JP2003519011A - Enhanced hydrocarbon synthesis catalysts with hydrogen and ammonia - Google Patents

Abstract

  (57) [Summary] By contacting the hydrocarbon synthesis catalyst with a reducing gas consisting of a mixture of hydrogen and ammonia at a high temperature and pressure effective for conventional synthesis catalyst reduction, the catalyst is enhanced to obtain improved performance. Part of the reduction is preferably performed with a reducing gas containing ammonia and hydrogen, and the rest is preferably performed with a hydrogen reducing gas containing no ammonia.

Description

Detailed Description of the Invention

[0001]BACKGROUND OF THE INVENTION Field of the invention   The present invention relates to the enhancement of hydrocarbon synthesis catalysts with hydrogen and ammonia. Yo
More specifically, the present invention relates to charcoal such as Fischer-Tropsch type hydrocarbon synthesis catalyst.
Contacting a hydride synthesis catalyst with a reducing gas mixture containing a mixture of hydrogen and ammonia
To improve the performance of the catalyst, and to use the enhanced catalyst.
Existing hydrocarbon synthesis method.

[0002]BACKGROUND OF THE INVENTION   H_TwoHydrocarbons (acids such as methanol) from syngas containing a mixture of
It is well known to synthesize (including elementary hydrocarbons). This syngas feedstock
H in the gas raw material_TwoAnd a compound effective in reacting CO to form hydrocarbons.
Contact the Fischer-Tropsch catalyst. This synthesis is Fisher
• Known as Tropsch hydrocarbon synthesis. Depending on the catalyst and conditions
Unlike oxygenated compounds such as methanol and higher molecular weight alcohols
, Up to high molecular weight paraffins, which are waxy solids at room temperature. This way
Alkenes, aromatic compounds, organic acids, ketones, aldehydes and esters,
Generates in smaller amounts. Synthesis can be carried out in fixed or fluidized catalyst bed reactors, or in liquid phase.
It is carried out in a slurry reactor. Hydrocarbon synthesis catalysts are also well known and typical
As an example, at least one iron group catalyst metal component is alumina, amorphous silica.
At least one inorganic refractory metal oxide support material such as alumina, zeolite
Examples thereof include a complex supported or complexed. To form a hydrocarbon synthesis catalyst
For various purposes, including impregnation, incipient wetting, complexation, ion exchange and other known methods.
Formation of catalyst precursors has been performed using catalyst preparation methods. To form a catalyst
In order to do so, the precursor must be activated. A typical activation method is acid
Or calcination and subsequent reduction under hydrogen flow, multiple oxidation-reduction cycles
And reduction without pre-oxidation. Fischer-Tropsch hydrocarbons
Examples of methods for preparing and activating synthetic catalysts are described, for example, in US Pat. No. 4,086,26.
2, No. 4,492,774 and No. 5,545,674.
There is.

[0003]Summary of the invention   The present invention provides for the catalyst to be hydrolyzed under conventional catalytic reduction conditions effective to form an active catalyst.
By contacting with a reducing gas consisting of a mixture of element and ammonia,
The performance of active hydrocarbon synthesis catalysts such as the T. Tropsch type hydrocarbon synthesis catalyst
Or to improve and to hydrocarbon synthesis processes with enhanced catalysts.
A catalyst is a hydrogen-reducing gas that does not contain ammonia under conventional hydrogen-reducing conditions.
As a result of the reduction achieved by contacting the catalyst precursor with
At least a portion, preferably only a portion, of the catalytic metal (eg Co, Fe, Ni)
Is a catalyst for synthesizing active hydrocarbons present in the form of reduced metal or catalytically active metal.
Means medium. Therefore, in the practice of the present invention, the catalyst is a mixture of hydrogen and ammonia.
Prior to contacting, the catalyst was fully reduced and fully active.
However, in order to achieve complete reduction and activation, ammonia-free water
Partially reduced in hydrogen and then partially in reducing gas containing hydrogen and ammonia
It is preferable to reduce. Catalyst for reducing gas consisting of a mixture of hydrogen and ammonia
When touched, C₅₊Increased selectivity, α of synthetic reaction (Schulz-Flory
At least one of increasing α) and decreasing methane production in cloth
, Found that the hydrocarbon synthesis characteristics of the obtained active catalyst are enhanced. Ammo
Considering the fact that Near is a poison for known hydrocarbon synthesis catalysts,
Their advantage is surprising. For the purposes of the present invention, catalyst enhancement refers to the following properties:
Nozawa: (I) The catalyst was not contacted with a reducing gas consisting of a mixture of hydrogen and ammonia
Than the catalyst C₅₊High selectivity, (Ii) Do not contact the catalyst with a reducing gas consisting of a mixture of hydrogen and ammonia
Is larger than that of the hydrocarbon synthesis reaction, and (Iii) Do not contact the catalyst with a reducing gas consisting of a mixture of hydrogen and ammonia
Lower methane production than when At least one, preferably at least two, more preferably three
Is achieved during hydrocarbon synthesis.

The catalyst precursor may or may not be calcined at a point prior to activation by reduction. Either or both of the hydrogen-reducing gas and the reducing gas consisting of a mixture of hydrogen and ammonia contain one or more diluent gases that do not adversely affect or interfere with the reduction and associated activation of the catalyst. Need not be included. Examples of such gas include methane and argon. The amount of ammonia present in the hydrogen reducing gas is 0.0 based on the total amount of the gas composition.
It is preferably 0.01 to 10 mol%, more preferably 0.1 to 10 mol%, and even more preferably 0.5 to 7 mol% over a wide range of 1 to 15 mol%. The molar ratio of hydrogen to ammonia in the gas will range from 1000: 1 to 5: 1, preferably 200: 1 to 10: 1.

In one embodiment, the present invention provides a Fischer-Tropsch hydrocarbon synthesis catalyst comprising at least one catalytic metal component, preferably at least one catalytic metal component and a metal oxide support type component, Comprising enhancing one or more catalytic metal components by contacting with a reducing gas comprising a mixture of hydrogen and ammonia under catalytic reducing conditions effective to reduce the reduced catalytically active metal form. Is the way. Here, preferably a portion of the one or more catalytic metal components is reduced to the catalytically active metal form as a result of the contacting. In another embodiment, the invention includes a method of synthesizing a hydrocarbon from syngas that includes a mixture of H ₂ and CO. Here, the syngas is contacted with an enhanced Fischer-Tropsch hydrocarbon synthesis catalyst under reaction conditions effective to react the H ₂ and CO in the gas to form hydrocarbons. The enhanced catalyst comprises a complex of at least one catalytic metal component and a metal oxide support component and is effective in reducing one or more catalytic metal components to a reduced catalytically active metal form. It is enhanced by bringing the catalyst into contact with a reducing gas consisting of a mixture of hydrogen and ammonia under catalytic reduction conditions.
Here, preferably a portion of the one or more catalytic metal components is reduced to the catalytically active metal form as a result of the contacting. In still yet another embodiment, at least some of the synthesized hydrocarbons are liquid under reaction conditions. Conventional catalytic reduction conditions include temperatures, pressures, hydrogen partial pressures and conventional hydrogen reducing gas conditions sufficient to reduce one or more catalytic metal components in the precursor to a metal to form an active catalyst. It means the condition of space velocity.

[0006]Detailed Description of the Invention   Hydrocarbon synthesis catalysts are well known and are typical of Fischer-Tropsch hydrocarbons.
Synthetic catalysts include, for example, one or more VI groups such as Fe, Ni, Co and Ru.
The Group II metal catalyst component will be included in a catalytically effective amount. Preferably touch
The medium includes a supported catalyst, and one or more support components of the catalyst are inorganic refractory metal oxides.
Things will be included. The metal oxide support component is preferably a group III, IV,
Metal acids that are difficult to reduce, such as oxides of one or more metals of groups V, VI, and VII
It is a compound. The group of metals described herein is Sargent-Welc.
h Periodic Table of the Elements, (Author
Rights) found in 1968. Alumina is a typical carrier component.
, Silica, and amorphous and crystalline aluminosilicates (eg zeolites)
One or more of them are listed. Particularly preferred carrier components are Group IVB metal oxides.
Things, especially 100m^Two/ G or less, further 70 m^Two/ G surface area
It is a thing. These carrier components themselves may also be sequentially supported on one or more carrier materials.
You may stay. Particularly when the catalyst contains a cobalt catalyst component, titania,
Rutile titania is a particularly preferred carrier component. Titania is especially higher
Slurries with a desired molecular weight product, consisting mainly of paraffinic liquid hydrocarbons, are desired.
Lee is a useful component when utilizing the hydrocarbon synthesis method. The catalyst is
When it contains an effective amount of Co, Re, Ru, Fe, Ni, Th, Zr, Hf, U, M
g and La and one or more components of the compound may also be included.
There will be. Some of these ingredients and compounds are effective as accelerators
is there. In many cases a combination of Co and Ru is preferred. Useful catalysts and
Are known in the art, see for example US Pat. No. 4,568,663,
No. 4,663,305, No. 4,542,122, No. 4,621,072
And specific examples can be found in the above-mentioned No. 5,545,674.
It is not limited.

The catalyst can be any convenient known method, for example, impregnation, incipient wetness, ion exchange, kneading, precipitation or coprecipitation, melt precipitation, or any other complexing method to form a catalyst precursor. Is prepared by. The catalytic metal component is typically added as a solution of compounds that decompose during subsequent calcination and / or reduction. For example, the cobalt component is typically added as a nitrate. It is not uncommon for the precursor to be calcined after addition of the reducible catalytic metal compound in order to better disperse the catalytic metal. Preparation and extrusion of the precursor composite is typically followed by pilling and drying. Next, the catalyst is formed by reducing or calcining and reducing the precursor. The reduction is carried out by flowing hydrogen or a hydrogen reducing gas under the conditions effective for reducing the catalytically active metal component (for example, cobalt) to a metal form, and bringing the precursor into contact therewith. The general method is known as the R-O-R process, in which the precursor is reduced in hydrogen, then calcined and subsequently reduced again. As mentioned above, the reducing hydrogen gas may be a pure substance (all hydrogen), or a mixture of one or more diluent gases inert to reduction (eg, methane, argon). May be In practicing the present invention, the R-O-R process may be used and a conventional hydrogen reducing gas may be used for the first reduction and for at least a portion of the second reduction. May be, preferably at this time,
Part of the final reduction is carried out with a reducing gas consisting of a mixture of hydrogen and ammonia. Typical reducing conditions effective to form a catalyst containing a reduced metal component supported on a support from a precursor are 1 / 2-24 hours, 200-500 ° C, 1-
It is in the range of 100 bar and GHSV 50-10,000. The actual conditions will depend not only on the hydrogen concentration in the reducing gas, but also on the metal to be reduced and its precursor form (eg salt or oxide). In the catalyst enhancement method of the present invention, the at least partially reduced active catalyst is treated under typical reducing conditions similar to those used for conventional reduction and associated activation, as described above. , Contact with a mixture of hydrogen reducing gas and ammonia. The enhancement of the catalyst by the method of the invention is
It may be done before the catalyst is loaded into the hydrocarbon synthesis reactor, or it may be done in situ in the hydrocarbon synthesis reactor.

The enhanced catalyst can be used in either fixed bed, fluidized bed or slurry hydrocarbon synthesis processes to form hydrocarbons from syngas consisting of a mixture of H ₂ and CO. These methods are well known and are described in the literature. In any of these methods, the synthesis gas is contacted with a suitable Fischer-Tropsch hydrocarbon synthesis catalyst under reaction conditions effective to react H ₂ and CO in the gas to form hydrocarbons. Especially when using a catalyst with a catalytic cobalt component, depending on the method, the catalyst and the synthetic reaction variables, some of these hydrocarbons have a standard room temperature condition of 25 ° C. and 1 atmosphere temperature and pressure, There will be some that are liquids, some that are solids (eg, waxes), and some that are gases. In fluidized bed hydrocarbon synthesis, all products are steam or gas at the reaction conditions. In fixed bed and slurry processes, the reaction products will contain both hydrocarbons that are liquid and hydrocarbons that are vapor at the reaction conditions. Slurry hydrocarbons because of their excellent heat transfer (and mass transfer) properties for fairly exothermic synthetic reactions and the relatively high molecular weight paraffinic hydrocarbons that are obtained when using cobalt catalysts. Synthetic methods may be preferred. In the slurry hydrocarbon synthesis method, a synthesis gas consisting of a mixture of H ₂ and CO is passed through a slurry in a reactor,
Bubble as the third phase. This slurry contains a particulate Fischer-Tropsch type hydrocarbon synthesis catalyst dispersed and suspended in a slurry liquid containing a hydrocarbon product of a synthesis reaction which is a liquid under the reaction conditions. The molar ratio of hydrogen to carbon monoxide in the syngas can range over a wide range of about 0.5-4, but more typically about 0.7-2.75, preferably about 0.7-2. The range is 5. The stoichiometric molar ratio in the Fischer-Tropsch hydrocarbon synthesis reaction is 2.0, but the molar ratio can be increased to obtain the required amount of hydrogen for the synthesis gas other than the hydrocarbon synthesis reaction. In the slurry hydrocarbon synthesis method, the molar ratio of H ₂ to CO is
It is typically about 2.1 / 1. The effective reaction conditions for various hydrocarbon synthesis processes will vary somewhat depending on the process type, catalyst composition and desired product. In a slurry process utilizing a catalyst comprising a supported cobalt component, mainly _{C 5+} paraffins _(e.g., C _{5+ -C 200),} preferably as an effective Typical conditions for forming hydrocarbons comprising _{C 10+} paraffins , For example, temperature, pressure and gas hourly space velocity are about 320-600 ° F, 80-600 psi and 100-40,000 V / hr / V (standard state of gas mixture of CO and H ₂ (
The conditions are in the range of volume / time / catalyst volume) at 0 ° C. and 1 atm). These conditions nominally apply to other methods as well.

Hydrocarbons produced by the hydrocarbon synthesis process according to the practice of the invention are typically upgraded by subjecting all or part of the C ₅₊ hydrocarbons to fractionation and / or conversion, An even more valuable product. Conversion refers to one or more operations in which the molecular structure of at least some hydrocarbons is altered, including non-catalytic treatments (eg steam cracking) and catalytic treatments in which the cut is contacted with a suitable catalyst (eg. Both catalytic cracking) are included. When hydrogen is present as a reactant, such processing step is typically referred to as hydroconversion, and examples include hydroisomerization, hydrocracking, hydrodewaxing, hydrorefining, and hydrotreating. The more severe hydrorefining process is called. All of these processing steps are carried out under conditions well known in the literature for hydroconversion of hydrocarbon feeds, including paraffin-rich hydrocarbon feeds. Examples of more valuable products produced by conversion include synthetic crude oil, liquid fuels,
Examples include, but are not limited to, one or more of olefins, solvents, lubricating, industrial or medical oils, waxy hydrocarbons, nitrogen and oxygen containing compounds, and the like. Liquid fuels include one or more of automotive gasoline, diesel fuel, jet fuel and kerosene. On the other hand, examples of the lubricating oil include oils for automobiles, jets, turbines, and metal workings. Industrial oils include oil well drilling fluids, agricultural oils, heat transfer fluids, and the like.

[0010]   The invention will be further understood by reference to the following examples.

[0011]Example Example 1 (silica carrier)   KCKG # 4 (Salavat Petrochemical Complete
x Salavat catalyst plant (manufactured at Salavant, Russia)
Crushing commercially available silica gel with a diameter of 2-4 mm known as
Thus, a fraction having a size of 0.106 to 0.250 mm was obtained. Next, empty this substance
Calcination under air flow for 5 hours at 450 ° C to form a carrier for preparing a catalyst below
It was

[0012] Example 2 (Catalyst A precursor) 5.18 g of _{Co (NO 3) 2 · 6H} 2 O to prepare a solution in distilled water 15 ml. 21 ml (8.38 g) of this solution was added to the calcined silica carrier obtained in Example 1.
To form a catalyst precursor. The catalyst precursor was then dried on the steam bath. At this stage, the catalyst precursor nominally contained 11 wt% cobalt. This is used as a catalyst A precursor.

[0013] Example 3 (Catalyst B precursor)   In a volume of water sufficient to sufficiently wet the silica, 4.9 g ZrO (NO _Three )_Two・ 2H_TwoAn aqueous solution containing O was added to 33.2 g of the pyrogenic silica support of Example 1.
, Dried on a steam bath and then calcined at 450 ° C for 1 hour under air flow.
This formed the first complex. Next, 75 g of Co (NO_Three)_Two・ 6H_TwoO
A solution dissolved in 30 ml of water was added to the complex, and the composite was immersed at room temperature for 2 hours. Excessive
The excess solution was decanted and stored. Steaming the resulting second composite
It was dried above and then calcined at 450 ° C. for 2 hours under air flow. Save after cooling
The excess solution saved was added to the second complex. Co (NO_Three)_Two・ 6H_TwoO solution
Of dipping, decanting, drying, and firing until the composite is all impregnated
The steps were repeated to form the final catalyst precursor. This final catalyst precursor is designated as catalyst B
Use as a precursor. The catalyst B precursor thus formed contained 27% by weight of
And 4.1% by weight zirconium oxide.

Example 4 (Reduction of Catalyst B in H ₂ ) The catalyst B precursor of Example 3 (20 ml) was mixed with 80 ml of 1-3 mm quartz particles and the mixture was placed in a quartz reactor with an inner diameter of 25 mm. I placed it. The catalyst / quartz mixture was held in place at the bottom of the reactor using glass wool and a layer of 10 ml of 1-3 mm quartz particles was placed on the catalyst / quartz mixture. Hydrogen was then passed through the reactor for 15 minutes at room temperature, atmospheric pressure and a gas hourly space velocity (GHSV) of 100 hr ⁻¹ . Prior to entering the reactor, hydrogen was added to the KOH pellets (to remove impurities).
It was passed through a column with a nominal pellet diameter of 3-5 mm). The reactor temperature was raised to 450 ° C. over 40 to 45 minutes and kept under these conditions for 5 hours. Next, the reactor was cooled to room temperature under flowing hydrogen. After the reactor was cooled, the hydrogen flow was changed to H ₂ : CO ratio 2: 1 at atmospheric pressure over 15 minutes (GHSV: 100 hr ⁻¹ ).
I replaced it with. As with hydrogen, the syngas is K to remove impurities.
Passed through a column of OH pellets. After that, the reactor inlet and outlet valves were closed and the catalyst was stored under syngas.

[0015] Example 5 (H_TwoMedium and then NH_Three/ H_TwoReduction of catalyst B in)   A catalyst B precursor sample (20 ml) of Example 3 was added to 80 ml of 1 to 3 mm quartz grains.
The mixture was mixed with the pups and the mixture was placed in a quartz reactor with an internal diameter of 25 mm. Catalyst / quartz mixture
The material is held in place at the bottom of the reactor using glass wool and the catalyst / quartz mixture is
A layer of 10 ml of 1 to 3 mm quartz particles was placed on the mixture. Then room temperature, large
Atmospheric pressure, and 100 hr^-1Hydrogen at the gas hourly space velocity (GHSV) into the reactor
Passed for 15 minutes. Before feeding to the reactor, hydrogen was added to KOH to remove impurities.
Column of pellets (nominal pellet diameter 3-5 mm) and entry of NaOH pellets
It was passed through a 3-necked flask. The central neck of the three-necked flask has 29 wt% NH_Three/
71% by weight H_TwoA syringe for adding O solution is connected, and
NaOH in this is NH_Three/ H_TwoAbsorbs water from O solution and NH_ThreeRelease the steam
It is for the purpose. NH_ThreeThe steam was then flushed from the flask to the reactor.
It The reactor temperature was raised to 400 ° C over 40-45 minutes. When preparing the catalyst
The procedure used in Example 4 was used until the reactor reached a temperature of 450 ° C (4
Raise the reactor temperature from room temperature to 450 ° C over 0 to 45 minutes and
Held for hours). After this, as shown in Table 2 below, (i) the first sun
H for pull_Two(Ii) H in the next four samples_TwoFollowed by H_TwoAnd NH _Three And (iii) H in the fifth sample._TwoAnd NH_ThreeWith a mixture of
Reduction was carried out for 5 hours. H_Two/ NH_ThreeH to provide a reducing gas mixture_Two Addition of ammonia to the gas is carried out using a syringe containing 29 wt% NH_Three/ 71 wt% H_Two The O solution was continuously added dropwise. NH_Three/ H_TwoWhen adding O solution, return
NH in original gas_ThreeWas nominally 5 mol%. As shown in Table 2
And (i) all H_Two, (Ii) H_TwoFollowed by H_Two/ NH_Three, Or (iii)
All H_Two/ NH_ThreeRegardless of which method is used, the total reduction time is 5 o'clock
It was between. After the reduction, the reactor was cooled to room temperature under flowing hydrogen. Reactor cooled
After that, the hydrogen flow is changed to H for 15 minutes under atmospheric pressure._Two: CO ratio of 2: 1
Low (GHSV: 100hr^-1). Impure, as with hydrogen
Syngas was passed through a column of KOH pellets to remove material. Then anti
The reactor inlet and outlet valves were closed to store the catalyst under syngas.

Example 6 (Reduction of Catalyst A with NH ₃ / H ₂ ) The catalyst A precursor sample of Example 2 (20 ml) was mixed with 80 ml of 1 to 3 mm quartz particles, and the mixture was added to a quartz reactor with an inner diameter of 25 mm. I placed it inside. The catalyst / quartz mixture was held in place at the bottom of the reactor using glass wool and a layer of 10 ml of 1-3 mm quartz particles was placed on the catalyst / quartz mixture. Hydrogen was then passed through the reactor for 15 minutes at room temperature, atmospheric pressure, and gas hourly space velocity (GHSV) of 3000 hr ⁻¹ . Before feeding into the reactor, hydrogen was added to KO to remove impurities.
It was passed through a column of H pellets (nominal pellet diameter 3-5 mm) and a 3-necked flask containing NaOH pellets. The center neck of the three-necked flask, 29 wt% _NH 3/71 wt% _{H 2} O solution syringe is connected for adding, NaOH in a three neck _flask, water from the NH 3 / _{H 2} O solution For absorbing NH ₃ vapor and liberating NH ₃ vapor. NH ₃ vapor is then swept from the flask to the reactor. The reactor temperature was raised to 400 ° C over 40-45 minutes. Temperature is 40
After reaching _{0 ℃, 29wt% NH 3 /} 71wt% H 2 O solution begins to continuously dropwise from a syringe, by changing the addition rate, the nominal concentration of NH ₃ in the reducing gas 0 (H ₂ only) was adjusted to be 3.0 mol% and kept in this state for 1 hour.
Next, the reactor was cooled to room temperature under flowing hydrogen. After the reactor was cooled down, the hydrogen flow was carried out under atmospheric pressure for 15 minutes with a H ₂ : CO ratio of 2: 1 to a synthesis gas flow (GHSV
: 100 hr ⁻¹ ). As with hydrogen, syngas was passed through a column of KOH pellets to remove impurities. After that, the reactor inlet and outlet valves were closed and the catalyst was stored under syngas.

Example 7 (Test of Catalyst A) Using the catalyst of Example 6 (Catalyst A reduced by H ₂ + NH ₃ ) for 100 h
The flow of syngas into the reactor was restarted at r ⁻¹ GHSV and 1 atm. Prior to entering the reactor, synthesis gas was passed through a column of KOH pellets (nominal pellet diameter 3-5 mm) to remove impurities. The composition of the synthesis gas was 2: 1 by volume ratio of H ₂ : CO. The reactor temperature was raised from room temperature to 160 ° C in about 40 minutes. After holding in this state for 5 hours, the reactor was cooled to room temperature under a syngas flow, and the catalyst was stored under syngas as described in Example 6. The next day, the test was restarted by the same procedure except that the test temperature was raised by 10 ° C. This was repeated daily until the optimum operating temperature was found. Optimum operating temperature was a temperature at which the yield of C ₅₊ product (g number of C ₅₊ product per syngas one cubic meter fed to the reactor (under standard conditions)) is maximized. To find the optimum operating temperature, it was necessary to increase the reactor temperature by 10 ° C. until the C ₅₊ yield was lower than in the previous test. The temperature of the previous test at this time is the optimum temperature. Catalytic performance was determined by measuring the rate of gas reduction, the product gas composition by gas chromatography, and the C5 ₊ liquid product yield. Recovery of the C5 ₊ liquid product from the reactor effluent was done using two traps. The first trap was cooled with water and the second trap was cooled with dry ice / acetone (-80 ° C). The C ₅₊ product in the first trap was weighed directly. The liquid product in the second trap was first warmed to room temperature to volatilize the C _4- component and then weighed. The combined weight of hydrocarbon liquid product in both traps was used to determine C ₅₊ product yield. The C ₅₊ product obtained at the optimum temperature was further analyzed to determine the hydrocarbon type and carbon chain length distribution. From time to time, C ₅₊ products obtained from non-optimal temperature tests were also combined and analyzed. In these experiments, the catalyst precursor was not calcined prior to reduction. The results are shown in Table 1 below.

[0018]

[Table 1]

[0019]   These results show that NH in the reducing gas used to convert the precursor to the catalyst. _Three The effect of concentration on catalyst performance is shown. NH in reducing gas_ThreeIs about 2 moles
% CO conversion and C₅₊Both yields are good and C₅₊Election
The selectivity has a peak at about 80%. NH in reducing gas_ThreeIf you use
Sex decreased, but this decrease was mainly due to C_4-It is derived from a gas product. Also
, Catalyst reducing gas is NH_ThreeContent of Schultz-Flory α increases
However, NH in reducing gas_ThreeIs kept essentially constant in the range of 0.5-3.0 mol%.
Dripping As can be seen from these results, during the catalytic reduction, NH was added in the reducing gas._ThreeTo
By being present, catalytic performance was improved. In this case, in any case
Also NH_ThreeΑ in hydrocarbon synthesis reaction was increased by reduction in the presence of
. NH in reducing gas_ThreeThe maximum difference between the presence and absence of_Tworeduction
0.5 mol% NH in natural gas_ThreeFound in an experiment containing. In this experiment
Is C of 76%₅₊High yield C with selectivity₅₊Hydrocarbons are obtained, and methane is produced
The yield was only 9%. 2 mol% NH_ThreeThen C₅₊Selectivity
Higher, C₅₊The yield was still good, albeit with a decrease.

Example 8 (Test of catalyst B after reduction with H ₂ , then H ₂ + NH ₃ ) Catalyst of example 5 (catalyst B reduced with H ₂ first, then H ₂ + NH ₃ ).
Was used to restart the flow of synthesis gas into the reactor at 100 hr ⁻¹ GHSV and 1 atm. Prior to entering the reactor, the syngas was K to remove impurities.
It was passed through a column of OH pellets (nominal pellet diameter 3-5 mm). The composition of the synthesis gas was 2: 1 by volume ratio of H ₂ : CO. The reactor temperature was raised from room temperature to 160 ° C in about 40 minutes. After maintaining in this state for 5 hours, the reactor was cooled to room temperature under a synthetic gas flow, and the catalyst was stored under the synthetic gas. Next day, test temperature is 10 ℃
The test was restarted using the same procedure except that it was raised. This was repeated daily until the operating temperature reached 190 ° C. The catalytic performance was determined by measuring the gas reduction rate, the product gas composition by gas chromatography, and the C5 ₊ liquid product yield at 190 ° C. Recovery of the C5 ₊ liquid product from the reactor effluent was done using two traps. The first trap was cooled with water and the second trap was cooled with dry ice / acetone (-80 ° C). The C ₅₊ product in the first trap was weighed directly. The liquid product in the second trap was first warmed to room temperature to volatilize the C _4- component and then weighed. The combined weight of hydrocarbon liquid product in both traps was used to determine C ₅₊ product yield. The C ₅₊ product obtained at the optimum temperature was further analyzed to determine the hydrocarbon type and carbon chain length distribution. From time to time, C ₅₊ products obtained from non-optimal temperature tests were also combined and analyzed. The catalyst precursor used in these experiments was calcined before reduction. It should be noted that the cobalt oxide formed by calcination is converted to metal upon reduction, but the zirconium component remains as an oxide and is not reduced to metal. The results at 190 ° C are shown in Table 2 below.

[0021]

[Table 2]

[0022] Table 2, in the constant reduction time 5 hours and, and if performed sequentially reduced with _H 2 + NH ₃ Following _{H 2,} when performing reduction only in H 2 + NH _3, catalytic It shows how the performance of B is affected by the presence of NH _{3 in} the H ₂ reducing gas. It should be noted that, as a result of the test, when the hydrogen treatment gas ratio was 100 hr ^-1 GHSV, the characteristics of the catalyst reduced with hydrogen became clear when the reduction time was 5 hours. . Therefore, a total reduction time of 5 hours was chosen for this experiment. However, the reduction of some of the metal and the consequent activation is achieved in one hour. Therefore, in the experiments of Table 2 above, where the contact time with the hydrogen reducing gas was 1, 2, 3 and 4 hours, the active catalyst was present before the hydrogen and ammonia were contacted with the reducing gas. In the last experiment in the table, a mixture of hydrogen and ammonia
It was the precursor that was contacted for a time. Therefore, this last experiment and the first (reduction with hydrogen only) are not within the scope of the invention and are presented for comparison.

As shown in Table 2, in the second to fifth experiments, the precursor was at least partially reduced before being contacted with the mixture of hydrogen and ammonia. Treatment with H ₂ for 4 hours followed by H ₂ + NH ₃ for 1 hour significantly increases the yield and selectivity of C ₅₊ , while significantly reducing methane production. Therefore, when the time for reduction with H ₂ + NH ₃ was increased, the C ₅₊ yield, the C ₅₊ selectivity, and the Schulz-Flory α reached peaks in the H ₂ + NH ₃ reduction for _{2 to} 4 hours. The catalytic activity decreases with the increase of H ₂ + NH ₃ reduction time, but this decrease in activity is due to C ₄ gas, and the yield of C ₅₊ can be obtained by H ₂ / NH ₃ treatment for up to 3 hours. It is almost constant. Over 3 hours, the yield and selectivity of C ₅₊ decreased, but the α of the reaction remained high. As can be seen from this, introducing NH ₃ into the reducing gas in at least part of the catalytic reduction is effective in improving the catalytic performance.

Various other embodiments and modifications of the procedure of the invention will be apparent to those skilled in the art and are considered to be readily feasible without departing from the scope and spirit of the invention described above. To be Therefore, the claims appended hereto are not to be limited to the above detailed description, and the claims are equivalent to those skilled in the art to which the present invention pertains. All patentable novel features belonging to this invention are considered to be encompassed, including all features and embodiments treated as.

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Claims (20)

[Claims] 1. A method for enhancing the performance of a hydrocarbon synthesis catalyst, comprising contacting the catalyst containing at least one catalytic metal component with a reducing gas containing a mixture of hydrogen and ammonia under catalytic reducing conditions. How to include. 2. The enhanced catalyst comprises the following (i) to (i) during hydrocarbon synthesis.
A method for enhancing the performance of a hydrocarbon synthesis catalyst according to claim 1, characterized in that it exhibits at least one property selected from the group consisting of ii). (I) Higher C ₅₊ selectivity than when the catalyst was not enhanced with the reducing gas mixture containing hydrogen and ammonia. (Ii) a larger Schulz-Flory distribution α of the hydrocarbon synthesis reaction than when the catalyst was not enhanced with the reducing gas mixture containing hydrogen and ammonia. (Iii) Methane production reduced to a lower level than when the catalyst was not enhanced with the reducing gas mixture containing hydrogen and ammonia. 3. The method for enhancing the performance of a hydrocarbon synthesis catalyst according to claim 2, wherein the catalyst comprises a Fischer-Tropsch type hydrocarbon synthesis catalyst. 4. A portion of said at least one catalytic metal component is reduced to a catalytically active metal form as a result of said contacting with said reducing gas comprising hydrogen and ammonia. 4. A method for enhancing the performance of the hydrocarbon synthesis catalyst according to 3. 5. The performance of a hydrocarbon synthesis catalyst according to claim 4, wherein the catalyst further comprises a metal oxide support component, and the catalyst metal component comprises at least one Group VIII metal. How to strengthen. 6. The method of claim 5, wherein a portion of the at least one catalytic metal component is reduced to the catalytically active metal form as a result of the ammonia-free reduction in hydrogen. To enhance the performance of hydrocarbon synthesis catalysts of. 7. The hydrocarbon synthesis according to claim 6, wherein the ammonia is present in the hydrogen reducing gas in an amount of 0.01 to 15 mol% of the entire reducing gas composition. A method of enhancing the performance of a catalyst. 8. The hydrocarbon synthesis according to claim 6, wherein the molar ratio of hydrogen to ammonia in the reducing gas consisting of a mixture of hydrogen and ammonia is in the range of 1000: 1 to 5: 1. A method of enhancing the performance of a catalyst. 9. The catalytic metal component comprises at least one of Co or Ru and the support component comprises at least one selected from the group consisting of alumina, silica, alumino-silicates and titania. A method for enhancing the performance of the hydrocarbon synthesis catalyst according to claim 8. 10. A catalyst produced according to the method for enhancing the performance of a hydrocarbon synthesis catalyst according to claim 1. 11. A method for synthesizing a hydrocarbon from a synthesis gas comprising a mixture of H ₂ and CO, wherein the H ₂ and the CO in the gas react to form a hydrocarbon. Under conditions, the gas is contacted with an enhanced Fischer-Tropsch hydrocarbon synthesis catalyst; the enhanced catalyst comprises at least one catalytic metal component; and the catalyst is a reducing catalyst comprising a mixture of hydrogen and ammonia. A method for synthesizing a hydrocarbon, which is enhanced by bringing the gas into contact with the catalyst under catalytic reduction conditions. 12. The enhanced catalyst comprises the following (i) to (
The method for synthesizing a hydrocarbon according to claim 11, which exhibits at least one property selected from the group consisting of iii). (I) Higher C ₅₊ selectivity than when the catalyst was not enhanced with the reducing gas mixture containing hydrogen and ammonia. (Ii) a larger Schulz-Flory distribution α of the hydrocarbon synthesis reaction than when the catalyst was not enhanced with the reducing gas mixture containing hydrogen and ammonia. (Iii) Methane production reduced to a lower level than when the catalyst was not enhanced with the reducing gas mixture containing hydrogen and ammonia. 13. The method of synthesizing hydrocarbons of claim 12 wherein said catalyst further comprises a metal oxide support component, said catalyst metal component comprising at least one Group VIII metal. 14. A portion of said at least one catalytic metal component is reduced to a catalytically active metal form as a result of said contacting with said reducing gas comprising hydrogen and ammonia. 13. The method for synthesizing a hydrocarbon according to 13. 15. The method of claim 14, wherein a portion of the at least one catalytic metal component is reduced to a catalytically active metal form as a result of the reduction in hydrogen without the ammonia. Method for the synthesis of hydrocarbons. 16. The ammonia is present in the hydrogen reducing gas in an amount of 0.01 to 15 mol% of the total reducing gas composition, and the molar ratio of hydrogen to ammonia in the reducing gas is 16. The method for synthesizing hydrocarbons according to claim 15, wherein the method is in the range of 1000: 1 to 5: 1. 17. The method for synthesizing a hydrocarbon according to claim 16, wherein the carrier component contains at least one selected from the group consisting of alumina, silica, alumino-silicate, and titania. 18. The activated catalyst is present in a fluidized bed or a fixed bed during the hydrocarbon synthesis, or is dispersed in a slurry liquid, and at least one of the synthesized hydrocarbons is used. Process according to claim 17, characterized in that the parts are upgraded by one or more operations involving fractionation and / or one or more conversion operations. 19. The method for synthesizing a hydrocarbon according to claim 18, wherein at least a part of the hydrocarbon to be improved is a solid in a normal state of room temperature and pressure. 20. The method for synthesizing a slurry hydrocarbon according to claim 19, wherein the catalyst metal component contains at least one of Co and Ru.