CN101573181B - 活性催化剂浆料的浓缩 - Google Patents

活性催化剂浆料的浓缩 Download PDF

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CN101573181B
CN101573181B CN2007800493859A CN200780049385A CN101573181B CN 101573181 B CN101573181 B CN 101573181B CN 2007800493859 A CN2007800493859 A CN 2007800493859A CN 200780049385 A CN200780049385 A CN 200780049385A CN 101573181 B CN101573181 B CN 101573181B
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oil
catalyst
slurry catalyst
active slurry
metallic compound
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CN101573181A (zh
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B·E·雷诺兹
A·布雷特
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Chevron USA Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/10—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles
    • C10G49/12—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles suspended in the oil, e.g. slurries

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

本申请公开了为便于运输至加氢处理单元而将活性浆料催化剂料流浓缩并脱油的方法。所述浆料催化剂然后可以用油稀释以供使用。通过将VI族金属化合物和VIII族金属化合物传送至催化剂合成单元而形成催化剂，在所述单元它们与油、硫化氢气体和氢气合并以在油中产生活性浆料催化剂。然后在送往加氢处理地点之前将所述浆料催化剂浓缩。

Description

活性催化剂浆料的浓缩
发明领域
本申请公开了活性浆料催化剂料流的浓缩和脱油方法。
发明背景
浆料催化剂组合物、其制备方法及其在重质原料的加氢处理中的用途在炼油领域是已知的。下面讨论一些实例：
美国专利4,710,486公开了分散的VIB族金属硫化物烃油加氢处理催化剂的制备过程。工艺步骤包括使氨水与VIB族金属化合物如氧化钼或氧化钨反应，形成水溶性含氧化合物如钼酸铵或钨酸铵。
美国专利4,970,190公开了用于烃油加氢处理的分散的VIB族金属硫化物催化剂的制备过程。用VIII族金属可以增效这种催化剂。工艺步骤包括用氨溶解VIB族金属化合物如氧化钼或氧化钨，形成水溶性化合物如钼酸铵或钨酸铵溶液。
美国专利5,053,376公开了制备硫化钼催化剂浓缩物的方法。通过将下述物质混合在一起来形成前体催化剂浓缩物：(i)包含沸点高于约1050°F的组分的烃油；(ii)选自元素周期表中II、III、IV、V、VIB、VIIB和VIII族的金属化合物，其量提供了约0.2％至2wt％的金属，％基于所述烃油；和(iii)元素硫，其量使硫与金属的原子比例为约1/1至8/1，然后(b)将混合物加热至产生催化剂浓缩物的有效温度。制备过程中也可以使用铵化合物。
在催化剂合成步骤之后，本发明的浆料催化剂物料需要浓缩。在油料流中输送该浆料催化剂。为了保持该催化剂浆料的可泵性，并减少金属回收单元必须处理的物料体积，期望减少油量。
发明概述
本申请公开了为脱油和增强可泵性而在催化剂合成后浓缩催化剂浆料的方法。
该方法的主要步骤如下：
将存在于油料流中的活性浆料催化剂浓缩的方法，所述方法包括下述步骤：(a)将VI族金属化合物和VIII族金属化合物传送至催化剂合成单元，在那里它们与油、硫化氢气体和氢气混合以在油中产生活性浆料催化剂；(b)将步骤(a)的流出物传送至催化剂浓缩区，在那里产生浓缩的活性催化剂；(c)将步骤(b)的浓缩的催化剂传送至加氢处理单元所在地，在那里将其稀释在稀释区中。
在认定为最佳地产生活性的催化剂浓度下生产催化剂浆料。然而，从船运的角度看，使得到的催化剂活性最佳的浓度提供在经济上不切实际的浆料体积。过去，这导致主要的缺点：需要将催化剂合成单元与使用该油基催化剂的加氢处理单元放在同一地点。为了克服这个问题，我们设计了在催化剂合成后浓缩催化剂的方法，用这种方法，得到的浓缩的浆料能经济地从中心催化剂合成地点船运走。这允许使用一个催化剂合成单元用于多个加氢处理单元地点的规模经济性。在加氢处理单元所在地重新稀释该浓缩的催化剂以便于处理并确保在加氢处理单元中的高活性。
附图简述
附图说明了本发明中公开的在催化剂合成后对催化剂浆料进行浓缩和脱油的方法。
发明详述
VIII族金属化合物(料流1)和VI族金属化合物(料流2)进入催化剂合成单元(CSU10)，在这里与硫化氢(料流3)、轻质真空瓦斯油或载体油(料流4)和氢气(料流5)混合。优选的VIII族金属化合物是硫酸镍，而优选的VI族金属化合物是二钼酸铵。
在催化剂合成单元(CSU10)中，条件包括温度为80°F至200°F，优选为100°F至180°F，和最优选为130°F至160°F。压力为100至3000psig，优选为200至1000psig，和最优选为300至500psig。在CSU10中将各组分混合，以在油中形成活性浆料催化剂。
CSU是连续搅拌釜反应器(CSTR或可替代地，优选混合反应器)。为了防止催化剂结块而使用这类反应器。
离开CSU10并进入催化剂浓缩区20(CCZ 20)的料流6，包含催化剂浆料和载体油，比例为10％固体对90％油。料流7包含回收的载体油，所述回收的载体油循环至CSU 10或去往最终供料至CSU 10的储存罐。
可以得到多种方法以在CCZ 20中将所述浆料催化剂浓缩并脱油。优选的方法包括浓缩油浆料中的固体，然后使用溶剂清洗或过滤。特别有用的是公知的过滤技术如错流过滤，其允许分离约30％至约80％的油，并将该油循环至催化剂合成单元10。优选的范围是去除约40％至约75％的所述油。将浓缩的催化剂料流，料流8，输送至稀释区30，其位于加氢处理单元所在地点。
CCZ 20的合适的操作条件包括温度为约194°F至约212°F。用于初始浓缩的压力为约100至约120psi，而用于溶剂过滤的压力为90psi。
用于稀释区30的油的合适选择可以与催化剂合成单元10中所用的油相同。所使用的油(料流12)取决于可得性和经济性。理想地，它应该是易于船运的高闪点油(为了避免环境和安全危险)，它应该具有低倾点以最小化低温处理问题(冷流问题)。典型的料流是轻质真空瓦斯油、重质常压瓦斯油和其他粘度适中的料流(在100℃下为4-10cst)。在低粘度下密度更高的料流是最好的。可以在料流9中加入补充氢气。适用于加氢处理的活性催化剂浆料作为料流11离开所述稀释区。
在浓缩、清洗和过滤中所用膜的选择中使用的因素包括渗透流通率、滤液品质、膜的化学相容性、膜的机械强度和膜的温度耐受性。

Claims (14)

1.将存在于油料流中的活性浆料催化剂浓缩的方法，所述方法包括下述步骤：
(a)将VI族金属化合物和VIII族金属化合物传送至催化剂合成单元，在那里它们与油、硫化氢气体和氢气混合以产生在油中的活性浆料催化剂；
(b)将所述在油中的活性浆料催化剂传送至催化剂浓缩区，在那里将油从所述在油中的活性浆料催化剂中除去以形成降低体积的在油中的活性浆料催化剂；
(c)将所述降低体积的在油中的活性浆料催化剂传送至加氢处理单元所在地；和
(d)通过用稀释油在稀释区中稀释再造所述在油中的活性浆料催化剂。
2.权利要求1的方法，其中所述VI族金属化合物是钼酸铵。
3.权利要求1的方法，其中所述VIII族金属化合物是硫酸镍。
4.权利要求1的方法，其中所述在油中的活性浆料催化剂包含催化剂浆料，其比例为10％固体对90％油。
5.权利要求1的方法，其中从所述在油中的活性浆料催化剂中去除30％至80％的所述油。
6.权利要求5的方法，其中从所述在油中的活性浆料催化剂去除40％至80％的所述油。
7.权利要求1的方法，其中将从步骤(b)去除的油再循环至步骤(a)中或送去存储。
8.权利要求1的方法，其中所述稀释油在100℃下的粘度为4至10cSt。
9.权利要求1的方法，其中稀释油是真空瓦斯油或重质常压瓦斯油。
10.权利要求1的方法，其中步骤(a)中的条件包括温度为80°F至200°F。
11.权利要求10的方法，其中步骤(a)中的条件包括压力为100至3000psig。
12.权利要求1的方法，其中步骤(b)中的条件包括温度为194°F至212°F。
13.权利要求1的方法，还包括溶剂清洗或过滤所述降低体积的在油中的活性浆料催化剂。
14.权利要求1的方法，其中所述催化剂浓缩区包含错流过滤系统。
CN2007800493859A 2006-12-06 2007-12-05 活性催化剂浆料的浓缩 Expired - Fee Related CN101573181B (zh)

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US11/567,628 US20080139380A1 (en) 2006-12-06 2006-12-06 Concentration of active catalyst slurry
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PCT/US2007/086534 WO2008070735A2 (en) 2006-12-06 2007-12-05 Concentration of active catalyst slurry

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EA015029B1 (ru) 2011-04-29
EP2101913A2 (en) 2009-09-23
EA200970546A1 (ru) 2009-12-30
JP5372770B2 (ja) 2013-12-18
EP2101913A4 (en) 2013-09-04
WO2008070735A3 (en) 2008-08-07
CA2671762C (en) 2015-06-02
BRPI0720150A2 (pt) 2014-02-04
KR20090087085A (ko) 2009-08-14
CA2671762A1 (en) 2008-06-12
JP2010512240A (ja) 2010-04-22
US20080139380A1 (en) 2008-06-12
CN101573181A (zh) 2009-11-04

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