CN108472554A - 用于从固体材料移除污染物的萃取系统和工艺 - Google Patents
用于从固体材料移除污染物的萃取系统和工艺 Download PDFInfo
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Classifications
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- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/005—After-treatment of coke, e.g. calcination desulfurization
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D11/02—Solvent extraction of solids
- B01D11/0215—Solid material in other stationary receptacles
- B01D11/0223—Moving bed of solid material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0292—Treatment of the solvent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
- B09C1/025—Extraction using liquids, e.g. washing, leaching, flotation using an oil as solvent or extracting agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/06—Reclamation of contaminated soil thermally
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1033—Oil well production fluids
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- 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
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- C10G2300/20—Characteristics of the feedstock or the products
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- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
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- Processing Of Solid Wastes (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
一种用于纯化含有例如石油焦炭等污染物的固体材料的技术可涉及将污染的固体材料连同有机溶剂一起引入到萃取器容器中。所述污染的固体材料和有机溶剂可在逆流方向上输送,在此期间从所述固体材料中至少部分地萃取出所述污染物并将所述污染物萃取入所述溶剂中。在萃取之后,所得萃取固体材料可在脱溶剂单元中处理且将回收的溶剂传送回所述萃取器。另外,含有萃取污染物的溶剂可在溶剂回收单元中处理,从而进一步回收可传送回所述萃取器的溶剂。
Description
相关主题
本申请要求2015年12月17日提交的美国临时申请第62/268,713号的优先权,所述美国临时申请的全部内容以引用的方式并入本文中。
技术领域
本公开涉及溶剂萃取,且更确切地说,涉及使用液体溶剂萃取器从固体材料萃取污染物。
背景技术
例如泥土、石油焦炭和油砂尾渣等固体材料可含有污染物,其阻止材料用于所要应用或阻止以安全且具有成本效益的方式而被处置。举例来说,固体材料可含有硫、汞、重金属或其它污染物,期望将其移除以便使用或安全地处置固体材料。
发明内容
一般来说,本公开涉及用于从固体材料移除污染物的系统和技术。虽然所公开的系统和技术可利用经合理处理的各种不同固体材料,但是在一些实例中,固体材料是由炼油厂焦化器单元或其它裂化处理产生的石油焦炭。可形成石油焦炭的实例焦化工艺包含接触焦化、流体焦化、灵活焦化和延迟焦化。此焦化可含有可能需要从焦炭中被移除和回收的重金属或其它污染物。
在一些实例中,描述一种技术,其涉及将含有污染物的固体材料引入到萃取器中且使用萃取器内的溶剂从固体材料萃取固体材料中含有的污染物中的至少一些,由此产生具有增大浓度的污染物的溶剂和具有减小浓度的污染物的固体材料。具有减小浓度的污染物的固体材料可被从萃取器排出且被输送到脱溶剂器。此外,具有增大浓度的污染物的溶剂可被从萃取器排出且被输送到溶剂回收单元。可使用脱溶剂器对具有减小浓度的污染物的固体材料进行脱溶剂且可在溶剂回收单元中处理具有增大浓度的污染物的溶剂以回收污染物。这样可产生多个产物流,包含具有减小浓度的污染物的固体材料流和从用以处理固体材料的溶剂中回收的材料(例如,一个或多个金属)流。
随附图式和以下描述中阐述一个或多个实例的细节。其它特征、目标和优势将从描述和图式以及权利要求书而显而易见。
附图说明
图1是说明实例固体-溶剂萃取系统的功能框图。
图2是说明实例固体-溶剂萃取工艺的框图。
具体实施方式
本公开涉及用于从固体材料移除污染物的萃取器系统和萃取工艺。在一些实例中,固体材料是含碳材料,例如粗油萃取或处理设施的残留物或副产物。举例来说,固体材料可以是来自炼油厂的石油焦炭、油砂尾渣或从粗油处理导出的其它含碳材料。石油焦炭的实例类型包含海绵状焦炭、针状焦炭和球状焦炭。在其它实例中,固体材料是土质材料,例如尘土,其可以是或包含粘土、沙石和/或砾石。固体材料可含有污染物,其可或可不含碳。举例来说,固体材料可含有硫、汞、重金属或其它污染物。实例重金属污染物包含铝、锑、钴、铜、铁、锰、钼、镍、硒、银、锡、钒、锌和其组合。
根据本公开,萃取器系统和萃取工艺用以从经受处理的固体材料中移除污染物。在一个实例中,连续固-液萃取器用以从固体材料萃取污染物。在不同实例中,萃取器可以是螺旋萃取器、浸入萃取器或其它类型的萃取器。萃取器可具有接纳经受处理的固体材料的进料口、在萃取之后排出固体材料的出料口、接纳引入溶剂的溶剂入口,以及排出具有从固体材料萃取出的增大浓度的污染物的溶剂的溶剂出口。萃取器还可具有将固体材料从进料口移动到出料口的传输系统。
在操作中,固体材料在萃取器内部与溶剂接触,以使得污染物从固体材料浸出或转移到溶剂中。在一些实例中,萃取器是连续逆流萃取器,在其中经受处理的固体材料在方向上从进料口移动到出料口,而溶剂在相反的方向上从溶剂入口移动到溶剂出口。随着污染物从溶剂入口移动到溶剂出口,其在溶剂中的浓度可逐渐增大,而随着固体在进料口中移动到出料口污染物的浓度对应地减小。用于萃取工艺的溶剂可以是任何所要类型的溶剂。举例来说,溶剂可以是例如己烷、甲苯、丙酮、醇(例如,异丙醇、乙醇)等等的有机溶剂。
图1是说明可根据本公开使用的实例固体-溶剂萃取系统的功能框图。如所示出,固体-溶剂萃取系统10包含萃取器12、固体脱溶剂器14、溶剂回收或蒸馏单元16,和污染物分离单元18。萃取器12接纳污染的固体20和溶剂22且使污染的固体在萃取器内部与溶剂接触。溶剂从污染的固体20萃取污染物,从而产生具有增大浓度的污染物24的溶剂流和具有减小浓度的污染物26的固体流。萃取器12内部的温度可在环境温度与所用溶剂的沸点之间变化。取决于系统的配置和经受处理的材料,萃取器12可从污染的固体材料20移除污染物的至少20重量百分比,例如至少50重量百分比,至少75重量百分比,或至少90重量百分比。举例来说,萃取器12可移除一种或多种污染物的30重量百分比到95重量百分比,例如50重量百分比到90重量百分比。
为制备具有减小浓度的污染物26的固体流以供下游使用,系统10包含固体脱溶剂器14。固体脱溶剂器14可接纳具有减小浓度的污染物26的固体流且加热所述流以从固体移除残留溶剂。举例来说,可使用脱溶剂器烤箱或增加具有减小浓度的污染物26的固体流温度的其它脱溶剂装置实施固体脱溶剂器14。流的温度可增大到高于萃取器12中所用溶剂的沸点的温度,从而使得残留溶剂挥发。在一些配置中,除了或代替任何其它直接或间接加热,将蒸汽注入固体脱溶剂器14中。
从图1中的萃取器12排出具有增大浓度的污染物24的溶剂流。为了回收溶剂,以用于再循环到萃取器12和/或出于其它再使用目的,系统10可包含溶剂回收或蒸馏单元16。溶剂回收单元可接纳具有增大浓度的污染物24的溶剂流且将溶剂中的污染物与溶剂自身分离。在不同配置中,溶剂回收单元16可以是过滤单元、蒸馏单元或将溶剂与其中的污染物分离的其它设备。溶剂回收单元16可生成相比于引入的溶剂流24具有减小浓度的污染物的回收溶剂流28。在一些实例中,溶剂回收单元16移除被拾起到萃取器12中的溶剂流中的基本上所有污染物。
溶剂回收单元18可部分或完全蒸发具有增大浓度的污染物24的溶剂流。这样可产生污染物流30,其为含有在萃取器10内部萃取的污染物的沉淀物或残留物。此沉淀物或残留物可任选地在污染物分离单元18中进一步处理。举例来说,污染物流30可以是富含污染物的含溶剂流。污染物流30可以是来自用以回收再循环到萃取器12的溶剂的蒸馏塔的塔底流。污染物分离单元18可使从污染固体20萃取到溶剂中的污染物与溶剂自身分离。举例来说,在其中有机溶剂用于萃取器10的情况下,污染物分离单元18可使污染物流30中的污染物与残留溶剂分离。用作污染物分离单元18的分离单元的特定类型可基于经受处理的材料的类型和被移除的污染物的组成而变化。
图2是说明实例固体-溶剂萃取工艺的框图。工艺包含连同溶剂一起将含污染物的固体材料引入到萃取器中,且将污染物中的至少一些从固体材料萃取到溶剂中(40)。在一个实例中,固体材料是含重金属的石油焦炭。连同有机溶剂一起将石油焦炭引入到连续萃取器(例如,逆流浸入萃取器)中。随着污染的石油焦炭和溶剂移动通过萃取器,重金属可从石油焦炭中萃取出且到有机溶剂中。
图2的工艺还包含使已进行萃取且已从萃取器排出的固体材料脱溶剂(42)。举例来说,在石油焦炭已进行溶剂萃取以移除重金属的状况下,可使用残留溶剂润湿从溶剂萃取器排出的石油焦炭。为准备具有减小浓度的重金属的石油焦炭用于运输、存储和/或使用,可将石油焦炭加热(任选地在存在蒸汽的情况下)到高于萃取器中使用的溶剂的沸点的温度。升高温度可驱使残留有机溶剂离开石油焦炭。
在图2中,处理从萃取器排出的具有增大浓度的污染物的溶剂以回收溶剂(44)。在使用有机溶剂萃取的石油焦炭的实例中,可将具有增大浓度的污染物(已从石油焦炭萃取)的有机溶剂传送到一个或多个蒸馏塔。有机溶剂可在蒸馏塔内部分汽化,从而产生基本上不含污染物的有机溶剂流和富含浓缩污染物的塔底有机溶剂流。基本上不含污染物的有机溶剂流可再循环回萃取器的溶剂入口。可或可不进一步处理富含浓缩污染物的塔底有机溶剂流。
图2的工艺示出进一步处理富含浓缩污染物的塔底有机溶剂流以使污染物与残留溶剂分离(44)。在石油焦炭的状况下,可处理有机溶剂流以从浓缩重金属污染物移除残留溶剂。移除溶剂还可或可不再循环回萃取器。另外,重金属污染物可或可不彼此分离,例如以提供彼此分离的特定重金属,以供进一步处理或处置。
如上文所提及,根据本公开的技术可在广泛各种不同的含有污染物的固体材料上执行。可合乎需要地处理的固体材料的一个实例是已经煅烧的石油焦炭。虽然可例如基于用以产生焦炭的粗油的组成改变这种焦炭的组成,但在一些实例中,焦炭具有大于90重量百分比的碳,例如大于95重量百分比的碳,或者大于98重量百分比的碳。焦炭可以是为污染物的一种或多种金属,例如按重量计5ppm到50ppm铬,10ppm到60ppm钴,50ppm到5000ppm铁,2ppm到100ppm锰,10ppm到20ppm钼,10ppm到500ppm镍,和/或5ppm到500ppm钒。如本文中所描述萃取技术可将这些污染物中的一个或多个的浓度减少上文所论述那些百分比。
已经描述各种实例。这些和其它实例在所附权利要求书的范围内。
Claims (16)
1.一种方法,包括:
将含有至少一种污染物的固体材料引入到萃取器中;
将溶剂引入到所述萃取器中;
将所述固体材料中含有的所述至少一种污染物中的至少一些从所述固体材料萃取到所述萃取器内的所述溶剂中,由此产生具有增大浓度的污染物的溶剂和具有减小浓度的污染物的固体材料;
从所述萃取器排出所述具有减小浓度的污染物的固体材料且将所述具有减小浓度的污染物的固体材料输送到脱溶剂器;
从所述萃取器排出所述具有增大浓度的污染物的溶剂且将所述具有增大浓度的污染物的溶剂输送到溶剂回收单元;
在所述脱溶剂器内部使所述具有减小浓度的污染物的固体材料脱溶剂;以及
在所述溶剂回收单元内部使萃取到所述具有增大浓度的污染物的溶剂中的至少一些污染物与所述溶剂分离。
2.根据权利要求1所述的方法,进一步包括将在所述溶剂回收单元中回收的溶剂再循环到所述萃取器。
3.根据权利要求1或2所述的方法,其中所述溶剂回收单元生成富含污染物的液流,且进一步在污染物分离单元中包括所述富含污染物的液流。
4.根据前述权利要求中任一项所述的方法,其中所述含有至少一种污染物的固体材料包括石油副产物。
5.根据权利要求4所述的方法,其中所述石油副产物包括石油焦炭。
6.根据前述权利要求中任一项所述的方法,其中所述至少一种污染物包括重金属。
7.根据前述权利要求中任一项所述的方法,其中所述溶剂包括有机溶剂。
8.根据前述权利要求中任一项所述的方法,其中将所述固体材料中含有的所述至少一种污染物中的至少一些从所述固体材料萃取到所述溶剂中包括在逆流方向上输送所述固体材料和所述溶剂通过所述萃取器。
9.根据前述权利要求中任一项所述的方法,进一步包括将在所述脱溶剂器中回收的溶剂再循环到所述萃取器。
10.一种纯化石油焦炭的方法,包括:
将含有选自由锑、钴、锰、钼、镍、硒、银、锡、钒、锌和其组合组成的组的污染物的石油焦炭引入到萃取器中;
将有机溶剂引入到所述萃取器中;
在所述萃取器内将至少20重量百分比的所述污染物从所述石油焦炭萃取到所述有机溶剂中,由此产生含有所述污染物和萃取石油焦炭的有机溶剂;
从所述萃取器排出所述萃取石油焦炭且将所述萃取石油焦炭输送到脱溶剂器;
从所述萃取器排出含有所述污染物的所述有机溶剂且将含有所述污染物的所述溶剂输送到溶剂回收单元;
在高于所述有机溶剂的沸点的温度下在所述脱溶剂器内部使所述萃取石油焦炭脱溶剂;以及
在所述溶剂回收单元内部使所述污染物中的至少一些与含有所述污染物的所述溶剂分离。
11.根据权利要求10所述的方法,进一步包括将在所述溶剂回收单元中回收的溶剂再循环到所述萃取器。
12.根据权利要求10或11所述的方法,其中所述溶剂回收单元生成富含污染物的液流,且进一步在污染物分离单元中包括所述富含污染物的液流。
13.根据权利要求10到12中任一项所述的方法,进一步包括在炼油厂焦化器单元中生成所述石油焦炭。
14.根据权利要求10到13中任一项所述的方法,其中将至少20重量百分比的所述污染物从所述石油焦炭萃取到所述有机溶剂中包括在逆流方向上输送所述石油焦炭和所述有机溶剂通过所述萃取器。
15.根据权利要求10到14中任一项所述的方法,进一步包括将在所述脱溶剂器中回收的所述有机溶剂再循环到所述萃取器。
16.根据权利要求10到15中任一项所述的方法,其中将至少20重量百分比的所述污染物从所述石油焦炭萃取到所述有机溶剂中包括将从50重量百分比到90重量百分比的所述污染物从所述石油焦炭萃取到所述有机溶剂中。
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