1或2所述的助剂,其特征在于,以所述助剂的总量为基准,所述粘土和沸石的总含量为35-80重量%。 The adjuvant of claim 1 or claim 2, wherein the total amount of the aid as a reference, the total content of the clay and 35 to 80 wt% zeolite.
  4. 4.根据权利要求3所述的助剂,其特征在于,以所述助剂的总量为基准,所述粘土和沸石的总含量为40-75重量%。 4. The adjuvant according to claim 3, wherein the total amount of the aid as a reference, the total content of the clay and the zeolite is 40-75 wt%.
  5. 5.根据权利要求1或2所述的助剂,其特征在于,所述金属组分的平均价态与其最高价态的比值为0-0.95。 The adjuvant of claim 1 or claim 2, wherein the ratio of the average valence of the metal components to their highest valency state is from 0 to 0.95.
  6. 6.根据权利要求5所述的助剂,其特征在于,所述金属组分的平均价态与其最高价态的比值为0.1-0.7。 6. The adjuvant according to claim 5, characterized in that the ratio of the average valence of the metal components to their highest valency state of 0.1 to 0.7.
  7. 7.根据权利要求1或2所述的助剂,其特征在于,所述金属组分选自镓、锗、锡、锑、铋、铅、铜、银、锌、镉、钒、钼、钨、锰、铁、钴、镍中的一种或几种。 The adjuvant of claim 1 or claim 2, wherein said metal component selected from gallium, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, , manganese, iron, cobalt, nickel, one or several.
  8. 8.根据权利要求7所述的助剂,其特征在于,所述金属组分选自镓、锡、铜、银、锌、钒、钼、锰、铁、钴中的一种或几种。 8. The aid according to claim 7, wherein said metal component selected from gallium, one or more of tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, cobalt.
  9. 9.根据权利要求1或2所述的助剂,其特征在于,所述耐热无机氧化物选自氧化铝、氧化硅、无定型硅铝、氧化锆、氧化钛、氧化硼、碱土金属氧化物中的一种或几种。 9. The adjuvant of claim 1 or claim 2, wherein the heat-resistant inorganic oxide selected from alumina, silica, amorphous silica-alumina, zirconium oxide, titanium oxide, boron oxide, an alkaline earth metal oxide of one or more thereof.
  10. 10.根据权利要求1或2所述的助剂,其特征在于,所述粘土选自高岭土、多水高岭土、蒙脱土、硅藻土、埃洛石、皂石、累托土、海泡石、凹凸棒石、水滑石、膨润土中的一种或几种。 10. The adjuvant of claim 1 or claim 2, wherein said clay is selected from kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite one or more stone, attapulgite, hydrotalcite, bentonite.
  11. 11.根据权利要求1或2所述的助剂,其特征在于,所述分子筛选自大孔沸石和中孔沸石中的一种或几种。 11. The adjuvant of claim 1 or claim 2, wherein said one or more molecular sieve is selected large pore zeolite and medium pore zeolite.
  12. 12.根据权利要求11所述的助剂,其特征在于,所述分子筛选自Y型沸石、含磷和/或稀土的Y型沸石、超稳Y沸石、含磷和/或稀土的超稳Y沸石,Beta沸石、具有MFI结构的沸石、含磷和/或稀土的具有MFI结构的沸石中的一种或几种。 12. The adjuvant according to claim 11, wherein the molecular sieve is selected from zeolite Y, phosphorus and / or rare earth Y zeolite, ultrastable Y zeolite, phosphorus and / or rare earth ultrastable zeolite Y, zeolite Beta, with one or several MFI structure zeolite having a MFI structure zeolite, phosphorus and / or the rare earth.
  13. 13.根据权利要求1或2所述的助剂,其特征在于,该助剂还含有稀土金属组分,以助剂总量为基准,以氧化物计,所述稀土金属组分的含量为0-50重量%。 13. The adjuvant of claim 1 or claim 2, wherein the adjuvant further comprises a rare earth metal component, with reference to the total amount of additives, on an oxide basis, the content of the rare earth metal component is 0-50% by weight.
  14. 14.根据权利要求13所述的助剂,其特征在于,所述稀土金属组分的含量为0-15重量%。 14. The adjuvant according to claim 13, wherein the content of said rare earth metal component is 0-15 wt%.
  15. 15.根据权利要求13所述的助剂,其特征在于,所述稀土金属为镧、铈、富镧混合稀土金属或富铈混合稀土金属。 15. The adjuvant according to claim 13, wherein the rare earth metal is lanthanum, cerium, lanthanum-rich mischmetal or cerium-rich misch metal.
  16. 16.根据权利要求1或2所述的助剂,其特征在于,该助剂还含有磷组分,以助剂总量为基准,以元素磷计,所述磷组分的含量为0-15重量%。 16. The adjuvant of claim 1 or claim 2, wherein the adjuvant further comprises a phosphorus component, the basis of the total amount of additives, as elemental phosphorus, the phosphorus content of the component is 0- 15% by weight.
  17. 17.根据权利要求16所述的助剂,其特征在于,所述磷组分的含量为0-8重量%。 17. The adjuvant according to claim 16, wherein the content of the phosphorous component is 0-8% by weight.
  18. 18.权利要求1助剂的制备方法,该方法包括将含有金属组分化合物、耐热无机氧化物和粘土,含或不含分子筛的组合物与一种含有还原气体的气氛接触,所述接触的温度和接触的时间足以使所述金属组分的平均价态低于其最高氧化态,所述金属选自元素周期表IIIA族非铝金属、IVA族金属、VA族金属、IB族金属、IIB族金属、VB族金属、VIB族金属、VIIB族金属、VIII族非贵金属中的一种或几种,组合物中各组分的含量使最终助剂中含有,以助剂总量计,2-68重量%的耐热无机氧化物,大于30-80重量%的粘土,以最高价态金属的氧化物计,0.1-30重量%的金属组分,0-40重量%的分子筛。 18. A method of preparation of claim 1 aid, which comprises a compound containing a metal component, the heat-resistant inorganic oxide and clay, with or without molecular sieve composition with an atmosphere containing a reducing gas, said contacting the contact time and temperature sufficient to cause the average valence state of the metal component is less than its highest oxidation state, the metal is selected from non-aluminum metal group IIIA, IVA metals, VA metals, IB metals of the Periodic Table, IIB metals, VB metals, VIB metals, VIIB metals, VIII non-noble metal of group one or more, the content of each component in the final composition contain adjuvants, additives to the total count, 2-68 wt% of the thermotolerant inorganic oxide, greater than 30 to 80 wt% of clay, calculated as the oxide in the highest valence state of the metal, from 0.1 to 30 wt% of metal component, 0-40 wt% of molecular sieve.
  19. 19.根据权利要求18所述的方法,其特征在于,所述含有还原气体的气氛指纯的还原气体或含有还原气体和惰性气体的气氛。 19. The method according to claim 18, wherein the atmosphere containing the reducing gas means pure gas or a reducing atmosphere containing a reducing gas and an inert gas.
  20. 20.根据权利要求19所述的方法,其特征在于,所述纯的还原气体包括氢气、一氧化碳及含有1-5个碳原子的烃类中的一种或几种。 20. The method of claim 19, wherein said reducing gas comprises pure one or more hydrogen, carbon monoxide and hydrocarbon containing 1-5 carbon atoms in the.
  21. 21.根据权利要求20所述的方法,其特征在于,所述纯的还原气体包括氢气、一氧化碳、甲烷、乙烷、丙烷、丁烷及其各种异构体、戊烷及其各种异构体中的一种或几种。 21. The method of claim 20, wherein said reducing gas comprises pure hydrogen, carbon monoxide, methane, ethane, propane, butane, and various isomers thereof, and various iso-pentane configuration of one or more thereof.
  22. 22.根据权利要求19所述的方法,其特征在于,所述含有还原气体和惰性气体的气氛包括氢气、一氧化碳、含有1-5个碳原子的烃类中的一种或几种与惰性气体中的一种或几种的混合物,炼油厂中的干气。 22. The method of claim 19, wherein the atmosphere containing the reducing gas and an inert gas comprising hydrogen, carbon monoxide, hydrocarbons containing one or more 1-5 carbon atoms in the inert gas mixture of one or more, refinery dry gas.
  23. 23.根据权利要求19或22所述的方法,其特征在于,所述含有还原气体的气氛中,还原气体含量至少为10体积%。 23. The method of claim 19 or claim 22, wherein the atmosphere containing reducing gas, the reducing gas content is at least 10% by volume.
  24. 24.根据权利要求18所述的方法,其特征在于,所述接触的温度为100-900℃,接触的时间为0.1秒至10小时。 24. A method according to claim 18, wherein the contacting temperature is 100-900 deg.] C, the contact time is from 0.1 to 10 seconds.
  25. 25.根据权利要求18所述的方法,其特征在于,含有还原气体的气氛的用量为每克助剂每小时不小于5毫升还原气体。 25. The method of claim 18, wherein the reducing gas atmosphere containing an amount per gram of not less than 5 ml per hour aids reducing gas.
  26. 26.根据权利要求18所述的方法,其特征在于,组合物中各组分的含量使最终助剂中含有,以助剂总量计,10-60重量%的耐热无机氧化物,35-60重量%的粘土,0-30重量%的分子筛和以最高价态金属的氧化物计,0.5-20重量%的金属组分。 26. A method according to claim 18, wherein the content of each component in the final composition contain adjuvants, the total amount of additives to 10 to 60 weight% of the thermotolerant inorganic oxide, 35 60% by weight clay, and 0-30% by weight of molecular sieve in terms of oxide of the highest valence state of the metal, from 0.5 to 20 wt% of the metal components.
  27. 27.根据权利要求18所述的方法,其特征在于,所述含有金属组分化合物、耐热无机氧化物和粘土,含或不含分子筛的组合物中还含有稀土化合物和/或磷化合物。 27. The method of claim 18, wherein said compound containing a metal component, the heat-resistant inorganic oxide and clay, with or without a molecular sieve composition further contains a rare earth compound and / or phosphorus compounds.
  28. 28.一种具有脱硫作用的裂化助剂,该助剂含有一种耐热无机氧化物、粘土和一种金属组分,含或不含分子筛,其特征在于,以助剂总量为基准,耐热无机氧化物的含量为2-68重量%,粘土的含量为大于30至80重量%,分子筛的含量为0-40重量%,以所述最高价态的金属氧化物计,金属组分的含量为0.1-30重量%,所述金属组分选自元素周期表IIIA族非铝金属、IVA族金属、VA族金属、IB族金属、IIB族金属、VB族金属、VIB族金属、VIIB族金属、VIII族非贵金属中的一种或几种,所述助剂采用权利要求18-22和24-27中的任意一种方法制备。 28. A desulfurization of cracked aid with the aid comprising a heat-resistant inorganic oxide, clay and one metal component, with or without a molecular sieve, characterized in that, with reference to the total amount of additives, content of the thermotolerant inorganic oxide is 2-68% by weight, clay content of greater than 30 to 80 wt%, the content of zeolite is 0-40 wt%, to the highest valency state metal oxides, metal components an amount of 0.1-30 wt%, the metal component is selected from non-aluminum metal of the Periodic Table group IIIA, IVA metals, VA metals, IB metals, IIB metals, VB metals, VIB metals, VIIB 18-22 and 24-27 in the preparation method of any one metal, one or more non-noble metal of group VIII, the use of additives as claimed in claim.
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