CN103025850A - Process and agents to remove metals from high-boiling hydrocarbon fractions - Google Patents

Process and agents to remove metals from high-boiling hydrocarbon fractions Download PDF

Info

Publication number
CN103025850A
CN103025850A CN2011800363334A CN201180036333A CN103025850A CN 103025850 A CN103025850 A CN 103025850A CN 2011800363334 A CN2011800363334 A CN 2011800363334A CN 201180036333 A CN201180036333 A CN 201180036333A CN 103025850 A CN103025850 A CN 103025850A
Authority
CN
China
Prior art keywords
hydrocarbon
fraction
metal
sulphur
metal remover
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2011800363334A
Other languages
Chinese (zh)
Inventor
I·鲍尔
R·本施
U·拉布-布里尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Publication of CN103025850A publication Critical patent/CN103025850A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G29/00Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20Organic compounds not containing metal atoms
    • C10G29/28Organic compounds not containing metal atoms containing sulfur as the only hetero atom, e.g. mercaptans, or sulfur and oxygen as the only hetero atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G19/00Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G29/00Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20Organic compounds not containing metal atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1022Fischer-Tropsch products
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/205Metal content

Abstract

The object of the invention is a process and agents to remove metal contaminants from hydrocarbon fractions like those obtained as a product from the Fischer-Tropsch synthesis involving the use of suspended catalyst. As per the present invention, the feed hydrocarbon fraction is treated with a demetallizing agent, comprising at least one sulfur source and at least one basic compound, under anhydrous conditions. The metals to be removed are obtained in the form of precipitate that can be easily separated by means of a mechanical separation process such as filtration, for example.

Description

Be used for removing from the high boiling hydrocarbon cut method and the reagent of metal
Invention field
The present invention relates to a kind of method of from the high boiling hydrocarbon cut, removing metal, and be used for its reagent that removes.Particularly, it is synthetic to the present invention relates to separation source autocatalysis agent and hydrocarbon, for example according in the Primary product of Fischer-Tropsch method method and the reagent of nickeliferous, cobalt and aluminum pollution thing.
Description of the Prior Art
Hydrocarbon can be used as synthetic product and is produced by chemical catalysis method such as Fischer-Tropsch method, the key element of the method is described in greater detail in the Encyclopedia of Industrial Chemistry of thematic literature such as Ullmann, the 6th edition, 1998Electronic Release, keyword " Coal Liquefaction " is in the 2.2nd chapter " Fischer-Tropsch Synthesis ".The modernism change programme is at Solid particulate catalyst transformation of synthetic gas (so-called slurry process) in the suspension of product liquid hydrocarbon.In the method, use high activated catalyst, its active ingredient contains metal such as cobalt and solid support material such as aluminum oxide, as described in US Patent No. 4801573.Except a large amount of other publications, International Patent Application WO 98/27181A1 proposes a kind of method that catalyst suspension is separated with hydrocarbon product.The products therefrom hydrocarbon usually contains the heavy metal of significant quantity in the method.The possible cause of this undesirable heavy metal contamination is the abrasion and corrosion process that occurs on catalyst system therefor and/or the tank material in the synthetic method.Yet, only be suitable for the separating particles metal pollutant and be unsuitable for separating chemical bonding or finely divided and/or colloidal metal in the hydrocarbon phase based on these methods of mechanical separation method.
Outside the heavy metal pollution removing, also observe by catalyst support substrate (for example aluminium) and pollute.Described metallic pollution may be destructive for the further chemical catalysis conversion of product hydrocarbon, because it can serve as catalyzer poison.In addition, no matter comprise its material, heavy metal contamination demonstrates potential environment and Health hazard.Particularly, must mention herein and classify as carcinogenic nickel and cobalt.On the other hand, the valuable catalyst elements of recirculation to avoid damage answered in the representative of two heavy metal species.
Prior art becomes known for the whole bag of tricks that metal pollutant is separated with hydrocarbon.Publication AT205229, DD26308, EP0009935B1, GB1001190, US3449243, US3617530 and WO2009113095A2 have described the washing methods that is used for removing from hydrocarbon phase metal pollutant.In these methods, hydrocarbon phase with the aqueous solution of some reagent or by reagent is added in the organic phase, is transferred to the aqueous phase processing with after washing with the dissolution of metals pollutent and with them.The shortcoming of these methods is to process with the two-phase mixture that separates subsequently hydrocarbon phase and water and in its processing or re-use work with the required water of pre-treatment.
German patent application DE1212662 has described a kind of hydrocarbon ils of processing to remove the method for the harmful metal pollutant of the catalyzer of its conversion.Suggestion herein changes into metal almost insoluble precipitate thus with the contaminated hydrocarbon ils of the solution-treated of hydrogen fluoride in organic solvent, and this throw out can separate by mechanical separation method in downstream procedures.Like this, the problems referred to above during having avoided the two-phase mixture of hydrocarbon phase and water to process.Yet the use of hyperergy gaseous hydrogen fluoride in the preparation treatment soln is owing to Occupational safety and process reason, demonstrates shortcoming.
DE patent application 2346058 demonstrates a kind of method of removing metal impurities from the hydrocarbon material, the method is by making this material contact under hydrogenation conditions with catalyzer, thus the containing metal pollutent is reduced into metal element, described metal element is as throw out and hydrocarbon phase separation.The shortcoming of the method be complicated technology controlling and process to guarantee very completely hydrogenation of metal pollutant, avoid simultaneously the hydrocracking of hydrocarbon.
US Patent No. 4518484 has been described a kind of method of processing the incoming flow of containing metal hydrocarbon, the method relates to following steps: hydrocarbon solvent that hydrocarbon incoming flow and at least a per molecule contain 2-10 carbon atom is being contacted in the presence of based on the metal remover of organophosphorus chemistry product under the super critical condition, (b) from extraction section, reclaim the bottom stream that contains the hydrocarbon that pollutes the substantive reduction of metal content, and contain the bottoms that carries metal solvent.A shortcoming is the generation of technology controlling and process, the especially super critical condition of complexity.
Invention is described
Therefore the task of the present invention below is to propose a kind ofly to remove the simple technique of metal pollutant and be used for carrying out simple method-particularly the do not use this suitable tools that removes of water-bearing media-sign by can not using the material that relates to high potential risk to use from the high boiling hydrocarbon cut.
Mainly result from the feature of sign part claim 1 according to solution of the present invention together with the feature of the sign part of this claim, it is---in the method for the hydrocarbon-fraction that obtains having low-metal content, wherein the metal in the hydrocarbon-fraction is with colloidal state or finely divided form chemical bonding or be scattered in the hydrocarbon-fraction, and the metal remover that will comprise following component adds in the liquid hydrocarbon fraction:
(a) at least a at least part of sulphur source that dissolves in the hydrocarbon-fraction,
(b) at least a at least part of basic cpd that dissolves in the hydrocarbon-fraction,
And be that after adding metal remover metal separates with the sedimentary form precipitation of dissolubility hardly and by mechanical separation method.
Other favourable embodiment of the present invention results from dependent claims.The invention still further relates to according to claim 2-6 and 10 metal remover.
With regard to regard to the processing of the method for the object of the invention, pending feed hydrocarbon cut is necessary for liquid.If necessary, must be with wax-like hydrocarbon, those meltings before processing that for example obtain as the product of Fischer-Tropsch method.
Known metal such as nickel or cobalt precipitate from the aqueous solution with the form of its insoluble sulfur compound, therefore can separate with inorganic many metal mixtures quantitatively.This needs sulfonium ion (S 2-) and the alkaline condition of appointment, or say more accurately 〉=8 pH (Jander; Blasius, " Lehrbuch der analytischen und Anorganischen Chemie ", the 14th edition, Hirzel Verlag, Stuttgart1995).Surprisingly, demonstrate nickel and be transferred in vogue anhydrous condition with the hydrocarbon of metallic pollution by this principle of separating as sulfide precipitation with cobalt.To demonstrate the existence of basic cpd be important for reaction to simultaneous test herein.This allows and infers that the reaction most probable is undertaken by the middle sulfide and/or the hydrogen sulfide that form.Sulphur source is with free or also be possible in conjunction with the direct base catalyzed reactions of metal.
Especially advantageously this fact: along with removing of nickel and cobalt, also realize being derived from the removing fully of aluminum pollution thing of solid support material.Therefore, discovery can realize nickel and cobalt with other metal such as aluminium with the dilution of simple single stage method.The gained metallic sulfide precipitates from reaction mixture as fine and close throw out, and it can separate by suitable mechanical separation method easily, and can send into metal recirculation with this height conc forms.
The reaction that is formed metallic sulfide by divalent metal (Ni, Co) can be described below:
Me 2++S 2-=MeS
Metal ion sulfonium ion=metal (II) sulfide
According to the present invention, for being precipitated required sulfide concentration, must satisfy two requirements:
(a) there is the alkali that dissolves at least in part in the hydrocarbon.Example can for ammonia, amine, alkanolamine, pyridine, ammonium,
Figure BDA00002773304700031
And sulfonium compound; Other basic cpd that dissolves at least in part in principle in the pending hydrocarbon phase also is possible.
(b) there is the sulphur source.The example in sulphur source is: organosulfur compound such as urea, thiocarbonic ester, dithiocarbonates, thiocarbamate, dithiocarbamate, mercaptan, organic disulfide, organic polysulfide, thioamides; Inorganic sulfide compound such as gas vulcanization hydrogen, ammonium sulfide, inorganic monosulphide, without organic disulfide, inorganic polysulfide or elementary sulfur.In principle, can produce or be provided for the sulfonium ion of precipitin reaction and/or any sulfocompound of active sulphur atom under processing condition can be used among the present invention.
Other preferred embodiment of the present invention
In the preferred embodiment of the invention, elementary sulfur is as the sulphur source.It can be added in the pending hydrocarbon-fraction as powder, stir simultaneously, it is dissolved in the hydrocarbon equably thus.
In another preferred embodiment, the inventive method uses the gac comprise the sulphur dipping to carry out as the metal remover in its sulphur source.Advantageously, under desired treatment temp, avoided the formation of molten sulfur herein, described molten sulfur can treatment unit than cool region in solidify and cause fouling or obstruction in this class zone.As powder or as formed body, the gac of the sulphur dipping that for example adds with the form of extrudate keeps its structure and characteristics and can easily separate by mechanical separation method.
In another embodiment of the inventive method, plan adds gas vulcanization hydrogen in the hydrocarbon-fraction as the sulphur source.
, preferably undertaken by filtration, sedimentation, decant or centrifugal or its combination by mechanical separation method according to the sedimentary separation of metallic hardly dissolubility of the present invention.
In another embodiment of the inventive method, the gac of sulphur dipping is as metal remover, and after adding alkali, pending hydrocarbon-fraction is fed the fixed-bed reactor that contain this metal remover bed, thus poor metal hydrocarbon cut is taken out from fixed-bed reactor as product.Like this, separate the required effort of metallic almost insoluble precipitate and be down to minimum.
By adding the sulfur-bearing metal remover, the sulphur content of the hydrocarbon-fraction that obtains as product is compared with the feed hydrocarbon cut and is significantly improved.Depend on and be intended to the purposes type or for the processing of product hydrocarbon-fraction, this may be favourable.Wherein optionally produce after the wax-like hydrocarbon product of long-chain synthetic according to the hydrocarbon of Fischer-Tropsch method normally the hydrocracking step for generation of short hydrocarbon such as diesel oil distillate or Otto fuel fraction.With regard to hydrocracking, it is catalyst based usually to use sulphuring treatment by in advance to reach its final active cobalt-molybdenum.Therefore, other embodiment of the inventive method the demetalization hydrocarbon-fraction that obtains in the methods of the invention is provided since its higher sulphur content and in the activation of sulphur deactivated catalyst as the purposes of sulfur donor.
Higher sulfur content in the hydrocarbon-fraction of processing according to the present invention is always not acceptable.Therefore, another favourable embodiment of the present invention provides organic sulfur compound, preferred mercaptan, and more particularly tri-thiol-s-triazine is as the purposes of sulfur-bearing metal remover.Surprisingly, the use of this component only produces with using the metal remover based on elementary sulfur and compares, a small amount of raising of sulphur content in the hydrocarbon-fraction of processing according to the present invention.
Embodiment and digital embodiment
Other embodiment of the present invention, advantage and application choice also result from the following non-exhaustive description of embodiment and digital embodiment.All features are summarized in claim or the Rights Concerned requirement regardless of them separately or with any the present invention of being combined to form.
Embodiment 1
(from the synthetic wax slop of Fischer-Tropsch, it has about 325ppm (nickel 100ppm, cobalt 25ppm, aluminium 200ppm with the 1kg hydrocarbon mixture under 100 ℃; Measure by x ray fluorescence analysis (XRF), by the assessment of Uniquant2 method) total metal contents in soil) melting.200mg elementary sulfur powder and 1.2g trolamine are added in the melt.Because powerful stirring is heated to 180 ℃ simultaneously, two kinds of materials be distributed in equably liquid HC mutually in.Then with mixture heating up to 180 ℃, strong stirring simultaneously, and kept this temperature 5 minutes.Already since 160 ℃ temperature, to observe significantly dark brownly, this is to be caused by the NiS that forms and/or CoS.After stopping stirring means, dark brown throw out is deposited in the bottom of reaction vessel very fast.This throw out separates with reaction mixture easily by pleated filter.But the analysis of filtrate shows nickel, cobalt and the aluminium (limit of detection 5ppm) that does not have detectable level.Sulphur content in the filtrate amounts to about 150ppm.
Embodiment 2
1kg had the hydrocarbon mixture (from the synthetic wax slop of Fischer-Tropsch) of the total metal contents in soil of about 325ppm (nickel 100ppm, cobalt 25ppm, aluminium 200ppm) 100 ℃ of lower meltings.Metal concentration is such as mensuration as described in the embodiment 1 time.300mg elementary sulfur and 3g trolamine are added in the melt, and because powerful stirring, be heated to simultaneously 180 ℃ and be distributed in equably liquid HC mutually in.Thereafter with mixture heating up to 180 ℃, strong stirring simultaneously, and kept this temperature 5 minutes.Also originate in 160 ℃ temperature, observe dark brown obvious raising, this is to be caused by the NiS that forms and/or CoS.After stopping stirring, dark brown throw out is deposited in the bottom of reaction vessel very fast.This throw out separates with reaction mixture easily by pleated filter.But the analysis of filtrate does not demonstrate nickel, cobalt and the aluminium (limit of detection 5ppm) of any detectable level.Sulphur content in the filtrate amounts to about 250ppm, i.e. its significantly higher than among the embodiment 1.This shows can be by correspondingly adding the sulphur source that is higher than the required stoichiometry of complete metal separation so that the sulphur that it adapts to steps downstream such as Co-Mo hydrocracking catalyst best activates the sulphur content of controlling hydrocarbon product.On the other hand and if necessary, the sulphur content of hydrocarbon product can be down to minimum value by being metered into accordingly.
Embodiment 3
1kg had the hydrocarbon mixture (from the synthetic wax slop of Fischer-Tropsch) of the total metal contents in soil of about 325ppm (nickel 100ppm, cobalt 25ppm, aluminium 200ppm) 100 ℃ of lower meltings.The 10g Desorex HGD2S (1/8 " the DONAU CARBON activated carbon product that contains the 10-15% elementary sulfur of having an appointment of extrudate form) that will be equivalent to the sulphur content of 1000-1500ppm, and the 0.5g trolamine adds in the melt.Thereafter in 30 minutes with mixture heating up to 185 ℃, strong stirring simultaneously, and kept this temperature 5 minutes.Already since 160 ℃ temperature, can be observed by the NiS that forms and/or CoS cause obviously dark brown.When the temperature that reaches 185 ℃, the throw out of observing the flocculation form forms.When stopping to stir, thermal reaction mixture is poured on the pleated filter.Throw out separates with reaction mixture by filtering easily.The gac that adds the sulphur dipping in the mixture as extrudate is deposited in the bottom of reaction vessel after its feature and structure aspects keep complete and stopping to stir.But the analysis of filtrate shows nickel, cobalt and the aluminium (limit of detection 5ppm) that does not have detectable level.It is about 1 that sulphur content in the filtrate amounts to, 100ppm.
Embodiment 4
1kg had the hydrocarbon mixture (from the synthetic wax slop of Fischer-Tropsch) of the total metal contents in soil of about 325ppm (nickel 100ppm, cobalt 25ppm, aluminium 200ppm) 90 ℃ of lower meltings.With 200mg's TMT (Evonik Degussa GmbH) contains 98% tri-thiol-S-triazine) add in the melt.During churning, originally powder formulation is insoluble in the molten wax and only is suspended in this mixture.Solid matter is dissolving after adding the 2g trolamine in the reaction mixture only.This causes the obvious muddiness of liquid phase.Mixture 90-100 ℃ under stirred other 10 minute thereafter.Then muddiness can use pleated filter to separate with reaction mixture easily.But the analysis of filtrate does not produce the nickel of detectable level and the aluminium (limit of detection in every kind of situation: 5ppm).Cobalt concentration amounts to 5ppm, and the sulphur content in the filtrate amounts to about 50ppm.Filtrate is kept 1 hour slight muddiness of generation in loft drier.Repeat to filter in this sample demonstration filtrate and can not detect more cobalt.Sulphur content remains unchanged.In this article, the analysis of metal and sulphur content also uses the UNIQUANT2 method to carry out by x ray fluorescence analysis (XRF).
Simultaneous test
Repeat the test of embodiment 1 under the same conditions and with identical feed hydrocarbon mixture, but do not add trolamine or other alkali.Even be heated to 180 ℃, can not observe colour-change and the precipitation of hydrocarbon phase.The subsequently XRF analysis of hydrocarbon is presented in the accuracy of analysis three kinds of independent metals and the constant metal content of their sums.Therefore, contained alkali is the prerequisite of the feasibility of the method according to this invention in the metal remover.
Commercial suitability
For the present invention, a kind of method of removing metal pollutant from hydrocarbon-fraction is provided, compare with the method that prior art is known, the method is characterized in that its simple device and do not have additional extraction agent, especially do not relate to reagent such as the aqueous solution of the method.In addition, advantageously only use and have the material that is low to moderate middle potentially dangerous and avoid using material such as the hydrogen fluoride with high potentially dangerous.

Claims (10)

1. preparation has the method for hydrocarbon-fraction of low-metal content, and wherein institute's containing metal is characterized in that the metal remover that will comprise following component adds in the liquid hydrocarbon fraction with colloidal state or finely divided form chemical bonding or be scattered in the hydrocarbon-fraction in the hydrocarbon-fraction:
(a) at least a at least part of sulphur source that dissolves in the hydrocarbon-fraction,
(b) at least a at least part of basic cpd that dissolves in the hydrocarbon-fraction,
And be that after adding metal remover metal separates with the sedimentary form precipitation of dissolubility hardly and by mechanical separation method.
2. be used for hydrocarbon-fraction, especially for the metal remover in the method according to claim 1, it comprises:
(a) at least a at least part of sulphur source that dissolves in the hydrocarbon-fraction,
(b) at least a at least part of basic cpd that dissolves in the hydrocarbon-fraction.
3. according to claim 2 metal remover is characterized in that selecting at least a following compound to originate as sulphur:
Thiocarbamide, thiocarbonic ester, dithiocarbonates, thiocarbamate, dithiocarbamate, mercaptan, organic disulfide, organic polysulfide, thioamides, hydrogen sulfide, ammonium sulfide, inorganic monosulphide, without organic disulfide, inorganic polysulfide or elementary sulfur.
4. according to claim 2 or 3 metal remover, it is characterized in that selecting at least a following compound as basic cpd:
Ammonia, amine, alkanolamine, preferred trolamine, pyridine, ammonium compound,
Figure FDA00002773304600011
Compound, sulfonium compound.
5. according to claim 2,3 or 4 metal remover, it is characterized in that elementary sulfur or hydrogen sulfide are as the sulphur source.
6. according to claim 2 or 4 metal remover, it is characterized in that the gac of sulphur dipping is as the sulphur source.
7. according to claim 1 method is characterized in that filtration, sedimentation, decant or centrifugal or its combination are as mechanical separation method.
8. according to claim 1 or 7 method, it is characterized in that using metal remover according to claim 6, and after adding alkali, in the metal remover bed in the pending hydrocarbon-fraction adding fixed-bed reactor, thus poor metal hydrocarbon cut is taken out from fixed-bed reactor as product.
According to claim 1, in 7 or 8 the method demetallated hydrocarbon-fraction as the purposes of sulfur donor with the activation of sulphur deactivated catalyst.
10. according to claim 2 or 4 metal remover, it is characterized in that mercaptan, preferred tri-thiol-s-triazine is as the sulphur source.
CN2011800363334A 2010-07-26 2011-07-21 Process and agents to remove metals from high-boiling hydrocarbon fractions Pending CN103025850A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE102010032263.6 2010-07-26
DE102010032263 2010-07-26
DE102011013470.0 2011-03-09
DE102011013470A DE102011013470A1 (en) 2010-07-26 2011-03-09 Process and means for removing metals from high boiling hydrocarbon fractions
PCT/EP2011/062587 WO2012013581A2 (en) 2010-07-26 2011-07-21 Process and agents to remove metals from high-boiling hydrocarbon fractions

Publications (1)

Publication Number Publication Date
CN103025850A true CN103025850A (en) 2013-04-03

Family

ID=44629994

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011800363334A Pending CN103025850A (en) 2010-07-26 2011-07-21 Process and agents to remove metals from high-boiling hydrocarbon fractions

Country Status (5)

Country Link
US (1) US20130180887A1 (en)
EP (1) EP2598607A2 (en)
CN (1) CN103025850A (en)
DE (1) DE102011013470A1 (en)
WO (1) WO2012013581A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109890944A (en) * 2016-10-04 2019-06-14 因莱坦恩创新公司 The method of the particle of alkali metal containing salt is separated from liquid hydrocarbon

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013104696A1 (en) 2013-05-07 2014-11-13 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Process for removing metals from high boiling hydrocarbon fractions
DE102013106441A1 (en) 2013-06-20 2014-12-24 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Process for removing metals from high boiling hydrocarbon fractions
DE102013106439A1 (en) 2013-06-20 2014-12-24 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Process for removing metals from high boiling hydrocarbon fractions
DE102014107375A1 (en) 2014-05-26 2015-11-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Process for removing metal from high-boiling hydrocarbon fractions
DE102014107374A1 (en) 2014-05-26 2015-11-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Process for removing metals from high boiling hydrocarbon fractions
EP3103858A1 (en) 2015-06-08 2016-12-14 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Method for washing organic liquids with a liquid comprising flurohydrocarbons

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2683683A (en) * 1951-04-06 1954-07-13 Houdry Process Corp Purification of oils
CN1330698A (en) * 1998-12-18 2002-01-09 埃克森美孚研究工程公司 Method for decreasing methods contents of petroleum streams
US20020179493A1 (en) * 1999-08-20 2002-12-05 Environmental & Energy Enterprises, Llc Production and use of a premium fuel grade petroleum coke
US20050004415A1 (en) * 2003-07-02 2005-01-06 Chevron U.S.A. Inc. Ion exchange methods of treating a Fischer-Tropsch derived hydrocarbon stream
WO2005089931A2 (en) * 2004-03-17 2005-09-29 Advanced Minerals Corporation A mercury adsorbent composition, process of making same and method of separating mercury from fluids
WO2006048746A2 (en) * 2004-11-02 2006-05-11 Pfizer Inc. Methods for the removal of heavy metals
WO2009116988A1 (en) * 2008-03-17 2009-09-24 Shell Oil Company Process for the preparation of middle distillates from kerogen
US20090261017A1 (en) * 2008-04-22 2009-10-22 Rashid Iqbal Systems and methods for upgrading hydrocarbons

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD26308A (en)
AT205229B (en) 1957-04-18 1959-09-10 Ici Ltd Process for removing metal-containing catalyst residues from solid polymers of unsaturated hydrocarbons
GB1001190A (en) 1961-10-16 1965-08-11 Synthesewerk Schwarzeide Veb Process for the removal of metal contaminents from hydrocarbons
DE1212662B (en) 1962-05-09 1966-03-17 Universal Oil Prod Co Process for removing metallic and nitrogenous impurities from hydrocarbon oils
US3449243A (en) 1966-09-30 1969-06-10 Standard Oil Co Treating of heavy oils to remove metals,salts and coke forming materials employing a combination of an alcohol,organic acid and aromatic hydrocarbon
US3617530A (en) 1969-11-12 1971-11-02 Atlantic Richfield Co Metals removal from heavy hydrocarbon fractions
CA999821A (en) 1972-10-04 1976-11-16 Chevron Research And Technology Company Process for removing metalliferous contaminants from hydrocarbons
AU533444B2 (en) 1978-09-28 1983-11-24 Salusinszky, A.L. Regeneration of used lubricating oils
US4518484A (en) 1984-02-16 1985-05-21 Phillips Petroleum Company Metals removal with a light hydrocarbon and an organophosphorous compound
US4801573A (en) 1987-10-23 1989-01-31 501 Den Norske Stats Oljeslenskap A.S. Catalyst for production of hydrocarbons
WO1998027181A1 (en) 1996-12-16 1998-06-25 Rentech, Inc. Catalyst/wax separation device for slurry fischer-tropsch reactor
BRPI0905734B1 (en) 2008-01-24 2017-11-14 Dorf Ketal Chemicals I METHOD FOR REMOVAL OF METALS FROM RAW MATERIALS USING CARBOXYLIC ACID ESTERS

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2683683A (en) * 1951-04-06 1954-07-13 Houdry Process Corp Purification of oils
CN1330698A (en) * 1998-12-18 2002-01-09 埃克森美孚研究工程公司 Method for decreasing methods contents of petroleum streams
US20020179493A1 (en) * 1999-08-20 2002-12-05 Environmental & Energy Enterprises, Llc Production and use of a premium fuel grade petroleum coke
US20050004415A1 (en) * 2003-07-02 2005-01-06 Chevron U.S.A. Inc. Ion exchange methods of treating a Fischer-Tropsch derived hydrocarbon stream
WO2005089931A2 (en) * 2004-03-17 2005-09-29 Advanced Minerals Corporation A mercury adsorbent composition, process of making same and method of separating mercury from fluids
WO2006048746A2 (en) * 2004-11-02 2006-05-11 Pfizer Inc. Methods for the removal of heavy metals
WO2009116988A1 (en) * 2008-03-17 2009-09-24 Shell Oil Company Process for the preparation of middle distillates from kerogen
US20090261017A1 (en) * 2008-04-22 2009-10-22 Rashid Iqbal Systems and methods for upgrading hydrocarbons

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109890944A (en) * 2016-10-04 2019-06-14 因莱坦恩创新公司 The method of the particle of alkali metal containing salt is separated from liquid hydrocarbon
CN109890944B (en) * 2016-10-04 2020-07-03 因莱坦恩创新公司 Process for separating particles containing alkali metal salts from liquid hydrocarbons

Also Published As

Publication number Publication date
EP2598607A2 (en) 2013-06-05
DE102011013470A1 (en) 2012-01-26
WO2012013581A3 (en) 2012-05-24
WO2012013581A2 (en) 2012-02-02
US20130180887A1 (en) 2013-07-18

Similar Documents

Publication Publication Date Title
CN103025850A (en) Process and agents to remove metals from high-boiling hydrocarbon fractions
Ali et al. A review of methods for the demetallization of residual fuel oils
AU2008329625B2 (en) Process for recovering base metals from used hydroprocessing catalyst
ES2548589T3 (en) Hydroconversion process for heavy and extra heavy oils and waste
US8372776B2 (en) Hydroprocessing bulk catalyst and methods of making thereof
US8389433B2 (en) Hydroprocessing bulk catalyst and methods of making thereof
ES2728566T3 (en) Load conversion process comprising a hydrocracking stage, a precipitation stage and a sediment separation stage for the production of fuel oils
US8431511B2 (en) Hydroprocessing bulk catalyst and methods of making thereof
JP5232833B2 (en) Metal recovery method to recover metal from hydrocracked heavy emissions
US8420565B2 (en) Hydroprocessing bulk catalyst and methods of making thereof
EP0189633B1 (en) Supported, mn sulfide promoted mo and w sulfide hydroprocessing catalysts and uses thereof
EP2504099B1 (en) Hydroprocessing bulk catalyst, it's use and methods of making thereof
NL8302109A (en) CATALYST FOR HYDRO CRACKING OF HEAVY HYDROCARBON OILS AND METHOD FOR HYDRO CRACKING OF HEAVY HYDROCARBON OILS.
CN113260440B (en) Process for the selective recovery of transition metals from organic residues
WO2014137419A1 (en) Recovery of vanadium from petroleum coke slurry containing solubilized base metals
CN109890944B (en) Process for separating particles containing alkali metal salts from liquid hydrocarbons
SE453197B (en) PROCEDURE FOR TRANSFER OF COAL TO FLUID
US20230398528A1 (en) Tungsten-containing bulk catalysts, method of making the same, and their use in low pressure diesel hydroprocessing
WO2014202594A1 (en) Process for removing metals from high-boiling hydrocarbon fractions
Iwamoto Regeneration of residue hydrodesulfurization catalyst
Hadebe et al. Iron Removal from High-Temperature Fischer–Tropsch-Derived Distillate through Thermal Treatment
WO2014180759A1 (en) Process for removing metals from high-boiling hydrocarbon fractions

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20130403