JP2000210567A - Catalyst for reforming gasoline and usage thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a zeolite catalyst in which zeolite coexists with zinc oxide and zinc aluminate which stably reforms gasoline containing an olefinic sulfur through eliminating causes for the deterioration and the like of the catalyst such as caulking by using the catalyst treated by steam prior to the use in chemical reaction. SOLUTION: This catalyst for reforming gasoline is a zeolite catalyst used in the process to stably reform gasoline containing an olefinic sulfur. At the point of time before the use of the catalyst, 0.5-20 wt.% zinc oxide is allowed to coexist with 3-50 wt.% zinc aluminate. In addition, the gasoline containing an olefinic sulfur is supplied to a catalytic bed filled with the steam-treated zeolite catalyst under conditions such as 350-550 deg.C reaction temperature, 2-10 hr1 weight time space velocity(WHSV) and 0-50 kg/cm2.G pressure. In this case, the mol ratio of SiO2/Al2O3 of the zeolite is preferably 20 or more as the mol ratio of SiO2/Al2O3 of the zeolite skeleton before steam treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst used for gasoline reforming and a method for using the same, and more particularly, to reforming gasoline containing olefins and sulfur without lowering octane number without lowering octane number. The present invention relates to a catalyst and a method for reducing the same. Furthermore, the present invention
The present invention relates to a catalyst for stably reforming olefinic sulfur-containing gasoline for a long period of time, that is, little temporary deterioration due to coking, and little permanent deterioration due to repetition of reaction and regeneration, and a method thereof.

[0002]

2. Description of the Related Art Gasoline is produced by mixing various gasoline base materials so that the product properties are within specified values and the gasoline performance is good. In recent years, a catalytic cracking apparatus (Catalyt) has been used.
The composition ratio of cracked gasoline has greatly increased due to the enhancement of irally cracked gasoline. This catalytic cracking gasoline is made from a relatively heavy fraction such as vacuum gas oil generated from a vacuum distillation unit or distillation residue generated from an atmospheric distillation unit, and selected using a solid acid catalyst such as alumina or zeolite. Octane number is about 85 to 95, but the olefin content is about 20 to 50, and the sulfur content varies depending on the boiling range of the produced gasoline.
It is relatively large at ~ several thousand wtppm.

For catalytic cracking, a moving bed type TCC (Ther
mofor Catalytic Cracking),
Fluid bed type FCC (Fluid Catalytic)
Cracking). Among the FCC processes, those mainly processing residual oil are RFCC (Residu).
e FCC). In addition to these catalytic cracking gasolines, pyrolysis gasolines such as visbreaking and caulking processes exist as gasoline base materials having a large amount of olefin components.

In recent years, the quality of automobile gasoline has been strictly regulated in Japan, the United States and EU countries in order to reduce emissions (exhaust gas and vaporized gas) emitted from automobiles. In the United States, CARB (California) is particularly important in California, where urban air pollution is severe.
Nia Air Resources Board) is required to use gasoline with fuel quality standards, benzene 1.0 vol% or less, sulfur content 40 wtpp
m and olefin 6.0 vol% or less are standard values. Benzene is known to be carcinogenic, and sulfur and olefins have a large effect on exhaust gas (NOx, SOx). Olefins also have a significant effect on gasoline stability.

In Europe, CE established in 1993
N standard (European Committee fo
rStandardization) with benzene 5.
Although it is 0 vol% or less and sulfur content is 500 wtppm or less, benzene is 2.0 vol% or less and sulfur content is 200 wtppm in the Commission Commission Proposal after 2000 (Commission Proposal).
Below, 18.0 vol% or less of olefin was presented.
The EU Parliament's amendment is even more rigorous, with benzene below 1.0 vol%, sulfur below 30 wtppm, olefins below 10.0 vol% in 2000, benzene below 1.0 vol%, sulfur below 30 wtppm in 2005,
Up to 10.0 vol% of olefins has been proposed.

In Japan, the sulfur content was reduced to 100 by the end of 1998.
It is required that the content of benzene be not more than 1.0 ppm by weight and the content of benzene be not more than 1.0 ppm by weight. In order to produce gasoline that meets such a gasoline standard value, that is, gasoline with little effect on the environment, it is strongly desired to reduce the olefin component, sulfur content, and benzene concentration in gasoline.

For example, in the case of catalytic cracking gasoline, there is a method in which the sulfur content is hydrogenated before charging the raw material into the catalytic cracking device, and the reaction rigor of the catalytic cracking device is increased to lower the olefin concentration. Is not realistic because the cost of installing a feedstock hydrogenation apparatus is high and H2 is large. Further, there is a method of hydrodesulfurizing catalytic cracking gasoline, but in this case, the octane number decreases because the olefin concentration decreases.

[0008] Therefore, there has been proposed a method of removing sulfur while retaining an olefin component having a relatively high octane number. U.S. Pat. No. 3,957,625 takes advantage of the fact that sulfur impurities are concentrated in heavy fractions of gasoline to maintain the octane number contribution from olefins mainly contained in lighter fractions. Also, the present invention provides a method for removing sulfur by hydrodesulfurizing a heavy fraction of catalytic cracked gasoline.

US Pat. No. 4,049,542 discloses a process using a copper catalyst for desulfurization of olefinic hydrocarbon feedstocks, such as lightly cracked light naphtha. This catalyst promotes desulfurization while retaining the olefin,
It is said to promote the contribution of olefins to the octane number of the product. However, these methods do not conform to the gasoline standard values described above because the purpose is to maintain the olefin as an octane base material.

On the other hand, several methods have been disclosed for reducing the olefin concentration and the sulfur concentration without lowering the octane number by using a zeolite catalyst. Tokio Hei 9-5038
No. 14 discloses that an olefinic cracking feed fraction is brought into contact with a hydrodesulfurization catalyst to produce an intermediate product having a lower sulfur content than the feed, and then the olefin is reduced by the hydrogenation, resulting in an octane number. Gasoline boiling range portion of the intermediate product,
Zeolite beta combined with molybdenum hydrogenation component
A method for obtaining gasoline having a high octane number by contact with an acidic catalyst containing Tokiohei 10-5
No. 05127 and US Pat. No. 5,500,108,
JP-A-9-503814 discloses the same method as that of JP-A-9-503814 except that zeolite having an intermediate pore size is used as the zeolite.

Also, US Pat. No. 5,041,208 discloses that the initial boiling point is at least 180F and at least 5 ° C.
An olefinic catalytic cracking gasoline containing sulfur of 0 ppm or more is converted to a LHSV with a pressure of 1435 psig or less in a temperature range of 750 to 1200 F using a large pore zeolite having a silica / alumina ratio of 50 or more containing a noble metal such as platinum. A method is disclosed in which the reaction is carried out under a reaction condition of 0.1 to 20 to lower the sulfur content and the olefin concentration without lowering the octane number. Similarly, JP-A-6
No. 3-159494 discloses a method for simultaneously reducing the sulfur content and increasing the octane number of an olefin-containing feedstock, comprising converting the olefin-containing crude oil into a crystalline zeolite containing a noble metal such as platinum and having a silica / alumina ratio of 50 or more. A method of contacting is disclosed.

[0012] Processes for producing gasoline streams with reduced benzene and olefin content are also known. Tokiohei 8
The -507564 discloses, by flowing contact of C ₅ ⁺ FCC gasoline feed stream comprising benzene and C ₅ ⁺ olefins in shape selective aluminosilicate catalyst, the hydrocarbon stream comprising C ₅ ⁺ olefins A method for reducing the benzene content and the olefin content by using alkylation is disclosed. In this way, at the same time during the alkylation reaction, some of the olefins in the gasoline stream are added to hydrocarbons in the gasoline boiling range, reducing the sulfur content of the gasoline feed stream and increasing the octane number of the feed stream.

A method for desulfurizing zinc by loading it on a zeolite catalyst is also known. Japanese Patent Application Laid-Open No. Sho 61-263634 discloses that when removing trace amounts of sulfur compounds in a gas, a metal belonging to Group VIII of the periodic table (Fe, Co, Ni, Ru, Rh, Rh,
One or more of Pd, Os, Ir, Pt)
It shows a method for removing a trace amount of a sulfur compound, which comprises contacting a desulfurizing agent supported on an inorganic substance carrier containing 50% by weight or more of zinc oxide with the gas. In this case, the inorganic substance compound may be zeolite.

[0014]

However, none of the above methods considers a method for simultaneously avoiding temporary deterioration due to coking of the catalyst and permanent deterioration due to repeated reaction regeneration. For example, Japanese Patent Publication No. 9-503814
The publication discloses a method for reducing olefins and sulfur content without lowering the octane number by using zeolite β combined with a molybdenum hydrogenation component, but does not solve catalyst deterioration.

On the other hand, Examples of Japanese Patent Application Laid-Open No. 10-505127 and US Pat. No. 5,500,108 show that the reaction temperature is used as a parameter to reduce deterioration. That is, for one month, the temperature is set to 50 F /
They only need to increase at the speed of the moon. However, there is no information on the subsequent deterioration, and permanent deterioration due to repeated reaction / regeneration remains as an issue.

US Pat. No. 5,041,208 and JP-A-6
The method disclosed in Japanese Patent Application Laid-Open No. 3-159494 is a method of reforming gasoline using a large-pore zeolite having a silica / alumina ratio of 50 or more containing a noble metal such as platinum. Although described, this also does not address long-term permanent degradation. The method disclosed in JP-T-8-507564 is limited to a fluidized bed. The reason why the fluidized bed must be used is not specified, but it is considered that the fluidized bed is used because the catalyst is quickly deactivated or heat is supplied smoothly.

JP-A-61-263634 discloses that desulfurization is carried out using a catalyst in which zinc is supported on zeolite.
It is reduced at a temperature of 20 ° C. or higher, and metallic zinc has a vapor pressure, so if the reaction temperature is 420 ° C. or higher, it will scatter outside the system. Zinc is supported for the purpose of improving the desulfurization performance and recovering the octane number that has been reduced due to the reduction of olefins.
Scattering out of the system means that the reaction results decrease with time. Further, if zinc scatters outside the system, it is not preferable in that it is deposited as scale on a downstream heat exchanger or the like.

An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a zinc-containing zeolite-based catalyst used in a method for stably reforming an olefinic sulfur-containing gasoline, wherein the catalyst is temporarily deteriorated by coking of the catalyst. And a method for stably reforming an olefinic sulfur-containing gasoline using the catalyst.

[0019]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that zinc oxide and zinc aluminate coexist in zeolite as a zeolite-based catalyst used in a method for reforming olefinic sulfur-containing gasoline. The present inventors have found that the use of a zeolite-based catalyst which has been subjected to a steam treatment before being subjected to the reaction can solve the above-mentioned problems at once, and completed the present invention.

That is, the present invention relates to a zeolite-based catalyst used in a method for stably reforming an olefinic sulfur-containing gasoline, wherein zinc oxide 0.5
To provide a steam-treated zeolite-based catalyst, characterized in that -20% by weight and 3-50% by weight of zinc aluminate coexist.

The present invention further relates to an olefinic sulfur-containing gas.
Soline reacts at a reaction temperature of 350 ° C to 550 ° C,
Speed (WHSV) 2-10hr^-1, Pressure 0-50Kg /
cm ^Two・ Under the condition of G, before using the catalyst, zinc oxide
0.5-20% by weight and zinc aluminate 3-50% by weight
Packed with coexisting and steam treated zeolite catalyst
Gasoline, which is supplied to
A reforming method is provided.

The olefinic sulfur-containing gasoline in the method of the present invention is a gasoline containing 10% by weight or more of an olefin and 30% by weight or more of a sulfur compound, that is, a gasoline mainly composed of a hydrocarbon having 4 to 11 carbon atoms and having a boiling point of 110 to 110. It is a petroleum product of about 200 ° C. The olefin content is preferably 15 to 80% by weight, more preferably 15 to 50% by weight.

If the olefin concentration is too high, heat generation is large, and the control of the reaction temperature becomes complicated, for example, the reactor is divided into multiple stages and intermediate cooling is required between the reactors, and the coke is deposited on the catalyst. Severely deteriorates due to coking. On the other hand, when the olefin concentration is low, the sulfur content can be reduced by hydrodesulfurization even in gasoline having a high sulfur compound concentration, and since the olefin concentration is originally low, the octane number due to hydrogenation of the olefin that occurs simultaneously with the hydrodesulfurization is obtained. There is no decrease. Therefore, the effect of the present invention is small for gasoline having a low olefin concentration.

The sulfur compound is 100 to 5000 watts as S
tppm, and more preferably 100 ppm.
１０００1000 wtppm. Sulfur compounds are thought to be reduced by desulfurization reaction at the acid sites of zeolite and adsorption to zinc oxide, but when the sulfur compound concentration in the raw material is high,
It is necessary to increase the activity of the zeolite catalyst in order to keep it within the gasoline specification value. If the activity of the zeolite-based catalyst is too high, deterioration due to coking is severe, and the catalyst activity is deactivated in a short period of time.

The nitrogen compound is 5 to 250 wtpp as N.
m, more preferably 5 to 100,
More preferably, it is 5 to 30 wtppm. Since the nitrogen compound is basic, if the concentration of N is high, it is adsorbed on the zeolite acid sites and reduces the zeolite activity.

The olefinic sulfur-containing gasoline in the method of the present invention includes catalytic cracking gasoline and pyrolysis gasoline. The catalytic cracking includes a moving bed type TCC process, a fluidized bed type FCC process, and the like. Among the FCC processes, a process mainly treating residual oil is called an RFCC process. More recently, MGs that improve the total yield of LPG and gasoline based on the FCC process
G (MaximumGas plus Gasolin)
e) Process and DCC (Deep Catalytic) that co-produces C3-C5 light olefins from heavy oil
A cracking process has also been developed and commercialized.

The catalytic cracking gasoline in the method of the present invention includes all of these. As the pyrolysis process, a visbreaking process (Visbreaking Pr)
ocess), a caulking process (Coking p
process) and the steam cracking process of Naphtha (Steam Cracking Process)
ss) and the like, and the visbreaker gasoline, coker gasoline, and pyrolysis gasoline obtained from those processes are also olefinic sulfur-containing gasolines.

The zeolite in the method of the present invention includes, for example, β-zeolite, Ω-zeolite, Y-zeolite, L-zeolite, erionite, offretite, mordenite, ferrierite, ZSM-5, ZSM-
8, ZSM-11, ZSM-12, ZSM-22, ZS
M-23, ZSM-35, ZSM-38, ZSM-4
8, MCM-22 and the like, ZSM-5, ZS
Preferred are crystalline aluminosilicates or metallosilicates of the ZSM-5 type, such as M-8 and ZSM-11. ZS
As for the M-5 zeolite, for example, U.S. Pat. No. 5,268,162 can be referred to.
Other zeolites are also known.

In the method of the present invention, zeolite SiO
_{The 2} / Al ₂ O ₃ molar ratio is preferably 20 or more, more preferably 25 to 500, as the SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite skeleton before steam treatment.
If the SiO ₂ / Al ₂ O ₃ molar ratio is less than 20, the carbonaceous material that accumulates on the catalyst when the olefinic sulfur-containing gasoline is passed through the catalyst may be burned and removed with the oxygen-containing inert gas. In addition, permanent activity degradation due to dealumination in a high temperature atmosphere in which water is present is accelerated.

The permanent activity deterioration due to dealumination is X
It is considered that the higher the relative value of the crystallinity by the line diffraction method is, the more the crystallinity is suppressed, but the relative value of the crystallinity is SiO ₂ / Al ₂
O ₃ is affected by the molar ratio, the SiO ₂ / Al ₂ O ₃ molar ratio of 2
If it is smaller than 0, the relative value of the crystallinity becomes small, and permanent deterioration due to dealumination is fast, which is not preferable. When the SiO ₂ / Al ₂ O ₃ molar ratio is larger than 500,
In some cases, the catalyst does not have sufficient activity and does not have sufficient activity for reforming olefinic sulfur-containing gasoline.

The zeolite constituting the catalyst of the present invention, Si
The O ₂ / Al ₂ O ₃ molar ratio is a hydrothermally synthesized zeolite that does not contain alumina or silica as a binder, and is determined by measuring the zeolite with a fluorescent X-ray apparatus before performing steam treatment. Molar ratio. Further, it refers to a SiO ₂ / Al ₂ O ₃ molar ratio of fresh zeolite not subjected to a dealumination treatment such as an acid treatment or a reaction for reforming an olefinic sulfur-containing gasoline.

In the method of the present invention, 0.5 to 20% by weight of zinc oxide and 3 to 5% of zinc aluminate are used before the catalyst is used.
It is necessary that 50% by weight coexist. Zinc oxide is reduced in a reducing atmosphere to form metallic zinc, and metallic zinc is reduced to 42%.
It melts and scatters because it has a vapor pressure around 0 ° C. On the other hand, since zinc aluminate has a spinel structure, the scattering of zinc from the zeolite-based catalyst is suppressed, but the original purpose of supporting zinc is to reduce sulfur and olefins, and to recover the octane number lowered by reducing olefins. Therefore, the effect of improving the aromatic selectivity is reduced, and therefore, it is necessary to coexist zinc oxide exhibiting the above-described effect.

Although the effect of improving the aromatic selectivity and the effect of reducing sulfur and olefin of zinc aluminate itself are small, it serves as a supply source of zinc oxide and suppresses the reduction of zinc oxide. As a result, the effect of reducing sulfur and olefin is reduced. The effect of recovering the octane number, which has been reduced by the reduction of olefins, can be maintained for a long time. Furthermore, the presence of zinc aluminate also has the effect of suppressing the scattering speed of zinc oxide due to reduction. Therefore, the coexistence of zinc aluminate with zinc oxide in the catalyst is effective for maintaining the above-mentioned improvement effect.

In the method of the present invention, the preferred amounts of zinc oxide and zinc aluminate are 0.5 to 20% by weight of zinc oxide and 3 to 3% by weight of zinc aluminate before use of the catalyst.
50% by weight, more preferably 1.0 to 0.5% by weight of zinc oxide.
5.0% by weight, zinc aluminate is 14 to 40% by weight.

The melting and scattering of zinc oxide does not occur in a reaction of several days or several tens of days. Therefore, even when only zinc oxide is supported and zinc aluminate does not coexist, it can be used in several days or several tens of days. The above improvement effect can be maintained. However, due to repeated reactions and reaction regeneration for several months and years,
When exposed to the reducing atmosphere for a long time, the reduced zinc oxide is gradually scattered. Therefore, when zinc aluminate does not coexist, the concentration of zinc oxide in the catalyst decreases, and as a result, the effects of improving aromatic selectivity, reducing sulfur, and reducing olefins decrease. In the present invention, by causing zinc oxide contributing to the reforming of olefinic sulfur-containing gasoline and zinc aluminate, which is a source of the zinc oxide, to coexist, performance degradation due to repeated reaction regeneration for several months and several years Can be suppressed.

The term "before use of the catalyst" in the present invention means a point in time before the reaction in which the olefinic sulfur-containing gasoline is supplied to the zeolite catalyst, and the reaction and regeneration are repeated in a cycle of several days or tens of days. If so, it refers to the point in the first cycle before the reaction.

The zinc oxide referred to in the present invention is one measured by the following analytical method. That is, 1 g of the catalyst is ground in a mortar to about several hundred microns, dried at 120 ° C. for 1 hour, accurately weighed out about 0.5 g, and put into a 200 cc beaker. 150 cc of a 3% hydrochloric acid aqueous solution is added thereto, and the mixture is heated at 80 ° C. for 2 hours on an electric heater. Thereafter, the mixture was filtered through a 0.2 μm membrane filter, and the filtrate was subjected to atomic absorption spectrometry (Shimadzu atomic absorption / flame spectrophotometer AA-
640-12) and flame analysis, and quantitative analysis of zinc oxide by the standard addition method. The zinc compound quantified here includes not only ZnO but also zinc present at zeolite cation sites.

Although the state of zinc at the cation site is not clear, it is estimated that zinc exists in the form of Zn ²⁺ or Zn (OH) ⁺ . In any case, the zinc oxide in the present invention is not limited to ZnO, but includes all zinc compounds analyzed and measured by the above method.

The weight of zinc aluminate in the present invention is obtained by subtracting the weight of zinc oxide quantitatively analyzed by the above method from the total weight of zinc. The term “total zinc weight” as used herein refers to the value obtained from a calibration curve of a standard substance using a fluorescent X-ray analyzer (Rigaku RIX1000).

The catalyst in the method of the present invention is used before the catalyst is used.
Must have been steamed at the time of. The present invention
Steam treatment at 0.3 to 0.9 atm steam
At a partial pressure, 500-700 ° C, preferably 600-700
° C, atmospheric pressure-10 kg / cm ^TwoUnder a pressure of G, preferably
Atmospheric pressure to 5 kg / cm^Two0.5 to 30 hours in G, preferred
For 0.5 to 20 hours. The method of the present invention
Steam treatment is described in WO95-09050 and US
Performed by the method described in US Pat. No. 5,789,331.
It is desirable to be done.

By performing the steam treatment, it is possible to suppress deterioration due to coking when treating the olefinic sulfur-containing gasoline. The coking deterioration in zeolite is caused by the formation of coke at acid points in the pores of the zeolite, which hinders the diffusion of reactants and products, and the case in which coke is generated at the acid points on the surface, preventing the reactants from entering the catalyst pores. There are cases. In the latter case, the pores are closed before the acid sites in the pores are used up, so that the activity may be deteriorated even though the absolute amount of coke is small.

This phenomenon is likely to occur when heavy hydrocarbons (hydrocarbons having 8 or more carbon atoms) are present in the raw material. By the steam treatment, unnecessary surface acid sites and acid sites having particularly high coke generation activity in pores can be reduced, and deterioration due to coking can be suppressed. Since gasoline contains hydrocarbons of C8 or more, it is necessary to perform steam treatment in the present invention.

When the zeolite-based catalyst uses alumina (Al ₂ O ₃ ) as a binder, ZnO and alumina (Al ₂ O ₃ ) react by steam treatment, and zinc aluminate (ZnAl ₂ O ₄₎ ). Therefore, it is possible to control the weight of zinc aluminate and the weight of zinc oxide by adjusting the weight of alumina and ZnO and the conditions of steam treatment.

The zeolite catalyst of the present invention preferably uses the above alumina or silica (SiO ₂ ) as a binder. As an alumina source of alumina, anhydrous alumina or hydrated alumina is used. In addition, for example, a raw material that produces anhydrous alumina or alumina hydrate by hydrolysis or thermal decomposition, oxidation, etc., such as an aluminum salt, is used. Can also be used.

In the present invention, it is also preferable to use an alumina sol as the alumina source. When an alumina sol is used as the alumina source, the zinc component reacts with the alumina to produce zinc aluminate without performing the steam treatment, so that zinc is further stabilized.

In the present invention, the zinc source of zinc oxide is, for example, zinc, zinc oxide, zinc hydroxide, or a salt such as zinc nitrate, zinc carbonate, zinc sulfate, zinc chloride, zinc acetate, zinc oxalate, or alkyl. An organic zinc compound such as zinc is exemplified.

(Method of Measuring Primary Reaction Rate Constant of n-Hexane Decomposition) The primary reaction rate constant of n-hexane decomposition of the catalyst in the present invention is defined by using the apparatus shown in FIG. From the bottom in the order of quartz wool 2, catalyst 3 substantially free of carbonaceous (coke), Raschig ring 4, and the temperature of catalyst 6 measured by thermometer 5 is 500 ° C.
The quartz reaction tube 1 is heated in an electric furnace 8 whose temperature can be adjusted by a thermocouple 7 for temperature adjustment so that the temperature becomes equal to that of n-hexane under the conditions of atmospheric pressure, weight hourly space velocity (WHSV) 4 hr ^-1. Is supplied from the raw material inlet 9 and the reaction product 0.75 to 1 hour after the supply of n-hexane is cooled by the condenser 10, and further cooled by the oil trap 11 with a dry ice / ethanol refrigerant. Oil trap 1
All the oil components separated in 2 and the gas components separated in the generated gas collecting bag 13 are collected.

Then, a FID-TCD gas chromatography (HP-589) manufactured by Hewlett-Packard Company was used.
0 Series II), and substitute the gas composition in the reaction product obtained by analyzing the oil composition by FID gas chromatography (GC-17A) manufactured by Shimadzu Corporation into the following formula. Means the first-order rate constant of decomposition of n-hexane based on zeolite on the average of the above-mentioned gas / oil sampling time of 0.25 hours.

[0049]

(Equation 1)

The above first-order reaction rate constant is representative of the activity of the catalyst, and the first-order reaction rate constant for the decomposition of the zeolite catalyst in n-hexane according to the present invention is 0 at the time of the reaction. .2 or more,
0.3 or more is more preferable. A catalyst having a first-order reaction rate constant of less than 0.2 for the n-hexane decomposition has a low activity and the olefin and sulfur components in the olefinic sulfur-containing gasoline are insufficiently reduced.

The reaction conditions for gasoline reforming in the method of the present invention are preferably such that the reaction temperature is 350 ° C. to 550 ° C., more preferably 400 ° C. to 530 ° C. When the temperature is lower than 350 ° C., the reduction of olefin and sulfur components in the olefinic sulfur-containing gasoline becomes insufficient. Increasing the temperature can reduce the amount of olefins and sulfur components, but the concentration of aromatic compounds (benzene, toluene, xylene, etc.) generated by cyclodehydrogenation of olefins increases accordingly. The gasoline specifications mentioned above have restrictions on benzene concentration, and furthermore, aromatic compounds (Aromat
ics) There are also specifications for the concentration, and if the temperature is too high, these specifications will be exceeded. Further, as the temperature rises, the liquid yield decreases and the yield of product gasoline decreases.

In the method of the present invention, the weight hourly space velocity
Degree (WHSV) is 0.5 to 10 hours ^-1Preferably
And more preferably 2 to 6 hours^-1It is. WHSV
Large, i.e., short contact time,
Insufficient reduction of olefins and sulfur components in gasoline
In addition, deterioration by caulking is fast. WHSV
If the contact time is too long,
Higher concentrations of aromatic compounds containing benzene and lower liquid yield
Less.

In the method of the present invention, the pressure is from 0 to 50.
Kg / cm ² · G, preferably 0 to 20 Kg / cm ² · G
It is desirable to be carried out under the following conditions. When the catalyst of the present invention is used, H ₂ is generated by cyclodehydrogenation of an olefin, so that a sufficient effect can be obtained without mixing and aerating H ₂ with the olefinic sulfur-containing gasoline at the inlet of the reactor. Therefore, in order it is possible to without modifying the olefinic sulfur-containing gasoline to the addition of H _2, to further promote the reduction of the olefinic sulfur reduction of sulfur-containing gasoline (desulfurization) and olefin, it is of course also possible to add and H ₂ with olefinic sulfur-containing gasoline at the inlet of the reactor.

In the method of the present invention, as described above, 1
5-80 wt% olefin, 100-50 as S content
00wtppm sulfur compound, 5-250w as N content
Reforming olefinic sulfur-containing gasoline containing tppm nitrogen compounds. At this time, the above reaction conditions are set so that the product gasoline has lower S content and N content than the raw olefinic sulfur-containing gasoline.

The olefin in the product gasoline is at least 10 wt.
%, More preferably 10% by weight or less as the absolute amount of olefin in the product gasoline.

In the process of the present invention, olefin reduction can be achieved by the cyclodehydrogenation of olefins to produce aromatics (benzene, toluene, xylene). Usually, olefins are reduced by producing paraffins by a hydrogenation reaction between olefins and H _2, but in this case, octane numbers are also reduced because paraffins have lower octane numbers than olefins. On the other hand, since the aromatic hydrocarbon has a high octane number, in the present invention, even if the olefin is reduced, the octane number becomes equal to or higher than that of the raw material olefinic sulfur-containing gasoline.

Benzene is formed by the above reaction, which is further reacted with olefin to be converted to alkylbenzene (toluene, xylene). Therefore, the benzene concentration in the product gasoline is substantially equal to or lower than that of the raw olefinic sulfur-containing gasoline.

In the method of the present invention, it is preferable to use an adiabatic reactor. The adiabatic reactor refers to a purely adiabatic reactor described in “Industrial Reactor” edited by Kenji Hashimoto (Baifukan, 1984), pp. 25-26, and includes a fixed-bed adiabatic reactor, a moving-bed adiabatic reactor, Fluidized bed adiabatic reactors are mentioned. In the present invention, a fixed-bed adiabatic reactor having a fixed catalyst bed is preferably used. A fixed-bed one-stage adiabatic reactor having only one catalyst layer is more preferable, but an intermediate heat exchange / multi-stage adiabatic type in which the catalyst layer is divided into several stages and a heat exchanger is provided between the stages to supply or remove heat. It may be a reactor.
Since carbonaceous matter accumulates on the catalyst during the reaction, a fixed-bed one-stage adiabatic reactor of a two-column or multi-column switchable type capable of burning and removing the carbonaceous matter while continuing the reaction is preferable.
Further, the reactor may be provided with a catalyst support such as a distributor or a ceramic ball for improving the dispersion of the reaction gas.

In the method of the present invention, the reaction temperature is 350
° C to 550 ° C, weight hourly space velocity (WHSV) 2 to 10
Under the conditions of hr ^-1 and a pressure of 0 to 50 kg / cm ² · G, VII
Olefinic sulfur-containing gasoline can be reformed on a catalyst bed packed with a desulfurization catalyst containing a Group I and / or VIB metal and the zeolite-based catalyst. The above reaction conditions are the same as described above.

In the method of the present invention, the group VIII and / or
Alternatively, a desulfurization catalyst containing a group VIB metal may be filled in the upper portion or the lower portion of the zeolite-based catalyst. Group VIII and / or VI in the method of the invention
Examples of the desulfurization catalyst containing a Group B metal include Co / Mo /
Al ₂ O ₃ catalyst and Ni / Mo / Al ₂ O ₃ based catalyst. By filling the upper or lower part of the zeolite-based catalyst, a higher sulfur reduction effect can be obtained.

[0061]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be specifically described below with reference to examples.

[0062]

EXAMPLE 1 60 parts of ammonium ion type ZSM-5 crystalline aluminosilicate (SiO ₂ / Al ₂ O ₃ molar ratio 70), 15 parts of γ-alumina and 25 parts of zinc nitrate were kneaded and extruded. Then, it was formed into a diameter of 1.6 mm and a length of 4 to 6 mm. Next, after drying at 120 ° C. for 4 hours, it was calcined at 500 ° C. for 3 hours to obtain a ZSM-5 zeolite shaped catalyst containing 10% by weight of zinc.

Next, 300 g of the catalyst was charged into a Hastelloy C reactor having an inner diameter of 1 inch, and a pressure of 1 kg / cm ² · G, in a steam-nitrogen mixed gas containing 40% by volume of steam.
Heat treatment was performed at 650 ° C. for 5 hours. The catalyst was taken out of the reactor, and an isothermal n-hexane conversion test of this zeolite molded catalyst was performed using the apparatus described in the text. Under the conditions of pressure and atmospheric pressure, temperature of 500 ° C., and weight hourly space velocity (WHSV) of 4 hr ⁻¹ , the decomposition reaction of n-hexane was carried out for 0.25 hours. It was 0.28 when calculated by the formula (1) (hereinafter referred to as the above formula).

Further, the catalyst was treated with fluorescent X-rays and hydrochloric acid according to the method described above, and atomic absorption analysis was performed. As a result, 2.9% by weight of zinc oxide and 22.4% by weight of zinc aluminate were calculated based on the weight of the catalyst. %Met. Repeat the above catalyst for 10
0 g, 1 inch inner diameter into a Hastelloy C reactor,
FCC light gasoline shown in Table 1 was heated at 425 ° C and W
24 hours under conditions of HSV 6 hr ^-1 and pressure 5 kg / cm ² · G
Oil passed for hours. Table 2 shows the results. In addition, the liquid yield in the following tables was calculated | required by the following formula.

[0065]

(Equation 2)

The liquid volume of C ₅ ⁺ as used herein means that the gas and oil separated by cooling the gas at the outlet of the reactor at 5 ° C. are respectively separated by FID-TCD gas chromatography (HP-HP) manufactured by Hewlett-Packard Company. 5890 Series II)
And the yield of components heavier than 5 carbon atoms in the reaction product obtained by analysis with FID gas chromatography (GC-17A) manufactured by Shimadzu Corporation. Benzene and aromatics in C ₅ ⁺ were obtained from Hewlett-Packard FID-
The gas composition was analyzed by TCD gas chromatography (HP-5890 series II) and the oil composition was analyzed by FID gas chromatography (GC-17A) manufactured by Shimadzu Corporation. It was determined as the concentration of benzene and aromatics in heavy components.

C ₅ ⁺ RON (research octane number) was measured by GC-15A gas chromatography manufactured by Shimadzu Corporation with a value of 50.
PONA determined by a FID detector PONA analyzer equipped with a capillary column having a thickness of 0.25 μm and a thickness of 0.25 μm.
Composition and API Technical Data Boo
From the octane number of each pure component described in k, it was calculated assuming that additivity was established as in the following equation.

[0068]

(Equation 3)

COMPARATIVE EXAMPLE 1 After kneading 80 parts of ammonium ion type ZSM-5 crystalline aluminosilicate (SiO ₂ / Al ₂ O ₃ molar ratio 70) and 20 parts of γ-alumina, extrusion molding was carried out and the diameter was 1.6 mm. , Formed into a length of 4 to 6 mm. Then 12
After drying at 0 ° C. for 4 hours, it was calcined at 500 ° C. for 3 hours to obtain a zinc-free ZSM-5 zeolite shaped catalyst.

Next, 300 g of this catalyst was charged into a Hastelloy C reactor having an inner diameter of 1 inch, and a pressure of 1 kg / cm ² · G, in a steam-nitrogen mixed gas containing 40% by volume of steam.
Heat treatment was performed at 650 ° C. for 1.5 hours. The catalyst was taken out of the reactor, and an isothermal n-hexane conversion test of this zeolite molded catalyst was performed using the apparatus described in the text. The decomposition reaction of n-hexane was carried out for 0.25 hours under the conditions of pressure and atmospheric pressure, temperature of 500 ° C., and weight hourly space velocity (WHSV) of 4 hr ^-1. Was found to be 0.30.

100 g of the above catalyst was again charged into a Hastelloy C reactor having an inner diameter of 1 inch, and FCC light gasoline shown in Table 1 was heated at a temperature of 425 ° C., a WHSV of 6 hr ⁻¹ and a pressure of 5 kg / cm ² · G for 24 hours. Oil passed for hours. Table 2 shows the results. Since it does not contain zinc, the sulfur reduction effect is small and the octane number is low.

Comparative Example 2 After kneading 80 parts of ammonium ion type ZSM-5 crystalline aluminosilicate (SiO ₂ / Al ₂ O ₃ molar ratio 70) and 20 parts of γ-alumina, extrusion molding was carried out to obtain a diameter of 1.6 mm. , Formed into a length of 4 to 6 mm. Then 12
After drying at 0 ° C. for 4 hours, it was calcined at 500 ° C. for 3 hours to obtain a zinc-free ZSM-5 zeolite shaped catalyst.

The above catalyst was subjected to an isothermal n-hexane conversion test of this zeolite shaped catalyst using the apparatus described in the text. The decomposition reaction of n-hexane was carried out for 0.25 hours under the conditions of pressure and atmospheric pressure, temperature of 500 ° C., and weight hourly space velocity (WHSV) of 4 hr ^-1. Was 1.8.

100 g of the above catalyst was again charged into a Hastelloy C reactor having an inner diameter of 1 inch, and FCC light gasoline shown in Table 1 was heated at a temperature of 425 ° C., a WHSV of 6 hr ⁻¹ and a pressure of 5 kg / cm ² · G for 24 hours. Oil passed for hours. Table 2 shows the results. Since steam treatment is not performed, the activity is too high, the liquid yield is low, and the coking deterioration is very fast.

Example 2 60 parts of ammonium ion type ZSM-5 crystalline aluminosilicate (SiO ₂ / Al ₂ O ₃ molar ratio 70), 15 parts of γ-alumina and 25 parts of zinc nitrate were kneaded, and extruded. , 1.6 mm in diameter and 4 to 6 mm in length. Next, after drying at 120 ° C. for 4 hours, it was calcined at 500 ° C. for 3 hours to obtain a ZSM-5 zeolite shaped catalyst containing 10% by weight of zinc.

Next, 300 g of this catalyst was charged into a Hastelloy C reactor having an inner diameter of 1 inch, and a pressure of 1 kg / cm ² · G in a steam-nitrogen mixed gas containing 40% by volume of steam.
Heat treatment was performed at 650 ° C. for 5 hours. The catalyst was taken out of the reactor, and an isothermal n-hexane conversion test of this zeolite molded catalyst was performed using the apparatus described in the text. The decomposition reaction of n-hexane was carried out for 0.25 hours under the conditions of pressure and atmospheric pressure, temperature of 500 ° C., and weight hourly space velocity (WHSV) of 4 hr ^-1. 0.28
Met.

Further, according to the method described above, the catalyst was treated with X-ray fluorescence and hydrochloric acid, and atomic absorption analysis was performed. As a result, 2.9% by weight of zinc oxide and 22.4% by weight of zinc aluminate were calculated based on the weight of the catalyst. %Met. Repeat the above catalyst for 10
0 g, 1 inch inner diameter into a Hastelloy C reactor,
The following steps a) and b) were repeated 150 times. Table 3 shows the results.

A) FCC light gasoline shown in Table 1 was heated at a temperature of 425 ° C., a WHSV of 6 hr ⁻¹ and a pressure of 5 kg / cm ^2.
-It passed for 24 hours under the condition of G. b) The above catalyst with coke was heated at a maximum temperature of 550 ° C. and a pressure of 5
Regeneration was performed for 20 hours under the conditions of Kg / cm ² · G and an oxygen concentration of 1 vol%. Since the regeneration was carried out, the activity of the zeolite was reduced due to the regeneration deterioration, but the weight of zinc oxide and zinc aluminate after 150 repetitions did not change at all.

Comparative Example 3 After kneading 80 parts of ammonium ion type ZSM-5 crystalline aluminosilicate (SiO ₂ / Al ₂ O ₃ molar ratio 70) and 20 parts of γ-alumina, extrusion molding was carried out to obtain a diameter of 1.6 mm. , Formed into a length of 4 to 6 mm. Then 12
After drying at 0 ° C. for 4 hours, it was calcined at 500 ° C. for 3 hours to obtain a zinc-free ZSM-5 zeolite shaped catalyst. The catalyst was impregnated with zinc nitrate so that the zinc concentration was 3% per catalyst.

Next, 300 g of this catalyst was charged into a Hastelloy C reactor having an inner diameter of 1 inch, and a pressure of 1 kg / cm ² · G, in a steam-nitrogen mixed gas containing 40% by volume of steam.
Heat treatment was performed at 650 ° C. for 5 hours. The catalyst was taken out of the reactor, and an isothermal n-hexane conversion test of this zeolite molded catalyst was performed using the apparatus described in the text. The decomposition reaction of n-hexane was carried out for 0.25 hours under the conditions of pressure and atmospheric pressure, temperature of 500 ° C., and weight hourly space velocity (WHSV) of 4 hr ^-1. 0.28
Met.

Further, according to the method described above, the catalyst was treated with fluorescent X-rays and hydrochloric acid, and atomic absorption analysis was performed. As a result, 2.9% by weight of zinc oxide and 2.5% by weight of zinc aluminate were calculated based on the weight of the catalyst. %Met. Repeat the above catalyst for 100
g, a 1-inch inner diameter reactor made of Hastelloy C, and the steps a) and b) described in Example 2 were repeated 150 times.
Table 3 shows the results. Since the amount of zinc oxide was the same as in Example 2, the initial performance was almost the same, but the amount of zinc oxide gradually decreased due to the low concentration of zinc aluminate.
The 50th gasoline reforming performance is low.

Comparative Example 4 Ammonium ion type ZSM-5 crystalline aluminosilicate (SiO ₂ / Al ₂ O ₃ molar ratio 70) and γ-alumina at a ratio of 8: 2, and an alkoxide method manufactured by Soekawa Riken Co., Ltd. After kneading the zinc aluminate so as to have a zinc concentration of 10%, extrusion molding was performed to form a diameter of 1.6 mm and a length of 4 to 6 mm. Then, after drying at 120 ° C. for 4 hours, baking at 500 ° C. for 3 hours, ZS containing 10% of zinc
An M-5 zeolite molded catalyst was obtained.

Next, 300 g of this catalyst was charged into a Hastelloy C reactor having an inner diameter of 1 inch, and a pressure of 1 kg / cm ² · G, in a steam-nitrogen mixed gas containing 40% by volume of steam.
Heat treatment was performed at 650 ° C. for 5 hours. The catalyst was taken out of the reactor, and an isothermal n-hexane conversion test of this zeolite molded catalyst was performed using the apparatus described in the text. The decomposition reaction of n-hexane was carried out for 0.25 hours under the conditions of pressure and atmospheric pressure, temperature of 500 ° C., and weight hourly space velocity (WHSV) of 4 hr ^-1. 0.28
Met.

Further, according to the method described above, the catalyst was treated with fluorescent X-rays and hydrochloric acid, and atomic absorption analysis was performed. As a result, it was found that zinc oxide was 0% by weight and zinc aluminate was 28.2% by weight based on the weight of the catalyst. there were. Repeat the above catalyst for 100
g, a 1-inch inner diameter reactor made of Hastelloy C, and the steps a) and b) described in Example 2 were repeated 150 times.
Table 3 shows the results. Since there is no zinc oxide, the zinc concentration is stable, but the reforming performance of gasoline is low even at the initial stage of repetition.

Example 3 The same catalyst as that described in Example 2 was prepared and subjected to steam treatment in the same manner as in Example 2. 100g of the above catalyst
It was filled in a Hastelloy C reactor with an inner diameter of 1 inch, H ₂
Was aerated at 550 ° C. for 50 hours at a linear velocity of 30 cm / sec. The zinc oxide concentration before and after H ₂ aeration was measured according to the method described above. Table 4 shows the results.

Comparative Example 5 The same catalyst as that described in Comparative Example 3 was prepared, and subjected to steam treatment in the same manner as in Comparative Example 3. 100g of the above catalyst
It was filled in a Hastelloy C reactor with an inner diameter of 1 inch, H ₂
Was aerated at 550 ° C. for 50 hours at a linear velocity of 30 cm / sec. The zinc oxide concentration before and after H ₂ aeration was measured according to the method described above. Table 4 shows the results. In the case of Comparative Example 5,
It can be seen that the scattering of zinc in a reducing atmosphere is large due to the small amount of zinc aluminate.

Example 4 A catalyst was prepared in the same manner as in Example 1, and steam treatment was performed in the same manner as in Example 1. 100 g of the above catalyst,
A 1 inch inner diameter Hastelloy C reactor was charged, and FCC heavy gasoline shown in Table 5 was heated at 460 ° C and WHSV.
Oil was passed for 24 hours under the conditions of 4 hr ^-1 and a pressure of 5 kg / cm ² · G. Table 7 shows the results.

Example 5 A catalyst was prepared in the same manner as in Example 1, and steam treatment was performed in the same manner as in Example 1. 100 g of the above catalyst,
A 1-inch inner diameter Hastelloy C reactor was charged, and FCC light gasoline shown in Table 6 was heated at 425 ° C and WHSV.
Oil was passed for 24 hours under the conditions of 6 hr ^-1 and a pressure of 5 kg / cm ² · G. Table 7 shows the results.

Example 6 A catalyst was prepared in the same manner as in Example 1, and steam treatment was performed in the same manner as in Example 1. i) Commercially available UOP S-12H (Co / Mo / Al
20 g of ₂ O ₃ ) and ii) 80 of the above zeolite-based catalyst.
g, i from above), was charged into 1 inch inside diameter of Hastelloy C-made reactor in the order of ii), the temperature 425 ° C. The FCC Heavy gasoline described in Table 5, WHSV6hr ^-1, pressure 5Kg /
Oil was passed for 24 hours under the condition of cm ² · G. Table 7 shows the results.

Comparative Example 6 Using the same catalyst as in Example 1, gasoline reforming was carried out under the same conditions as in Example 1 except that the oils shown in Table 1 were passed at a temperature of 300 ° C. Table 8 shows the results. Because of the low temperature,
Small reduction of olefins and sulfur compounds.

Comparative Example 7 Using the same catalyst as in Example 1, gasoline reforming was performed under the same conditions as in Example 1 except that the raw materials shown in Table 1 were passed at 580 ° C. Table 8 shows the results. Because of the high temperature,
Although olefins and sulfur compounds are reduced, the liquid yield is low and the concentration of aromatic compounds including benzene is high.

Comparative Example 8 Using the same catalyst as in Example 1, gasoline reforming was carried out under the same conditions as in Example 1 except that the raw materials shown in Table 1 were passed at a WHSV of 0.5 hr ^-1 . Table 8 shows the results. Owing to the long contact time, olefins and sulfur compounds are reduced, but the liquid yield is low and the concentration of aromatic compounds including benzene is high.

Comparative Example 9 Using the same catalyst as in Example 1, gasoline reforming was carried out under the same conditions as in Example 1 except that the raw materials shown in Table 1 were passed at a WHSV of 15 hr ^-1 . Table 8 shows the results. The reduction in olefin and sulfur compounds is small due to the short contact time.

[0094]

[Table 1]

[0095]

[Table 2]

[0096]

[Table 3]

[0097]

[Table 4]

[0098]

[Table 5]

[0099]

[Table 6]

[0100]

[Table 7]

[0101]

[Table 8]

[0102]

According to the method of the present invention as described above, in the reaction for reforming olefinic sulfur-containing gasoline, a temporary decrease in the activity due to carbonaceous material accumulated on the catalyst during the reaction is suppressed. In addition, it is possible to suppress the deterioration of permanent activity, which gradually occurs when the reaction and regeneration are repeated and used for a long period of time, that is, a catalyst excellent in coking resistance and permanent deterioration resistance can be obtained. Therefore, the method of the present invention can be widely used for gasoline reforming in the field of petroleum refining, in which olefinic sulfur-containing gasoline is reduced in olefin and sulfur content while maintaining the octane number.

[Brief description of the drawings]

FIG. 1 is a schematic view of an isothermal reactor in the method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Quartz reaction tube 2 Quartz wool 3 Catalyst 4 Raschig ring 5 Thermometer 6 Thermocouple for temperature control 7 Electric furnace 8 Material inlet 9 Condenser 10 Oil trap 11 Bag for repairing generated gas

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C10G 45/12 C10G 45/12 Z F term (Reference) 4G069 AA15 BA07A BB04A BB04B BB04C BB06A BB06B BB06C BC16A BC16B BC16C BC35A BC35B BC35C CC08 ZA11A ZA11B ZC04 ZD03 ZF01A ZF01B 4H029 CA00 DA00

Claims (17)

[Claims] 1. A zeolite catalyst used in a method for stably reforming an olefinic sulfur-containing gasoline, wherein 0.5 to 20% by weight of zinc oxide and 3 to 50% of zinc aluminate are used before the catalyst is used. A zeolite-based catalyst which has been subjected to steam treatment, wherein the zeolite-based catalyst is present in an amount of 10% by weight. 2. The zeolite of the zeolite-based catalyst has a SiO ₂ / Al ₂ O ₃ molar ratio of 20 before steam treatment.
The catalyst according to claim 1, wherein the catalyst has the above zeolite skeleton. 3. The zeolite of the zeolite catalyst is ZS.
The catalyst according to claim 1 or 2, wherein the catalyst is an M-5 type zeolite. 4. The catalyst according to claim 1, wherein the zeolite-based catalyst contains alumina, zinc and zeolite as a binder. 5. The steam treatment of the zeolite-based catalyst is performed by applying steam having a water pressure of 0.3 to 0.9 atm to 500 to 700 ° C.
^2. A steam treatment in which aeration is performed for 0.5 to 30 hours under a pressure of atmospheric pressure to 10 kg / cm ² G.
A catalyst according to any one of claims 1 to 4. 6. The catalyst before use has an activity of 500 ° C.
The catalyst according to any one of claims 1 to 5, wherein a value of an initial first-order rate constant of n-hexane decomposition measured at atmospheric pressure is 0.2 sec ^-1 or more. 7. An olefinic sulfur-containing gasoline reacts
Temperature 350 ° C to 550 ° C, weight hourly space velocity (WHS
V) 2 to 10 hours^-1, Pressure 0-50Kg / cm ^Two・ G
7. The method according to claim 1, which is used for a method of reforming under conditions.
A catalyst according to any of the preceding claims. 8. An olefinic sulfur-containing gasoline reacts
Temperature 350 ° C to 550 ° C, weight hourly space velocity (WHS
V) 2 to 10 hours^-1, Pressure 0-50Kg / cm ^Two・ G
Under the conditions, at the time before using the catalyst, 0.5 to 20 weight of zinc oxide was used.
% And zinc aluminate 3 to 50% by weight
To the catalyst bed filled with the zeolite-based catalyst
A gasoline reforming method characterized by being supplied. 9. The method according to claim 8, wherein the catalyst bed is a fixed bed. 10. The process according to claim 8, wherein the process for reforming olefinic sulfur-containing gasoline is carried out without adding H ₂ . 11. An olefinic sulfur-containing gasoline comprising:
5-80 wt% olefin, 100-50 as S content
00wtppm sulfur compound, 5-250w as N content
The method according to any one of claims 8 to 10, comprising tppm of a nitrogen compound. 12. The olefinic sulfur-containing gasoline has a lower S content and a lower N content than the olefinic sulfur-containing gasoline.
The process according to claim 11, characterized in that the product gasoline is reformed to a content gasoline. 13. The method according to claim 11, wherein the olefin in the product gasoline is reduced by at least 10 wt% as compared to the raw olefinic sulfur-containing gasoline. 14. The process according to claim 11, wherein the octane number of the product gasoline is equal to or higher than that of the raw olefinic sulfur-containing gasoline. 15. The benzene concentration in the product gasoline is:
The process according to claim 11, characterized in that it is equal to or less than the raw olefinic sulfur-containing gasoline. 16. An olefinic sulfur-containing gasoline comprising:
9. A gasoline selected from the group consisting of CC gasoline, TCC gasoline, RFCC gasoline and pyrolysis gasoline, wherein the gasoline is at least one gasoline.
16. The method according to any of 15 above. 17. An olefinic sulfur-containing gasoline reacts
Temperature 350 ° C to 550 ° C, weight hourly space velocity (WHS
V) 2 to 10 hours^-1, Pressure 0-50Kg / cm ^Two・ G
Under conditions, contains a Group VIII and / or VIB metal
And a catalyst according to any one of claims 1 to 6.
9. The catalyst is supplied to a packed catalyst bed.
The method for reforming gasoline according to 1.