CN1423687A - Method for removing mercury from liquid hydrocarbon - Google Patents
Method for removing mercury from liquid hydrocarbon Download PDFInfo
- Publication number
- CN1423687A CN1423687A CN01808104A CN01808104A CN1423687A CN 1423687 A CN1423687 A CN 1423687A CN 01808104 A CN01808104 A CN 01808104A CN 01808104 A CN01808104 A CN 01808104A CN 1423687 A CN1423687 A CN 1423687A
- Authority
- CN
- China
- Prior art keywords
- liquid hydrocarbon
- mercury
- container
- sulphur compound
- mole
- 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
Links
Classifications
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/06—Metal salts, or metal salts deposited on a carrier
- C10G29/10—Sulfides
Abstract
A method for removing the mercury in an ionic state from a liquid hydrocarbon, characterized in that it comprises circulating the liquid hydrocarbon containing the mercury in an ionic state held in a vessel having a circulation means to the vessel and, simultaneously, injecting a sulfur compound represented by the general formula (I): M<1>-S-M<2> - - - (I) , wherein each of M<1> and M<2> represents a hydrogen atom, an alkali metal or an ammonium group, to the suction side and/or the delivery side of the circulation means, to thereby contact the liquid hydrocarbon containing the mercury in an ionic state with the sulfur compound with good efficiency. The method allows the mercury in an ionic state to be removed from a liquid hydrocarbon with ease and good efficiency.
Description
Technical field
The present invention relates to be used for removing the method for mercury, more particularly, relate to, remove the suitable method of a kind of industry of the ionic mercury in the liquid hydrocarbon that contains ionic mercury that is placed in the container with simple and effective way from liquid hydrocarbon.
Background technology
As known in the art, from natural-gas field, contain the mercury of tens to hundreds of ppb amounts, though it changes according to the producing region by the natural gas condensate (NGL) of deviating from the liquefied petroleum gas (LPG) recovery., can reduce the activity or the etching apparatus of hydrogenation catalyst, or reduce its physical strength, when producing the raw material of ethene etc. with this mercurous liquid hydrocarbon because mercury and platinum, palladium, copper or aluminium have formed amalgam.For this reason, research is removed the existing strong request of method of mercury in the liquid hydrocarbon.
Japanese patent application is not examined open No.10-251667 and is proposed, and utilizes a kind of equipment of hydrogenation catalyst packed bed hydrogenation zone and porous carbonaceous material packed bed adsorption zone that comprises to remove mercury.In this way, after 100-400 ℃ of hydrogenation process, mercury is adsorbed on the gac that its performance such as specific surface area and pore size be strictly controlled.Therefore, this method complicated operation, and, also have the complicated and strict shortcoming of operational condition control of sorbent material preparation because of relating to adsorption process.
The inventor has carried out removing with simple method the various researchs of the mercury in the mercurous liquid hydrocarbon, finds to make the mercury ionization in the liquid hydrocarbon, and this ionization mercury is contacted with special sulphur compound, can make mercury removal effectively.
Disclosure of the Invention
One object of the present invention is, the industrial usability methods of the ionization mercury in a kind of liquid hydrocarbon that contains ionization mercury with simple effective means with special removal of sulfur compounds is provided.
In view of above-mentioned purpose, pass through broad research, the inventor finds as a result, the special sulphur compound of ionic mercury and this is contacted effectively, and by a kind of circulation device, the hydro carbons that will contain ionic mercury is recycled in the container, simultaneously will this special sulphur compound be added to the suction side and/or the discharge end of this circulation device, and the liquid hydrocarbon in the mechanical stirring container randomly, can remove the ionic mercury in the hydro carbons that contains ionic mercury effectively.Based on this discovery, the present invention is accomplished.
Therefore, the invention provides a kind of method that is used for removing liquid hydrocarbon mercury, this method comprises the step that the liquid hydrocarbon that contains ionic mercury that is placed in the container is contacted with the sulphur compound shown in the general formula (I);
M
1-S-M
2(I) M wherein
1And M
2Can be identical or different, and be separately hydrogen atom, basic metal or ammonium group separately, remove ionic mercury thus, wherein this container is equipped with a circulation device, be used for circulating contain ionic mercury liquid hydrocarbon to container, wherein this sulphur compound is introduced into the suction side and/or the discharge end of this circulation device, circulating by this circulation device simultaneously, this contains the liquid hydrocarbon of ionic mercury.If desired, the liquid hydrocarbon that contains ionic mercury in also can the mechanical stirring container.
Implement optimal mode of the present invention
The handled liquid hydrocarbon that contains ionization mercury of the inventive method is not particularly limited, and can comprises any hydro carbons of liquid that is at normal temperatures.
The example of liquefied hydrocarbon comprises crude oil, virgin naphtha, kerosene, gas oil, vacuum distillate, topped oil and natural gas condensate (NGL).In these liquid hydrocarbons, natural gas condensate (NGL) is preferred.
In the liquid hydrocarbon contained mercury can be element state or ionic state.Element mercury is converted to ionic state by described ionising treatment after this.Mercury concentration in the handled liquid hydrocarbon is not particularly limited, is generally the 2-1000 micrograms per litre, preferred 5-100 micrograms per litre.
To handled crude oil among the present invention is hard-core.The example of crude oil is those crude oil of being produced by Saudi Arabia, the United Arab Emirates, Nigeria, Canada, Mexico, Iran, Iraq, China, Kuwait, Malaysia, Venezuela, the U.S., Australia, Russia, Libya, Philippines, Indonesia, Norway, Thailand, Qatar, Argentina, Britain and Japan.Can use in conjunction with two or more these crude oil.
Virgin naphtha, kerosene, gas oil, vacuum distillate and topped oil all obtain crude oil processing with currently known methods.
In the methods of the invention, before from liquid hydrocarbon, removing mercury, must make the contained mercury ionization of liquid hydrocarbon.Although ioning method is not particularly limited, can contact with a kind of material that can make element mercury be converted into ionic mercury by making liquid hydrocarbon, make the element mercury ionization.These make the example of the material of mercury ionization comprise iron cpd such as ferric sulfate, iron(ic) chloride, iron sulphide, ferric oxide and iron nitrate; Copper compound such as copper sulfate, cupric chloride, cupric oxide, cupric nitrate and cupric sulfide; Vanadium compound such as vanadium oxide, vanadium sulfide and Vanadosulfuric acid; Manganic compound such as manganese oxide, manganese sulfide and manganous sulfate; Nickel compound such as nickel oxide, nickelous sulfide and single nickel salt; Inorganic peroxide such as hydrogen peroxide; Organo-peroxide such as peracetic acid; Atmosphericoxygen; And petroleum tank mud.These make the material of mercury ionization can be separately or two or more use in combination.This petroleum tank mud is a kind of silting in the crude oil storage tank bottom, and contains the element such as iron, silicon, sodium, aluminium, phosphorus, zinc, copper, calcium, magnesium, vanadium, potassium, chromium, manganese, nickel, carbon, hydrogen, nitrogen, oxygen and sulphur etc.
Manganic compound such as manganese oxide can be an Any shape, such as powdery (powderyform), the powdery (pulverized form) that grinds to form, cylindrical, spherical, fiber shape and honeycombed.In addition, manganic compound is carried on the carrier, as silicon-dioxide, aluminum oxide, silica-alumina, zeolite, pottery, glass, resin and gac.Charge capacity is not particularly limited, and preferred 0.1-30 weight % is by vehicle weight.
For contacting with the material that makes mercury ionization by liquid hydrocarbon, make the Ionized condition of element mercury, be not particularly limited.The ionization temperature is generally-50-100 ℃, and preferably 0-60 ℃.Ionization pressure is not particularly limited, as long as under used ionization temperature, can make liquid hydrocarbon keep liquid state.Make the preferred consumption of material of mercury ionization, by every mole of element mercury contained in liquid hydrocarbon, be 1-10,000 mole.
In the methods of the invention, the liquid hydrocarbon that will contain ionization mercury contains in a container, makes it to be subjected to removing the processing of ionization mercury.The example of this container comprises crude oil storage tank, petroleum naphtha storage tank, condensate trap etc., but it is not limited only to this.In addition, also can there be water to exist in the container.
Being used for from the sulphur compound that liquid hydrocarbon removes ionic mercury is compound with general formula (I) expression:
M
1-S-M
2(I) M wherein
1And M
2Can be identical or different, they are separately hydrogen atom, basic metal or ammonium group separately.
For M in the formula (I)
1And M
2Alkali-metal example comprise sodium, potassium, lithium and caesium.The example of the sulphur compound that general formula (I) is represented comprises, hydrogen sulfide, sodium sulphite, sodium sulfhydrate, potassium sulphide, potassium hydrosulfide, ammonium sulfide and hydrosulfide of ammonia.These sulphur compounds can use separately or two or more are used in combination.In these sulphur compounds, preferably hydrogen sulfide, sodium sulphite and sodium sulfhydrate.
In the methods of the invention, the liquid hydrocarbon that contains ionic mercury that is injected in the container is contacted, so that ionic mercury is converted into the solid mercury compound that is not dissolved in liquid hydrocarbon with the sulphur compound of formula (I).By filtration, sedimentation etc., deviate from the solid mercury compound in the liquid hydrocarbon then.For this sulphur compound is contacted effectively with ionic mercury, the liquid hydrocarbon that contains ionic mercury in the container is circulated by circulation device, suction side and/or the discharge end at this circulation device adds sulphur compound simultaneously.This circulation device comprises that a suction pump from container send liquid hydrocarbon and its pumping is disposed to pump in this container, comprises that also is used to carry the conduit by liquid hydrocarbon.Generally, suction port is set near the container bottom periphery, and discharge outlet is set near the container top periphery.Cycle rate is preferably 1-5,000 cubic metre/hour.
Can utilize a part to be used for liquid hydrocarbon is added the existing conduit of container or a part existing conduit that is used for liquid hydrocarbon is discharged from container as circulation tube.In addition, also can use usually store receive be used for the dried up and crude oil of branchs in the crude oil circulation line as circulation tube.
Form to the sulphur compound that added is not particularly limited.For example, when with hydrogen sulfide when the sulphur compound, it directly can be added with the inherent gaseous state or with the form of the solution in water or fluid organic material such as petroleum naphtha, kerosene, light oil and heavy oil.When using sulphur compound,, this solid sulfur compound can be added with aqueous solution form such as at room temperature being solid sodium sulphite.
The feeding coal of the sulphur compound of formula (I) by every mole of mercury contained in liquid hydrocarbon, is 1-10,000 mole, and preferred 100-5,000 mole.In the circulation liquid hydrocarbon, provide the sulphur compound of total amount in the time about 1-300 hour.After total amount is provided, preferably continued the circulation liquid hydrocarbon 1-300 hour.
Contact conditions between sulphur compound and the ionic mercury is not particularly limited.The contact temperature is generally at-50-100 ℃, preferred 0-60 ℃.Can suitably pressurize, as long as under used contact temperature, can make liquid hydrocarbon keep liquid.
In the methods of the invention, the liquid hydrocarbon in this container of mechanical stirring can further strengthen contacting between ionic mercury and the sulphur compound.
Refer now to following examples, describe the present invention in more detail.But, should be noted that following examples are illustrative, be not to limit the invention with this.
Embodiment 1
With 38,000 cubic metres the liquid hydrocarbons that the contain 15.3 micrograms per litre ionic mercuries (density under 15 ℃: 0.7363 gram per centimeter
3) add in the jar that is equipped with circulation tube.The pump of 15 cubic metres/hour of capacity is set between the circulation tube entrance and exit.In operating pumps, hydrogen sulfide is introduced the suction side of pump with 4.8 kilograms/hour feeding rates.After introducing hydrogen sulfide is about 21.4 hours, other 24 hours of recirculation liquid hydrocarbon.In cycle period, respectively controlled temperature and pressure to 20 ℃ and normal pressure.In the circulation liquid hydrocarbon, with the liquid hydrocarbon in the agitator stirred pot.
The liquid hydrocarbon liquid level is high 12 meters at the bottom of the jar in jar.After stirring that stops the liquid towards hydrocarbon and circulation, gather liquid hydrocarbon sample portion in the position high 1 meter immediately apart from jar end.Strainer with 0.5 micron pore size size filters this liquid hydrocarbon sample.Mercury concentration is 1 micrograms per litre in the gained filtrate.
Stop after agitator and the recycle pump 10 days, apart from jar high 1 meter station acquisition liquid hydrocarbon sample portion in the end.Mercury concentration is 1 micrograms per litre in the liquid hydrocarbon sample of filtered.
Industrial applicibility
According to the present invention, the mode so that extremely simple and industry are suitable for can remove placement effectively Ionic mercury in the liquid hydrocarbon that contains ionic mercury in container.
Claims (7)
1, a kind of method that is used for removing liquid hydrocarbon mercury comprises the step that the liquid hydrocarbon that contains ionic mercury that is positioned in the container is contacted with the sulphur compound shown in the general formula (I):
M
1-S-M
2(I) M wherein
1And M
2Can be identical or different, and be hydrogen atom, basic metal or ammonium group separately separately, thereby remove ionic mercury,
Wherein this container is equipped with a circulation device, be used for making the liquid hydrocarbon circulation that contains ionic mercury enter this container and
Wherein this sulphur compound is introduced into the suction side and/or the discharge end of circulation device, contains the liquid hydrocarbon of ionic mercury simultaneously by this circulation device circulation.
2, according to the process of claim 1 wherein this liquid hydrocarbon that contains ionic mercury in container by mechanical stirring.
3, according to the method for claim 1 or 2, wherein this sulphur compound is at least a compound that is selected from hydrogen sulfide, sodium sulphite, sodium sulfhydrate, potassium sulphide, potassium hydrosulfide, ammonium sulfide and hydrosulfide of ammonia.
4, according to each method among the claim 1-3, wherein this liquid hydrocarbon be with the 1-5000 cubic meter/hour speed be recycled.
5, according to each method among the claim 1-4, wherein this sulphur compound add-on is counted 1-10 by every mole of mercury that comprises in liquid hydrocarbon, 000 mole.
6, according to each method among the claim 1-5, wherein in 1-300 hour time by every mole of mercury that in liquid hydrocarbon, comprises, add 1-10, this sulphur compound of 000 mole.
7, according to each method among the claim 1-6, wherein after adding this sulphur compound, this liquid hydrocarbon of recirculation other 1-300 hour.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37972/2001 | 2001-02-15 | ||
| JP2001037972A JP2002241767A (en) | 2001-02-15 | 2001-02-15 | Method for removing mercury from liquid hydrocarbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1423687A true CN1423687A (en) | 2003-06-11 |
Family
ID=18901030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01808104A Pending CN1423687A (en) | 2001-02-15 | 2001-10-19 | Method for removing mercury from liquid hydrocarbon |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20030075484A1 (en) |
| JP (1) | JP2002241767A (en) |
| KR (1) | KR100825152B1 (en) |
| CN (1) | CN1423687A (en) |
| AU (1) | AU2001295976B2 (en) |
| MY (1) | MY129007A (en) |
| WO (1) | WO2002064705A1 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080207443A1 (en) * | 2007-02-28 | 2008-08-28 | Kishor Purushottam Gadkaree | Sorbent comprising activated carbon, process for making same and use thereof |
| US7998898B2 (en) * | 2007-10-26 | 2011-08-16 | Corning Incorporated | Sorbent comprising activated carbon, process for making same and use thereof |
| US8741243B2 (en) | 2007-05-14 | 2014-06-03 | Corning Incorporated | Sorbent bodies comprising activated carbon, processes for making them, and their use |
| EP2205338A2 (en) * | 2007-08-29 | 2010-07-14 | Corning Incorporated | Process for removing toxic metals from a fluid stream |
| US20090297885A1 (en) * | 2008-05-30 | 2009-12-03 | Kishor Purushottam Gadkaree | Composite Comprising An Inorganic Substrate With A Coating Comprising Activated Carbon And Metal Sulfide |
| US8124213B2 (en) * | 2008-05-30 | 2012-02-28 | Corning Incorporated | Flow-through sorbent comprising a metal sulfide |
| US8691722B2 (en) * | 2008-07-03 | 2014-04-08 | Corning Incorporated | Sorbent comprising activated carbon particles, sulfur and metal catalyst |
| US8080156B2 (en) * | 2008-08-11 | 2011-12-20 | Conocophillips Company | Mercury removal from crude oil |
| GB0905896D0 (en) * | 2009-04-06 | 2009-05-20 | Univ Belfast | Process for removing metals from hydrocarbons |
| US8790510B2 (en) | 2009-10-29 | 2014-07-29 | Phillips 66 Company | Mercury removal with amine sorbents |
| CA2818273A1 (en) * | 2010-11-19 | 2012-05-24 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| US20120125820A1 (en) * | 2010-11-19 | 2012-05-24 | Sujin Yean | Process, method, and system for removing heavy metals from fluids |
| US8721874B2 (en) * | 2010-11-19 | 2014-05-13 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| US8721873B2 (en) * | 2010-11-19 | 2014-05-13 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| US8728303B2 (en) * | 2010-11-19 | 2014-05-20 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| CA2872808A1 (en) * | 2012-05-16 | 2013-11-21 | Chevron U.S.A. Inc. | In-situ method and system for removing heavy metals from produced fluids |
| US9447675B2 (en) | 2012-05-16 | 2016-09-20 | Chevron U.S.A. Inc. | In-situ method and system for removing heavy metals from produced fluids |
| CN104736678A (en) * | 2012-05-16 | 2015-06-24 | 雪佛龙美国公司 | Process, method, and system for removing mercury from fluids |
| US9523043B2 (en) * | 2013-09-16 | 2016-12-20 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| MY175927A (en) * | 2015-03-03 | 2020-07-15 | Petroliam Nasional Berhad Petronas | Process for removing heavy metals from hydrocarbons |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5401392A (en) * | 1989-03-16 | 1995-03-28 | Institut Francais Du Petrole | Process for eliminating mercury and possibly arsenic in hydrocarbons |
| FR2644472B1 (en) * | 1989-03-16 | 1991-06-21 | Inst Francais Du Petrole | PROCESS FOR THE REMOVAL OF MERCURY AND POSSIBLY ARSENIC IN HYDROCARBONS |
| JPH0343495A (en) * | 1989-07-12 | 1991-02-25 | Jgc Corp | Process for removing mercury |
| JPH0674429B2 (en) * | 1990-01-22 | 1994-09-21 | ドン リー サン | Final disposal method and equipment for various waste oils |
| JP2611900B2 (en) * | 1992-06-05 | 1997-05-21 | 財団法人生産開発科学研究所 | Method for removing halogenated aromatic compounds from hydrocarbon oil |
| JPH0740917A (en) * | 1993-07-21 | 1995-02-10 | Kioritz Corp | Packing apparatus |
| JP2649024B2 (en) * | 1995-07-27 | 1997-09-03 | 太陽石油株式会社 | Method for removing mercury from liquid hydrocarbons |
| JP3824457B2 (en) * | 1998-11-16 | 2006-09-20 | 出光興産株式会社 | Mercury removal from liquid hydrocarbons |
-
2001
- 2001-02-15 JP JP2001037972A patent/JP2002241767A/en active Pending
- 2001-10-17 MY MYPI20014824A patent/MY129007A/en unknown
- 2001-10-19 US US10/257,474 patent/US20030075484A1/en not_active Abandoned
- 2001-10-19 CN CN01808104A patent/CN1423687A/en active Pending
- 2001-10-19 WO PCT/JP2001/009196 patent/WO2002064705A1/en active Application Filing
- 2001-10-19 KR KR1020027013792A patent/KR100825152B1/en not_active IP Right Cessation
- 2001-10-19 AU AU2001295976A patent/AU2001295976B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| KR100825152B1 (en) | 2008-04-24 |
| JP2002241767A (en) | 2002-08-28 |
| AU2001295976B2 (en) | 2006-07-27 |
| WO2002064705A1 (en) | 2002-08-22 |
| KR20020086952A (en) | 2002-11-20 |
| US20030075484A1 (en) | 2003-04-24 |
| MY129007A (en) | 2007-03-30 |
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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 |