JPH05212291A - Gasoline reforming catalyst - Google Patents

Abstract

PURPOSE:To provide a catalyst used when a reformed gasoline containing ethers and having good quality and high octane number is produced from a mixed raw material of a light gasoline and an alcohol. CONSTITUTION:At least one kind of metal belonging to the group VIII metals is added at a state of metal or a state of combined material of the metal to a cation exchange material in a ratio of 0.01-10% by weight calculated in terms of the metal and mixed physically without introducing the metal into the cation exchange material itself. When the raw material of the light gasoline and the alcohol are allowed to react by using this catalyst, the reformed gasoline having a high octane number and good quality can be obtained without lowering the production of the ethers compared to the case that a catalyst in which the metal is introduced into the cation exchange material itself is used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gasoline reforming catalyst, and in particular, it is used for producing a reformed gasoline containing ethers and having a good quality and a high octane number from a mixed raw material of light gasoline and alcohol. Related to the catalyst.

[0002]

2. Description of the Related Art Generally, MTBE synthesized from a mixed raw material of a tertiary olefin such as isobutene and isoamylene and methanol, respectively.
Ethers such as (methyl tertiary butyl ether) and TAME (tertiary amyl methyl ether)
Since it has a high octane number, has a small impact on the environment, and has no problems such as corrosiveness and phase separation like alcohol, it is already used as a gasoline base material for automobiles in Europe and America.

On the other hand, even in Japan, studies have been made to cope with the diversification of gasoline base materials in consideration of international trends, and at present, only MTBE is permitted to be used. It is expected that the range of mixing ratio will be expanded.

Against this background, light gasoline containing a large amount of tertiary olefins such as isobutene and isoamylene is not directly used by separating the tertiary olefins, but is directly reacted with alcohol to produce ether. It is considered to be preferable from the viewpoint of efficiency and economy to produce a reformed gasoline having a high octane number containing a group of compounds.

Furthermore, according to this method, a part of the tertiary olefin, which is contained in a light gasoline in a large amount and volatilizes into the atmosphere and causes photochemical smog, is partially converted into an ether, and its content is increased. It also has the merit that the impact on the environment can be further mitigated.

Therefore, US Pat. No. 3,482,952
The specification discloses a method for producing a reformed gasoline having a high octane number from a mixed raw material of light gasoline and methanol using a cation exchanger.

However, since light gasoline as a raw material contains many kinds of hydrocarbons, in the presence of a cation exchanger, besides the etherification reaction of the main reaction, polymerization reaction, isomerization reaction, etc. Side reactions are likely to proceed. In particular, diene compounds and acetylene compounds produce a small amount of non-volatile components (gum substance) and unstable components by a side reaction,
It becomes a factor that deteriorates the quality. It should be noted that the gum substance here is a causative substance that causes troubles to the spray nozzle of the engine, the intake valve, etc., and can be measured by the method specified in JISK2261. In addition, the amount of unstable components is JISK2
It can be estimated from the measured value (min) of the induction period method defined in 287.

Therefore, for the purpose of improving the quality of reformed gasoline containing ethers, which is produced from a mixed raw material of light gasoline and alcohol, a platinum group metal is introduced into the cation exchanger itself in the presence of hydrogen. Has been proposed (see DE-3,538,564).

However, in this case, since the introduced metal exists in the catalyst (cation exchanger) pores, it inhibits the movement of the protozoa to diffuse into the catalyst pores. As a result, the amount of ether produced is reduced, which affects the octane number of the reformed gasoline. Therefore, introducing the active metal into the cation exchanger itself is not always a preferable method.

In consideration of the above points, the present invention has a good quality octane number containing ethers from a mixed raw material of light gasoline and alcohol, which does not inhibit the diffusion of the raw material into the catalyst pores. It is an object of the present invention to provide a catalyst capable of obtaining high reformed gasoline.

[0011]

Means and Actions for Solving the Problems The present inventors have
As a result of repeated studies for achieving the above-mentioned object, it was found that a specific metal is not introduced into the cation exchanger itself, but a metal or a complex containing the metal is physically mixed with the cation exchanger. When a mixed raw material of light gasoline and alcohol was used as a catalyst and reacted in the presence of hydrogen, it was found that a good reformed gasoline of high octane number and quality can be obtained without lowering the ether production amount, and the present invention It came to completion.

That is, the present invention relates to Periodic Table VIII.
At least one metal selected from the group of group metals (hereinafter sometimes referred to as an active metal) or a complex containing the metal is physically mixed with a cation exchanger, and the active metal content is a cation exchanger. The gasoline reforming catalyst is characterized in that it is about 0.01 to 10% by weight, preferably about 0.01 to 5% by weight.

The catalyst of the present invention will be described in detail below. The cation exchanger constituting the catalyst of the present invention may be one that is used as a catalyst for ordinary ether synthesis,
For example, cross-linked polystyrene having a functional group such as a so-called strongly acidic cation exchange resin in which a sulfonic acid group is introduced into a styrene-divinyl copolymer, or an organic or zeolite having ether activity or an inorganic cation exchanger such as a complex oxide. And so on.

Proton-type cation exchangers are usually used, and cation exchangers ion-exchanged with other metal cations are not preferred because the ether activity is lowered in most cases.

The strongly acidic cation exchange resin, the substrate, for example sulfonic acid groups of the three-dimensional structure _- by the union of (-SO 3 ^{H +),} since the H ⁺ of the functional groups are replaced with other cations, ether It functions as an acid catalyst in the chemical reaction. Generally, a copolymer of styrene and divinylbenzene (D.V.B.) is often used as the three-dimensional substrate. V. B. The structure of the substrate, that is, the surface area, the porosity, the average pore diameter, etc., can be arbitrarily changed by changing the amount of the above or the polymerization method. A catalyst used for ether synthesis is, for example, a product name “Amberlyst” manufactured by Rohm & Haas, and has a BET surface area of 30.
-50 m < ² > / g and an average pore diameter of 100-500Å are used. The one in which H ⁺ of the functional group is exchanged with another cation is not preferable because the ability as an acid catalyst is deteriorated, and therefore it is usually used in the H form. The amount of ion-convertable H ⁺ , the so-called exchange capacity, is 1.5 meq / l to 2.5 m.
eq / l is used.

At least one active metal selected from Group VIII of the Periodic Table, particularly preferably palladium, which is used by physically mixing with a cation exchanger as described above, is a salt such as a metal or chloride (hereinafter , Called a metal salt).

In order to physically mix the active metal with the cation exchanger, fine particles or powder of a simple metal, an alloy (an alloy of Group VIII metals, the same applies hereinafter), and a metal salt are directly added to the cation exchanger. Or a complex in which an aqueous solution containing an active metal is added to a specific carrier by an appropriate conventional method such as an impregnation method or an ion exchange method, and the complex is cation exchanged. A method such as physically mixing with the body is adopted.

At this time, if the particle size of the fine particles or powder of the metal simple substance, alloy, or metal salt is too small, they enter into the pores of the cation exchanger to block the pores or mix with the reaction product. Then, inconvenience such as flowing out from the catalyst bed occurs, and on the contrary, if it is too large, the contact area with the raw material becomes too small and the effect of the active metal is not sufficiently exhibited,
About 1 to 1000 μm is preferable.

Further, as the above-mentioned carrier which is a constituent material of the composite, an inorganic porous carrier such as silica, alumina, magnesia, silica-alumina, silica-magnesia is preferable, but an anion exchange resin is preferable. It can be organic. The BET surface area and average pore size of the carrier are
Although not particularly limited, if the amount is too small, the amount of the active metal added becomes too small, and conversely if the amount is too large, the mechanical strength of the catalyst of the present invention becomes too low, so the BET surface area is about 5 to 200 m ² / g. , The average pore size is about 50 to 10
00Å is preferable.

If the content of the active metal in the cation exchanger is too small, the mixing effect does not appear, and if it is too large, the improvement of the mixing effect cannot be expected. % By weight, preferably about 0.05
It is used by mixing so as to be up to 5% by weight.

The above-mentioned catalyst of the present invention is, as described above,
When reforming gasoline, specifically, it is used when reacting light gasoline and alcohol in the presence of hydrogen to produce reformed gasoline containing ethers. At this time, if a metal salt is used as the active metal,
Prior to the reaction, it is preferable to reduce the metal salt to the active metal in the hydrogen atmosphere of the catalyst of the present invention.

The above light gasoline is a gasoline containing a tertiary olefin and having a boiling point of about -10 ° C to 120 ° C, and examples thereof include a light fraction of FCC gasoline obtained by catalytically cracking light oil. The concentration of the tertiary olefin is usually about 50% by weight or less. In addition, the above alcohol is
Primary and secondary alcohols, specifically methanol,
Ethanol, n-propanol, i-propanol, n
Lower alcohols having 4 or less carbon atoms such as -butanol, sec-butanol, and i-butanol.

The mixing ratio of the light gasoline and the alcohol is about 0.7 to 2, preferably about 0.9 to 1. in terms of the molar ratio of the tertiary olefin to the alcohol in the light gasoline (tertiary olefin / alcohol). 5 is suitable. Molar ratio is about 2
If the amount exceeds, that is, if the amount of alcohol is small, the amount of produced ether does not increase. On the contrary, if the molar ratio is less than about 0.7, that is, if the amount of alcohol is large, the amount of produced ether does not increase and it is not economical This is because.

The method of bringing a mixed raw material of light gasoline and alcohol into contact with the catalyst of the present invention and the method of recovering alcohol from the reaction product can be carried out by using known techniques as they are. Specifically, any of a continuous system, a batch system and a semi-batch system may be used, and any of a stirring tank, a fixed bed and a fluidized bed may be used.

The reaction conditions may be such that the raw material is at a pressure higher than the liquid phase and is in a hydrogen atmosphere.
It can be carried out by supplying hydrogen to the catalyst bed together with the raw material under a pressure of 30 kg / cm ² G. If hydrogen is not supplied, the quality of the reformed gasoline is deteriorated, which is not preferable. The reaction temperature is usually in the range of about 50 to 120 ° C., and the liquid hourly space velocity (LHSV) is about 0.2 to 20 hr.
⁻¹ , preferably about 0.5 to 10 Hr ⁻¹ is suitable.

The method for removing unreacted alcohol from the reaction product obtained in the present invention is carried out by, for example, distillation, extraction with water or ethylene glycol, or selective adsorption of alcohol with an adsorbent having a small pore size. be able to.

[0027]

【Example】

Example 1 Commercially available strong acid cation exchange resin catalyst 3 for ether synthesis
0.0 g, a complex 6.0 g in which 0.5 wt% of palladium is supported on a carrier containing SiO ₂ as a main component, 1875 g of light gasoline having a boiling range of 35 to 90 ° C. excluding isobutene shown in Table 1, and methanol 180g together with 5
Charged in a liter autoclave, reaction temperature 80 ℃,
The reaction was carried out at a reaction pressure of 10 kg / cm ² (pressurized with hydrogen) for 2 hours. The molar ratio of methanol to the tertiary olefin in the light gasoline at this time was 1.0.
Ether production in the reformed gasoline after removal of unreacted methanol from the reaction product, gum production, induction period,
And the research method octane number (RO
N) and the octane number (MON) by the motor method are shown in Table 1.

Further, the strongly acidic cation exchange resin catalyst was separated from the mixed catalyst after the reaction, the cation exchange resin catalyst was treated with potassium pyrosulfate, and then subjected to ICP analysis [Induc.
As a result of analysis of the metal by means of a tube coupled plasma (inductively coupled plasma emission spectrometry), no precipitation of palladium was observed.

Comparative Example 1 The reaction was carried out under the same conditions as in Example 1 except that 30 g of the same strongly acidic cation exchange resin catalyst for ether synthesis as in Example 1 was loaded with 0.1% by weight of palladium. Table 1 shows the amount of ether produced in the reformed gasoline after removing unreacted methanol from the reaction product, the amount of gum, the induction period, and the RON and MON of the reformed gasoline.

After the reaction, the catalyst was treated with potassium pyrosulfate in the same manner as in Example 1 and then subjected to ICP analysis. As a result, palladium was found to be 0.
It was confirmed that 1% by weight was deposited.

Comparative Example 2 The reaction was carried out under the same conditions as in Example 1 except that 30 g of the same strongly acidic cation exchange resin catalyst for ether synthesis as in Example 1 was used alone, and unreacted methanol was removed from the reaction product. The amount of ether produced in the reformed gasoline after removal, the amount of gum substance, the induction period, and the RON of the reformed gasoline,
The MON is shown in Table 1.

[0032]

[Table 1]

As is clear from Table 1, in comparison with the case of using the strongly acidic cation exchange resin catalyst supporting palladium of Comparative Example 1, the complex supporting palladium of Example 1 was mixed (palladium was added). It can be seen that the amount of ether produced is larger and the quality is sufficiently improved when the strongly acidic cation exchange resin catalyst that is physically mixed) is used.

Example 2 187 of light gasoline containing 10% by weight of isobutene
The reaction was performed in exactly the same manner as in Example 1 except that 5 g was used, and the results are shown in Table 2.

Comparative Examples 3 and 4 The reaction was carried out in the same manner as Comparative Example 1 and Comparative Example 2 except that light gasoline containing 10% by weight of isobutene was used, and the results are shown in Table 2.

[0036]

[Table 2]

As is clear from Table 2, even when a raw material containing isobutene is used, the use of the catalyst of the present invention produces a larger amount of ether and improves the quality.

Examples 3 to 6 and Comparative Example 5 The same complex as in Example 1 was physically mixed with 30 g of the same strong acid cation exchange resin catalyst for ether synthesis as in Example 1 at various ratios. Reacted in the same manner as in Example 1, and the results are shown in Table 3.

[0039]

[Table 3]

Example 7 Except that a composite having 0.5 wt% of platinum supported on the carrier containing SiO ₂ as a main component instead of palladium was used.
The reaction was carried out in the same manner as in Example 3, and the results are shown in Table 4.

Example 8 The reaction was carried out in the same manner as in Example 3 except that a composite having 1.5 wt% of nickel supported in place of palladium on the carrier containing SiO ₂ as a main component was used to carry out the reaction. Is shown in Table 4.

Example 9 The reaction was carried out in the same manner as in Example 3 except that a composite having 3.0 wt% of cobalt supported on the carrier having SiO ₂ as a main component was used instead of palladium. Is shown in Table 4.

Example 10 0.5% by weight of palladium on a carrier containing SiO ₂ as a main component
The reaction was performed in the same manner as in Example 3 except that the composite material carrying 1.0 wt% of platinum and 1.0 wt% of platinum was used, and the results are shown in Table 4.

[0044]

[Table 4]

Example 11 Commercially available strong acid cation exchange resin catalyst 30 for ether synthesis
g and commercially available palladium powder (particle size 10 to 100 μm)
Was reacted in exactly the same manner as in Example 1 except that 0.15 g of was used. As a result, the amount of ether produced was 8.8 (wt%) for C6 ether and 1.9 (wt%) for C7 ether, and the reformed gasoline had a gum quality of 3.0 (mg / mg).
100 ml) and the induction period was 700 (min).

Further, the strongly acidic cation exchange resin catalyst was separated from the mixed catalyst after the reaction, the cation exchange resin catalyst was treated with potassium pyrosulfate, and the metal was analyzed by ICP analysis. I was not able to admit.

[0047]

INDUSTRIAL APPLICABILITY As described above, according to the catalyst of the present invention in which the cation exchanger is physically mixed with at least one metal of Group VIII metals of the Periodic Table or a complex containing the metal, Compared to the catalyst in which the above metal is introduced into the cation exchanger itself, it is necessary to increase the amount of ether produced in the reforming of gasoline, specifically in the production of reformed gasoline by the reaction of a mixed raw material of light gasoline and alcohol. You can That is, according to the catalyst of the present invention,
A reformed gasoline having a high octane number and good quality can be produced from light gasoline and alcohol without reducing the amount of ether produced.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukie Shiraishi 22-5 Hasemachi, Furukawa City, Ibaraki Prefecture

Claims (1)

[Claims] 1. A cation exchanger containing at least one metal selected from Group VIII metals or a complex containing the metal is 0.01 to 10% by weight based on the cation exchanger. A gasoline reforming catalyst characterized by being physically mixed.