WO2007092410A2 - Separation of light gases from halogens - Google Patents
Separation of light gases from halogens Download PDFInfo
- Publication number
- WO2007092410A2 WO2007092410A2 PCT/US2007/003090 US2007003090W WO2007092410A2 WO 2007092410 A2 WO2007092410 A2 WO 2007092410A2 US 2007003090 W US2007003090 W US 2007003090W WO 2007092410 A2 WO2007092410 A2 WO 2007092410A2
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- WO
- WIPO (PCT)
- Prior art keywords
- halogen
- bromine
- recited
- vapor
- light gas
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/10—Vacuum distillation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/16—Evaporating by spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
- B01D53/685—Halogens or halogen compounds by treating the gases with solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/04—Purification or separation of nitrogen
- C01B21/0405—Purification or separation processes
- C01B21/0433—Physical processing only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/04—Purification or separation of nitrogen
- C01B21/0405—Purification or separation processes
- C01B21/0433—Physical processing only
- C01B21/045—Physical processing only by adsorption in solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0743—Purification ; Separation of gaseous or dissolved chlorine
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/096—Bromine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/202—Single element halogens
- B01D2257/2022—Bromine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/202—Single element halogens
- B01D2257/2025—Chlorine
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0009—Physical processing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0009—Physical processing
- C01B2210/0014—Physical processing by adsorption in solids
- C01B2210/0015—Physical processing by adsorption in solids characterised by the adsorbent
Definitions
- This invention generally relates to processes for separating inert gases and other compounds from halogens.
- a conventional method of capturing trace bromine in inert gas streams is to use an
- alkaline scrubber for example, an aqueous NaOH solution. It is not easy to recover the captured bromine from the conventional scrubbing method.
- Other conventional methods include the use of sodium sulfite, sodium bisulfite, or an aqueous solution of calcium hydroxide, etc., each of which suffers from the same drawback that the captured bromine is difficult to recover.
- the halogen that is generated contains inert gases such as nitrogen and carbon dioxide which, if not removed, would pass through the halogenation section and the coupling section where higher hydrocarbons are produced.
- hydrocarbons are formed by reacting alkyl halides with halogen in the presence of a catalyst, HX is formed as a byproduct.
- HX is oxidized with air or oxygen in the presence of a catalyst.
- N 2 , CO 2 , and other light gases such as unreacted light hydrocarbons
- gases particularly nitrogen
- a process for separating one or more light gases from bromine or chlorine using one or more physical separations and contact with a chemical scrubber to recover additional halogen.
- the process comprises (a) providing a feed of halogen containing one or more light gases to a distillation column or flash vaporizer; (b) operating the distillation column or flash vaporizer to separate the feed into (i) a first liquid containing a major amount of halogen and no more than a minor amount of light gas(es), and (ii) a first vapor containing a major amount of light gas(es) and no more than a minor amount of halogen; and (c) providing the vapor to a chemical scrubber to recover halogen from the vapor.
- two or more physical separations are used, with each separation leading to successively greater enrichment of, respectively, the halogen in the liquid phase and the light gas(es) in the vapor phase.
- the vapor from a distillation column enriched in light gas(es)
- a second distillation column which further separates the material into a new vapor and a new liquid, the new vapor being more enriched in light gas(es), and the new liquid being more enriched in halogen.
- the chemical scrubber utilized in the invention contains one or more halogen scavengers, materials which are capable of chemically sorbing halogen, in some embodiments through a redox reaction with the halogen.
- a preferred material is copper (I) bromide (CuBr, "cuprous bromide”), which can adsorb bromine by conversion into copper (II) bromide (CuBr2, "cupric bromide”).
- Figure 1 is a schematic diagram of a process for separating light gases from bromine according to one aspect of the invention
- Figure 2 is a schematic diagram of the process shown in Figure 1, with the additional elements of bromine formation ("bromine regeneration") and water adsorption;
- Figure 3 is a schematic diagram of a process for separating light gas(es) from bromine, utilizing three flash vaporizers run in series, according to another aspect of the invention;
- Figure 4 is a schematic diagram of a continuous process for converting natural gas into higher hydrocarbons and including a subprocess for separating bromine formed during the process from light gases, according to one aspect of the invention;
- Figure 5 is a schematic illustration of an experimental method of determining halogen breakthrough in a halogen scavenger used in one embodiment of the invention;
- Figure 6 is a photograph of a tube of CuBr that has been exposed to a bromine/nitrogen stream, according to one aspect of the invention.
- one or more light gases are separated from bromine or chlorine by physically separating a feed of the halogen containing one or more light gases into a liquid and a vapor, the liquid containing a major amount of halogen and no more than a minor amount of light gas(es), and the vapor containing a major amount of light gas(es) and no more than a minor amount of halogen. Additional halogen is removed from the vapor by passing it through a chemical scrubber containing a halogen scavenger.
- a "light gas" is one having a lower boiling point than the halogen with which it is mixed.
- the boiling points of bromine and chlorine at atmospheric pressure approximately 59 0 C and -34 0 C, respectively. Included in the definition are such gases as nitrogen (N 2 ), carbon dioxide (CO 2 ), and "light hydrocarbons” — Ci - C 4 hydrocarbons, with the caveat that C 4 hydrocarbons (butanes and butenes) are not considered “light gases” if chlorine is the halogen of interest, as the boiling point of chlorine is less than that of C4 hydrocarbons.
- the terms "major amount” and “minor amount” are relative; a liquid (or vapor) containing a major amount of a first component and a minor amount of a second component contains more of the first component than of the second component. In general, in most of the embodiments of the invention, a given liquid (or vapor) phase will consist predominately of one component (halogen or light gas(es), with very little of the other component.
- FIG. 1 depicts a system 10 for separating light gases (in this case, nitrogen and carbon dioxide) from bromine.
- a feed 12 of bromine containing N 2 and CO 2 is provided to a distillation column 14 having a top 16 and a bottom 18.
- Heat exchangers 20 and 22 act as partial condenser and total reflux, respectively, allowing a liquid "bottoms" enriched in bromine (and containing no more than a minor amount of light gases — typically, no more than the solubility limit of the two gases in bromine) to be withdrawn from the distillation column, with additional lowering of temperature achieved by heat exchanger 24.
- typical pressures range from 0.1 bar to 50 bar, more preferably 5 to 20 bar, with a temperature dependent on the distillation system pressure, keeping in mind that the normal boiling point of bromine is approximately 59 0 C.
- the number of stages can range from 2 to 200, more preferably 5 to 30.
- FIG. 2 illustrates a variation on the embodiment shown in Figure 2, with the halogen feed (e.g., Br 2 ) coming from a halogen regeneration unit 28.
- the halogen feed from 28 contains water, which is removed in a water adsorption unit (containing a desicant).
- the feed is first distilled to remove the bromine from the water, up to the limits of the bromine-water azeotrope that forms, with residual water being removed in a water-sorbing column of desicant.
- flash vaporizers are used to separate the feed of halogen and light gases, followed by additional separation in the chemical scrubber.
- Figure 3 illustrates one such a system 50, in which a feed of bromine, containing nitrogen and carbon dioxide, is provided to a first flash vaporizer 52. The contents of the vaporizer are flashed, yielding a first liquid enriched in bromine (e.g., 97% Br 2 recovery), and a first light gas-enriched vapor (N 2 , CO2) containing only a minor amount of bromine.
- a first liquid enriched in bromine e.g., 97% Br 2 recovery
- N 2 , CO2 first light gas-enriched vapor
- the first vapor is fed to a second flash vaporizer and the contents are flashed, yielding a second bromine-enriched liquid (where, e.g., an additional 1.5% Br 2 is recovered) and a second light-gas enriched vapor, which passes through a second heat exchanger 58 and then fed to a third flash vaporizer 60.
- the contents of the third flash vaporizer are then flashed, yielding, e.g., an additional 0.5% Br 2 (liquid) and a vapor very highly enriched in light gases.
- the trace amount of bromine in this third stream of vapor is removed in a bromine scrubber 62.
- additional flash vaporizes can be utilized.
- each flash vaporizer is operated at a temperature of from -6O 0 C to 40 0 C, more preferably -20 0 C to 10 0 C and a pressure of 0.1 to 50 bar, more preferably 5 to 20 bar, keeping in mind the differences in boiling points between the halogen and the contained light gas(es).
- One to three flashes are preferred.
- the pressure can be varied in the flashes; however, to reduce costs, it is desirable to operate the flashes at the system pressure to avoid compression, which is expensive.
- the temperature for operating the flashes is dependent on the pressure. For example, a high- pressure operation can allow good bromine separation even at modestly high temperatures. For lower pressures, however, a refrigerant may be needed for cooling the flash units.
- the series of vapor-liquid flashes can consist of one or more flashes.
- An important aspect of this invention is the method of chemically scrubbing bromine or chlorine) from a very dilute gas stream consisting mostly of light gases.
- the method uses a halogen scavenger capable of sorbing halogen.
- the scavenger absorbs bromine vapors from the diluted gas stream and then can reversibly release it back as free bromine, quantitatively. Adsorption of bromine can occur at room or elevated temperature.
- any material capable of reacting with bromine and releasing it upon heating can be used as bromine scavenger.
- materials considered to be suitable for use as halogen scavengers include CuBr, CuCl, FeBr 2 , FeCl 2 , AuCl, AuBr, InBr, InCl, FeO, Cu 2 O, Hg 2 Br 2 , Cu, Ag, Au, Hg, Pt, Pd, Ru, Rh, Fe, Os, and Ir, used alone or in combination.
- CuBr is preferred. If copper bromide with high surface area (on a support) is used, much higher activity is observed even though the total mount of copper bromide is much smaller. It has also been found that CuBr made by a precipitation process is better than stock CuBr.
- Copper (I) bromide reacts with bromine to form copper (II) bromide according to the following reaction: 2CuBr + Br 2 -> 2CuBr 2 .
- the reaction is quick and complete and, advantageously, occurs at low temperatures. The reaction appears to be surface-bound. When using bulk CuBr, approximately 1 % of the solid is used before breakthrough occurs. (The density of CuBr and CuBr 2 is very similar and the surface does not refresh well; 4.6 versus 4.0 g/cm 3 ). Because the reaction of CuBr with Br 2 vapor is a reaction of a gas with a solid, the reaction rate is limited by the solid-gas interface and, correspondingly, the higher the surface area, the higher the reactivity.
- the halogen scavenger can be used as a bulk powder or deposited on a support.
- Nonlimiting examples include silica, alumina, zirconia, titania, WO3, CaO, MgO, Cr 2 O 3 , and various carbides, nitrides, and similar materials.
- the primary requirement is that the support have a surface area of from 5 to 1500 M 2 /g.
- solid Cu(I)Br or Cu(I)Br deposited on Davicat SiZr4700 or Davicat SiI 151A (Davidson Corporation) silicas with high surface area (approximately 300 m 2 /g. Si4700B contains ⁇ 3wt.% ZrO 2 .
- the halogen scavenger, or scavenger plus support can be utilized in a packed column reactor configuration or other configurations, such as a shell and tube reactor. Standard heat transfer mediums can be used to deliver the required heat to bring the active ingredients of the scrubber to the regeneration temperature.
- the process scheme can include two reactors, in which one undergoes scrubbing, while the other one undergoes regeneration.
- the solid scrubbing agent is capable of completely retaining all bromine content from the inert gas flow (bromine loss from the scrubber was estimated to be less than 1 ppb). Supported copper (I) bromide shows reproducible results after multiple cycles of exhaustion and regeneration.
- the mhomogeneous surface When a support (such as silica) is used, the mhomogeneous surface generates nucleation sites which cause the formation of smaller crystallites, with appreciably larger surface area. Even where the supported material contains only 15wt.% CuBr, its higher CuBr surface area renders it a better material for bromine vapor retention.
- the % is the amount of total Br retained by the scavenger. Regeneration is complete at 275 0 C within 10-15 min.
- Figure 6 is a photograph of a tube of precipitated CuBr exposed to a bromine/nitrogen stream for thirty minutes at room temperature.
- the dark material is CuBr 2 .
- the color reverses back to the pale green of CuBr, releasing bromine.
- Experimental Protocol 30 sccm/min. N 2 mixed with 1.5 seem N 2 going through Br 2 bubbler cooled to 0 0 C.
- the solid adsorbent bed was contained in a cylindrical glass tube with a diameter of 1 cm.
- the duration of the exposure to such created diluted bromine in nitrogen was 40 minutes at room temperature.
- the scrubber treated gas was bubbled through a trap containing 1 M NaOH.
- Preparation of the supported CuBr materials The support was dispersed in a ⁇ 20 wt.% CuBr 2 solution in water and bubbled with SO 2 until the color of the solution became almost colorless. The suspension was filtered and dried at 115°C overnight.
- Regeneration The regeneration of the retained bromine was conducted by heating the reactor with the solid scrubbing agent after exhaustion at 275°C for 20 minutes. The released bromine was collected and quantified by capturing the released bromine in a IM NaOH trap solution. Near complete recovery of the captured bromine is possible.
- Bromine breakthrough is determined by using a precipitation of the Br and BrO " with Ag + , wherein, the NaOH trap is acidified with HNO 3 until acidic; AgNo 3 is added until no more precipitation form; the suspension is allowed to age for 40 minutes then filtered on a dry, pre-weighted glass-fritted funnel, dried until constant weight and the mass difference is AgBr.
- the bromine capture from the inert gas stream was complete, and the scrubbing bed performed complete bromine capture for a period of 40 min.
- the exhausted scrubbing bed containing copper (II) bromide and copper (I) bromide was heated to 275 0 C, and a near complete bromine recovery was observed in a time period of 15 min.
- the invention should find utility in a large number of industrial processes that use halogens as a feedstock or intermediates for chemicals production, where the halogen recovery or purification is improved by the removal of inerts or light gases, resulting in significantly reduced capital and operating costs. Among these are the processes for making alcohols, ethers, olefins, and alkoxylates described in U.S.
- the nitrogen and carbon dioxide carry forward into the bromination and the metathesis section.
- separation of nitrogen from methane is required, which is cost-intensive.
- the carbon dioxide generated during regeneration must be separated from the unconverted methane either using pressure swing adsorption or by using an amine-based system, both of which are cost intensive.
- the separation of light gases from bromine not only reduces the reactor size but also simplifies the separation of light gases from the products and unconverted reactants.
- the separation process described herein offers a cost-effective way to separate light gases (including nitrogen and carbon dioxide) from halogens such as bromine.
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Abstract
Description
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Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07763277.6A EP1993951B1 (en) | 2006-02-03 | 2007-02-05 | Separation of light gases from bromine |
CA2641426A CA2641426C (en) | 2006-02-03 | 2007-02-05 | Separation of light gases from halogens |
BRPI0707490-5A BRPI0707490A2 (en) | 2006-02-03 | 2007-02-05 | halogen light gas separation |
AU2007212493A AU2007212493B2 (en) | 2006-02-03 | 2007-02-05 | Separation of light gases from halogens |
CN2007800081079A CN101395088B (en) | 2006-02-03 | 2007-02-05 | Separation method of light gases from halogens |
JP2008553404A JP5275817B2 (en) | 2006-02-03 | 2007-02-05 | Separation of light gases from halogens |
KR1020087021011A KR101335397B1 (en) | 2006-02-03 | 2007-02-05 | Separation of light gases from halogens |
EA200870229A EA013629B1 (en) | 2006-02-03 | 2007-02-05 | Separation of light gases from halogens |
TNP2008000318A TNSN08318A1 (en) | 2006-02-03 | 2008-08-01 | Separation of light gases from halogens |
NO20083776A NO20083776L (en) | 2006-02-03 | 2008-09-01 | Separation of light gases from halogens |
HK09108876.3A HK1130758A1 (en) | 2006-02-03 | 2009-09-25 | Separation of light gases from halogens |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US76547306P | 2006-02-03 | 2006-02-03 | |
US60/765,473 | 2006-02-03 |
Publications (2)
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WO2007092410A2 true WO2007092410A2 (en) | 2007-08-16 |
WO2007092410A3 WO2007092410A3 (en) | 2007-12-27 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US2007/003090 WO2007092410A2 (en) | 2006-02-03 | 2007-02-05 | Separation of light gases from halogens |
Country Status (17)
Country | Link |
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US (1) | US7883568B2 (en) |
EP (1) | EP1993951B1 (en) |
JP (1) | JP5275817B2 (en) |
KR (1) | KR101335397B1 (en) |
CN (1) | CN101395088B (en) |
AU (1) | AU2007212493B2 (en) |
BR (1) | BRPI0707490A2 (en) |
CA (1) | CA2641426C (en) |
EA (1) | EA013629B1 (en) |
EC (1) | ECSP088711A (en) |
HK (1) | HK1130758A1 (en) |
MY (1) | MY153701A (en) |
NO (1) | NO20083776L (en) |
SG (1) | SG187456A1 (en) |
UA (1) | UA95943C2 (en) |
WO (1) | WO2007092410A2 (en) |
ZA (1) | ZA200807230B (en) |
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US20050171393A1 (en) | 2003-07-15 | 2005-08-04 | Lorkovic Ivan M. | Hydrocarbon synthesis |
RU2366642C2 (en) | 2003-07-15 | 2009-09-10 | Джи Ар Ти, Инк. | Hydrocarbons synthesis |
US20060229228A1 (en) * | 2005-04-11 | 2006-10-12 | Zachary John Anthony Komon | Method of making alkoxylates |
EP1993979A4 (en) | 2006-02-03 | 2011-07-06 | 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 |
EP2499090B1 (en) * | 2009-11-13 | 2016-10-26 | Basf Se | Method for purifying a chlorine supply |
JP5617623B2 (en) * | 2010-12-28 | 2014-11-05 | 株式会社島津製作所 | Total organic carbon measuring device |
US8940954B2 (en) | 2011-05-23 | 2015-01-27 | Reaction35, LLC | Conversion of propane to propylene |
WO2013006427A1 (en) * | 2011-07-01 | 2013-01-10 | Sun Catalytix Corporation | Methods and systems useful for solar energy storage |
MY156181A (en) * | 2011-10-11 | 2016-01-15 | Hong In Chemical Co Ltd | Method and system for producing high-purity hydrogen chloride |
WO2014193957A1 (en) * | 2013-05-30 | 2014-12-04 | Reaction 35, Llc | Recovery of halogens by partial condensation |
WO2014210016A1 (en) | 2013-06-24 | 2014-12-31 | Reaction 35, Llc | Coupling of light alkanes to liquid fuels |
WO2015191580A1 (en) | 2014-06-12 | 2015-12-17 | Reaction35, LLC | Production of 1,3-butadiene |
CN105478000B (en) * | 2015-12-30 | 2017-11-14 | 沈阳三聚凯特催化剂有限公司 | It is a kind of to be used to purify antichlor for reforming regeneration gas and preparation method thereof |
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AU2007212493A1 (en) | 2007-08-16 |
CN101395088B (en) | 2012-04-04 |
CA2641426A1 (en) | 2007-08-16 |
BRPI0707490A2 (en) | 2011-05-03 |
EP1993951B1 (en) | 2014-07-30 |
MY153701A (en) | 2015-03-13 |
UA95943C2 (en) | 2011-09-26 |
CA2641426C (en) | 2015-06-09 |
HK1130758A1 (en) | 2010-01-08 |
ECSP088711A (en) | 2008-11-27 |
EA200870229A1 (en) | 2009-02-27 |
JP2009525257A (en) | 2009-07-09 |
KR101335397B1 (en) | 2013-12-02 |
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