EP2265695A1 - Verfahren zur abtrennung von quecksilber aus kohlenwasserstoffströmen - Google Patents

Verfahren zur abtrennung von quecksilber aus kohlenwasserstoffströmen

Info

Publication number
EP2265695A1
EP2265695A1 EP09720628A EP09720628A EP2265695A1 EP 2265695 A1 EP2265695 A1 EP 2265695A1 EP 09720628 A EP09720628 A EP 09720628A EP 09720628 A EP09720628 A EP 09720628A EP 2265695 A1 EP2265695 A1 EP 2265695A1
Authority
EP
European Patent Office
Prior art keywords
mercury
absorbent
copper
oxide
hydrocarbon stream
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.)
Withdrawn
Application number
EP09720628A
Other languages
German (de)
English (en)
French (fr)
Inventor
Peter Rudolf
Michael Bender
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP09720628A priority Critical patent/EP2265695A1/de
Publication of EP2265695A1 publication Critical patent/EP2265695A1/de
Withdrawn legal-status Critical Current

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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0233—Compounds of Cu, Ag, Au
    • B01J20/0237—Compounds of Cu
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/868—Chromium copper and chromium
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/202—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/56—Use in the form of a bed
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper

Definitions

  • the invention relates to a process for the separation of mercury and / or arsenic from a mercury-containing hydrocarbon stream.
  • Mercury is present as an impurity in numerous streams that are produced or processed in the chemical or petrochemical industry. Often, these are material flows that occur in the processing or thermal utilization of fossil fuels such as oil, natural gas or coal, as well as the recycling of waste, as these raw materials or waste contain traces of mercury in elemental form or chemically bound. Also, mercury contaminant streams fall into processes in which mercury or mercury-containing substances are used as the reagent or catalyst. An example of this is the electrolysis hydrogen produced in the chlorine production by the A-malgam process. Because of the high toxicity of mercury, it is necessary in most cases to separate these metal or metal-containing compounds from the streams occurring in the processes in question.
  • mercury has the property of attacking aluminum-based apparatus by amalgamation, destroying the surface oxide layer of the aluminum, so that streams passing through aluminum apparatus or containers must be virtually free of mercury.
  • noble metal-containing catalysts such as those used in petrochemical processes, are poisoned by traces of mercury.
  • EP-A-0 761 830 discloses a simple, purely mechanical process in which finely divided mercury is collected by coalescence into larger mercury droplets which are easily separable.
  • WO 2004/048624 describes a process for the removal of mercury by filtration on electrographite.
  • DE-A 26 43 478 describes the separation of mercury from liquids by adsorption on activated carbon having a specific surface area of at least 250 m 2 / g.
  • carbon-supported adsorbents are used, as described in US Pat. No. 3,755,989.
  • No. 4,500,327 describes sulfur-impregnated activated carbon for the separation of mercury from gaseous streams, while JP 52-53793 describes the separation of iodide-containing activated carbon for the separation of mercury from liquid streams.
  • EP-A 0 385 742 describes a process for the removal of mercury from liquid hydrocarbon streams of hydrocarbons having up to 8 C atoms by contacting with metallic copper or copper compounds present on a support.
  • DE-A 21 02 039 discloses a method for separating mercury from gases, in which the mercury-containing gases are brought into contact with a mass containing copper on a porous alumina support.
  • US 4,230,486 discloses a process for separating mercury from liquids by passing the liquids over an absorbent containing metallic silver on a porous support such as activated carbon or a ceramic support.
  • DE-A 42 21 207 teaches a method for the separation of mercury from alkali or alkali koholatains by passing the solutions over silver-coated fibers.
  • DE-A 41 16 890 discloses absorbents for the removal of mercury, which in particular Cu, Ag, Fe and Bi, but also Au, Sn, Zn and Pd and mixtures of said metals in metallic or oxidic or sulphidic form on an activated carbon support with a BET Surface of 300 to 1000 m 2 / g.
  • US Pat. No. 4.91 1, 825 describes the separation of mercury and arsenic from hydrocarbon streams, in which, in the presence of hydrogen, these are reacted in a first step with a catalyst comprising nickel and palladium on alumina and in a second Step comprising an absorbent containing sulfur or a metal sulfide, preferably copper sulfide or a combination of copper and silver sulfide, on a support.
  • a catalyst comprising nickel and palladium on alumina
  • a second Step comprising an absorbent containing sulfur or a metal sulfide, preferably copper sulfide or a combination of copper and silver sulfide, on a support.
  • the process can also be carried out in one stage on a mixture of the catalyst and the absorbent.
  • FR-A 2 310 795 describes the removal of mercury from a gaseous natural gas stream using an absorbent containing metallic gold, silver, copper or nickel on a support of silica, alumina or aluminosilicate having a BET surface area of 40 to 250 m 2 / G.
  • WO 91/15559 discloses a process for separating mercury from liquid hydrocarbon streams by contacting it with an absorbent obtained by mixing a powdery oxide, preferably selected from nickel oxide, copper oxide and cobalt oxide, with a porous support material, such as alumina, silica, zeolites or Toning, and subsequent reduction is made.
  • the object of the invention is to provide an improved process for the separation of mercury from a mercury-containing hydrocarbon stream.
  • the object is achieved by a method for separating mercury from a mercury-containing hydrocarbon stream in which the hydrocarbon stream is contacted with an absorbent containing copper on a porous oxidic support material, characterized in that the hydrocarbon stream in the presence of hydrogen with the absorbent in Contact is brought.
  • the absorbent used according to the invention contains copper, preferably in reduced form, on a porous support material.
  • the absorbent used in the invention is effective as a hydrogenation catalyst.
  • Suitable porous support materials are amorphous and crystalline aluminosilicates, alumina, silica, clays and metal oxides.
  • Suitable clays are, for example, attapulgite, kaolin, bentonite, fuller earth.
  • Suitable metal oxides are, for example, in addition to aluminum oxides and silicon dioxide, magnesium oxide, zirconium dioxide, titanium dioxide, zinc oxide, chromium (III) oxide, barium oxide and mixtures thereof.
  • Preferred alumina is ⁇ -alumina. - A -
  • the copper-containing hydrogenation-active absorption agents used according to the invention are obtainable by mixing copper oxide with a support material and subsequent conversion of copper into the metallic form by reduction, preferably in a hydrogen stream.
  • the absorbents used according to the invention can be further prepared by impregnating the support material with an aqueous solution of a copper salt, drying, optionally calcining, and converting the copper into the metallic form by reduction, preferably with a hydrogen-containing gas stream, but also with a reducing agent such as hydrazine.
  • the absorbents used according to the invention contain from 10 to 50% by weight of copper on an oxidic support material.
  • suitable compositions on the basis of which the absorbents used according to the invention are obtained are compositions comprising copper oxide, zinc oxide and aluminum oxide or compositions comprising copper oxide, magnesium oxide, barium oxide, chromium (III) oxide, zinc oxide and silicon dioxide.
  • Particularly preferred is a mixture of 10 to 60 wt .-% copper oxide, 0 to 40 wt .-% zinc oxide, 0 to 20 wt .-% alumina, 5 to 25 wt .-% magnesium oxide, 10 to 40 wt .-% silica , 0 to 5 wt .-% chromium (III) oxide and 0 to 10 wt .-% barium oxide.
  • Hydrocarbon streams from which mercury can be separated according to the invention are any hydrocarbon streams which may be contaminated with mercury. These generally contain aliphatic, aromatic, alicyclic and / or heterocyclic hydrocarbons having 1 to 14 carbon atoms.
  • hydrocarbon mixtures which can be freed from mercury according to the invention are LNG (Liquefied Natural Gas), LPG (Liquefied Petroleum Gas), Napththa and kerosene.
  • pure hydrocarbons which can be purified according to the invention are ethylene and propylene and also aliphatic hydrocarbons.
  • the mercury content of the hydrocarbons or hydrocarbon mixtures before carrying out the process according to the invention can be up to 100 ppm, In general, it is up to 1 ppm Hg. Mercury is generally present in the form of organomercury compounds.
  • the process according to the invention can be carried out in suspension or fixed bed mode. If it is carried out in fixed bed mode, it can be carried out in sump or breeze mode.
  • the mercury or arsenic-containing hydrocarbons or mixtures can be used in gaseous or liquid form.
  • the hydrocarbons or hydrocarbon mixtures are preferably used in liquid form.
  • Hydrogen is introduced together with the gaseous or liquid hydrocarbon or hydrocarbon mixture into a suitable reaction vessel and, generally in cocurrent, passed through the lumped absorbent arranged in a fixed bed. It can be worked in sump or trickle way. However, hydrogen and hydrocarbon or hydrocarbon mixture can also be passed in countercurrent over the absorbent bed.
  • the absorbent may further be suspended in the hydrocarbon or hydrocarbon mixture.
  • the process is carried out at a temperature of 30 to 250 ° C., preferably 60 to 180 ° C., and a hydrogen pressure of 1 to 20 bar.
  • the pressure is preferably chosen such that the hydrocarbon or the hydrocarbon mixture is present as a liquid.
  • the amount of hydrogen introduced generally corresponds to a load of 10 to 650 Nl per kg of absorbent and hour.
  • this can be thermally regenerated by this is heated in an inert gas or a hydrogen-containing gas stream, generally to temperatures of 180 to 400 0 C, for example 200 to 220 0 C, and evaporated mercury is condensed out.
  • Example 1 The procedure was as in Example 1. However, the reduced catalyst was added in powder form (Absorbent C). Samples were taken at regular intervals and their mercury content determined. The results are shown in Table 1.
  • Example 2 The procedure was as in Example 1, but the solution was heated to 25 0 C. Samples were taken at regular intervals and their mercury content determined. The results are shown in Table 2.
  • Example 2 The procedure was as in Example 1. The temperature was thus 60 ° C. Samples were taken at regular intervals and their mercury content was determined. The results are shown in Table 2.
  • Example 2 The procedure was as in Example 1, but was heated to 100 0 C. Samples were taken at regular intervals and their mercury content was determined. The results are shown in Table 2.
  • the experiments were carried out in a monoline reactor with an internal diameter of 6 mm and a total length of 5 m.
  • the reactor consisted of 4 segments connected by a capillary. The reactor was operated in trickle mode. The reactor segments were heated to 60 0 C.
  • the liquid hydrocarbon feed was mixed with hydrogen.
  • the reactor effluent was cooled by means of an intensive condenser and the gas phase separated from the liquid phase. The liquid phase was used to determine the mercury content, the gas phase was disposed of via a mercury Guardbed.
  • the reactor were 80 g of a catalyst of 45 wt .-% CuO, 16 wt .-% MgO, 35 wt .-% SiO 2 , 0.9 wt .-% Cr 2 O 3 , 1, 1 wt. % BaO and 0.6% by weight ZnO in the form of 3 ⁇ 5 mm tablets. Between the individual tablets was in each case a glass sphere of 2 mm diameter.
  • the catalyst was first activated in a hydrogen stream at 180 to 220 0 C. Subsequently, the reactor was cooled to 60 ° C. in a hydrogen stream. The reactor was operated at atmospheric pressure.
  • the feed used was octane, which was saturated with an organomercury compound.
  • organomercury compound phenylmercuric acetate PhHgOAc was used in one part of the experiments and mercury acetate Hg (OAc) 2 in another part of the experiments. In each case several batches with different mercury concentrations were used. 100 Nl / h of the mercury-containing octane and 2 Nl / h of hydrogen were added. The results of the experiments are summarized in Table 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
EP09720628A 2008-03-10 2009-03-09 Verfahren zur abtrennung von quecksilber aus kohlenwasserstoffströmen Withdrawn EP2265695A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09720628A EP2265695A1 (de) 2008-03-10 2009-03-09 Verfahren zur abtrennung von quecksilber aus kohlenwasserstoffströmen

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08152517 2008-03-10
EP09720628A EP2265695A1 (de) 2008-03-10 2009-03-09 Verfahren zur abtrennung von quecksilber aus kohlenwasserstoffströmen
PCT/EP2009/052693 WO2009112440A1 (de) 2008-03-10 2009-03-09 Verfahren zur abtrennung von quecksilber aus kohlenwasserstoffströmen

Publications (1)

Publication Number Publication Date
EP2265695A1 true EP2265695A1 (de) 2010-12-29

Family

ID=40558912

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09720628A Withdrawn EP2265695A1 (de) 2008-03-10 2009-03-09 Verfahren zur abtrennung von quecksilber aus kohlenwasserstoffströmen

Country Status (6)

Country Link
US (1) US20110005975A1 (enExample)
EP (1) EP2265695A1 (enExample)
JP (1) JP5455939B2 (enExample)
KR (1) KR20100133394A (enExample)
CN (1) CN101970614A (enExample)
WO (1) WO2009112440A1 (enExample)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007147781A1 (de) * 2006-06-21 2007-12-27 Basf Se Absorptionsmasse und verfahren zur entfernung von quecksilber
CN102764655B (zh) * 2011-12-23 2015-03-04 盐城工学院 一种脱汞催化剂
US9006508B2 (en) * 2012-02-06 2015-04-14 Uop Llc Protected adsorbents for mercury removal and method of making and using same
JP6076854B2 (ja) * 2013-08-07 2017-02-08 Ｊｘエネルギー株式会社 炭化水素油中の水銀の除去方法
CN105148913B (zh) * 2015-10-08 2017-11-07 宁波海越新材料有限公司 一种用于仲丁醇制备甲乙酮的催化剂的制备方法
CN108249955B (zh) * 2018-04-02 2020-12-29 中科京投环境科技江苏有限公司 一种脱除废、污水中汞的复合陶瓷材料的制备方法
CN115698231A (zh) * 2020-05-29 2023-02-03 埃克森美孚化学专利公司 含汞进料的烃热解

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1570903A1 (en) * 2002-11-18 2005-09-07 ICT Co., Ltd. Exhaust gas purifying catalyst and method for purifying exhaust gas

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3227645A (en) * 1962-01-22 1966-01-04 Chevron Res Combined process for metal removal and hydrocracking of high boiling oils
US3755989A (en) * 1972-06-16 1973-09-04 Union Carbide Corp Removal of mercury from gas streams
IT1043119B (it) * 1975-10-03 1980-02-20 Tecneco Spa Metodo per la rimozione di mer curio metallico
DE2656803C2 (de) * 1975-12-18 1986-12-18 Institut Français du Pétrole, Rueil-Malmaison, Hauts-de-Seine Verfahren zur Entfernung von in einem Gas oder in einer Flüssigkeit vorhandenem Quecksilber
US4230486A (en) * 1978-04-28 1980-10-28 Olin Corporation Process for removal and recovery of mercury from liquids
AU559284B2 (en) * 1982-07-08 1987-03-05 Takeda Chemical Industries Ltd. Adsorption of mercury vapour
FR2628338B1 (fr) * 1988-03-10 1991-01-04 Inst Francais Du Petrole Procede pour l'elimination du mercure dans les hydrocarbures
US4909926A (en) * 1989-02-01 1990-03-20 Mobil Oil Corporation Method for removing mercury from hydrocarbon oil by high temperature reactive adsorption
JP2578514B2 (ja) * 1989-03-03 1997-02-05 三井石油化学工業株式会社 液体炭化水素化合物中の水銀の除去方法
FR2644472B1 (fr) * 1989-03-16 1991-06-21 Inst Francais Du Petrole Procede pour l'elimination du mercure et eventuellement d'arsenic dans les hydrocarbures
US5401392A (en) * 1989-03-16 1995-03-28 Institut Francais Du Petrole Process for eliminating mercury and possibly arsenic in hydrocarbons
WO1991015559A2 (en) * 1990-04-04 1991-10-17 Exxon Chemical Patents Inc. Mercury removal by dispersed-metal adsorbents
US5080799A (en) * 1990-05-23 1992-01-14 Mobil Oil Corporation Hg removal from wastewater by regenerative adsorption
FR2673191B1 (fr) * 1991-02-27 1994-02-04 Institut Francais Petrole Procede d'enlevement de mercure et/ou d'arsenic des charges des unites de desaromatisation de solvants. .
DE4221207A1 (de) * 1992-06-27 1994-01-05 Huels Chemische Werke Ag Verfahren zur Entfernung von Quecksilber aus Flüssigkeiten
FR2701270B1 (fr) * 1993-02-08 1995-04-14 Inst Francais Du Petrole Procédé d'élimination du mercure dans les hydrocarbures par passage sur un catalyseur présulfuré.
US5948726A (en) * 1994-12-07 1999-09-07 Project Earth Industries, Inc. Adsorbent and/or catalyst and binder system and method of making therefor
FR2764214B1 (fr) * 1997-06-10 1999-07-16 Inst Francais Du Petrole Procede et masses de captation pour l'elimination du mercure et de l'arsenic dans les coupes hydrocarbonees
DE10255240A1 (de) * 2002-11-26 2004-06-09 Basf Ag Verfahren zur Entfernung von Quecksilber aus mit Quecksilber verunreinigten Lösungen
WO2007147781A1 (de) * 2006-06-21 2007-12-27 Basf Se Absorptionsmasse und verfahren zur entfernung von quecksilber

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1570903A1 (en) * 2002-11-18 2005-09-07 ICT Co., Ltd. Exhaust gas purifying catalyst and method for purifying exhaust gas

Also Published As

Publication number Publication date
JP5455939B2 (ja) 2014-03-26
KR20100133394A (ko) 2010-12-21
JP2011513565A (ja) 2011-04-28
WO2009112440A1 (de) 2009-09-17
CN101970614A (zh) 2011-02-09
US20110005975A1 (en) 2011-01-13

Similar Documents

Publication Publication Date Title
DE69026351T2 (de) Entfernung von Quecksilber aus flüssigen Kohlenwasserstoffen
DE68902710T2 (de) Verfahren zum entfernen von quecksilber aus einem fluessigen kohlenwasserstoff.
DE68902272T2 (de) Methode zur entfernung von quecksilber aus kohlenwasserstoffoelen.
EP2265695A1 (de) Verfahren zur abtrennung von quecksilber aus kohlenwasserstoffströmen
DE69904310T2 (de) Kupfer enthaltende materialien
EP0983794B1 (de) Katalysator und Verfahren zur Reinigung von Stoffströmen
DE69119541T2 (de) Verfahren zur Beseitigung von Quecksilber und eventuell vorhandenem Arsen aus einem Fluidum in Gegenwart einer Absorptionsmasse für Quecksilber und Arsen
WO2021224287A1 (en) Process for purifying a crude pyrolysis oil originating from the pyrolysis of plastic waste
DE69411775T2 (de) Verfahren zur Entfernung von Quecksilber aus Kohlenwasserstoffen mittels einem vorgeschwefeltem Katalysator
DE69608183T2 (de) Verfahren zur Entfernung von Quecksilber aus flüssigen Kohlenwasserstoffen
DE4116890A1 (de) Verfahren zum abtrennen von quecksilber aus einem abfallstrom und verfahren zur herstellung eines adsorptionsmittels hierfuer
DE69002941T2 (de) Verfahren zur entfernung von quecksilber und gegebenenfalls arsen aus kohlenwasserstoffen.
DE2525732A1 (de) Verfahren zur regenerierung eines festen reaktionsmittels
DE3229897A1 (de) Schwefelsorbens und verfahren zu seiner herstellung
CA1286087C (en) Process for cleaning of waste materials by refining and/or elimination of biologically difficult to degrade halogen-, nitrogen- and/or sulfur compounds
EP2035136A1 (de) Absorptionsmasse und verfahren zur entfernung von quecksilber
EP2097159A1 (de) Adsorptionsmasse und verfahren zur entfernung von co aus stoffströmen
DE69205096T2 (de) Entfernung von Arsenverbindungen aus leichten Kohlenwasserstoffströmen.
DE69007407T2 (de) Reinigung eines Umwandlungssystems für verschmutzte Kohlenwasserstoffe, um es mit einem verunreinigungsempfindlichen Katalysator gebrauchen zu können.
DE69603630T2 (de) Verfahren zur Entfernung von Verunreinigungen aus einer gasförmigen Verbindung
DE3401197A1 (de) Verfahren zur katalytischen feinreinigung von inertgasen
DE60303453T2 (de) Reinigung von H2S durch poröse Medien
EP0966508B1 (de) Verfahren zur reinigung von stoffströmen
DE2754393A1 (de) Fester akzeptor fuer schwefeldioxid und dessen verwendung
EP2102102B1 (de) Verfahren zur entfernung von no und n2o aus gasgemischen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20101011

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA RS

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20140403

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20141014