JP2009102460A - Manufacturing process for hydrocarbons by fischer-tropsch synthesis process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing process for hydrocarbons for efficiently converting a synthesis gas composed mainly of hydrogen and carbon monoxide generated in a biomass gasifying process or the like into gaseous or liquid hydrocarbons usable easily at production site. <P>SOLUTION: In this manufacturing process, the mixed gas prepared by adding olefin to the synthesis gas composed of carbon monoxide and hydrogen is brought into contact with a catalyst containing cobalt of 5 mass% or more and 25 mass% or less in terms of cobalt metal and based on the catalyst mass in a carrier containing single porous silica or a carrier containing at least one kind of metal oxide selected from the group III in the periodic table or lanthanoids in the porous silica at pressure of normal pressure or more and less than 5 kg/cm<SP>2</SP>, G, at space velocity of 300 or more and 30,000 or less, and at reaction temperature of 220°C or more and 260°C or less. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing hydrocarbons.

  In recent years, there is an urgent need to reduce carbon dioxide, and the effective use of biomass has attracted attention. For example, in the case of forest biomass, gasification and carbonization are considered to be effective uses.

The gas obtained from biomass may contain carbon dioxide in addition to hydrogen and carbon monoxide. These alcohols from Shiwan (C ₁₎ Chemistry and inorganic gas 1 carbon atoms called, hydrocarbons, be convertible of dimethyl carbonate, the fuel for the next generation such as dimethyl ether (DME) can become higher raw material gas However, because the area where biomass is handled is remote from the industrial area, it is often used as a heat source because it is transported and used as a heat source, and the potential value is not fully utilized. Currently.

  By the way, as a method for synthesizing hydrocarbons, Fischer-Tropsch synthesis using iron-based, cobalt-based, and ruthenium-based catalysts has been found from 1920 to 1940s (Non-patent Document 1).

  Fischer-Tropsch synthesis is intended to obtain hydrocarbons by hydrogenation of carbon monoxide using synthesis gas (mixed gas of carbon monoxide and hydrogen) as a starting material. In the old days, it was developed as a technology for synthesizing fuel from dry distillation gas (coal gas) obtained by coal dry distillation. In South Africa, a large-scale plant is operating by the Synthol method or the ARGE method using abundantly produced coal.

  In recent years, there has been increased interest in the effective use of petroleum resources and low environmental impact fuels that do not contain sulfur and nitrogen, and the process of synthesizing liquid fuel from natural gas (GTL: gas to liquid) ) Is attracting attention. Many of these GTL processes have relatively large process developments due to the large scale of natural gas fields, and pilot plants are operating or planning to operate from several BPDs (barrel per day) to several tens of BPDs (non-patent literature). 1).

  However, when considering biomass gas, it is highly possible that the amount of biomass resources will be limited to a certain region or scale of a farmer's farm, and the above-mentioned coal-based and natural gas-based liquid fuel conversion technologies are applied by downsizing them as they are. There are many difficult aspects. Many Fischer-Tropsch synthesis technologies in recent years are suitable for slurry bed reactors (Patent Document 1), and although it is excellent in productivity, it is considered difficult to adapt to medium to small farming scales.

Regarding conversion of carbon number of olefins, there are attempts to use supported molybdenum oxide catalyst, supported cobalt catalyst, etc., but these aimed at the selective oligomerization of lower olefins obtained by the accompanying gas and FT synthesis. This is a technology (Non-patent Document 2) and is not a technology that leads to a fundamental promotion effect of the FT reaction.
Suzuki, Hirayama Ecoindustry Vol. 5, No. 10, pp. 24-31 (2000) Suzuki, Functional Materials, Vol. 27, No. 6, pp. 48-54 (2007) Japanese Patent Laid-Open No. 2004-322085

  The Fischer-Tropsch reaction as a method for synthesizing hydrocarbons disclosed so far is operated using synthesis gas as a raw material, and there is a limit to further improving the reaction rate.

  The present invention is capable of efficiently converting hydrogen and carbon monoxide gas (synthetic gas) generated in a biomass gasification step into gas or liquid hydrocarbons that are easy to use at the production site. An object of the present invention is to provide a method for producing a hydrocarbon that can be produced.

  The present invention is characterized by the following in order to solve the above problems.

1: A mixed gas obtained by adding an olefin to a synthesis gas composed of carbon monoxide and hydrogen is porous at an atmospheric pressure of 5 kg / cm ² and less than G, a space velocity of 300 to 30,000, a reaction temperature of 210 ° C. to 260 ° C. In the form of cobalt metal, a support containing at least one metal oxide selected from Group III of the periodic table or a lanthanoid series in porous silica alone or in a porous metal content of 5% by mass to 25% by mass based on the catalyst mass A method for producing hydrocarbons, comprising contacting with a catalyst containing cobalt.

  2: The catalyst has a ratio (mol / atom ratio) between the number of moles of at least one metal oxide selected from Group III of the periodic table or the lanthanoid series and the number of supported cobalt metal atoms (0.09 to 1.00). The manufacturing method of said 1st hydrocarbon characterized by the above-mentioned.

  Third: The catalyst is characterized in that the amount of carbon monoxide adsorbed per catalyst weight at 35 ° C when hydrogen reduced at 500 ° C for 1 hour or more under hydrogen flow is 0.60 mL / g or more in terms of standard conditions. The manufacturing method of the said 1st or 2nd hydrocarbons.

  Fourth: The catalyst is reduced to 50 ° C after hydrogen reduction at 500 ° C and atmospheric pressure for 1 hour or more, and helium gas containing 8% to 12% by volume of carbon monoxide is equilibrated and adsorbed at the same temperature every minute. In the process of increasing the temperature from 50 ° C to 400 ° C at 5 ° C, the amount of carbon monoxide desorbed in the temperature range from 200 ° C to 260 ° C is 0.06 mL / g or more in terms of standard state per catalyst mass The method for producing any one of the first to third hydrocarbons.

  According to the present invention, biomass-derived hydrogen or carbon monoxide, which has only a low added-value utilization method, such as being used as a heat source by being transported and used as a heat source in a production area that is remote from an industrial area such as biomass, is provided. A gas having a low calorific value as a main component can be efficiently converted into a gas or liquid hydrocarbon that is easy to use at the production site under a relatively moderate pressure. As biomass sources, use of livestock waste (including feces and urine), wood, and food residues can be considered.

  In addition, according to the present invention, gas mainly composed of hydrogen and carbon monoxide obtained from a small oil field or gas field existing at home and abroad by processing such as associated gas, natural gas, and coal bed gas. Can also be preferably used, so that it can be converted into an energy source with excellent transportability such as LPG to naphtha fraction and high calorie value added.

Details of the present invention will be disclosed below, but this is intended to explain the technical contents of the present invention more specifically, and does not limit the scope of the present invention. In this specification, “normal pressure” refers to atmospheric pressure (760 mmHg = 1013 hPa), and corresponds to 0 in gauge pressure (kg / cm ² , G).
(Method for producing hydrocarbons)
In the method of the present invention, hydrocarbons are synthesized by passing a gas mainly composed of carbon monoxide, hydrogen, and olefin through a fixed bed catalyst layer.
(Olefin)
As the olefin, linear alkenes such as ethylene, propylene, butene and pentene can be preferably used. In particular, α-olefins having a double bond at the terminal are preferable, and 1-butene, 1-pentene, and the like are preferable for butene, pentene, and the like. Ethylene contained in the accompanying gas or biogas can be most preferably used. Further, the olefin to be used only needs to mainly contain the olefin component. The olefin content is preferably about 60% or more. If it is less than this, the synthesis efficiency of hydrocarbons may be lowered.
(hydrogen)
As the gas containing hydrogen gas, hydrogen alone, hydrogen and water vapor, hydrogen and nitrogen, hydrogen and rare gases, hydrogen and water vapor and nitrogen, hydrogen, water vapor and rare gases can be preferably used. The hydrogen content in the gas containing hydrogen gas is preferably 30 vol.% Or more. If the hydrogen content is less than this, the reduction time becomes longer, and the technical significance is diminished from the viewpoint of productivity.
(Carbon monoxide)
If carbon monoxide is a main component, it can be preferably used, and the content of carbon monoxide is preferably about 60% or more. If it is less than this, there is a possibility that the synthesis efficiency of hydrocarbons is lowered due to the reason that the partial pressure decreases.
(Raw material gas)
A mixed gas of hydrogen, carbon monoxide and olefin is used as the raw material gas. The ratio of hydrogen to carbon monoxide (H ₂ / CO ratio) in the raw material gas is preferably 0.4 or more and 2.5 or less, more preferably 0.5 or more and 2.3 or less, and most preferably 1.8 or more and 2.2 or less. If it is less than this range, it becomes difficult to ensure sufficient productivity because hydrogen is insufficient, and if it exceeds this range, the olefin in the feed gas is hydrogenated and the technical advantage becomes dilute. The olefin content in the raw material gas is preferably 5 vol.% Or more and 50 vol.% Or less. Below this, the advantage over the general Fischer-Tropsch reaction using only synthesis gas is diminished, and the technical meaning is lost. If this value is exceeded, the partial pressure of the synthesis gas (mixed gas of hydrogen and carbon monoxide) will decrease relatively, and the reaction rate of the Fischer-Tropsch reaction, which is the main reaction, will tend to decrease and productivity will decrease. The trend of technical significance is expected to be sparse.
(Reason for reaction promotion)
The mechanism of the Fischer-Tropsch reaction, which is the central reaction of hydrocarbon synthesis, is thought to be the sequential increase of alkylidene species generated from carbon monoxide and hydrogen, as shown in the following formula.

In this way, alkylidene species (M = CH ₂ etc.) are supplied from carbon monoxide and hydrogen, and the number of carbons is successively increased in the vicinity of the active point on the catalyst surface to produce LPG, light naphtha, heavy naphtha and the like. .

  In the present invention, in order to improve the activity, attention is paid to the smooth generation of alkylidene species in the vicinity of the active site on the catalyst surface, which easily causes the synthesis of hydrocarbons. In order to promote the production of alkylidene species, olefin is added to a mixed gas of carbon monoxide and hydrogen (synthesis gas) to promote the production of alkylidene species from olefins and to promote hydrocarbon synthesis by the Fischer-Tropsch reaction. (See formula below).

That is, by contacting an olefin having a terminal methylene group such as ethylene, propylene, and 1-butene with a catalyst described later, an alkylidene species is supplied from the olefin to the vicinity of the active point on the catalyst surface, and supplied from carbon monoxide and hydrogen. It is characterized by being incorporated into the FT reaction together with the alkylidene species. Therefore, if the olefin is hydrogenated and added to paraffin as described above, the concentration of the alkylidene species supplied from the olefin decreases, and the advantage over the Fischer-Tropsch reaction using only ordinary synthesis gas becomes dilute. Become.
(Reaction temperature)
The reaction temperature is preferably 210 ° C or higher and 260 ° C or lower, more preferably 210 ° C or higher and 250 ° C or lower, and most preferably 225 ° C or higher and 245 ° C or lower. If it is less than this, there is a high possibility that a sufficient reaction rate will not be obtained, and if this is exceeded, chain growth is likely to be suppressed, and the production of lower hydrocarbons becomes remarkable. As a result, the yield of a hydrocarbon fraction having excellent transportability may be reduced, which is not preferable.
(Internal pressure)
Even if the pressure is normal pressure, the reaction proceeds and is not particularly limited. Therefore, it is preferably at least normal pressure and less than 5 kg / cm ² and G. Considering when supplying the obtained hydrocarbons to the user or when supplying to the gas engine when exchanging power, it is desirable to have some pressure, from that viewpoint 0.2 kg / cm ² , G to 5 kg / cm ² , G is more preferable. If it is less than this range, the productivity tends to decrease, and the technical significance is diminished. When this range is exceeded, the hydrogenation reaction of olefins becomes active, and the superiority of the present invention that provides highly efficient synthesis techniques for hydrocarbons by supplying olefins becomes dilute.
(Rubber flow rate of raw material gas)
Aeration rate of raw material gas is GHSV (number obtained by dividing the volume converted to the standard state through which the one-hour feed passes by the volume of the catalyst; gas hourly space velocity), 300 (vol / vol) h ^{-1 to} 30,000 (vol / vol) h ^-1 or less is preferable, 1,000 (vol / vol) h ^{-1 to} 27,000 (vol / vol) h ^-1 or less is more preferable, 1,500 (vol / vol) h ^{-1 to} 12,000 (vol / vol) h ^-1 The following are most preferred. If the aeration rate is less than this, the space time yield is reduced, which is uneconomical. If the aeration rate is exceeded, the conversion rate reaches a peak and the separation process may become difficult. Note that the standard state (STP) is converted to the gas volume depending on the reaction pressure and reaction temperature, so that the number of reaction molecules passing over the catalyst can be quantitatively evaluated by converting the volume to a certain standard. is there.
(Catalyst carrier components)
The catalyst carrier is porous silica alone or contains at least one metal oxide selected from Group III of the periodic table or a lanthanoid series in the porous silica. Among these, when the latter is used as a catalyst carrier, the catalyst performance is improved. Specific examples of Group III metal elements used in the metal or metal oxide include yttrium and scandium. Of these, yttrium is preferable. Specific examples of the lanthanoid series metal elements used for the metal or metal oxide include lanthanum, cerium, praseodymium, and neodymium. Of these, lanthanum and cerium are most preferred.
(Physical properties of catalyst carrier)
The specific surface area of silica used as a component of the carrier is preferably not less than 250m ² / g, more preferably more than ^{300m 2 / g, 320m 2 /} g or more is most preferred. The upper limit of the specific surface area is not particularly limited, but the substantial upper limit when considering industrial use is considered to be about 500 m ² / g.

  The pore volume of silica is preferably 0.6 mL / g or more, more preferably 0.8 mL / g or more, and most preferably 1.0 mL / g or more. When a carrier having a pore volume less than the above range is selected, there is a risk that performance fluctuations between product lots may increase, which is important in terms of filling a stable catalyst. There is no limit on the upper limit of the pore volume, but it is considered that the upper limit is substantially about 1.5 mL / g.

The average pore diameter of silica is preferably 5 nm to 60 nm, more preferably 6 nm to 15 nm, and most preferably 9 nm to 12 nm. When the average pore size is less than the above range, in the case of a catalyst having a large amount of active metal supported, there is a possibility that the performance may be deteriorated due to pore size blockage or the like. The upper limit is not particularly limited, but the substantial upper limit is considered to be about 50 to 60 nm.
(Catalyst for hydrocarbon synthesis)
The catalyst for synthesizing hydrocarbons used in the present invention contains cobalt as an active metal in the above-described silica alone support or a silica support to which a group III metal or a lanthanoid series metal is added.
(Cobalt content)
The cobalt content is preferably 5% by mass or more and 25% by mass or less, more preferably 8% by mass or more and 25% by mass or less, and most preferably 9.5% by mass or more and 15% by mass or less based on the mass of the catalyst in terms of Co. If the cobalt content is outside this range, it may be difficult to obtain sufficient activity and selectivity. In addition, it does not prevent adding metals other than cobalt as a co-catalyst, and adding components, such as a mold release agent.
(Content of periodic table group III or lanthanoid series metal oxide)
In the case where at least one metal oxide selected from Group III of the periodic table or lanthanoid series is added as a catalyst component, the ratio of the number of moles of the metal oxide to the number of supported cobalt metal atoms is 0.09 mol / mol. The atom ratio is preferably not less than 1.00 (mol / atom ratio).
(Method for preparing catalyst)
As a method for preparing the catalyst, a known method can be preferably used. For example, it may be prepared by a known method such as a kneading method, an impregnation method, a sol-gel method (alkoxide method). Various shapes such as tablets, spheres, cylinders, prisms, four-leaf, three-leaf, Raschig ring, hollow, fiber, spindle, powder, granule, and honeycomb are preferably used as the catalyst shape. I can do it.
(Physical and chemical characteristics of the catalyst)
(Physical and chemical properties of catalyst 1: Adsorption amount of carbon monoxide)
The preferred catalyst working state for this reaction is a low oxidation state cobalt species. Carbon monoxide has the property of being easily chemisorbed to cobalt species in a low oxidation state, and the amount of carbon monoxide adsorbed is an indicator of catalytic activity. Preferably, the adsorption amount of carbon monoxide per catalyst weight at 35 ° C when hydrogen reduction is performed at 500 ° C for 1 hour or more under hydrogen flow is 0.60 mL / g or more in terms of standard state (stp) . If the adsorption amount of carbon monoxide is less than this, it may be difficult to obtain sufficient catalytic activity.
(Physical and chemical properties of catalyst 2: amount of carbon monoxide desorption)
The amount of carbon monoxide desorbed is considered to reflect the number of active sites, and the amount of carbon monoxide desorbed by the catalyst suitable for the reaction handled in the present invention is as follows. That is, the catalyst is reduced to 50 ° C. after hydrogen reduction at 500 ° C. and normal pressure for 1 hour, and helium gas containing 8% to 12% by volume of carbon monoxide is equilibrated and adsorbed at the same temperature at 5 ° C. per minute. In the step of raising the temperature from 50 ° C. to 400 ° C., the amount of carbon monoxide desorbed in the temperature range of 200 ° C. or more and 260 ° C. or less is preferably 0.06 mL / g or more in terms of standard state per catalyst weight. If the carbon monoxide desorption amount is less than this, it may be difficult to obtain a sufficient number of active points.
(Catalyst pretreatment)
In the method for synthesizing hydrocarbons according to the present invention, since the mixed gas mainly composed of carbon monoxide, hydrogen and olefin is vented, the Fischer-Tropsch reaction is performed even if the pretreatment is omitted. Although progressing, the pretreatment of the catalyst is carried out in order to bring most of the supported cobalt species close to a suitable working state, and it is desirable to carry out the pretreatment in order to ensure stable productivity from the beginning of the reaction.
(Content of pre-processing)
Prior to the carbon chain extension reaction, the catalyst is activated by the pretreatment described below. The catalyst is pretreated at 350 ° C or higher and 600 ° C or lower for 1 hour or longer in vacuum exhaust or in an inert gas atmosphere, and then reduced at 350 ° C or higher and 600 ° C or lower for 1 hour or longer with hydrogen gas or a gas mainly containing hydrogen gas. Thereafter, the substrate is treated at 350 ° C. or higher and 600 ° C. or lower for 1 hour or longer in a vacuum exhaust or inert gas atmosphere. Thereafter, the reaction temperature may be maintained and the Fischer-Tropsch reaction may be performed. When it is difficult to obtain an inert gas at the production site, heating and exhausting by vacuum exhaust is suitable, and the internal pressure at that time is preferably less than × 10 ^-3 mmHg.
(Air flow rate during pretreatment)
The pre-treatment aeration volume is GHSV (a value obtained by dividing the volume converted to the standard state through which the feed gas passes for 1 hour by the volume of the catalyst; gas hourly space velocity), 300 (vol / vol) h ^-1 or more and 30,000 (vol / vol ) h ^-1 or less are preferred, 1,000 (vol / vol) h -1 or 27,000 (vol / vol) h ^-1, more preferably less, 1,500 (vol / vol) h -1 or 6,000 (vol / vol) h ^- Most preferred is ¹ or less. If it is less than this, the reduction time will be extended, and if it exceeds this, hydrogen that is not used will increase and the cost will increase, and the superiority as a production technique will become dilute.
(Pressure during pretreatment inert gas ventilation)
There is no particular limitation on the pressure in the system when performing the heat treatment in an inert gas atmosphere, but it is realistic to carry out at a normal pressure or more and less than 10 kg / cm ² and G. As the inert gas, helium, neon, argon, nitrogen and the like can be preferably used, argon, helium and nitrogen are more preferable, and helium and nitrogen are most preferable.
(Reduction process pressure)
Pretreatment system pressure in the reduction step in performing is preferably less than 10kg / cm ^2, G 100mmHg, more 7 kg / cm ^2, more preferably at most G 200 mmHg, 300 mmHg or more 5 kg / cm ^2, G or less and most preferable. If it is less than this range, the pretreatment time will be extended and the technical advantage will be dilute, and even if the pressure in this range is exceeded, the tendency to saturate the shortening effect such as the time required for reduction will increase.

  Hereinafter, the present invention will be disclosed in more detail by way of examples. However, the examples and the like are for explaining the essence of the present invention, and the scope of the present invention should not be construed as being limited thereto.

(Catalyst preparation)
Cobalt nitrate (Co (NO ₃ ) ₂ · 6H ₂ O) aqueous solution in silica (SiO ₂ ) with an average particle size of 3 mm, specific surface area of 380 m ² / g, pore volume of 1.0 mL / g, pre-fired at 520 ° C. for 3 hours After impregnation, the water is removed from the aspirator while heating in a rotary evaporator at 40-60 ° C to remove water, and then calcined in a muffle furnace at 500 ° C for 3 hours to obtain a silica-supported cobalt catalyst (abbreviated as Co / SiO ₂ catalyst). It was. The composition at this time was 5% by mass of Co based on the weight of the metal-converted catalyst and the remaining silica.
(Reactor)
For the reaction, a gaseous reaction product was used for the reaction, and the gaseous product passed through a gas-liquid separator and was collected in a gas collection bag. Thermal conductivity type (TCD) and flame ionization detection type (FID) gas chromatograph (Shimadzu Corporation) GC-14B).
(Response results)
2 mL (1.8 g) of the catalyst was maintained at 500 ° C. in an electric furnace controlled by a temperature controller (FUJI ELECTRIC PXR3 type), and argon was GHSV3,000 (v / v) h ⁻¹ at normal pressure. After aeration for 1 hour, it switched to hydrogen and reduced with aeration at GHSV 3,000 (v / v) h ^-1 for 2 hours. After the hydrogen reduction was completed, the pretreatment was completed by switching to argon at 500 ° C. and normal pressure and venting for 1 hour. Subsequently, while bubbling argon at normal pressure and GHSV 3,000 (v / v) h ^-1 , the catalyst bed temperature was changed to 245 ° C, and the ratio of hydrogen to carbon monoxide was 90 vol. Of synthesis gas with H ₂ : CO = 2: 1. %, Olefin (ethylene) 10vol.% Mixed gas through a mass flow controller (Emerson, model 5850E) at a pressure of 0.5kg / cm ² , G, GHSV10,300 (v / v) h ^-1 A Tropsch reaction was performed. The space-time yield of hydrocarbons having 5 or more carbon atoms (abbreviated as C ₅₊ ), which is a standard for liquid hydrocarbons at this time, was 17.0 mmol / h.
(Measurement results of physicochemical properties)
(CO adsorption amount) The physicochemical characteristics of this catalyst are as follows. Regarding the CO adsorption amount, 1 g of the catalyst is precisely weighed and reduced at 500 ° C for 1 hour, and then the CO pulse is adsorbed at 35 ° C until the adsorption is saturated. The amount of CO adsorbed in terms of the standard state per catalyst weight was 0.60 mL / g.
(CO desorption amount)
In the step of precisely weighing 1 g of the catalyst and reducing it at 500 ° C. for 1 hour, bringing the CO pulse to adsorption equilibrium at 50 ° C. until the adsorption is saturated, and raising the temperature from 50 ° C. to 400 ° C. at 5 ° C. per minute, The amount of CO desorbed in the temperature range from ℃ to 260 ℃ was 0.08 mL / g in terms of standard state per catalyst weight.

Fischer-Tropsch was prepared under the same conditions as in Example 1 except that Co prepared in the same manner as in Example 1 was 10% by mass based on the weight of the metal-converted catalyst and the reaction temperature was 240 ° C. using a Co / SiO ₂ catalyst of the remaining silica. As a result of the reaction, the C ₅₊ yield reached 34.2 mmol / h, indicating a good result. Further, as a result of obtaining the CO adsorption amount and the desorption amount in the same manner as in Example 1, they showed 0.60 mL / g and 0.11 mL / g in terms of the standard state per catalyst weight, respectively. Comprehensive judgment was appropriate.

Co prepared in the same manner as in Example 1 was prepared using a Co / SiO ₂ catalyst of 15% by mass based on the weight of the metal-converted catalyst and the remaining silica, the reaction temperature was 210 ° C., and the synthesis gas having a hydrogen to carbon monoxide ratio of 2 As a result of performing the Fischer-Tropsch reaction under the same conditions as in Example 1 except that raw material gases of.% And 20% ethylene were used, the C ₅₊ yield reached 65.3 mmol / h, indicating a good result. Further, as a result of obtaining the CO adsorption amount and the desorption amount in the same manner as in Example 1, they showed 0.77 mL / g and 0.17 mL / g in terms of standard state per catalyst weight, respectively. Comprehensive judgment was appropriate.

Co prepared in the same manner as in Example 1 was 20% by mass based on the weight of the metal-converted catalyst and the remaining silica was a Co / SiO ₂ catalyst, the reaction temperature was 225 ° C., and the synthesis gas having a hydrogen to carbon monoxide ratio of 2 was 80 vol. As a result of performing the Fischer-Tropsch reaction under the same conditions as in Example 1 except that raw material gases of 20% and 20% ethylene were used, the C ₅₊ yield reached 71.0 mmol / h, indicating good results. In addition, as a result of obtaining the CO adsorption amount and the desorption amount in the same manner as in Example 1, they showed 0.83 mL / g and 0.20 mL / g in terms of the standard state per catalyst weight, respectively. Comprehensive judgment was appropriate.

After impregnating yttrium nitrate (Y (NO ₃ ) ₂ ) aqueous solution into silica (SiO ₂ ) with an average particle diameter of 3 mm, specific surface area of 380 m ² / g, and pore volume of 1.0 mL / g, which was calcined at 520 ° C. for 3 hours in advance, rotary While heating at 40 to 60 ° C. in an evaporator, the pressure was reduced with an aspirator to remove moisture, and then the mixture was baked in a muffle furnace at 500 ° C. for 3 hours to obtain an yttria-containing silica support. This was impregnated with an aqueous solution of cobalt nitrate (Co (NO ₃ ) ₂ · 6H ₂ O), followed by water removal under reduced pressure and calcination using a muffle furnace, and a yttria-containing silica-supported cobalt catalyst (Co / Y ₂ O _3- (Abbreviated as SiO ₂ catalyst). The composition of the catalyst at this time is 10% by mass of Co based on the weight of the metal-converted catalyst, the molecule / atom (mol / atom) ratio between yttria (Y ₂ O ₃ ) and supported cobalt is 0.1, and the rest is Silica. Except for using Co / Y ₂ O ₃ -SiO ₂ catalyst with a reaction temperature of 260 ° C, hydrogen and carbon monoxide ratio of 2 synthesis gas 60vol.%, Ethylene 40vol.% Source gas As a result of carrying out a Fischer-Tropsch reaction in the same manner as in Example 1, the C ₅₊ yield reached 50.3 mmol / h, indicating a good result. Further, as a result of obtaining the CO adsorption amount and the desorption amount in the same manner as in Example 1, they showed 0.75 mL / g and 0.15 mL / g in terms of the standard state per catalyst weight, respectively. Comprehensive judgment was appropriate.

Co prepared by the same method as in Example 5 was 10% by mass based on the weight of the metal-converted catalyst, and when supported with ceria (CeO ₂ ), the cobalt molecule / atom (mol / atom) ratio was 0.1. A silica-supported silica-supported cobalt catalyst (abbreviated as Co / CeO ₂ —SiO ₂ catalyst) was prepared. Example 1 was performed except that a Co / CeO ₂ —SiO ₂ catalyst was used, the reaction temperature was 250 ° C., a synthesis gas having a hydrogen to carbon monoxide ratio of 2 was used as a raw material gas of 60 vol.% And ethylene 40 vol.%. As a result of carrying out the Fischer-Tropsch reaction in the same manner as above, the C ₅₊ yield reached 51.4 mmol / h, indicating a good result. Further, as a result of obtaining the CO adsorption amount and the desorption amount in the same manner as in Example 1, 0.64 mL / g and 0.11 mL / g in terms of the standard state per catalyst weight were shown, respectively. Comprehensive judgment was appropriate.

10% by mass of Co prepared by the same method as in Example 5 based on the weight of the metal-converted catalyst, lanthania
The molecule / atom (mol / atom) ratio of (La ₂ O ₃ ) to the supported cobalt is 0.1, and the rest is silica-containing lanthanum-containing silica-supported cobalt catalyst (Co / La ₂ O ₃ —SiO ₂ catalyst). (Abbreviated) was prepared. The Fischer-Tropsch reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was 240 ° C. using a Co / La ₂ O ₃ —SiO ₂ catalyst. As a result, the C ₅₊ yield reached 40.1 mmol / h. Good results were shown. In addition, as a result of obtaining the CO adsorption amount and the desorption amount in the same manner as in Example 1, they showed 0.75 mL / g and 0.14 mL / g in terms of standard state per catalyst weight, respectively. Comprehensive judgment was appropriate.
<Comparative Example 1>

Fisher prepared under the same conditions as in Example 1 except that Co prepared by the same method as in Example 1 was 2 mass% based on the weight of the metal-converted catalyst and the reaction temperature was 240 ° C. using a Co / SiO ₂ catalyst of the remaining silica. -As a result of carrying out the Tropsch reaction, however, the C5 ₊ yield was only 4.1 mmol / h. Moreover, as a result of obtaining the CO adsorption amount and the desorption amount in the same manner as in Example 1, the results were as low as 0.30 mL / g and 0.04 mL / g in terms of standard state per catalyst weight, respectively. This is an example in which sufficient performance could not be exhibited because the supported amount of cobalt and the physicochemical characteristic values of the catalyst do not satisfy the desired values, and the comprehensive judgment was inappropriate.
<Comparative example 2>

Fisher prepared under the same conditions as in Example 1 except that Co prepared in the same manner as in Example 1 was 35% by mass based on the weight of the metal-converted catalyst and the reaction temperature was 240 ° C. using a Co / SiO ₂ catalyst of the remaining silica. -As a result of the Tropsch reaction, however, the C5 ₊ yield was only 6.5 mmol / h. Moreover, as a result of obtaining the CO adsorption amount and the desorption amount in the same manner as in Example 1, the results were as low as 0.50 mL / g and 0.05 mL / g in terms of the standard state per catalyst weight, respectively. This is an example in which the supported amount of cobalt is excessive and the physicochemical characteristic value that the catalyst should have does not satisfy the desired value, so that sufficient performance could not be exhibited, and the comprehensive judgment was unsuitable.
<Comparative Example 3>

10% by mass of Co prepared by the same method as in Example 7 based on the weight of the metal-converted catalyst, lanthania
The molecular / atom (mol / atom) ratio between (La ₂ O ₃ ) and supported cobalt is 1.2, and the remainder is silica-containing lanthanum-containing silica-supported cobalt catalyst (Co / La ₂ O ₃ —SiO ₂ catalyst). (Abbreviated) was prepared. As a result of performing the Fischer-Tropsch reaction under the same conditions as in Example 1 except that the reaction temperature was 240 ° C. using a Co / La ₂ O ₃ —SiO ₂ catalyst, the C ₅₊ yield was only 6.7 mmol / h. It was. In addition, as a result of obtaining the CO adsorption amount and the desorption amount in the same manner as in Example 1, it was 0.43 mL / g and 0.05 mL / g in terms of standard state per catalyst weight, respectively. This is an example in which the amount of lanthania, the third component, was excessive, and the number of active sites (Co in a low oxidation state) exposed on the catalyst was insufficient, so that sufficient performance could not be demonstrated. It was.
<Comparative example 4>

The Fischer-Tropsch reaction was carried out under the same conditions as in Example 7 except that the reaction pressure was set to 9 kg / cm ² and G. As a result, the C ₅₊ yield was only 6.1 mmol / h. This is an example in which the hydrogenation reaction of olefin (ethylene) was promoted because the reaction system pressure was high, and the characteristics of the present invention were not expressed, and the comprehensive judgment was inappropriate.
<Comparative Example 5>

The results are the same as in Example 7 except that argon was added instead of ethylene in the raw material gas. The C ₅₊ yield remained at 5.6 mmol / h. The feature of the present invention is to increase the Fischer-Tropsch reaction rate by adding ethylene to the synthesis gas, which is an example showing that a sufficient reaction promoting effect cannot be obtained when ethylene does not coexist. Therefore, the comprehensive judgment was inappropriate.
<Comparative Example 6>

The results are the results of the Fischer-Tropsch reaction as in Example 2 except that the reaction temperature was set to 200 ° C. The C ₅₊ yield remained at 2.2 mmol / h. This is an example showing that the reaction does not proceed sufficiently because the reaction was conducted at a temperature lower than the preferred reaction temperature. Therefore, the comprehensive judgment was inappropriate.
<Comparative Example 7>

The results are the results of the Fischer-Tropsch reaction as in Example 2 except that the reaction temperature was 290 ° C. The C ₅₊ yield remained at 2.7 mmol / h. This is an example in which the conversion was high because the reaction was carried out at a temperature higher than the preferred reaction temperature, but the formation of lower hydrocarbons was remarkably insufficient and the LPG or liquid hydrocarbon fraction was insufficient. Therefore, the comprehensive judgment was inappropriate.
These Examples and Comparative Examples are summarized in Table 1.

Claims (4)

A mixed gas obtained by adding olefin to synthesis gas consisting of carbon monoxide and hydrogen is porous silica alone at atmospheric pressure and below 5kg / cm ² , G, space velocity of 300 to 30,000, reaction temperature of 210 ° C to 260 ° C Cobalt or porous silica containing at least one metal oxide selected from Group III of the periodic table or a lanthanoid series contains cobalt in an amount of 5% by mass to 25% by mass in terms of cobalt metal, based on the catalyst mass A method for producing hydrocarbons, which comprises contacting with a catalyst to be used.   The catalyst is characterized in that the ratio (mol / atom ratio) between the number of moles of at least one metal oxide selected from Group III of the periodic table or the lanthanoid series and the number of supported cobalt metal atoms is 0.09 or more and 1.00 or less. The method for producing a hydrocarbon according to claim 1.   The catalyst has an adsorption amount of carbon monoxide per catalyst weight at 35 ° C of at least 0.60 mL / g in terms of standard condition when hydrogen reduction is performed at 500 ° C for 1 hour or more under hydrogen flow. Or the manufacturing method of hydrocarbons of 2.   The catalyst is reduced to 50 ° C after hydrogen reduction for 1 hour or more at 500 ° C and normal pressure, and helium gas containing 8% to 12% by volume of carbon monoxide is equilibrated and adsorbed at the same temperature at 5 ° C per minute. In the step of raising the temperature from 50 ° C to 400 ° C, the amount of carbon monoxide desorbed in the temperature range of 200 ° C or more and 260 ° C or less is 0.06 mL / g or more in terms of standard state per mass of the catalyst. Item 4. A method for producing a hydrocarbon according to any one of Items 1 to 3.