WO2000007718A1 - Catalyseur et procede d'oxydation de methane en methanol - Google Patents

Catalyseur et procede d'oxydation de methane en methanol Download PDF

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Publication number
WO2000007718A1
WO2000007718A1 PCT/EP1999/005576 EP9905576W WO0007718A1 WO 2000007718 A1 WO2000007718 A1 WO 2000007718A1 EP 9905576 W EP9905576 W EP 9905576W WO 0007718 A1 WO0007718 A1 WO 0007718A1
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WO
WIPO (PCT)
Prior art keywords
catalytic
methanol
temperature
composition according
methane
Prior art date
Application number
PCT/EP1999/005576
Other languages
English (en)
Inventor
Giuseppe Bellussi
Carlo Perego
Laura Zanibelli
Original Assignee
Enitecnologie S.P.A.
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 Enitecnologie S.P.A. filed Critical Enitecnologie S.P.A.
Priority to AU57301/99A priority Critical patent/AU5730199A/en
Publication of WO2000007718A1 publication Critical patent/WO2000007718A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a catalytic composition, its preparation and its use in the process for transforming methane into methanol in a single step.
  • Methane is a raw material which is widely available, often however in remote places.
  • the transportation costs are therefore very high and its compression to liquid which is easier to transport can only take place under extreme temperature and pressure conditions. Consequently, owing to the high availability of natural gas and its localisation in geographically remote places, the possibility of finding a way of converting it directly in loco to products which can be transported at a lower cost, is definitely of great interest. Attention is therefore directed towards hydrocarbon products with a higher molecular weight or to oxygenated products.
  • One of these products could be methanol, which is used as both an intermediate product for chemicals and a possible energy vector.
  • the activation of methane however is not easy owing to the strong stability of the C-H bond with respect to higher hydrocarbons; processes using oxidation reactions are therefore normally adopted.
  • the activation of methane takes place either by oxidation or by halogenation or a combination of the two processes (oxy-halogenation) .
  • the most favoured products in the first case are CO x , in the second case halogen-derivatives. In both cases subsequent treatment is necessary to obtain the desired products.
  • methanol can be produced starting from methane by means of two types of processes: a direct process, in which the methane is transformed into etha- nol in a single step; an indirect process, in which the reaction takes place in several steps, i.e. a first activation step of methane and one (or more) subsequent steps for the actual production of methanol.
  • Typical examples of direct processes are: a) Casey et al . In Ind. Eng. Chem. Res. (1994) who de-scribe a non-catalytic process at 350-550°C and at 50 bars, with a yield to methanol of 1.8%; b) Hunter, Gesser et al. in Appl. Cat. 1990, who describe a non-catalytic process at 350°C and 30 bars with a yield to methanol of 7%; c) Hunter, Gesser et al. in Appl. cat. 1990, who describe a catalytic process with Sn0/Cu/Si0 2 at 250°C and 30 bars with a yield to methanol of 3.3%; d) Chun, Anthony in Ind.
  • the present invention relates to a catalytic composition, optionally supported on an inert material, characterized in that it comprises (i) oxides and/or hydroxides of a first metal (Ml) and (ii) halides of a second metal (M2) , wherein Ml and M2, the same or different, are selected from metals belonging to groups Ila, lib, IVb, VIII, lb, lib, Va, Lanthanides, and relative mixtures .
  • the optional inert material supporting the catalytic composition is selected from metal oxides normally used for this purpose, for example, aluminum, silicon, titanium, zirconium, cerium, lanthanum, preferably aluminum and silicon.
  • the oxides and/or hydroxides and halides are selected from oxides, hydroxides and halides of Mg, Ca, Ba, La, Ni, Cu, Zn, Bi, even more preferably, Mg, Ba, Bi, Ni .
  • halides are preferably selected from chlorides, bromides and iodides, and are even more preferably bromides.
  • the catalytic composition of the present invention is also characterized by a molar ratio M1/M2 ⁇ 1, preferably from 1 to 2..
  • the catalytic composition of the present invention can be prepared by means of various techniques known to experts in the field, in particular by means of sol-gel synthesis, impregnation, physical mixing of oxides and/or hydroxides and halides.
  • the same metal halides or metal salts for example nitrates, acetates, oxalates
  • metal halides or metal salts for example nitrates, acetates, oxalates
  • acid solution of hydroha- logen acid can be introduced during the synthesis phase.
  • step (a) when a metal halide is used in step (a) , during step (c) it is sufficient to add water for the gelation to take place.
  • step (a) when the metal salt of step (a) is insoluble in alcohol, it is dissolved in an aqueous solution, preferably acid by hydrohalogen acid, whereas the Silicon source in step (b) is put in an alcohol solution. The gelation takes place by the simple addition of the Silicon solution to the metal solution.
  • a simplified preparation scheme of the catalytic composition of the present invention can therefore be represented as follows:
  • step (c) an aqueous solution is added which is acid by HN0 3 or basic by the addition of an a - monium salt in relation to the precipitation pH of the hydroxide, which produces the desired oxide during the calcination phase.
  • the materials thus obtained mainly consist of an amorphous carrier in which the halides and/or oxides- hydroxides are uniformly dispersed.
  • compositions can be prepared by impregnation of the carrier with solutions of metal salts in acid solution by hydrohalogen acid, preferably selected from HBr and HC1.
  • hydrohalogen acid preferably selected from HBr and HC1.
  • commercial carriers or carriers obtained by the sol-gel method, following the procedure described above, can be used.
  • the molar ratios used in the preparation of the catalytic composition of the present invention are:
  • M/Si0 2 from 0.05 to 0.40, preferably from 0.1 to 0.30;
  • EtOH/Si0 2 from 1.8 to 4.5, preferably from 2.2 to 3.2;
  • H 2 0/EtOH from 0.005 to 10, preferably from 0.01 to 4.6;
  • H 2 0/Si0 2 from 0.01 to 20, preferably from 0.04 to 10.5.
  • M/Si0 2 ratio applies when the impregnation technique or commercial oxides are used.
  • the present invention also relates to a process for the preparation of methanol starting from methane and oxygen, preferably air, under catalytic conditions, char- acterized in that the methanol is produced directly in the presence of the catalytic composition defined above.
  • the process of the present invention is carried out in a continuous system, in a stream of methane and air, at pressures close to atmos- pheric pressure, at temperatures ranging from 250°C to 450°C, preferably from 300°C to 350°C, with a WHSV in methane ranging from 0.01 to 1 h "1 and a CH 4 /0 2 ratio higher than 1.8/1 or lower than 0.7/1 within the temperature range indicated, to avoid falling within explosive limits.
  • H 2 0, in vapour form may optionally be fed, in a ratio CH 4 /H 2 0 ranging from 0.1/1 to 3/1, preferably from 0.3 to 2.5.
  • the process of the present invention does not co - prise feeding of the halogen (or organic halides) together with the reagent mixture, as described in 2-step processes (oxyhalogenation of methane and subsequent hydrolysis) .
  • the process of the present invention can be effected in the presence of one or more catalytic beds.
  • the gaseous mixture is sent to a sin- gle catalytic bed containing the catalytic composition of the present invention.
  • the CH 4 /0 2 mixture is fed to a first catalyst containing the metal halide
  • the first catalytic bed is put at a temperature ranging from 300°C to 360°C, whereas the second bed is put at a temperature ranging from 70°C to 150°C.
  • the flow of reagents or catalytic beds can be in- verted.
  • NiBr 2 3.1 grams of NiBr 2 are dispersed in 13.64 grams of EtOH under stirring at 50°C. 19.78 grams of TES (tetra- ethylorthosilicate) and then 8.40 grams of H 2 0 are added to this solution.
  • the solution is left under stirring at 50°C until gelation (about 48 hours) . This is followed by the ageing phase at room temperature for 16 hours, and then the drying phase in an oven at atmos- pheric pressure at 100°C for 1.5 hours. It is then calcined in muffle with the following temperature program: heating in N 2 to 340°C (5°C/min.); pause at 340°C for 3 hours; finally spontaneous cooling to room temperature.
  • catalyst A The characteristics of catalyst A are indicated in Table 1.
  • Catalyst B is prepared according to the procedure adopted in example 1 and using the same reagents as example 1 in the same molar ratio. The characteristics of catalyst B are indicated in Table 1. EXAMPLE 3 - Preparation of catalyst C
  • MgC 4 H ⁇ o0 2 Magnethylate
  • catalyst F The characteristics of catalyst F are indicated in Table 1.
  • EXAMPLE 7 Catalytic activity of the catalytic composition (A+E) .
  • the catalytic system consisting of two catalytic beds, is put in a quartz reactor using corindone (40 mesh) as filler.
  • the first catalytic bed consists of 2.2 grams of catalyst A, granulated to 30/50 mesh and diluted with 1 cc of quartz 18 mesh; the second catalytic bed consists of 1.02 grams of catalyst E (30/50 mesh) .
  • catalyst A is brought to 355°C for 1 hour in a stream of N 2 (30 ml/min) whereas catalyst E is maintained at 100°C in a stream of nitrogen (30 ml/min) .
  • EXAMPLE 8 Catalytic activity of the catalytic composi- tion (C + Ba(OH) 2 ) .
  • COMPARATIVE EXAMPLE 10 Catalytic activity of catalyst A. 1.02 grams of catalyst A alone, granulated to 30-50 mesh, are diluted and treated as in example 7, except that the oven is heated to a single temperature of 360°C and the WHSV is equal to 0.3 h "1 . The activity of this catalyst is indicated in Table 2.
  • EXAMPLE 11 Catalytic activity of the catalytic composi- tion (C + Ba(OH) 2 ) .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Industrial Gases (AREA)

Abstract

L'invention concerne une composition catalytique, éventuellement supportée sur une substance inerte, cette composition se caractérisant par le fait qu'elle renferme i) des oxydes et/ou des hydroxydes d'un premier métal (M1), et ii) des halogénures d'un second métal (M2), M1 et M2 étant identiques ou différents et choisis parmi les métaux appartenant aux groupes IIa, IIb, IVb, VIII, Ib, Va, les lanthanides, et les mélanges apparentés. L'invention concerne également la préparation de cette composition ainsi que son utilisation dans la transformation sélective de méthane en méthanol.
PCT/EP1999/005576 1998-08-05 1999-07-30 Catalyseur et procede d'oxydation de methane en methanol WO2000007718A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU57301/99A AU5730199A (en) 1998-08-05 1999-07-30 Catalyst and process for the oxidation of methane to methanol

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI98A001847 1998-08-05
IT1998MI001847A IT1302003B1 (it) 1998-08-05 1998-08-05 Procedimento per la trasformazione selettiva di idrocarburi.

Publications (1)

Publication Number Publication Date
WO2000007718A1 true WO2000007718A1 (fr) 2000-02-17

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Application Number Title Priority Date Filing Date
PCT/EP1999/005576 WO2000007718A1 (fr) 1998-08-05 1999-07-30 Catalyseur et procede d'oxydation de methane en methanol

Country Status (3)

Country Link
AU (1) AU5730199A (fr)
IT (1) IT1302003B1 (fr)
WO (1) WO2000007718A1 (fr)

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6403840B1 (en) 2001-06-20 2002-06-11 Grt, Inc. Process for synthesizing olefin oxides
US6465699B1 (en) * 2001-06-20 2002-10-15 Gri, Inc. Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
US6486368B1 (en) * 2001-06-20 2002-11-26 Grt, Inc. Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
US6689601B2 (en) 2000-09-01 2004-02-10 E. I. Du Pont De Nemours And Company High growth methanotropic bacterial strain
US6713655B2 (en) 2001-06-20 2004-03-30 Grt Inc Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes
US6818424B2 (en) 2000-09-01 2004-11-16 E. I. Du Pont De Nemours And Company Production of cyclic terpenoids
US7019182B2 (en) 2001-04-18 2006-03-28 Grt, Inc. Method of hydrocarbon preservation and environmental protection
US7161050B2 (en) 2001-06-20 2007-01-09 Grt, Inc. Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes
US7230150B2 (en) 2001-04-18 2007-06-12 Grt, Inc. Zone reactor
US7348464B2 (en) 2004-04-16 2008-03-25 Marathon Oil Company Process for converting gaseous alkanes to liquid hydrocarbons
US7361794B2 (en) 2001-04-18 2008-04-22 Grt, Inc. Zone reactor
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
US7847139B2 (en) 2003-07-15 2010-12-07 Grt, Inc. Hydrocarbon synthesis
EP2277847A2 (fr) 2002-01-24 2011-01-26 GRT, Inc. Procédé intégré pour la synthèse d'alcools, d'éthers et d'oléfines à partir d'alcanes
US7883568B2 (en) 2006-02-03 2011-02-08 Grt, Inc. Separation of light gases from halogens
US7964764B2 (en) 2003-07-15 2011-06-21 Grt, Inc. Hydrocarbon synthesis
US7998438B2 (en) 2007-05-24 2011-08-16 Grt, Inc. Zone reactor incorporating reversible hydrogen halide capture and release
US8008535B2 (en) 2004-04-16 2011-08-30 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8173851B2 (en) 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US8198495B2 (en) 2010-03-02 2012-06-12 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8273929B2 (en) 2008-07-18 2012-09-25 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
CN103949263A (zh) * 2014-04-27 2014-07-30 东北石油大学 用于甲烷制甲醇的钙钛矿复合氧化物催化剂及其制备方法
CN103949257A (zh) * 2014-04-27 2014-07-30 东北石油大学 用于生产可调控合成气的核壳钙钛矿型催化剂及应用
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
WO2015021352A2 (fr) 2013-08-08 2015-02-12 Knipbio Méthylotrophes pour aquaculture et alimentation animale
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
CN107098794A (zh) * 2017-05-18 2017-08-29 山西大学 一种固体乙醇镁的制备方法

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GB1244001A (en) * 1968-05-01 1971-08-25 Ici Ltd Oxygenated hydrocarbons production
EP0580356A1 (fr) * 1992-07-20 1994-01-26 SUN COMPANY, INC. (R&M) Oxydation catalytique d'alcanes
WO1994009897A1 (fr) * 1992-11-04 1994-05-11 Energia Andina Ltd. Procede de preparation d'alcanols et de glycols
RU2057745C1 (ru) * 1993-07-12 1996-04-10 Арутюнов Владимир Сергеевич Способ получения метанола
WO1998022414A1 (fr) * 1996-11-21 1998-05-28 E.I. Du Pont De Nemours And Company Fabrication catalytique de fluoroethene

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1244001A (en) * 1968-05-01 1971-08-25 Ici Ltd Oxygenated hydrocarbons production
EP0580356A1 (fr) * 1992-07-20 1994-01-26 SUN COMPANY, INC. (R&M) Oxydation catalytique d'alcanes
WO1994009897A1 (fr) * 1992-11-04 1994-05-11 Energia Andina Ltd. Procede de preparation d'alcanols et de glycols
RU2057745C1 (ru) * 1993-07-12 1996-04-10 Арутюнов Владимир Сергеевич Способ получения метанола
WO1998022414A1 (fr) * 1996-11-21 1998-05-28 E.I. Du Pont De Nemours And Company Fabrication catalytique de fluoroethene

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DATABASE WPI Section Ch Week 199702, Derwent World Patents Index; Class E17, AN 1997-019470, XP002124212 *

Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6818424B2 (en) 2000-09-01 2004-11-16 E. I. Du Pont De Nemours And Company Production of cyclic terpenoids
US6969595B2 (en) 2000-09-01 2005-11-29 E. I. Du Pont De Nemours And Company Carotenoid production from a single carbon substrate
US6958222B2 (en) 2000-09-01 2005-10-25 E. I. Du Pont De Nemours And Company Production of feed using a denitrifying methanotrophic bacterial strain
US6689601B2 (en) 2000-09-01 2004-02-10 E. I. Du Pont De Nemours And Company High growth methanotropic bacterial strain
US7361794B2 (en) 2001-04-18 2008-04-22 Grt, Inc. Zone reactor
US7230150B2 (en) 2001-04-18 2007-06-12 Grt, Inc. Zone reactor
US7019182B2 (en) 2001-04-18 2006-03-28 Grt, Inc. Method of hydrocarbon preservation and environmental protection
US6486368B1 (en) * 2001-06-20 2002-11-26 Grt, Inc. Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
US6713655B2 (en) 2001-06-20 2004-03-30 Grt Inc Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes
US6403840B1 (en) 2001-06-20 2002-06-11 Grt, Inc. Process for synthesizing olefin oxides
US6472572B1 (en) 2001-06-20 2002-10-29 Grt, Inc. Integrated process for synthesizing alcohols and ethers from alkanes
US6465699B1 (en) * 2001-06-20 2002-10-15 Gri, Inc. Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
US7148390B2 (en) 2001-06-20 2006-12-12 Grt, Inc. Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes
US7161050B2 (en) 2001-06-20 2007-01-09 Grt, Inc. Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes
US6465696B1 (en) 2001-06-20 2002-10-15 Grt, Inc. Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
US8415512B2 (en) 2001-06-20 2013-04-09 Grt, Inc. Hydrocarbon conversion process improvements
US6462243B1 (en) 2001-06-20 2002-10-08 Grt, Inc. Integrated process for synthesizing alcohols and ethers from alkanes
EP2060552A2 (fr) 2001-06-20 2009-05-20 GRT, Inc. Procédé intégré pour la synthèse d'alcools et d'éthers à partir d'alcanes
US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
EP2277847A2 (fr) 2002-01-24 2011-01-26 GRT, Inc. Procédé intégré pour la synthèse d'alcools, d'éthers et d'oléfines à partir d'alcanes
US7847139B2 (en) 2003-07-15 2010-12-07 Grt, Inc. Hydrocarbon synthesis
US7964764B2 (en) 2003-07-15 2011-06-21 Grt, Inc. Hydrocarbon synthesis
US7348464B2 (en) 2004-04-16 2008-03-25 Marathon Oil Company Process for converting gaseous alkanes to liquid hydrocarbons
US7880041B2 (en) 2004-04-16 2011-02-01 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to liquid hydrocarbons
US8008535B2 (en) 2004-04-16 2011-08-30 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US8173851B2 (en) 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US7883568B2 (en) 2006-02-03 2011-02-08 Grt, Inc. Separation of light gases from halogens
US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8921625B2 (en) 2007-02-05 2014-12-30 Reaction35, LLC Continuous process for converting natural gas to liquid hydrocarbons
US7998438B2 (en) 2007-05-24 2011-08-16 Grt, Inc. Zone reactor incorporating reversible hydrogen halide capture and release
US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
US8415517B2 (en) 2008-07-18 2013-04-09 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8273929B2 (en) 2008-07-18 2012-09-25 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
US8198495B2 (en) 2010-03-02 2012-06-12 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
WO2015021352A2 (fr) 2013-08-08 2015-02-12 Knipbio Méthylotrophes pour aquaculture et alimentation animale
CN103949263A (zh) * 2014-04-27 2014-07-30 东北石油大学 用于甲烷制甲醇的钙钛矿复合氧化物催化剂及其制备方法
CN103949257A (zh) * 2014-04-27 2014-07-30 东北石油大学 用于生产可调控合成气的核壳钙钛矿型催化剂及应用
CN107098794A (zh) * 2017-05-18 2017-08-29 山西大学 一种固体乙醇镁的制备方法

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Publication number Publication date
ITMI981847A0 (it) 1998-08-05
ITMI981847A1 (it) 2000-02-05
AU5730199A (en) 2000-02-28
IT1302003B1 (it) 2000-07-20

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