CATALYST FOR REFORMING BIO-GAS AND METHOD OF MANUFACTURING SAME

Hereinafter, with reference to the detailed drawing objects of the present invention preferred embodiment to less than 1000.

The disclosure of the present invention in the embodiment are defined herein as exemplified for the purpose of description only, various forms of the present invention in the embodiment are described in the embodiment can be limited to embodiment herein are interpreted don't substrate.

The present invention refers to various modification may have bar can apply in various forms, in the embodiment are the present invention disclosure form adjacent frames but is specified, all changing range of idea and techniques of the present invention, will be understood to uniformly including water to replacement.

In one embodiment of the present invention provide the means by which the biogas (bio-a gas), sewage sludge, such as fermentation biomass (biomass) anaerobic digestion a (anaerobic digester), gasification (gasification), gas fuel on stone and the pyrolysis (pyrolysis) are disclosed. This biogas methane as a main component (55 - 70%) and carbon dioxide (30 - 45%) which, contains impurities such as sulfur (S).

In one embodiment of the present invention dry reforming reaction (dry reforming reaction) RM, big reactions produce carbon monoxide and hydrogen by reacting carbon dioxide and methane. Dry reforming reaction useful in carbon dioxide can be reused side, endothermic reaction reactor low disclosed. With reference to, a compound reactive carbon dioxide 1 dry reforming reaction are disclosed.

[Compound 1]

CH₄ + CO₂ ↔ 2CO + 2H₂ (H Δ₂ =+ 247 kJ/mol)

In one embodiment of the present invention provide the means by which a homogeneous catalyst (homogenous catalyst), the lattice material substituted single phase (single phase) and an active material maintaining a catalyst capable big.

In one embodiment of the present invention provide the means by which term stability of the catalyst, catalyst conversion or hydrogen selectivity (the molar ratio of hydrogen fuel that is consumed for the oxidation reaction), i.e. the connection or more long activity means that can be maintained as high as 2000. The, improved long-term stability of alumina catalyst the catalyst life which means that the other.

In one embodiment of the present invention fetching (Pechini method) RM sludge method widely, polymeric resin contained acid (citric acid) solvent action between chelating (chelation) other end cation, and metal - chelating agent for treatment of alcohol (titanium ISO ) caused by the lack of cationic poly composite action of stabilizing precursors can be obtained together with obtain big powder synthesis.

In one embodiment of the present invention provide the means by which multi-stage micro pores (<2 nm) pore (hierarchically porous structures), mesoporous (2 - 50 nm), macro pores in the pores of the porous structure including two or more different sizes (50 nm>) simultaneously by big.

In one embodiment of the present invention, dip coating (dip-a coating) coating the slurry on the saline solution pico RM-insoluble material the use of a pico-insoluble material precursor coating and excellent method forms means other. Implementations of the present invention made from the perovskite catalyst solution [ni the law a monolith support pico-insoluble material a predefined number and excellent catalyst was about 650 °C heated high pressure liquid coolant.

In one embodiment of the present invention, 'monolith support' implies catalyst support, meaning that the cylindrical substrate. Number but not one, said monolith support ceramic, metal, alumina, silica, alumina, tie (alumina titanate), cordierite (Codierite) (2MgO. 2Al₂ O₃ . 5SiO₂ ) Can be like.

Hereinafter, embodiments of the present invention with reference to the drawing to the preface is detailed as follows. With reference to the attached drawing an exemplary implementations of the present invention described herein are described but for which, number and configuration and applications of the present invention this technical idea is not one.

Biogas dry reforming catalyst

Biogas for use in modifying the catalyst of the present invention, more specifically a methane and carbon dioxide as catalyst for the biogas including dry reforming (dry reforming of bio-a gas), multistage pore (hierarchically porous) structure monolith (monolithic) support; and said monoliths which a on a support, to comprise a compound [formula 1].

[Formula 1]

Sr_{1 A-y} Y_y Ti_{1 A-x} Ru_x O_{3 - Δ}

(Wherein, x is larger than 0 less than 1. Y 0 is larger than 0. 1 Less than the. 1 Hereinafter δ is 0 or more are disclosed.)

With reference to, SrTiO₃ A yttrium (Y) (Ru) of perovskite lattice structure when doped with an O content of doping of a metal fine changes can be caused. I.e., O of said perovskite in [formula 1]₃ The O_{3 - Δ} (Δ is 0 to 1 hereinafter) can be shifted into the genome.

Said compound is, SrTiO₃ Perovskite strontium (Sr) (perovskite) material represented by part (Ti) ruthenium (Ru) doped yttrium (Y) titanium doped substituted substituted part are disclosed. I.e., said compounds are, ABO₃ In perovskite material having a structure of a portion of (Ti) A sites (Sr) respectively having different material portions of B sites (place place A Y and B Ru) doped by substituted, perovskite structure can be maintained.

The, catalyst comprising an active substance of the existing method are generally support by heat-treating a number of so-called heterogeneous catalysts consisting of at least one tank to 2 (phase) unlike, when used as a single phase (single phase) of said compounds are acting as catalyst can be a homogeneous catalyst (homogeneous catalyst). the compounds including catalyst can be minimized through process efficiency and mirror number number tank absorbs catalyst synthesis processes than useful than in marks.

Said compound, Ru (ruthenium) titanium sites substituted (perovskite structure B sites) to high catalyst activity. In addition, substituted yttrium (Y) to strontium sites (perovskite structure A sites) the catalyst number can be improved electrical conductivity. Furthermore ABO₃ Perovskite catalyst having a structure inherently sulfur (S) and carbon (C) so that the resistance to, said biogas compounds including biogas reforming reaction may have high catalytic activity, in addition the amount of carbon deposition phenomena and/or catalyst poisoning against high-resistance may have.

In particular, said catalyst, carbon dioxide is included in a stand-alone biogas selectively number performed by steam reformed than reforming reaction, carbon dioxide reforming reaction that are not desired for direct use in the detaching process additionally separate carbon dioxide dry modification when used, its effect can be maximized.

In exemplary embodiments, catalyst single fat, the amount of carbon deposition and/or catalyst poisoning prevention, enhanced electrical conductivity when panel considers both the activity of the catalyst, a ruthenium (Ru) (perovskite structure B sites) amount of titanium sites substituted in, i.e. said [formula 1] is larger than 0 in x 0. 05 Hereinafter (<x ≤ 0 0. 5) Can be preferably. In particular, the x 0. 03 When can be desirable. In addition, the amount of yttrium (Y) (perovskite structure A sites) substituted with strontium sites, i.e. [formula 1] is greater than 0 in said y 0. 08 Hereinafter (<y ≤ 0 0. 08), In particular y is 0. 08 Can be preferably.

Y in said [formula 1] is 0. 08 While maintaining electrical conductivity when single phase are considered crucial. However in this case if x is 0 when the i.e., titanium site is substituted ruthenium catalyst activity is equal to where there is extremely low. However, even when x trace is substituted (e.g. x=0. 01), X=0. 02, 0. 05, 0. 1. Similar to exhibit very high degrees of making sure that the reforming performance such as can be.

In exemplary embodiments, said reforming catalyst biogas nitrogen (N), helium (He), including inert gas like argon (Ar) activated process are performed, using hydrogen (H) under reducing atmosphere to be a fact that an activated. In particular, the ambient temperature may be processed in said catalyst activation, reducing atmosphere in a stand-alone oxygen catalyst surface attached to the active point number is equal to adsorb chemical reactant.

On the other hand, compound [formula 1] said ultra thin-wall monoliths (monolithic) can be supported by the support, specifically through deep - coating (dip-a coating) can be answer. Deep - unit is conveniently [formula 1] (dip-a coating) coating said coating compound can be.

In an exemplary embodiment, said monolith (monolithic) support material may be included as if the number of monoliths (monolithic) support contains not one but a material which can be, for example, alumina, silica, alumina tie (alumina titanate), cordierite (Codierite) (2MgO. 2Al₂ O₃ . 5SiO₂ ) Can be like.

In addition, monoliths (monolithic) support may have a multi-pore (hierarchically porous) structure, in this case within the supporting body having the various sized pores the plurality resulting, represented by [formula 1] compounds rich in said amount can be supported.

In an exemplary embodiment said monolith support 34 to 37 cm and a specific surface area² /Cm³ It rises at once be range.

On the other hand, 100 parts by weight of said monolith support [formula 1] is 10 to 50 parts by weight of said compound can be supported on, specifically 20 to 45 parts by weight can be supported. 10 Parts by weight supported catalyst active site compared when less than compress the performance degradation, 50 parts by weight (mass transfer limitation) is exceeded mass transfer degradation due to catalyst can be portable.

As above-mentioned, the present invention according to reforming catalyst monoliths having multi-pore structure supported on support biogas represented by formula 1 compounds including bar, bio-gas including carbon dioxide reforming reaction can be very good catalyst performance.

In an exemplary embodiment, during operation of said catalyst at a temperature of 60 to 80 biogas for use in modifying 750 provided 900 °C performance time can be 80% or more of the catalysts. Specifically, modification of 750 °C 70 83% or more methane conversion catalyst during said time passes in biogas can be seen disclosed.

Dry bath method comprising a composite number biogas

According to exemplary implementations of the present invention their use represented by [formula 2] (perovskite) strontium (Sr) doped yttrium (Y) perovskite material portion is replaced with a, titanium (Ti) ruthenium (Ru) doped by substituting part, said compound represented by [formula 1] step number bath; and [formula 1] to said compound comprises an ultra thin-wall monoliths (monolithic) support for modification of step number biogas by coating the catalyst tank; comprising a composite oxide including a number bath method number tank through biogas can be disclosed.

[Formula 2]

SrTiO₃

One exemplary implementation , yttrium (Y) and ruthenium (Ru) said perovskite (perovskite) material partially substituting the doped, yttrium (Y), strontium (Sr), titanium (Ti) and ruthenium (Ru) including a solvent distilled water or deionized water (deionized water, DI water) as affect using, number of known dry catalyst for producing sludge method can be carried out by means of fetching (Pechini method).

More specifically, yttrium nitrate [Y (NO₃ )₃ , H₂ O] and nitrogen strontium [Sr (NO₃ )₃ , H₂ O] dissolved in a distilled water or deionized water (DI water) solution number number 1 high pressure liquid coolant therein. Titanium ISO [Ti (OCH (CH₃ )₂ )₄ ] And citric acid ethylene glycol sufficiently dissolving solution number number 2 high pressure liquid coolant therein. Ruthenium chloride [(Cl₃ Ru, xH₂ O)] are dissolved in distilled water or deionized water (DI water) solution number number 3 a high pressure liquid coolant therein. The, yttrium (Y), strontium (Sr), titanium (Ti) and ruthenium (Ru) of compounds are not dissolved in distilled water or deionized water (DI water) by an upper ethanol, in order to minimize the impurity content can be catalyst bath in number.

The solution number prepared by the number 1, number 2 and number 3 solution are mixed together to about 80 °C solution at a stirring, in high pressure liquid coolant is dried to about 110 °C number can be represented by said formula 1 compounds.

On the other hand, high pressure liquid coolant to said formula 1 compound number after, about 300 °C (calcination) 450 °C hereinafter more calcination temperatures may be disclosed. The calcination process said 1 or more times, for example about 300 °C perform 1 difference in calcination process, can be performed by performing calcination process in about 450 °C 2 difference. The, catalyst can be effectively number number can be generated during tank can be a stand-alone.

The device processes deionized water (deionized water, DI water) distilled water or as a solvent (Pechini method) using a fetch sludge method are disclosed.

The, said formula 1 compounds represented by the above-mentioned data on the number including gel solution can be high pressure liquid coolant.

Then, dip coating to said gel solution monolith support, represented by said formula 1 compounds monolith support is supported by a number biogas for use in modifying catalyst can tank.

In exemplary embodiments, said gel solution dipped coating it pico-insoluble material made from the Sr [ni the law a monolith support fetch_{1 A-y} Y_y Ti_{1 A-x} Ru_x O_{3 - Δ} Catalyst solution in which about 600 to 700 °C coated sintered, the, represented by said formula 1 compound monolith support a greater amount than can be supported.

On the other hand, said dip coating process can be performed iteratively adjusting the amount of catalyst. The dip coating process, such as vacuum coating or pyrolysis coating complex equipment that are not desired or more than simple method which can reduce time cost with the lower disclosed.

Then, number reforming catalyst for enhancing the activity of biogas produced therewith can be catalyst treatment.

In exemplary embodiments, the activating treatment said nitrogen, argon, or inert gas such as helium, or hydrogen can be performed using a gas including nitrogen balance. In particular, said activating treatment can be carried out in the ambient temperature. The surface of the catalyst in reducing atmosphere oxygen number attached to the active point equal to or higher than a stand-alone adsorb chemical reactant.

In one embodiment, the activating treatment using said hydrogen 750 °C to 900 °C, specifically 800 to 850 °C can be performed. Less than said range activated case process of the robot arm can be catalytically active waste, applied to said case rather catalyst activation process can be portable.

As aforementioned, according to an exemplary embodiments of the present invention biogas for use in modifying the catalyst monolith support prepared by the number includes a material having a perovskite structure can be supported. The, catalytic activity of higher than compared to conventional artificial pearl with compound can be supported on the catalyst support, can be attached to catalytic activity of said catalyst.

In one example, a compound represented by said formula 1 Sr_{0. 92} Y_{0. 08} Ti_{0. 97} Ru_{0. 03} O_{3 - Δ} (I.e., when ruthenium doped with 3 mole %) when as monolith support when doped, simple Sr_{0. 92} Y_{0. 08} Ti_{0. 95} Ru_{0. 05} O_{3 - Δ} Catalyst powder excellent catalytic activity equivalent to can be seen disclosed. The, using a small amount of precious metal catalyst can be role of catalyst activity.

In addition, biogas morning fair number said reforming catalyst, adhesive number, a binder or pore-forming number being used, catalyst of organic matter that allows the catalyst maintains its activity by poisoning phenomenon can be.

In addition, distilled water or deionized water according to exemplary implementations of the present invention using the catalyst as a solvent (deionized water, DI water) through (Pechini method) since the number tank sludge fetching method, does not contain a single homogeneous catalyst to substantially impurities on number bath 1308.

In addition, when a catalyst for hydrotreatment catalyst activity is only activated when performing treatment bath number reducing atmosphere, high catalytic activity and long-term stability number bath to can be disclosed.

Hereinafter, the present invention broadcast receiver through more detailed in the embodiment. The present invention is to provide a galvanic these in the embodiment is exemplified, in the embodiment of the present invention interprets these range number by one in the art-case is not in the person with skill in the art will.

In the embodiment

[In the embodiment 1]

Yttrium nitrate [Y (NO₃ )₃ , H₂ O (the [tu reach which it will know)] 3. 064G and nitrogen strontium [Sr (NO₃ )₃ , H2O (the [tu reach which it will know)] 19. 469G simultaneously a deionized water (DI water) was dissolved. Titanium ISO [Ti (OCH (CH₃ )₂ )₄ (The [tu reach which it will know)] 28. 13G and citric acid 76. 8G 200g ethylene glycol sufficiently seam sealing, then ruthenium chloride [(Cl₃ Ru, xH₂ O) (Brassica juncea is)] 0. 622G deionized water (DI water) was placed in a dissolving to stabilize. 24 Hours in 80 °C Sr each solution by mixing together_{0. 92} Y_{0. 08} Ti_{0. 97} Ru_{0. 03} O_{3 - Δ} Including a high pressure liquid coolant gel (gel) solution (3% doping Ru is minor) his number. Then, monolith support (voice synthesizer FLORA yarn^TM Article number) to Sr_{0. 92} Y_{0. 08} Ti_{0. 97} Ru_{0. 03} O_{3 - Δ} 0. 2G after dip coating to be specific, 110 °C in very dry. Finally 650 °C 5 heat in his time. The, monolith support Sr supported_{0. 92} Y_{0. 08} Ti_{0. 97} Ru_{0. 03} O_{3 - Δ} Including a catalyst (hereinafter, represented by Ru-a SYT coated monolith) is number bath take place.

[In the embodiment 2]

In in the embodiment 1, monolith support (voice synthesizer FLORA yarn^TM Article number) to Sr_{0. 92} Y_{0. 08} Ti_{0. 97} Ru_{0. 03} O_{3 - Δ} 0. 1G can be a specific number and conducting the same process dip coating that point.

[In the embodiment 3]

In in the embodiment 1, monolith support (voice synthesizer FLORA yarn^TM Article number) to Sr_{0. 92} Y_{0. 08} Ti_{0. 97} Ru_{0. 03} O_{3 - Δ} 0. 3G to be a specific number and conducting the same process dip coating that point.

[In the embodiment 4]

In in the embodiment 1, a number Ru-a SYT coated monolith after high pressure liquid coolant, gas including hydrogen and nitrogen balance in the same process that point number 750 °C conducting the activating treatment.

[In the embodiment 5]

In in the embodiment 1, a number Ru-a SYT coated monolith after high pressure liquid coolant, hydrogen nitrogen balance gas) activated at that point number using the same process and processing 800 °C conducting

[In the embodiment 6]

In in the embodiment 1, a number Ru-a SYT coated monolith after high pressure liquid coolant, hydrogen gas including nitrogen balance in the same process that point 850 °C number and conducting the activating treatment.

[In the embodiment 7]

In in the embodiment 2, a Ru-a SYT coated monolith number after high pressure liquid coolant, hydrogen gas including nitrogen balance in the same process that point 850 °C number and conducting the activating treatment.

[In the embodiment 8]

In in the embodiment 3, a number Ru-a SYT coated monolith after high pressure liquid coolant, hydrogen gas including nitrogen balance in the same process that point 850 °C number and conducting the activating treatment.

[Comparison example 1]

Yttrium nitrate [Y (NO₃ )₃ , H₂ O (the [tu reach which it will know)] 3. 064G and nitrogen strontium [Sr (NO₃ )₃ , H₂ (The [tu reach which it will know) O] 19. 469G simultaneously a deionized water (DI water) was dissolved. Titanium ISO [Ti (OCH (CH₃ )₂ )₄ (The [tu reach which it will know)] 28. 13G and citric acid 76. 8G 200g ethylene glycol sufficiently seam sealing, then ruthenium chloride [(Cl₃ Ru, xH₂ O) (Brassica juncea is)] 0. 622G deionized water (DI water) was placed in a dissolving to stabilize. Each solution mixing 80 °C 24 together in time, in a 110 °C a transparent conductive layer, the organic number 400 °C (calcination) was calcined in air every other. Finally 650 °C 5 heat in his time. The, 3% Ru is doped Sr_{0. 92} Y_{0. 08} Ti_{0. 97} Ru_{0. 03} O_{3 - Δ} Catalyst [hereinafter, Ru3 a-SYT represented (powder)] number bath take place.

[Comparison example 2]

Yttrium nitrate [Y (NO₃ )₃ , H₂ O (the [tu reach which it will know)] 3. 064G, strontium nitrate [Sr (NO₃ )₃ , H₂ (The [tu reach which it will know) O] 19. 469G, titanium ISO [Ti (OCH (CH₃ )₂ )₄ (The [tu reach which it will know)] 27. 6G, citric acid 76. 8G, ethylene glycol 200g and ruthenium chloride [(Cl₃ Ru, xH₂ O) (Brassica juncea is)] 1. 088G a number in the range of 0.1 and a , to perform the same process in the embodiment 1 to 5% Ru is doped Sr_{0. 92} Y_{0. 08} Ti_{0. 95} Ru_{0. 05} O_{3- Δ} Catalyst [hereinafter, represented Ru5 a-SYT(powder)] is number bath take place.

[Comparison example 3]

Monolith support (voice synthesizer FLORA yarn^TM Article number) was used as a comparison example 3.

[Experiment example 1: catalyst composition evaluation]

Composition of catalyst to evaluate, in the embodiment 1, comparison example 1 and comparison example 3 according to X-ray diffraction analysis (X-a ray Diffraction, X RD) catalysts for conducting. The result is also shown in 2 efined.

The reference 2 also, in the embodiment 1, SrTiO 3 according to comparison example 1 and comparison example basic structure as catalyst₃ Has a perovskite structure of, yttrium (Y) a titanium (Ti) part strontium (Sr) (Ru) nickel catalysts on each uniform doping substituted single part can be known. Through, [formula 1] of the present invention the catalyst is a homogeneous catalyst on said represented, not using ethanol as a solvent is distilled water or deionized water through the cylindrical tank sludge method (Pechini method) for fetching number be hereinafter can be.

[Experiment example 2: catalyst activation according to the presence or absence of catalyst performance evaluation]

In order to evaluate performance of the catalyst according to the presence or absence of catalyst activation, comparison example 3, and in the embodiment 6 in the embodiment 1 according to carbon dioxide catalyst prepared by the number comprising dry reforming reaction as well as biogas. The, surface of a scanning electron microscope (scanning electron microscope, SEM) before and after the dry reforming reaction is observed. The result is also shown in 3a to 3c efined.

The reference 3a to 3c also, it became work in the embodiment 1 according to the number of multiple pore catalyst monolith support (also 3a) contrast (also 3b) generated gas moved for hereinafter were confirm it. On the other hand, in the case of number (also 3c) catalyst according it became work in the embodiment 6, it became work is not performed in the embodiment 1 according to any of the activating treatment process chart number is also used for capable of porous structure formed catalyst contrast reduction.

[Experiment example 3: amount of pores of the catalyst according to one side of the evaluation]

According to evaluate performance of the catalyst to a catalyst activation conditions, in the embodiment 1 to 3 and 8 to the surface of the scanning electron microscope (scanning electron microscope, SEM) catalyst prepared by the number in the embodiment 6 according to observed. The result is also shown in 4a to 4c efined.

The 4a to 4c also refers, in the case of number 8 (lower end each of the drawings) in the embodiment 6 according to catalyst it became work, it became work number 3 in the embodiment 1 according to the standpoint of are not performed any activating treatment catalyst contrast (top of the drawings each) porous structure is sufficiently higher than the first call request to 1:1 by weight. The, reducing atmosphere surface activated catalyst catalyst in which the gas can flow channel increased refresh sintered according to that catalytically active performance and increased has been confirmed.

Only, such as in the embodiment 7 Sr_{0. 92} Y_{0. 08} Ti_{0. 97} Ru_{0. 03} O_{3- Δ} If catalyst active site compared performance deterioration has taken place as an interlayer dielectric, such as Sr in addition in the embodiment 8_{0. 92} Y_{0. 08} Ti_{0. 97} Ru_{0. 03} O_{3 - Δ} Is 0. 2G is put in than the mass transfer lowering (mass transfer limitation) phenomenon that some performance degradation due to his car. The, Sr_{0. 92} Y_{0. 08} Ti_{0. 97} Ru_{0. 03} O_{3- Δ} 0. 2G carrying a monolith support when first call receipt is most appropriate.

[Experiment example 4: evaluating performance of a catalyst temperature according to the activating treatment]

According to evaluate performance of the catalyst to a catalyst activation conditions, including dry reforming reaction catalyst prepared by the number 6 in the embodiment 4 according to carbon dioxide as well as biogas. The result is shown in table 1 for efined.

Said residual table, when activation temperature is 750 °C most methane conversion rate has been determined, the greater the reducing atmosphere activated catalyst surface temperature is raised activated catalyst in which the gas can flow channel increases according to refresh sintering and make sure that catalytically active performance were increased. In particular in the case of verify performance and provides a significant increase in the embodiment 6 activation temperature is 850 °C catalytically active queue.

[Experiment example 5: evaluating the performance of a catalyst according to amount]

[Formula 1] amount of compound according to change in order to evaluate performance of the catalyst, catalyst prepared by the number 3 in the embodiment 1 and comparison example 1 to 3 according to dry reforming reaction as well as bio-gas comprising carbon dioxide. The result is shown in table 2 for efined.

Said residual table, monolith support plate is (in the embodiment 1 to 3) carrying a Ru3 a-SYT, compared to make sure that the methane conversion is not performed much higher rate queue. In addition, in the embodiment 1 to 3 typically look over the amount of methane conversion rate can be enhanced Ru3 a-SYT occupation area to confirm that the machining, the catalyst active site compared amount if performance degradation phenomenon has taken place, in addition amount 0. 2G is put in than the mass transfer lowering (mass transfer limitation) phenomenon that some performance degradation due to his car.

[Experiment example 6: automatically according to methane conversion of a performance evaluation]

For automatically according to evaluate performance of the catalyst, including catalyst prepared by the number in the embodiment 1 according to carbon dioxide dry reforming reaction as well as biogas. 5 Result is also shown.

The heat also 5, when using the catalyst prepared by the number in the embodiment 1 according, 70 even after the amount of carbon deposition time rising after performing high-resistant catalyst response time and the second water maintained in spite were confirm it. The, long-term operation even when the fuel cell is used catalyst by maintaining high activity, bio-gas reforming, dry reforming in a methane and carbon dioxide in particular bio-gas including hydrogen, carbon monoxide or the like can be hereinafter for synthesis gas to high pressure liquid coolant including number were confirm it.