JP7406203B2 - Hydroisomerization catalyst for long-chain linear paraffins, method for producing hydroisomerization catalyst for long-chain linear paraffins, and method for producing branched paraffins by hydroisomerization reaction for long-chain linear paraffins - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Act - 49th Petroleum and Petrochemical Symposium Publication date of lecture abstract: October 31, 2020 Date of event: November 1, 2020 - 22nd Chemical Engineering Academic Society Student Presentation (Tokyo Conference) Date of presentation abstract posted on website: February 17, 2020 Website posting address of presentation abstract: http://www3. scej. org/meeting/stu22e/abst/A04. pdf

The present invention relates to a hydroisomerization catalyst for long-chain linear paraffins, a method for producing a hydroisomerization catalyst for long-chain linear paraffins, and a method for producing branched paraffins by hydroisomerization reaction of long-chain linear paraffins. .

In recent years, the effective use of biomass energy has attracted attention as a measure to prevent global warming, and various studies are being conducted in the field of transportation fuels.

From this perspective, attempts to produce diesel fuel and jet fuel using biomass, such as oils and fats derived from animals and plants, are attracting attention. When fats and oils derived from animals and plants are subjected to a hydrogenation deoxygenation reaction, long-chain linear paraffins having about 16 to 18 carbon atoms are obtained. On the other hand, although this long-chain linear paraffin has a high cetane number, it has low low-temperature fluidity and is difficult to use as a fuel as it is.

By subjecting such long-chain linear paraffins to a hydrocracking reaction and an isomerization reaction (hereinafter, the hydrocracking reaction and isomerization reaction are also collectively referred to as "hydroisomerization reaction"), diesel fuel can be produced. Studies are being conducted to produce branched paraffin with a carbon number that meets the standards for fuel and jet fuel. Non-Patent Document 1 uses n-decane as a model raw material for long-chain linear paraffins, and uses catalysts in which platinum is supported on various zeolites to increase the yield of branched paraffins with a zeolite structure having 6 or 7 carbon atoms. Discloses the impact it has.

Non-Patent Document 1 states that in the hydroisomerization reaction of n-decane, the yield of branched paraffins having 6 or 7 carbon atoms is higher when using MFI type zeolite than when using MTW type zeolite or FER type zeolite. It is disclosed that the amount will be higher.

Yusuke Yagita et al., Proceedings of the 83rd Society of Chemical Engineers, Lecture number: PE352, 2018

However, although the catalyst in which platinum is supported on MFI type zeolite described in Non-Patent Document 1 can increase the yield of branched paraffins having the desired number of carbon atoms, compared to when MTW type zeolite or FER type zeolite is used, The yield is not sufficient. In particular, excessive hydrogenolysis reaction produces a large amount of lower paraffins having about 3 to 5 carbon atoms, which reduces the yield of branched paraffins having the desired number of carbon atoms.

The present invention has been made in view of the above-mentioned circumstances, and is a hydroisomerization system capable of obtaining a branched paraffin having a desired number of carbon atoms in a high yield by subjecting a long-chain linear paraffin to a hydroisomerization reaction. An object of the present invention is to provide a hydroisomerization catalyst, a method for producing the hydroisomerization catalyst, and a method for producing branched paraffins using the hydroisomerization catalyst.

In order to solve the above problems, the present invention has the following aspects.
[1] In the MFI type zeolite, alkaline earth metal is based on the catalyst, 0.15 to 3% by mass in terms of oxide, and either one or both of platinum or palladium is based on the catalyst, 0.1 to 1 mass% in terms of metal. % supported hydroisomerization catalyst for long chain linear paraffins.
[2] The long-chain linear paraffin hydroisomerization catalyst according to [1], wherein the MFI type zeolite has an average particle diameter of 2000 nm or less.
[3] The long-chain linear paraffin hydroisomerization catalyst according to [1] or [2], wherein the ratio of the external surface area to the specific surface area of the MFI type zeolite is 0.3 to 5%.
[4] Hydrogen in the long-chain linear paraffin according to any one of [1] to [3], in which the alkaline earth metal is supported in an amount of 0.3 to 3% by mass in terms of oxide based on the catalyst. Chemical isomerization catalyst.
[5] Add an alkaline earth metal to the MFI type zeolite, based on the catalyst, 0.15 to 3% by mass in terms of oxide, and add one or both of platinum and palladium, based on the catalyst, 0.1 to 1 mass% in terms of metal. %, the method for producing a hydroisomerization catalyst for long-chain linear paraffins according to any one of [1] to [3].
[6] A catalyst precursor is obtained by supporting MFI type zeolite with an alkaline earth metal containing 0.15 to 3% by mass in terms of oxide, based on the catalyst, and adding either platinum or palladium to the catalyst precursor. The method for producing a hydroisomerization catalyst for long-chain linear paraffins according to [5], wherein one or both are supported in an amount of 0.1 to 1% by mass in terms of metal based on the catalyst.
[7] Add an alkaline earth metal to the MFI type zeolite, based on the catalyst, 0.3 to 3% by mass in terms of oxide, and one or both of platinum and palladium, based on the catalyst, 0.1 to 1 mass% in terms of metal. %, the method for producing a hydroisomerization catalyst for long-chain linear paraffins according to [4].
[8] A catalyst precursor is obtained by supporting an alkaline earth metal on MFI type zeolite so as to contain 0.3 to 3% by mass in terms of oxide based on the catalyst, and either platinum or palladium is added to the catalyst precursor. The method for producing a hydroisomerization catalyst for long-chain linear paraffins according to [7], wherein one or both are supported so as to contain 0.1 to 1% by mass in terms of metal based on the catalyst.
[9] In the presence of hydrogen, the long-chain linear paraffin is brought into contact with the long-chain linear paraffin hydroisomerization catalyst according to any one of [1] to [4], and the long-chain linear paraffin is A method for producing branched paraffin that obtains branched paraffin that has fewer carbon atoms than chain paraffin.

According to the present invention, there is provided a hydroisomerization catalyst capable of obtaining a branched paraffin having a target number of carbon atoms in a high yield by subjecting a long-chain linear paraffin to a hydroisomerization reaction, It is possible to provide a manufacturing method and a method for manufacturing branched paraffin using the hydroisomerization catalyst.

Hereinafter, embodiments of the present invention will be described in detail. However, the following description is an example of the embodiments of the present invention, and the present invention is not limited to these contents, and may be modified and implemented within the scope of the gist. can do.

In this specification, the "specific surface area", "outer surface area", and "pore volume" of the long-chain linear paraffin hydroisomerization catalyst and MFI type zeolite refer to nitrogen adsorption measured using a nitrogen adsorption device. It can be obtained from the isotherm. Specifically, the "specific surface area" can be obtained from the BET adsorption isotherm. "External surface area" and "pore volume" can be obtained by the t-plot method. The "pore volume" in this specification is the micropore volume obtained by the t-plot method.

In this specification, the "particle diameter" of the long-chain linear paraffin hydroisomerization catalyst, MFI type zeolite, can be obtained by observation using a scanning electron microscope (hereinafter also referred to as "SEM"). For example, the long axis and short axis of a long-chain linear paraffin hydroisomerization catalyst or MFI type zeolite can be observed, and their average value can be taken as the particle size. Furthermore, the particle size of 100 long-chain linear paraffin hydroisomerization catalysts or MFI type zeolite can be measured, and the average value can be taken as the "average particle size."

In this specification, the "average particle diameter", "surface area", and "dispersity" of platinum or palladium in the long-chain linear paraffin hydroisomerization catalyst can be measured by a CO pulse adsorption method.

In this specification, the catalyst basis of the alkaline earth metal in the hydroisomerization catalyst for long-chain linear paraffins, the supported amount in terms of oxide, the catalyst basis of either or both of platinum or palladium, the supported amount in metal terms The amount can be measured by X-ray fluorescence analysis (XRF).

<Hydroisomerization catalyst>
The long-chain linear paraffin hydroisomerization catalyst (hereinafter sometimes simply referred to as "hydroisomerization catalyst") of the present embodiment is one of MFI type zeolite, alkaline earth metal, and platinum or palladium. The MFI type zeolite contains 0.15 to 3% by mass of the alkaline earth metal on a catalyst basis, calculated as an oxide, and either or both of the platinum or palladium contains a catalyst basis, a metal Each is supported in an amount of 0.1 to 1% by mass.

(MFI type zeolite)
The hydroisomerization catalyst of this embodiment includes MFI type zeolite. MFI is a code defined by the International Zeolite Society that classifies zeolites by structure. In this embodiment, the MFI type zeolites include ZSM-5 which is an aluminosilicate zeolite, Fe-ZSM-5 which is an iron silicate zeolite, Ga-ZSM-5 which is a gallium silicate zeolite, and Zn-ZSM which is a zinc silicate zeolite. ZSM-5, which is an aluminosilicate, is preferred.

The counter cation for the aluminum element in the MFI type zeolite is preferably a proton, and the ratio of protons to the total aluminum elements contained in the MFI type zeolite (total number of moles of protons/total number of moles of aluminum x 100) is 50 It is preferably from 100% to 100%, more preferably from 60 to 100%, even more preferably from 70 to 100%. When the ratio of protons to all aluminum elements contained in the MFI type zeolite is at least the lower limit of the above range, sufficient acid sites are present in the hydroisomerization catalyst, and the hydrocracking reaction proceeds suitably.

The molar ratio of silicon element to aluminum element (hereinafter sometimes expressed as "Si/Al") of MFI type zeolite is preferably 100 to 300, more preferably 150 to 250, and 190 to 300. More preferably, it is 210. When Si/Al is at least the lower limit of the above range, the acid site density can be reduced and excessive decomposition can be suppressed. When Si/Al is below the upper limit of the above range, sufficient acid sites exist in the hydroisomerization catalyst, and the hydrocracking reaction progresses suitably.

The average particle diameter of the MFI type zeolite is preferably 2000 nm or less, more preferably 1800 nm or less, even more preferably 900 nm or less, and particularly preferably 800 nm or less. On the other hand, the lower limit is preferably 100 nm or more. When the average particle diameter is below the upper limit, the conversion rate of the hydroisomerization reaction increases. The upper limit value and lower limit value can be arbitrarily combined.

The specific surface area of the MFI type zeolite is not particularly limited as long as it has the effects of the present invention, but it is preferably 280 to 550 m ² /g, more preferably 400 to 500 m ² /g, and 420 to 440 m ² /g. More preferably, it is g. When the specific surface area is at least the lower limit of the above range, the acid sites, alkaline earth metals, platinum, palladium, etc. on the hydroisomerization catalyst become highly dispersed, and the conversion rate of the hydroisomerization reaction increases. When the specific surface area is less than or equal to the upper limit of the above range, the reaction site of the hydroisomerization reaction can be mainly limited to within the zeolite pores, and the yield of branched paraffin having the desired number of carbon atoms can be improved.

The outer surface area of the MFI type zeolite is not particularly limited as long as it has the effects of the present invention, but it is preferably 2 to 18 m ² /g, more preferably 3 to 15 m ² /g, and 7 to 13 m ^{2 /} g. More preferably, it is g. When the outer surface area is at least the lower limit of the above range, the conversion rate of the hydroisomerization reaction increases. When the outer surface area is less than or equal to the upper limit of the above range, the reaction site of the hydroisomerization reaction can be mainly limited to within the zeolite pores, and the yield of branched paraffin having the desired number of carbon atoms can be improved.

The ratio of the outer surface area to the specific surface area of the MFI type zeolite (outer surface area/specific surface area x 100) is not particularly limited as long as it has the effects of the present invention, but it is preferably 0.3 to 5%, and 0.5 to 5%. It is more preferably 4%, even more preferably 0.5 to 3%, and particularly preferably 2 to 3%. When the ratio of the external surface area to the specific surface area is at least the lower limit of the above range, the conversion rate of the hydroisomerization reaction increases. When the ratio of the external surface area to the specific surface area is below the upper limit of the above range, the reaction site of the hydroisomerization reaction can be mainly limited to within the zeolite pores, and the yield of branched paraffin having the desired number of carbon atoms is improved. do.

The pore volume of the MFI type zeolite is not particularly limited as long as it has the effects of the present invention, but it is preferably 0.15 to 0.25 mL/g, more preferably 0.15 to 0.23 mL/g. The amount is preferably 0.15 to 0.20 mL/g, and more preferably 0.15 to 0.20 mL/g. When the pore volume is at least the lower limit of the above range, the conversion rate of the hydroisomerization reaction increases. When the pore volume is less than or equal to the upper limit of the above range, the reaction site of the hydroisomerization reaction can be limited mainly to the zeolite pores, and the yield of branched paraffin having the desired number of carbon atoms can be improved.

(alkaline earth metal)
The hydroisomerization catalyst of this embodiment contains an alkaline earth metal. Examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, barium, and radium, with strontium, calcium, and magnesium being preferred, calcium and magnesium being more preferred, and magnesium being particularly preferred. The form of the alkaline earth metal is not particularly limited as long as it has the effects of the present invention, but hydroxides and oxides are preferred, and oxides are particularly preferred. In the hydroisomerization catalyst of the present embodiment, when the alkaline earth metal is in the form of an oxide, it is preferable that a part of the oxygen contained in the oxide is bonded to protons of the MFI type zeolite. It is thought that the above bond reduces the acid amount and acid strength of the MFI type zeolite and suppresses excessive hydrogenolysis reaction.

In the profile obtained by the ammonia temperature-programmed desorption method (hereinafter also referred to as "NH ₃ -TPD method"), MFI type zeolite has a low temperature range (100°C or more and less than 300°C) and a high temperature range (300 to 450°C). is known to have two peaks. The peaks in the low temperature range originate from relatively weak acid sites, and the peaks in the high temperature range originate from relatively strong acid sites. By containing a noble metal (platinum, palladium) and an alkaline earth metal, the hydroisomerization catalyst of this embodiment reduces the peak in the high temperature range and shifts to the low temperature range. (i.e. decrease in acid content). As used herein, the term "acid amount" refers to a value calculated from the amount of NH ₃ desorbed at 150 to 250° C. as measured by the NH ₃ -TPD method.

Based on the acid content (H) of the MFI type zeolite measured by the NH ₃ -TPD method, the MFI type zeolite contains an alkaline earth metal of 0.15 to 3% by mass in terms of oxide based on the catalyst, and either platinum or palladium. The acid amount (H2) ratio (H2/H x 100) of the hydroisomerization catalyst of the present invention in which one or both of them is supported in an amount of 0.1 to 1% by mass in terms of metal based on the catalyst is 12 to 85. %, more preferably 24 to 72%, even more preferably 35 to 72%.

The acid content of a hydroisomerization catalyst in which 0.1 to 1% by mass of either platinum or palladium, or both, is supported on the MFI type zeolite measured by the NH ₃ -TPD method (based on the catalyst, in terms of metal) For H1), the MFI type zeolite contains an alkaline earth metal of 0.15 to 3% by mass on a catalyst basis in terms of oxide, and one or both of platinum or palladium on a catalyst basis of 0.1 to 1% in terms of metal. The acid amount (H2) ratio (H2/H1 x 100) of the hydroisomerization catalyst of the present invention supported by mass% is preferably 30 to 90%, more preferably 45 to 80%. It is preferably 40 to 75%.

The acid amount of the hydroisomerization catalyst of this embodiment measured by the NH ₃ -TPD method is preferably 0.01 to 0.07 mmol/g, and preferably 0.02 to 0.065 mmol/g. is more preferable, and even more preferably 0.03 to 0.065 mmol/g.

The content ratio of alkaline earth metal in the hydroisomerization catalyst is 0.15 to 3% by mass, preferably 0.3 to 3% by mass, and preferably 0.3 to 3% by mass in terms of oxide based on the catalyst. It is more preferably 2% by mass, and even more preferably 0.3 to 1.2% by mass.
As another aspect of the present invention, the content of alkaline earth metal in the hydroisomerization catalyst is preferably 0.15 to 0.8% by mass in terms of oxide based on the catalyst, and 0.15% by mass. It is more preferably 0.6% by mass, and even more preferably 0.2% to 0.5% by mass.
When the content of the alkaline earth metal is at least the lower limit of the above range, excessive hydrogenolysis reaction is suppressed and the yield of branched paraffin having the desired number of carbon atoms is improved. When the alkaline earth metal content is below the upper limit of the above range, the conversion rate of the hydroisomerization reaction is improved.

The ratio of alkaline earth metals to all aluminum elements contained in the MFI type zeolite (total number of moles of alkaline earth metals/total number of moles of aluminum) is preferably 2.0 to 7.0, and 2.5 It is more preferably from 3.0 to 6.2, and even more preferably from 3.0 to 6.2.
Another aspect of the present invention is that the ratio of alkaline earth metals to all aluminum elements contained in the MFI type zeolite (total number of moles of alkaline earth metals/total number of moles of aluminum) is 0.45 to 3.0. It is preferably from 0.6 to 3.0, even more preferably from 0.9 to 3.0.

The ratio of alkaline earth metal to the total amount of acid contained in the hydroisomerization catalyst (total number of moles of alkaline earth metal/total number of moles of acid amount) is preferably from 3 to 15, and from 3.5 to The number is more preferably 12, and even more preferably 4 to 11.
As another aspect of the present invention, the ratio of alkaline earth metal to the total amount of acid contained in the hydroisomerization catalyst (total number of moles of alkaline earth metal/total number of moles of acid amount) is 2 to 10. The number is preferably 1, more preferably 2 to 7, and even more preferably 2 to 5.

(platinum, palladium)
The hydroisomerization catalyst of the present embodiment contains one or both of platinum and palladium (hereinafter also referred to as "platinum etc."). Preferably, platinum or palladium is a metal. That is, the hydroisomerization catalyst of the present embodiment may contain only platinum, only palladium, or both platinum and palladium.

The content of platinum, etc. in the hydroisomerization catalyst is 0.1 to 1% by mass, preferably 0.1 to 0.8% by mass, and preferably 0.1 to 0. More preferably, the content is .6% by mass. When the content of platinum or the like is at least the lower limit of the above range, the number of active sites on the hydroisomerization catalyst increases, and the yield of branched paraffin having the desired number of carbon atoms is improved. When the content rate of platinum or the like is below the upper limit of the above range, sintering of platinum or the like is suppressed, and a decrease in the surface area of platinum or the like is suppressed. As a result, the number of active sites on the hydroisomerization catalyst increases, improving the yield of branched paraffins having the desired number of carbon atoms.

The particle size of platinum or the like in the hydroisomerization catalyst is not particularly limited as long as it has the effects of the present invention, but is preferably 1 to 20 nm, more preferably 1 to 15 nm, and 1 to 11 nm. It is even more preferable. When the particle size of platinum or the like is below the upper limit of the above range, the number of active sites on the hydroisomerization catalyst increases and the yield of branched paraffin having the desired number of carbon atoms is improved.

The surface area of platinum or the like in the hydroisomerization catalyst is not particularly limited as long as it has the effects of the present invention, but in the case of platinum, it is preferably 0.05 to 15 m ² /g, and 0.1 to 10 m ² /g. g, more preferably 0.13 to 5 m ² /g. The preferred range of surface area for palladium is twice that of platinum. When the surface area of platinum or the like is at least the lower limit of the above range, the number of active sites on the hydroisomerization catalyst will increase, and the yield of branched paraffin having the desired number of carbon atoms will improve.

The degree of dispersion of platinum, etc. in the hydroisomerization catalyst is not particularly limited as long as it has an effect in this field, but is preferably 5% or more, more preferably 8% or more, and 10% or more. It is even more preferable. When the degree of dispersion of platinum or the like is equal to or higher than the lower limit, the number of active sites on the hydroisomerization catalyst increases, and the yield of branched paraffin having the desired number of carbon atoms increases.

The average particle diameter, specific surface area, outer surface area, and pore volume of the hydroisomerization catalyst of this embodiment are approximately equivalent to each physical property value of the MFI type zeolite used. Specifically, the average particle diameter, specific surface area, external surface area, and pore volume of the hydroisomerization catalyst of this embodiment are usually 0.7 to 1.1 times the corresponding physical property values of the MFI type zeolite used. It will be about.

The ratio of the total mass in terms of metals such as platinum to the total mass in terms of oxides of alkaline earth metals contained in the hydroisomerization catalyst (total mass in terms of metals such as platinum/total mass in terms of oxides of alkaline earth metals) mass) is preferably 0.15 to 0.7, more preferably 0.2 to 0.6, and even more preferably 0.24 to 0.52.
Another aspect of the present invention is the ratio of the total mass in terms of metals such as platinum to the total mass in terms of oxides of alkaline earth metals contained in the hydroisomerization catalyst (total mass in terms of metals such as platinum/alkali earth metals). The total mass of earth metals in terms of oxides is preferably 0.5 to 3.3, more preferably 1.0 to 3.3, and 1.5 to 3.3. is even more preferable.

The ratio of platinum, etc. to the alkaline earth metal contained in the hydroisomerization catalyst (total number of moles of platinum, etc./total number of moles of alkaline earth metal) is preferably 0.03 to 0.13, and 0. It is more preferably from .04 to 0.12, and even more preferably from 0.05 to 0.11.
Another aspect of the present invention is that the ratio of platinum, etc. to the alkaline earth metal contained in the hydroisomerization catalyst (total number of moles of platinum, etc./total number of moles of alkaline earth metal) is 0.1 to 1. It is preferably .5, more preferably 0.2 to 1.5, even more preferably 0.3 to 1.5.

The ratio of platinum, etc. to all aluminum elements contained in the MFI type zeolite (total number of moles of platinum, etc./total number of moles of aluminum) is preferably 0.28 to 0.35, and 0.3 to 0.33. More preferably, it is 0.31 to 0.32.

The ratio of platinum, etc. to the total amount of acids contained in the hydroisomerization catalyst (total number of moles of platinum, etc./total number of moles of acid amount) is preferably from 0.37 to 0.6, and from 0.4 to It is more preferably 0.58, and even more preferably 0.42 to 0.56.
Another aspect of the present invention is that the ratio of platinum, etc. to the total amount of acids contained in the hydroisomerization catalyst (total number of moles of platinum, etc./total number of moles of acid amount) is 0.37 to 0.9. It is preferably from 0.4 to 0.85, even more preferably from 0.42 to 0.77.

<Method for producing hydroisomerization catalyst>
The method for producing a hydroisomerization catalyst of the present embodiment includes adding an alkaline earth metal to MFI type zeolite, 0.15 to 3% by mass in terms of oxide, and one or both of platinum and palladium as a catalyst. This includes supporting the metal so that it contains 0.1 to 1% by mass in terms of metal.

(Method for manufacturing MFI type zeolite)
MFI type zeolite can be produced by methods known in the art. MFI-type zeolite can be produced by, for example, an aqueous solution preparation process for obtaining an aqueous solution containing a structure-directing agent, a Si raw material, and an Al raw material, an aging process for aging the aqueous solution, and a hydrothermal synthesis process for crystallizing the aqueous solution after aging under hydrothermal conditions. It can be obtained through a process.

- Aqueous solution preparation step As the Si raw material, any Si raw material known in the art can be used, such as tetraethyl orthosilicate, colloidal silica, dry silica gel powder, silica hydrogel, sodium silicate, potassium silicate, etc. be able to.

As the Al raw material, any Al raw material known in the art can be used, such as aluminum isopropoxide, sodium aluminate, aluminum chloride, etc.

The organic structure-directing agent (hereinafter also simply referred to as "OSDA") may be appropriately selected depending on the zeolite to be obtained. For example, when producing ZSM-5, tetrapropylammonium Hydroxide can be used as OSDA.

The ratio between the amount of Si raw material and the amount of Al raw material to be used may be adjusted as appropriate based on the desired Si/Al ratio. Further, a counter cation source for Al in the obtained zeolite may be appropriately selected and added. For example, when the counter cation is sodium, sodium chloride may be added. The ratio of the number of moles of counter cation to the number of moles of Al in the Al raw material (counter cation/Al) is not particularly limited, but may be, for example, 5 or less.

The ratio of the number of moles of OSDA to the number of moles of Si in the aqueous solution (OSDA/Si) is not particularly limited, but may be, for example, from 0.1 to 1, or from 0.1 to 0.5. Furthermore, by controlling the molar amount of Si (hereinafter also referred to as [Si]) relative to the total volume of the aqueous solution, it is possible to control the particle size of the obtained zeolite and the ratio of the outer surface area to the specific surface area. Specifically, by reducing [Si], it is possible to obtain MFI type zeolite which has a large particle diameter and a small ratio of external surface area to specific surface area. When [Si] is increased, it is possible to obtain an MFI type zeolite with a small particle diameter and a large ratio of external surface area to specific surface area. [Si] can be controlled by adjusting the amount of water in the aqueous solution.
[Si] is preferably 0.2 to 1.5 mol/L, more preferably 0.4 to 1.3 mol/L, and even more preferably 0.6 to 1.1 mol/L. .

- Ripening step Ripening is performed while stirring the aqueous solution. Conditions known in the art can be used for aging temperature and time. The aging temperature is usually 15 to 80°C, and the aging time is usually 1 to 24 hours.

・Hydrothermal synthesis process The aqueous solution after the aging process is transferred to an autoclave and crystallized under hydrothermal conditions. As the hydrothermal conditions, conditions known in the art can be adopted. The reaction temperature is usually 100 to 180°C, and the reaction time is usually 24 to 120 hours.

The solid content containing the MFI type zeolite thus obtained can be recovered, for example, by filtering the suspension containing the solid content after hydrothermal synthesis and drying the solid content. Further, a cleaning treatment may be performed as necessary before the drying.

In order to remove the structure-directing agent from the solid matter thus obtained, it is preferable to perform calcination in an air atmosphere. The firing temperature is not particularly limited as long as it is at least the temperature at which the above-mentioned structure directing agent can be removed, but for example, it is preferably 400 to 600°C, more preferably 500 to 600°C. Further, the firing time can be, for example, 3 to 24 hours.

The counter cation corresponding to the Al element in the MFI type zeolite thus obtained becomes the cation present in the aqueous solution. For example, when sodium chloride is added to an aqueous solution as a counter cation source as described above, the obtained MFI type zeolite becomes an Na type MFI type zeolite. When this Na-type MFI-type zeolite is made into a proton-type MFI-type zeolite, Na may be ion-exchanged with ammonium ions and then calcined in an air atmosphere.

The firing temperature is not particularly limited as long as it is a temperature at which ammonia is desorbed from ammonium cations, and may be, for example, 300 to 600°C. Further, the conversion from the ammonium type MFI type zeolite to the proton type MFI type zeolite may be carried out by supporting an alkaline earth metal, platinum, etc., which will be described later, and then firing.

The MFI type zeolite obtained as described above contains alkaline earth metals on a catalyst basis, 0.15 to 3% by mass in terms of oxides, and platinum etc. on a catalyst basis, 0.1 to 1% by mass in terms of metals. Have them carry it as they should. Hereinafter, the alkaline earth metals, platinum, and palladium supported on the MFI type zeolite are also collectively referred to as "supported components."

The raw material compound of the alkaline earth metal supported on the MFI type zeolite is not particularly limited, and examples thereof include magnesium nitrate hexahydrate, magnesium chloride hexahydrate, magnesium sulfate heptahydrate, calcium nitrate, etc. It is mentioned as.

The raw material compound for platinum or palladium supported on the MFI type zeolite is not particularly limited, and includes, for example, chloroplatinic acid, tetraammineplatinum chloride, diammine dinitroplatinic acid, bis(acetylacetonato)platinum, palladium nitrate, palladium sulfate, Examples include tetraamine palladium chloride, bis(acetylacetonato)palladium, and the like.

As a method for supporting the support component, any method known in the art can be employed, except for using MFI type zeolite as a carrier. Supporting methods known in this field include, for example, an impregnation method, a coprecipitation method, an ion exchange method, and the like, with the impregnation method being particularly preferred.

Impregnation methods include evaporation to dryness, in which MFI type zeolite is immersed in an impregnating solution in excess of its total pore volume, and then dried to support the supported components; Equilibrium adsorption method in which the supported component is supported by solid-liquid separation such as filtration after soaking in excess impregnating solution, impregnating MFI type zeolite with an impregnating solution of approximately the same volume as the pore volume and drying. An example is a pore filling method (Incipient Wetness method) in which a supported component is supported.
The pore filling method is preferred from the viewpoint of uniformly and highly dispersedly supporting a predetermined amount of supported components on the MFI type zeolite.

Methods for impregnating MFI type zeolite with alkaline earth metals, platinum, etc. include a simultaneous method and a sequential method. The simultaneous method is a method in which MFI type zeolite is impregnated with a solution in which all the raw material compounds are dissolved. The sequential method is a method in which solutions in which each raw material compound is dissolved separately are prepared, and MFI type zeolite is impregnated with each solution sequentially.

As an example of a sequential method, MFI type zeolite was impregnated with a first impregnating solution in which a raw material compound containing platinum etc. was dissolved to obtain catalyst precursor 1, and subsequently a raw material compound containing an alkaline earth metal was dissolved. An example is a method of impregnating the catalyst precursor 1 with a second impregnating solution (sequential method 1). In the above example, the alkaline earth metal is supported after platinum or the like is supported, but platinum or the like may be supported after the alkaline earth metal is supported. That is, MFI type zeolite is impregnated with a first impregnating solution in which a raw material compound containing an alkaline earth metal is dissolved to obtain the catalyst precursor 2, and then a second impregnating solution in which a raw material compound containing platinum or the like is dissolved is impregnated into MFI type zeolite. A method of impregnating the catalyst precursor 2 with (sequential method 2) may also be used.
Alkaline earth metals may dissolve in an acidic solution if the impregnating solution containing the raw material compound containing platinum etc. is dissolved in the acidic solution. The method is more preferred.
Further, from the viewpoint of improving the yield of branched paraffins having the desired number of carbon atoms, sequential method 2 is more preferable.

When producing a hydroisomerization catalyst by sequential method 1, the amount of alkaline earth metal supported is preferably 0.15 to 3% by mass in terms of oxide based on the catalyst, and 0.3% by mass. More preferably 3% by mass.
Another aspect of the present invention is that when producing a hydroisomerization catalyst by sequential method 1, the amount of alkaline earth metal supported is 0.3 to 2% by mass in terms of oxide based on the catalyst. It is preferable to support it, and 0.3 to 1.2% by mass is more preferable.

When producing a hydroisomerization catalyst by sequential method 2, the amount of alkaline earth metal supported is preferably 0.15 to 3% by mass in terms of oxide based on the catalyst, and 0.3% by mass. More preferably 3% by mass.
As another aspect of the present invention, when producing a hydroisomerization catalyst by sequential method 2, the amount of alkaline earth metal supported is 0.15 to 0.8% by mass in terms of oxide based on the catalyst. It is preferable that the amount of carbon dioxide is supported, more preferably 0.15 to 0.6% by mass, and even more preferably 0.2 to 0.5% by mass.

After supporting the supported component by impregnation, it is preferable to remove the solvent in the impregnation liquid by drying, and then to perform firing in an air atmosphere. The drying temperature and firing temperature can be determined as appropriate depending on the type of solvent and the like. For example, when the solvent is water, the drying temperature may be 80 to 300°C, and the calcination temperature may be 300 to 600°C. Further, drying may be performed under reduced pressure or normal pressure.

In the case of the above-mentioned sequential method, after impregnating with the first impregnating solution and drying, the second impregnating solution may be impregnated, or after impregnating with the first impregnating solution, drying and baking, A second impregnation solution may be impregnated.

<Production method of branched paraffin>
The method for producing branched paraffins of the present embodiment includes contacting long-chain linear paraffins with the above-mentioned hydroisomerization catalyst in the presence of hydrogen to produce branched paraffins having fewer carbon atoms than the long-chain linear paraffins. obtain. More specifically, it is preferable to obtain branched paraffins having 6 to 20 carbon atoms from long chain linear paraffins having 8 to 24 carbon atoms, and to obtain branched paraffins having 6 to 20 carbon atoms from long chain linear paraffins having 10 to 24 carbon atoms. More preferably, 6 to 15 branched paraffins are obtained.
Branched paraffins having 6 to 20 carbon atoms include 2-methyloctane, 2-methylheptane, 2-methylhexane, 2-methylpentane, 2-methylnonane, 2-methyldodecane, 2-methyloctadecane, and the like.

The long-chain linear paraffin used in the method for producing branched paraffin of the present embodiment may be a long-chain linear paraffin obtained in a petroleum refining process, or may be obtained by subjecting fats and oils derived from animals and plants to a hydrodeoxygenation reaction. It may also be a long-chain linear paraffin.

The reaction temperature in the method for producing branched paraffins of this embodiment is preferably 200 to 300°C, more preferably 200 to 250°C. When the reaction temperature is equal to or higher than the lower limit of the above range, the conversion rate of the hydroisomerization reaction increases. When the reaction temperature is below the upper limit of the above range, excessive hydrogenolysis reaction is suppressed and the yield of branched paraffins having the desired number of carbon atoms is improved.

The contact time between the long-chain linear paraffin, which is the raw material in the method for producing branched paraffin of the present embodiment, and the hydroisomerization catalyst (hereinafter referred to as "W/F [(g-catalyst)/(g-raw material/h)") ) is preferably 0.1 to 5 (g-catalyst)/(g-raw material/h), and 0.1 to 3 (g-catalyst)/(g-raw material/h). More preferably, the ratio is 0.2 to 1 (g-catalyst)/(g-raw material/h). A suitable W/F varies depending on the throughput and the performance of the hydroisomerization catalyst used, but when the W/F is at least the lower limit of the above range, the conversion rate of the hydroisomerization reaction increases. When W/F is below the upper limit of the above range, excessive hydrogenolysis reaction is suppressed and the yield of branched paraffins having the desired number of carbon atoms is improved.

The ratio of the partial pressure of hydrogen to the partial pressure of long-chain linear paraffin, which is the raw material in the method for producing branched paraffin of the present embodiment (hydrogen/raw material), is preferably 5 to 20, and preferably 7 to 20. is more preferable, and even more preferably 9 to 20. When the ratio of the partial pressure of hydrogen to the partial pressure of long-chain linear paraffin as a raw material is at least the lower limit of the above range, the desired reaction will proceed sufficiently. When the ratio of the partial pressure of hydrogen to the partial pressure of the long-chain linear paraffin that is the raw material is below the upper limit of the above range, sufficient reaction rate can be ensured without lowering the raw material partial pressure too much in addition to suppressing excessive decomposition. can. Moreover, there is no need to consume excessive hydrogen, and processing costs can be reduced. Further, if necessary, an inert gas such as nitrogen may be supplied together with hydrogen.

The hydroisomerization catalyst of this embodiment is activated by reduction treatment in a reaction apparatus before use (that is, prior to producing the branched paraffin of this embodiment). This reduction treatment is usually carried out at 300 to 500°C, preferably 400 to 450°C. It is preferable to use hydrogen gas as the reducing gas.

When the method for producing branched paraffins of this embodiment is carried out on a commercial scale, a catalyst layer of the hydroisomerization catalyst according to the present invention is formed in a reaction apparatus, and long-chain linear paraffins and hydrogen may be introduced, and the hydroisomerization reaction may be carried out under the above conditions.
The catalyst bed may be of a fixed bed, moving bed, or fluidized bed type. Specifically, a fixed bed catalyst layer is formed in the reactor, long chain linear paraffins and hydrogen are introduced into the top of the reactor, passed through the fixed bed from top to bottom, and generated from the bottom of the reactor. The most common method is to introduce the long-chain linear paraffins and hydrogen at the bottom of the reactor, pass through a fixed bed from the bottom to the top, and drain the product from the top of the reactor.

The method for producing branched paraffins according to the present invention may be a one-stage hydroisomerization reaction performed by filling a single reactor with the hydroisomerization catalyst according to the present invention, or may be a one-stage hydroisomerization reaction carried out by filling a single reactor with the hydroisomerization catalyst according to the present invention. A multi-stage continuous hydroisomerization reaction performed by charging the reactor may also be used.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.

<Characterization>
The specific surface area, external surface area, and pore volume of the MFI type zeolite were measured by nitrogen adsorption. The average particle diameter of the MFI type zeolite was measured by SEM observation. The average particle size, surface area, and dispersion degree of platinum in the hydroisomerization catalyst were measured by a CO pulse adsorption method. The acid properties of the MFI type zeolite and the hydroisomerization catalyst were measured by the NH ₃ -TPD method.

-Nitrogen adsorption MFI type zeolite A or B, which will be described later, was dried overnight at 300° C., and nitrogen adsorption was performed using BELSORP-mini manufactured by Microtrac Bell Co., Ltd. as a nitrogen adsorption device. Specific surface area, external surface area, and pore volume were obtained by the method described above.

- SEM observation SEM observation of MFI type zeolite A or B, which will be described later, was performed using a scanning electron microscope (JEOL JSM-7500F) manufactured by JEOL Ltd. under the conditions of an accelerating voltage of 15 kV and an irradiation current of 10 μA. The average particle size was obtained as described above.

・CO pulse adsorption method The hydroisomerization catalysts A to D described below were dried at 450°C for 1 hour, and then hydrogen reduction was performed, using BEL-METAL-1 manufactured by Microtrac Bell as a CO adsorption device. CO pulse adsorption was performed at 50°C.

-NH ₃ -TPD method MFI type zeolite A, MFI type zeolite B, and hydroisomerization catalysts A to H, which will be described later, were pretreated by heating at 550° C. for 1 hour. Thereafter, after adsorbing NH ₃ at 100° C., the temperature was raised at 5° C./min, and the amount of NH ₃ desorbed was determined from the weight loss resulting from the desorbed NH ₃ . Note that the measurement conditions were such that He gas was used as a desorption gas during temperature rise. Further, the weight loss was measured using TGA-50 manufactured by Shimadzu Corporation as a thermobalance. By subtracting the amount of physically adsorbed NH ₃ desorbed from the amount of NH 3 desorbed at 150 to 250°C, the amount of NH ₃ adsorbed to the acid site is determined, and the amount of NH ₃ adsorbed at the acid site is determined. The acid content of chemical isomerization catalysts A to H was determined.

<Raw materials>
・Tetraethyl orthosilicate (hereinafter also referred to as "TEOS", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Aluminum isopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Tetrapropylammonium hydroxide (hereinafter also referred to as "TPAOH", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Sodium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Ammonium nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Nitric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Chloroplatinic acid (manufactured by Sigma-Aldrich)
・Magnesium nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・n-Dodecane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

<Synthesis of MFI type zeolite>
[Manufacture example 1]
Pure water was added to a 10% by mass TPAOH aqueous solution, and sodium chloride as a cation source and aluminum isopropoxide as an Al source were dissolved to obtain an Al solution. TEOS was added to the Al solution and stirred overnight to obtain an aqueous solution containing a structure directing agent, a Si raw material, and an Al raw material. Nitric acid was added dropwise to the aqueous solution so that the pH was 10, and the mixture was stirred for 2 to 3 hours. The obtained solution was transferred to an autoclave, and the reaction was carried out under hydrothermal conditions of 150° C. for 72 hours while stirring at 10 rpm. After completion of hydrothermal synthesis, centrifugation was performed, and the obtained solid content was washed with distilled water. Thereafter, the solid content was calcined at 550° C. for 12 hours in an air atmosphere to remove TPAOH and obtain Na-type MFI-type zeolite. The Na-type MFI-type zeolite was stirred for 3 hours in a 0.83M ammonium nitrate aqueous solution at 75°C, and then centrifuged. The same operation was performed three times in total using 1.25M and 1.67M ammonium nitrate aqueous solutions, and then dried at 110°C overnight to obtain ammonium type MFI type zeolite A. The obtained ammonium type MFI type zeolite A was characterized.
Table 1 shows the preparation conditions and characterization results of ammonium type MFI type zeolite A.

[Manufacture example 2]
MFI type zeolite was synthesized in the same manner as in Production Example 1, except that the amount of water in the aqueous solution containing the structure directing agent, Si raw material, and Al raw material was adjusted to make the Si concentration 0.5 mol/L. Type zeolite B was obtained. The obtained ammonium type MFI type zeolite B was characterized.
Table 1 shows the preparation conditions and characterization results of ammonium type MFI type zeolite B.

[Example 1]
The above MFI type zeolite A was impregnated with a chloroplatinic acid solution prepared by dissolving chloroplatinic acid in distilled water using a pore filling method. The impregnated body was dried under reduced pressure, further dried at normal pressure at 110°C for 3 hours, and then calcined at 550°C for 3 hours in an air atmosphere to obtain Pt/MFI type zeolite A. In addition, the ammonium type MFI type zeolite A was converted into the proton type MFI type zeolite A by the above-mentioned calcination.
A magnesium nitrate solution prepared by dissolving magnesium nitrate hexahydrate in distilled water was impregnated into the above-mentioned Pt/MFI type zeolite A by a pore filling method. The impregnated body was dried under reduced pressure, further dried at normal pressure at 110°C for 3 hours, and then calcined at 550°C for 3 hours in an air atmosphere to produce a catalyst in which magnesium oxide and platinum were supported on proton type MFI type zeolite A. I got an A. Table 2 shows the Pt analysis results and acid property analysis results of catalyst A.

A quartz reaction tube with an inner diameter of 9 mm was filled with a predetermined amount of catalyst A to achieve W/F as described below, and pretreatment for hydrogen reduction was performed at 450° C. for 1 hour under hydrogen flow. As a model raw material for long-chain linear paraffin, n-dodecane was supplied to the reaction tube at a rate of 1.6 mL/h, and hydrogen and accompanying gas nitrogen were supplied at a total rate of 43 mL/min. The partial pressure of n-dodecane supplied to the reaction tube was 7 kPa, and the partial pressure of hydrogen was 63 kPa (ie, hydrogen/raw material = 9). The reaction temperature was 200° C., and the W/F was 0.8 [(g-catalyst)/(g-raw material (n-dodecane)/h)]. The outlet of the reactor was cooled, the liquid component was sampled, and the gas component was collected in its entirety using a gas bag. Liquid and gas components were analyzed by gas chromatography.
Table 2 shows the conversion rate and the yield of each component. In Table 2, "Cn" indicates a paraffin having n carbon atoms, "n-" indicates a straight chain, and "iso-" indicates a branched chain.
The conversion rate was calculated based on the amount of carbon material in the n-dodecane at the outlet of the reactor and the n-dodecane supplied. The yield of each component was calculated based on the amount of each component at the outlet of the reactor and the amount of n-dodecane carbon material supplied. The unknown portion in Table 2 means a component that could not be identified by gas chromatography, and the unquantitated portion means the difference in material balance between the supplied n-dodecane and the product based on carbon substances. "iso-C7+iso-C8+iso-C9" in Table 2 indicates the total of the yield of iso-C7, the yield of iso-C8, and the yield of iso-C9. "C1 to C6" in Table 2 indicates the total yield of C1 to C6.

[Example 2]
The hydroisomerization reaction of n-dodecane was carried out in the same manner as in Example 1 except that the reaction temperature was 225°C. The results are shown in Table 2.

[Example 3]
The hydroisomerization reaction of n-dodecane was carried out in the same manner as in Example 1 except that the reaction temperature was 250°C. The results are shown in Table 2.

[Example 4]
The hydroisomerization reaction of n-dodecane was carried out in the same manner as in Example 1, except that the loading amount of catalyst A was changed so that W/F = 0.24 and the reaction temperature was 250°C. The results are shown in Table 2.

[Example 5]
The hydroisomerization reaction of n-dodecane was carried out in the same manner as in Example 1, except that the loading amount of catalyst A was changed so that W/F = 0.08 and the reaction temperature was 250°C. The results are shown in Table 2.

[Example 6]
Catalyst B, in which magnesium oxide and platinum were supported on proton-type MFI-type zeolite B, was obtained in the same manner as in Example 1, except that MFI-type zeolite B was used instead of MFI-type zeolite A. Table 2 shows the Pt analysis results and acid property analysis results of catalyst B.

A quartz reaction tube with an inner diameter of 9 mm was filled with a predetermined amount of catalyst B to achieve W/F as described below, and pretreatment for hydrogen reduction was performed at 450° C. for 1 hour under hydrogen flow. As a model raw material for long-chain linear paraffin, n-dodecane was supplied to the reaction tube at a rate of 1.6 mL/h, and hydrogen and accompanying gas nitrogen were supplied at a total rate of 43 mL/min. The partial pressure of n-dodecane supplied to the reaction tube was 7 kPa, and the partial pressure of hydrogen was 63 kPa (ie, hydrogen/raw material = 9). The reaction temperature was 250° C., and the W/F was 0.24 [(g-catalyst)/(g-raw material (n-dodecane)/h)]. The outlet of the reactor was cooled, the liquid component was sampled, and the gas component was collected in its entirety using a gas bag. Liquid and gas components were analyzed by gas chromatography.
Table 2 shows the conversion rate and the yield of each component.

[Example 7]
A catalyst D in which magnesium oxide and platinum were supported on proton type MFI type zeolite A was obtained in the same manner as in Example 1, except that the amount of magnesium oxide supported was 2% by mass. Table 2 shows the Pt analysis results and acid property analysis results of catalyst D.

A quartz reaction tube with an inner diameter of 9 mm was filled with a predetermined amount of catalyst D to achieve W/F as described below, and pretreatment for hydrogen reduction was performed at 450° C. for 1 hour under hydrogen flow. As a model raw material for long-chain linear paraffin, n-dodecane was supplied to the reaction tube at a rate of 1.6 mL/h, and hydrogen and accompanying gas nitrogen were supplied at a total rate of 43 mL/min. The partial pressure of n-dodecane supplied to the reaction tube was 7 kPa, and the partial pressure of hydrogen was 63 kPa (ie, hydrogen/raw material = 9). The reaction temperature was 250° C., and the W/F was 0.27 [(g-catalyst)/(g-raw material (n-dodecane)/h)]. The outlet of the reactor was cooled, the liquid component was sampled, and the gas component was collected in its entirety using a gas bag. Liquid and gas components were analyzed by gas chromatography.
Table 2 shows the conversion rate and the yield of each component.

[Comparative example 1]
Zeolite A described above was impregnated with a chloroplatinic acid solution prepared by dissolving chloroplatinic acid in distilled water using a pore filling method. The impregnated body was dried under reduced pressure, further dried at normal pressure at 110°C for 3 hours, and then calcined at 550°C for 3 hours in an air atmosphere to obtain catalyst C in which platinum was supported on proton type MFI type zeolite A. Ta. Table 2 shows the Pt analysis results and acid property analysis results of catalyst C.

A quartz reaction tube with an inner diameter of 1/2 inch was filled with a predetermined amount of catalyst C to achieve W/F as described below, and pretreatment for hydrogen reduction was performed at 450° C. for 1 hour under hydrogen flow. As a model raw material for long-chain linear paraffin, n-dodecane was supplied to the reaction tube at a rate of 1.6 mL/h, and hydrogen and accompanying gas nitrogen were supplied at a total rate of 43 mL/min. The partial pressure of n-dodecane supplied to the reaction tube was 7 kPa, and the partial pressure of hydrogen was 63 kPa (ie, hydrogen/raw material = 9). The reaction temperature was 200° C., and the W/F was 0.8 [(g-catalyst)/(g-raw material (n-dodecane)/h)]. The outlet of the reactor was cooled, the liquid component was sampled, and the gas component was collected in its entirety using a gas bag. Liquid and gas components were analyzed by gas chromatography.
Table 2 shows the conversion rate and the yield of each component.

[Comparative example 2]
The hydroisomerization reaction of n-dodecane was carried out in the same manner as in Comparative Example 1 except that the reaction temperature was 225°C. The results are shown in Table 2.

[Comparative example 3]
The hydroisomerization reaction of n-dodecane was carried out in the same manner as in Comparative Example 1, except that the loading amount of catalyst C was changed so that W/F = 0.2 and the reaction temperature was 250°C. The results are shown in Table 2.

[Example 8]
The above MFI type zeolite A was impregnated with a chloroplatinic acid solution prepared by dissolving chloroplatinic acid in distilled water using a pore filling method. The impregnated body was dried under reduced pressure, further dried at normal pressure at 110°C for 3 hours, and then calcined at 550°C for 12 hours in an air atmosphere to obtain Pt/MFI type zeolite A. In addition, the ammonium type MFI type zeolite A was converted into the proton type MFI type zeolite A by the above-mentioned calcination.
A magnesium nitrate solution prepared by dissolving magnesium nitrate hexahydrate in distilled water was impregnated into the above-mentioned Pt/MFI type zeolite A by a pore filling method. The impregnated body was dried under reduced pressure, further dried at normal pressure at 110°C for 3 hours, and then calcined at 550°C for 12 hours in an air atmosphere to produce a catalyst in which magnesium oxide and platinum were supported on proton type MFI type zeolite A. I got an E. The acid property analysis results of catalyst E are shown in Table 2.

A quartz reaction tube with an inner diameter of 9 mm was filled with a predetermined amount of catalyst E to achieve W/F as described below, and pretreatment for hydrogen reduction was performed at 450° C. for 1 hour under hydrogen flow. As a model raw material for long-chain linear paraffin, n-dodecane was supplied to the reaction tube at a rate of 1.6 mL/h, and hydrogen and accompanying gas nitrogen were supplied at a total rate of 43 mL/min. The partial pressure of n-dodecane supplied to the reaction tube was 7 kPa, and the partial pressure of hydrogen was 63 kPa (ie, hydrogen/raw material = 9). The reaction temperature was 250° C., and the W/F was 0.6 [(g-catalyst)/(g-raw material (n-dodecane)/h)]. The outlet of the reactor was cooled, the liquid component was sampled, and the gas component was collected in its entirety using a gas bag. Liquid and gas components were analyzed by gas chromatography.

[Example 9]
A magnesium nitrate solution prepared by dissolving magnesium nitrate hexahydrate in distilled water was impregnated into the above MFI type zeolite A by a pore filling method. The impregnated body was dried under reduced pressure, further dried at normal pressure at 110°C for 3 hours, and then calcined at 550°C for 12 hours in an air atmosphere to obtain Mg/MFI type zeolite A. In addition, the ammonium type MFI type zeolite A was converted into the proton type MFI type zeolite A by the above-mentioned calcination.
A chloroplatinic acid solution prepared by dissolving chloroplatinic acid in distilled water was impregnated into the above-mentioned Mg/MFI type zeolite A by a pore filling method. The impregnated body was dried under reduced pressure, further dried at normal pressure at 110°C for 3 hours, and then calcined at 550°C for 12 hours in an air atmosphere to produce a catalyst in which magnesium oxide and platinum were supported on proton type MFI type zeolite A. I got an F. Table 2 shows the acid property analysis results of catalyst F.

A quartz reaction tube with an inner diameter of 9 mm was filled with a predetermined amount of catalyst F to achieve W/F as described below, and pretreatment for hydrogen reduction was performed at 450° C. for 1 hour under hydrogen flow. As a model raw material for long-chain linear paraffin, n-dodecane was supplied to the reaction tube at a rate of 1.6 mL/h, and hydrogen and accompanying gas nitrogen were supplied at a total rate of 43 mL/min. The partial pressure of n-dodecane supplied to the reaction tube was 7 kPa, and the partial pressure of hydrogen was 63 kPa (ie, hydrogen/raw material = 9). The reaction temperature was 250° C., and the W/F was 0.6 [(g-catalyst)/(g-raw material (n-dodecane)/h)]. The outlet of the reactor was cooled, the liquid component was sampled, and the gas component was collected in its entirety using a gas bag. Liquid and gas components were analyzed by gas chromatography.

[Example 10]
A catalyst G in which magnesium oxide and platinum were supported on proton type MFI type zeolite A was obtained in the same manner as in Example 8, except that the amount of magnesium oxide supported was 0.3% by mass. Hydroisomerization reaction of n-dodecane was carried out in the same manner as in Example 8. The results are shown in Table 2.

[Example 11]
A catalyst H in which magnesium oxide and platinum were supported on proton type MFI type zeolite A was obtained in the same manner as in Example 9, except that the amount of magnesium oxide supported was 0.3% by mass, and the obtained catalyst H was Hydroisomerization reaction of n-dodecane was carried out in the same manner as in Example 9. The results are shown in Table 2.

In Comparative Examples 1 to 3, which do not contain alkaline earth metals, the conversion rate improved as the reaction temperature increased, but the excessive hydrogenolysis reaction progressed accordingly, resulting in a lower yield of paraffins having 1 to 6 carbon atoms. The total yield of the target iso-C7, iso-C8, and iso-C9 reached a ceiling at the reaction temperature of 225°C. In particular, (iso-C7+iso-C8+iso-C9)/(C1 to C6) is extremely low at reaction temperatures of 225° C. or higher, indicating that the decomposition reaction is proceeding predominately.

In Examples 1 to 3 containing alkaline earth metals, the conversion rate improved as the reaction temperature increased, and the total yield of the target iso-C7, iso-C8, and iso-C9 also improved accordingly. , it was 19.8% at a reaction temperature of 250°C. Even when the reaction temperature becomes high, the decrease in (iso-C7+iso-C8+iso-C9)/(C1 to C6) is small, indicating that the decomposition reaction is suppressed.

The production of iso-C7, iso-C8, and iso-C9 was also confirmed in Examples 4 and 5 in which the reaction was carried out at a lower W/F. Moreover, compared to catalyst B produced using MFI type zeolite B of Example 6, catalyst A produced using MFI type zeolite A of Example 4, which has a smaller average particle diameter and a larger ratio of specific surface area to outer surface area. It was found that the conversion rate was higher and the total yield of iso-C7, iso-C8, and iso-C9 was higher. Furthermore, compared to Catalyst D of Example 7, in which 2% by mass of alkaline earth metals was supported on a catalyst basis, in terms of oxides, an example in which 1% by mass of alkaline earth metals was supported on catalyst basis, in terms of oxides. It was found that catalyst A of No. 4 had a higher conversion rate and a higher total yield of iso-C7, iso-C8, and iso-C9.

Comparing Example 8 and Example 9 in which the order of loading Pt and MgO was changed, the conversion rate was higher in Example 9 in which MgO and Pt were loaded in the order of iso-C7, iso-C8, and iso-C7. -C9 yield was low.

Comparing Examples 8 and 10, in which Pt and MgO were supported in that order, and the amount of MgO supported was changed, Example 10, in which MgO was 0.3% by mass, had a higher conversion rate, iso-C7, iso-C8, Both yields of iso-C9 were high.

Comparing Examples 9 and 11, in which MgO and Pt were supported in that order, and the amount of MgO supported was changed, the conversion rate was almost the same, but Example 11, in which MgO was 0.3% by mass, had a higher iso-C7 , iso-C8, and iso-C9 were extremely high.

By using the hydroisomerization catalyst of the present invention, it is expected that the production efficiency will be increased by increasing the reaction temperature under low W/F conditions.

The present invention provides a hydroisomerization catalyst capable of obtaining branched paraffins having a desired number of carbon atoms in high yield by hydroisomerizing long-chain linear paraffins, and a hydroisomerization catalyst for the long-chain paraffins. A method for producing a catalyst and a method for producing a branched paraffin using the hydroisomerization catalyst can be provided.

Claims (10)

MFI type zeolite supports 0.15 to 3% by mass of alkaline earth metals based on the catalyst, calculated as oxides, and 0.1 to 1% by mass of platinum or palladium, or both, based on the catalyst, calculated as metals. Hydroisomerization catalyst for long-chain linear paraffins. Ammonia temperature-programmed desorption method (NH ₃ - NH desorbed at 150-250°C measured by TPD method) ₃ The long-chain linear paraffin hydroisomerization catalyst according to claim 1, wherein the acid amount calculated from the amount is 0.01 to 0.07 mmol. The long-chain linear paraffin hydroisomerization catalyst according to claim 1 or 2 , wherein the MFI type zeolite has an average particle diameter of 2000 nm or less. The long-chain linear paraffin hydroisomerization catalyst according to any one of claims 1 to 3 , wherein the ratio of the external surface area to the specific surface area of the MFI type zeolite is 0.3 to 5%. The long-chain linear paraffin hydroisomerization catalyst according to any one of claims 1 to 4 , wherein the alkaline earth metal is supported in an amount of 0.3 to 3% by mass in terms of oxide based on the catalyst. MFI type zeolite contains alkaline earth metals based on the catalyst, 0.15 to 3% by mass in terms of oxides, and platinum and palladium, one or both of which are based on the catalyst, 0.1 to 1% by mass in terms of metals. The method for producing a long-chain linear paraffin hydroisomerization catalyst according to any one of claims 1 to 4 , wherein the catalyst is supported in such a manner that the long-chain straight paraffin hydroisomerization catalyst is supported. A catalyst precursor is obtained by supporting MFI type zeolite with an alkaline earth metal containing 0.15 to 3% by mass in terms of oxide based on the catalyst, and one or both of platinum and palladium is added to the catalyst precursor. The method for producing a long-chain linear paraffin hydroisomerization catalyst according to claim 6 , wherein the catalyst is supported so as to contain 0.1 to 1% by mass in terms of metal based on the catalyst. MFI type zeolite contains alkaline earth metals based on the catalyst, 0.3 to 3% by mass in terms of oxides, and platinum and palladium, one or both of which are based on the catalyst, 0.1 to 1% by mass in terms of metals. The method for producing a hydroisomerization catalyst for long-chain linear paraffins according to claim 5 , wherein the long-chain linear paraffin hydroisomerization catalyst is supported so as to be supported. A catalyst precursor is obtained by supporting an alkaline earth metal on MFI type zeolite so as to contain 0.3 to 3% by mass in terms of oxide based on the catalyst, and one or both of platinum and palladium is added to the catalyst precursor. The method for producing a hydroisomerization catalyst for long-chain linear paraffins according to claim 8 , wherein the catalyst is supported so as to contain 0.1 to 1% by mass in terms of metal based on the catalyst. In the presence of hydrogen, the long chain straight paraffin is brought into contact with the long chain straight paraffin hydroisomerization catalyst according to any one of claims 1 to 5 , so that the carbon A method for producing branched paraffin to obtain branched paraffin with a small number of branches.