WO2017001891A1 - One-step conversion of methane to methanol at ambient temperature and atmospheric pressure - Google Patents
One-step conversion of methane to methanol at ambient temperature and atmospheric pressure Download PDFInfo
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- WO2017001891A1 WO2017001891A1 PCT/IB2015/054899 IB2015054899W WO2017001891A1 WO 2017001891 A1 WO2017001891 A1 WO 2017001891A1 IB 2015054899 W IB2015054899 W IB 2015054899W WO 2017001891 A1 WO2017001891 A1 WO 2017001891A1
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- Prior art keywords
- methane
- methanol
- catalysts
- synthesis
- gas
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 97
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 3
- 239000002114 nanocomposite Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000003637 basic solution Substances 0.000 abstract description 2
- 238000007210 heterogeneous catalysis Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- -1 hydroxyl radicals Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/04—Methanol
-
- 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
- This present invention related to one-step converting gaseous methane to methanol.
- the invention is a novel method and apparatus (reactor) for chemically (catalytically) converting methane to methanol at ambient pressure and temperature.
- Methane containing natural gas is a clean and effective alternative energy source. But it is difficult and costly to transfer. Methanol is an important feed compound in petrochemical application.
- oxidation process involves indirect and complex method by reacting methane with steam at high temperature (1500 to 2000 °C) and high pressure (105 bar) to produce synthesis gas (CO + 3 ⁇ 4). Methanol is subsequently formed heating synthesis gas in a high pressure.
- Methane is a simplest organic molecule in nature consisting of one carbon atom bonded with four hydrogen atoms. Methanol is only one atom change away, with one of the hydrogen atoms replaced by an OH hydroxyl. Methanol, the initial product of methane oxidation, is a desirable product of conversion because it retains much of the original energy of methane in a room temperature transportable, storable liquid that can be used directly as a fuel or converted to other valuable products. In addition to its commercial importance as a chemical feedstock, there are many advantages of using methanol for broad use as an environmentally compatible and efficient vehicle fuel. It has lower combustion emissions of greenhouse gasses, evaporative hydrocarbons, and particulate pollutants, yet has high energy content.
- Methanol can even be converted into boiling grade gasoline if necessary. On the other hand, good methods necessitate high costs and high energy.
- VS. Pat. No. 4,374,288 to Scragg discloses combining methane and oxygen in a high energy electromagnetic field strong enough to atomize the oxygen for combining with methane.
- United Kingdom Pat. No. 1.244.001 discloses oxidation of methane over a (M0 2 O 3 ) Fe 2 0 3 catalyst on silica/aluminum at high temperature and pressure.
- Methanol is raw material for petrochemical industry.
- the methanol have -CH 2 OH bond and hydroxide agent, so, this can use in many reactions.
- the importance application for this material is production of formaldehyde and resins.
- Fig.l. shows a sample of GC-MS analysis from vaporizable materials that existing peak in vaporizable compounds are related to methanol.
- Fig.2. shows a schematic of methane to methanol plants
- the present inventor realized that there is a need for a process that produces methanol in a process that is cost effective, easy to operate, relatively fast and capable for achieving high conversion.
- One common source of methane can be natural gas. Although inexpensive and abundant, natural gas presents difficulties in its use caused by the fact that is contains a number of constituents besides methane including nitrogen, ethane, propane, butane and carbon dioxide.
- the present inventor realized that efficient synthesis of methanol from methane has been an elusive target for many years. It is difficult, if not impossible, because of a basic problem based on a chemistry of methane.
- the invention provides a process for the reaction uses catalyst agent to create reactive hydroxyl radicals in short time. Hydroxyl radicals diluted in methane gas, which oxidize the methane molecule to a methanol molecule in a one-step chemical conversion.
- methane gas as a capsule with 99% purity (Ml sample), the gas of Esfahan city with 80% methane (M2 sample) and biogas with 60% methane (M3 sample), in these tests.
- used reactor in this invention can converting methane with high selectivity, conversion efficiency over 97% and the period time less than 90 min.
- the used catalytic process in this invention is capable as one-step and in 25 °C and 1 atm pressure. Due to increasing temperature up to 70 °C in Ml and M2 samples, the conversion percent was increasing. But in biogas sample (M3) saw opposing state, that can related to kinds of existing gases in biogas.
- the biogas is containing methane, oxygen, 0 2 and H 2 S. In this project, the methane was removed after passing of reactor system. In addition, the percent compound quantity of other gases has changed with removing H 2 0, decreasing of C0 2 and increasing oxygen.
- the reactor catalytic reaction's base is hydroxide radical formations which according to kind of used catalysts in this reactor, operator can control the quantity of hydroxide radicals.
- the starters of preparation of radical are electro -catalyst compounds and quantity of preparation of radicals is related to amount injected electric charge.
- Electron injection process is controlled by electrical panel on reactor. Used electricity for this work is a kind of Direct Electricity (DC) with 1-20 V amount voltage.
- DC Direct Electricity
- the controlling of catalytic process is done by Chronopotentio- Coulometry process.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This present invention includes a one-step method for converting methane to methanol at ambient temperature and pressure. In this reactor, methane gas was blobbed in a basic solution containing homogenous and heterogeneous catalysis and partial selective oxidation of methane gas to methanol was done in ambient pressure and temperature. Complex catalytic reaction is one-step with high conversion efficiency (up to 98%).
Description
ONE-STEP CONVERSION OF METHANE TO METHANOL AT AMBIENT
TEMPERATURE AND ATMOSPHERIC PRESSURE
Background of the invention
This present invention related to one-step converting gaseous methane to methanol. The invention is a novel method and apparatus (reactor) for chemically (catalytically) converting methane to methanol at ambient pressure and temperature.
The word need for alternative energy is well known. Methane containing natural gas is a clean and effective alternative energy source. But it is difficult and costly to transfer. Methanol is an important feed compound in petrochemical application.
In previous technologies (EP0448019,
US20060235090,JPH04217635,EP2404888,US4277416,EP2021309) oxidation process involves indirect and complex method by reacting methane with steam at high temperature (1500 to 2000 °C) and high pressure (105 bar) to produce synthesis gas (CO + ¾). Methanol is subsequently formed heating synthesis gas in a high pressure.
Huge deposits of methane worldwide are economically "stranded" because of the high capital costs of using existing technology to make it transportable. A system, based on new technology, that would economically convert methane into fuel that could be transported and stored economically, would provide for the first time the capability to monetize the huge stranded gas reserves worldwide, and ultimately tap huge ocean floor deposits of methane hydrate reserves to supply world energy needs for 200 years after petroleum reserves have been exhausted.
Methane is a simplest organic molecule in nature consisting of one carbon atom bonded with four hydrogen atoms. Methanol is only one atom change away, with one of the hydrogen atoms replaced by an OH hydroxyl. Methanol, the initial product of methane oxidation, is a desirable product of conversion because it retains much of the original energy of methane in a room temperature transportable, storable liquid that can be used directly as a fuel or converted to other valuable products. In addition to its commercial importance as a chemical feedstock, there are many advantages of using methanol for broad use as an environmentally compatible and efficient vehicle fuel. It has lower combustion emissions of greenhouse gasses, evaporative hydrocarbons, and particulate pollutants, yet has high energy content. Methanol can even be converted into boiling grade gasoline if necessary.
On the other hand, good methods necessitate high costs and high energy. VS. Pat. No. 4,374,288 to Scragg discloses combining methane and oxygen in a high energy electromagnetic field strong enough to atomize the oxygen for combining with methane. United Kingdom Pat. No. 1.244.001 discloses oxidation of methane over a (M02O3) Fe203 catalyst on silica/aluminum at high temperature and pressure. US. Pat. No. 5,220,080 to Layons et al catalytic oxidation of methane employing surface oxide chromate catalyst on a metal oxide support of silica, alumina, magnesia, titania or zirconia.
Summary of invention
Methanol is raw material for petrochemical industry. The methanol have -CH2OH bond and hydroxide agent, so, this can use in many reactions. The importance application for this material is production of formaldehyde and resins.
In previous methods, methanol prepared from methane with multi -steps catalytic oxidation reaction, then, the methanol was purified. In this invention, methane is directly converted to methanol by one-step catalytic process. In previous technology, oxidation reaction was done from homogenate and expensive catalysts. Thus, the catalysts were sensitive to reaction conditions. The properties of used catalysts in this invention are reusability and stability. Also, in previous converting process, catalytic reactions were done in high pressure and temperature, while in this invention, all the process was done in ambient pressure and temperature.
In this invention, a novel and cheap technology with high efficiency has been shown. In this method, one step converting methane to methanol in a reactor was done with complex heterogeneous and homogenous catalysts. In this reactor, methane gas was bobbling in aqueous basic solution. In this solution, there are both heterogeneous and homogenous catalysts which prepared by titanium, chromium, carbon, magnesium, manganese, Iron, cobalt, nickel, copper, zinc, potassium, sodium elements and their nanoparticles and nanocomposites. Nanocomposite thin film of heterogeneous catalysts is prepared by dip-coating and spray coating methods on stainless steel plates. Partial oxidation of methane to methanol was done in one -step single reactor at ambient pressure and temperature. After oxidation, synthesized methanol converting to vapor phases in 70 °C and inter to condenser. Pure methanol produce was separated from vapor phases and was saved in tank.
Brief description of the drawing
Fig.l. shows a sample of GC-MS analysis from vaporizable materials that existing peak in vaporizable compounds are related to methanol.
Fig.2. shows a schematic of methane to methanol plants
Table.l. shows the results of catalytic reaction.
Detailed description
The present inventor realized that there is a need for a process that produces methanol in a process that is cost effective, easy to operate, relatively fast and capable for achieving high conversion. One common source of methane can be natural gas. Although inexpensive and abundant, natural gas presents difficulties in its use caused by the fact that is contains a number of constituents besides methane including nitrogen, ethane, propane, butane and carbon dioxide.
The present inventor realized that efficient synthesis of methanol from methane has been an elusive target for many years. It is difficult, if not impossible, because of a basic problem based on a chemistry of methane.
CH4 CH3OH
The invention provides a process for the reaction uses catalyst agent to create reactive hydroxyl radicals in short time. Hydroxyl radicals diluted in methane gas, which oxidize the methane molecule to a methanol molecule in a one-step chemical conversion.
The performance of a reactor has been proved with different analysis. That, for this thing, 3 kinds of gas feed used for consideration of process of reactor performance.
We used methane gas as a capsule with 99% purity (Ml sample), the gas of Esfahan city with 80% methane (M2 sample) and biogas with 60% methane (M3 sample), in these tests.
The quality and quantity for Ml and M2 samples and materials in vaporizable phase and non- vaporizable phase have examined with sampling of reactor's liquid and GC-Mass analysis, respectively. For controlling of PPM of import and output methane gas in variety times and
Debbie's, used Geotech gas tester (analyzer). The results of catalytic reaction were shown in table 1.
According to table 1, used reactor in this invention can converting methane with high selectivity, conversion efficiency over 97% and the period time less than 90 min. The used catalytic process in this invention is capable as one-step and in 25 °C and 1 atm pressure. Due to increasing temperature up to 70 °C in Ml and M2 samples, the conversion percent was increasing. But in biogas sample (M3) saw opposing state, that can related to kinds of existing gases in biogas. The biogas is containing methane, oxygen, 02 and H2S. In this project, the methane was removed after passing of reactor system. In addition, the percent compound quantity of other gases has changed with removing H20, decreasing of C02 and increasing oxygen.
As it was said, the reactor catalytic reaction's base is hydroxide radical formations which according to kind of used catalysts in this reactor, operator can control the quantity of hydroxide radicals. Thus, the starters of preparation of radical are electro -catalyst compounds and quantity of preparation of radicals is related to amount injected electric charge. Electron injection process is controlled by electrical panel on reactor. Used electricity for this work is a kind of Direct Electricity (DC) with 1-20 V amount voltage. The controlling of catalytic process is done by Chronopotentio- Coulometry process.
Claims
1. A method for synthesis of catalyst comprising the steps of:
a) Synthesis catalysts via sol-gel and hydrothermal routs
b) coating paste of catalysts on stainless steel
2. A method for converting methane to methanol comprising the steps of:
a) Oxidation reaction of methane with catalysts in ambient temperature and pressure b) Synthesis of methanol with vapor phase at 70 °C
c) Separation of methanol and vapor phase
3. An alternate methane to methanol conversion apparatus comprising:
a) A closed loop pipe where incoming feed gas is mixed.
b) A controller for incoming gas flow rate
c) An inlet port for methane.
d) Both homogenous and heterogeneous catalyst are working in an apparatus.
4. titanium, chromium, carbon, magnesium, manganese, Iron, cobalt, nickel, copper, zinc, potassium, sodium elements and their nanoparticles and nanocomposites in claim 1.
5. In claim 1, the properties of used catalysts in this invention are reusability and stability.
6. In claim 2, the method for converting methane to methanol is one-step.
7. The invention provides a process for the reaction uses catalyst agent to create reactive hydroxyl radicals in short time.
8. Hydroxyl radicals are reacted with methane gas, which oxidize the methane molecule to a methanol molecule in a one-step chemical conversion.
9. The apparatus in claim 3, where in the heterogeneous catalyst may be coated on stainless steel.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IR139350140003007965 | 2015-06-30 | ||
| IR13933007965 | 2015-06-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2017001891A1 true WO2017001891A1 (en) | 2017-01-05 |
Family
ID=83280631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2015/054899 WO2017001891A1 (en) | 2015-06-30 | 2015-06-30 | One-step conversion of methane to methanol at ambient temperature and atmospheric pressure |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2017001891A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252303A (en) * | 2019-06-25 | 2019-09-20 | 陕西延长石油（集团）有限责任公司 | A kind of catalytic methane cryogenic selective prepares loaded catalyst of methanol and the preparation method and application thereof |
| US11473204B2 (en) | 2018-02-12 | 2022-10-18 | Thrunnel Ltd, Oy | Method and device for the preparation of alcohols from hydrocarbons |
| US11578016B1 (en) | 2021-08-12 | 2023-02-14 | Saudi Arabian Oil Company | Olefin production via dry reforming and olefin synthesis in a vessel |
| US11617981B1 (en) | 2022-01-03 | 2023-04-04 | Saudi Arabian Oil Company | Method for capturing CO2 with assisted vapor compression |
| US11718575B2 (en) | 2021-08-12 | 2023-08-08 | Saudi Arabian Oil Company | Methanol production via dry reforming and methanol synthesis in a vessel |
| US11787759B2 (en) | 2021-08-12 | 2023-10-17 | Saudi Arabian Oil Company | Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel |
| US12258272B2 (en) | 2021-08-12 | 2025-03-25 | Saudi Arabian Oil Company | Dry reforming of methane using a nickel-based bi-metallic catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US11473204B2 (en) | 2018-02-12 | 2022-10-18 | Thrunnel Ltd, Oy | Method and device for the preparation of alcohols from hydrocarbons |
| CN110252303A (en) * | 2019-06-25 | 2019-09-20 | 陕西延长石油（集团）有限责任公司 | A kind of catalytic methane cryogenic selective prepares loaded catalyst of methanol and the preparation method and application thereof |
| CN110252303B (en) * | 2019-06-25 | 2022-04-15 | 陕西延长石油（集团）有限责任公司 | Supported catalyst for catalyzing methane to selectively prepare methanol at low temperature and preparation method and application thereof |
| US11578016B1 (en) | 2021-08-12 | 2023-02-14 | Saudi Arabian Oil Company | Olefin production via dry reforming and olefin synthesis in a vessel |
| US11718575B2 (en) | 2021-08-12 | 2023-08-08 | Saudi Arabian Oil Company | Methanol production via dry reforming and methanol synthesis in a vessel |
| US11787759B2 (en) | 2021-08-12 | 2023-10-17 | Saudi Arabian Oil Company | Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel |
| US12258272B2 (en) | 2021-08-12 | 2025-03-25 | Saudi Arabian Oil Company | Dry reforming of methane using a nickel-based bi-metallic catalyst |
| US11617981B1 (en) | 2022-01-03 | 2023-04-04 | Saudi Arabian Oil Company | Method for capturing CO2 with assisted vapor compression |
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