JPS60181192A - Production of hydrocarbon from synthesis gas - Google Patents

Abstract

PURPOSE:To obtain hydrocarbon within gasoline boiling point range in high yield, by bringing a synthesis gas into contact with a suspension of a specific catalyst in a heavy aromatic hydrocarbon mixture. CONSTITUTION:A composite catalyst of a metal (oxide) having a catalytic activity of hydrogenating CO and crystalline zeolite is suspended in a liquid medium, obtained by hydrogenating and desulfurizing heavy cycle oil formed in a catalytic cracking process as a by-product, and consisting of a heavy aromatic hydrocarbon mixture. A mixed gas of a gaseous carbon oxide, e.g. CO and/or CO2, and H2 is brought into contact with the above-mentioned suspension to produce a hydrocarbon.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides high yields of hydrocarbons, particularly hydrocarbons in the gasoline boiling range, from synthesis gas, a mixture of hydrogen and gaseous carbon oxides, such as carbon oxides and/or carbon dioxide. Regarding how to get the rate. More specifically, when producing hydrocarbons by bringing a composite catalyst of a metal or/and metal oxide and crystalline zeolite having catalytic activity for hydrogenating carbon oxide into contact with synthesis gas, the reaction is carried out. The present invention relates to a method in which heavy cycle oil from a hydrorefined catalytic cracking process is used as a liquid medium in a suspended bed. Gasoline range hydrocarbons, including motor gasoline and other light gases, are produced industrially by distillation of crude oil or by known processes such as catalytic reforming of naphtha, catalytic cracking of heavy fractions, and hydrocracking. Manufactured in However, due to the need to cope with the future high price of crude oil and the scarcity of crude oil supply sources, so-called new fuel oil production technology is being developed to produce hydrocarbons in the gasoline boiling point range, for which demand is expected to grow particularly in the future, from carbon resources other than petroleum. Attempts are being made to develop Up until now, the field of energy development has been exploring technologies to convert carbon resources other than crude oil into hydrocarbons equivalent to petroleum. has been studied. However, these methods require extremely high pressure, have complicated processes, and are not economically effective because the quality of the resulting product is inferior to that of petroleum. On the other hand, it is already commercially possible to convert carbon sources such as coal and natural gas into gas mixtures consisting of hydrogen and gaseous carbon oxides such as carbon monoxide and/or carbon dioxide in the presence of air, oxygen or water vapor. Established. Furthermore, from the mixed gas, the reaction temperature is 150°C.
Under conditions of ~500℃ and reaction pressure of 1000atm or less■
It is also possible to produce hydrocarbons using catalysts mainly composed of group elements.

For example, the most widely studied Fischer-Tropsch process has already been used in South Africa as a process for producing light gas, gasoline and other hydrocarbon oils from syngas.
It has been adopted by SOL Corporation to produce various hydrocarbons from coal on a commercial scale. However, in the Fischer-Tropsch process, the product is mainly composed of linear paraffinic hydrocarbons, so the research process octane number of the gasoline fraction is as low as about 50, making it unsuitable as a fuel for current automobiles. Further, the product has a drawback that the carbon number of the hydrocarbons is widely distributed from 1 to 3 o, and the selectivity for hydrocarbons in the gasoline boiling point range is poor.

On the other hand, it is well known that synthesis gas can be converted into oxygen-containing organic compounds such as methanol using metals such as copper, zinc, and chromium or metal oxide catalysts. n O'
It is also known that hydrocarbons in the gasoline boiling range can be selectively converted by contacting at conditions below C15n atm. ZSM is the crystalline zeolite for this purpose.
-5 (4g Publication No. 4'6-10064, JP-A-52-
ZSM series high silica crystalline aluminosilicate, mordenite zeolite, etc.

Recently, an efficient method for producing gasoline boiling range hydrocarbons directly from synthesis gas has been identified. This method is
Producing hydrocarbons from synthesis gas in one step using a composite melt of a metal or metal oxide having an activity to hydrogenate carbon monoxide and crystalline zeolite, such as a Fischer-Tropsch catalyst or a methanol synthesis catalyst. It is something.

One of the specific methods is - fusion, in which crystalline zeolite is mechanically mixed with a metal oxide having the activity of hydrogenating carbon oxide, and the other is hydrogenation of carbon monoxide. This catalyst is prepared by supporting active gold, Akatsuki, on a composite of crystalline zeolite I and other metal oxides that have the activity of hydrogenating carbon oxide.

The method of producing hydrocarbons from synthesis gas in one step using the composite catalyst shown above is still in the development stage, and all of the reactions are carried out using a fixed bed reactor, but in developing the process, However, there are still problems that need to be solved, such as catalyst life, catalyst activity/selectivity, and control of the melting layer reaction temperature. In particular, the reaction heat of the reaction for producing hydrocarbons and alcohols from synthesis gas generates a large amount of heat, as shown in Table 1, and in these synthesis reactions, removal of such reaction heat is an important consideration when selecting a reactor. Let's talk about important issues.

Table 1 Heat of reaction per carbon △HKcalO)i,
' , , -50 C+H11-42 ' C!6H14-39 (!1IH4, -26 06112-34 0H30H-23,9 C2HBr OH29,5 The methanol synthesis reaction that has already been carried out industrially is carried out in a fixed bed. However, this is possible because the conversion rate of -carbon oxide is low and a large amount of gas is recycled to remove the reaction heat.However, as in the reaction of the present invention, a high b-carbon oxide conversion rate is required. Furthermore, when the reaction intermediate is methanol, the final hydrocarbon product is produced through a dehydration reaction, which is an even more exothermic reaction. The bed reactor is
It's difficult to tame.

Although not the reaction of the present invention, the Fischer M-Tropsch process, which is known as a similar reaction process, has a large exothermic reaction, so a gas phase fluidized bed reactor or suspended bed reactor is ideal for ease of heat removal. Various studies have been conducted on gas-phase fluidized beds, including South Africa and 5ASO.
Industrialization is being carried out at Company L. Here, what is a gas phase fluidized bed?
It refers to a reaction method in which a powder catalyst of 10 to 100 μm in diameter is brought into contact with a reaction gas fluid rising from below in a reactor at an elevated temperature and a pressure of iK to form a fluid state. Suspended bed reaction is a method in which a powdered catalyst of 100 μm or less is suspended and dispersed in a liquid medium made of high-boiling paraffinic hydrocarbon oil, and the slurry-formed catalyst is brought into contact with a reaction gas fluid in an upward flow to carry out a reaction. means.

Gas-phase fluidized beds are preferable for the removal of reaction heat, but the abrasion resistance of the catalysts is a problem due to repeated collisions between the catalysts in the violently fluidized state, and precipitated iron-based Fischer beds, which have weak strength, have problems.
It is said that the Tropsch catalyst is not applicable. On the other hand, suspended beds are easier to prepare than fluidized beds, which have weaker strength, because the catalyst particle size is preferably finer. Usually, Fisher
To carry out the Tropsch reaction in a suspended bed, precipitated iron oxide powder of 5 μm or less is dispersed in paraffinic mineral oil with a boiling point of 300° C. or higher and used as a slurry with a concentration of 5 to 50°C.

From the previous knowledge of the Fischer-Tropsch process, it is natural to try to solve the problem of reaction heat removal by performing the reaction for producing hydrocarbons from synthesis gas, which is handled in the present invention, in a gas-phase fluidized bed or suspended bed. In particular, when dealing with a catalyst system in which the main component of the catalyst is crystalline zeolite, which is made up of fine particles and has relatively low strength, it is highly analogous that the suspended bed is the most preferable reaction method. It would be natural.

The paraffin suspension used in the Fischer-Tropsch process has a similar composition to the high-boiling fraction of hydrocarbon oil produced from synthesis gas in the Fischer-Tropsch reaction, so it can be extracted as a slurry, separated and recovered, and recycled again. It is recyclable and does not undergo any decomposition or other conversion to light fractions under the reaction conditions, so there is no loss.

For this reason, paraffinic hydrocarbons are preferred liquid media in the Fischer-Tropsch reaction. However, since paraffinic hydrocarbons are easily decomposed in the presence of crystalline zeolite, the paraffinic hydrocarbons used in the Fischer-Tropsch process cannot be used as they are in the reaction carried out in the present invention. For this reason, no attempt has been made to perform a one-stage reaction to produce hydrocarbons from synthesis gas in a suspended bed using a Fischer-Tropsch synthesis catalyst or a composite catalyst of a methanol synthesis catalyst and crystalline zeolite.

However, as a result of extensive research, the present inventors discovered a specific liquid medium that enabled them to produce hydrocarbons from synthesis gas using a suspended bed method even in a system using crystalline zeolite as a catalyst component. The present invention has been completed based on the discovery that the method of the present invention can be carried out, and that the method of the present invention has favorable effects on extending the life of the catalyst and improving the yield of hydrocarbons in the gasoline boiling point range.

That is, the present invention brings hydrocarbons, especially hydrocarbons in the gasoline boiling point range, into high yield by contacting synthesis gas with a composite catalyst made of metals and/or metal oxides having an activity for hydrogenating carbon monoxide and crystalline zeolite. The method relates to a suspended bed reaction method in which the catalyst is dispersed in a specific liquid medium and used as a slurry, in which a heavy cycle oil fraction, which is a by-product from the catalytic cracking process of heavy gas oil, is used as the liquid medium. with a boiling point of 250'C or more and an aromatic content of 50 wt% obtained by hydrodesulfurization and preferably catalytic waxing treatment.
The present invention relates to a method for directly producing hydrocarbons from synthesis gas using a mixture of the above-mentioned heavy aromatic hydrocarbons (nanthene hydrocarbons having a residual alkyl group and rough-heavy hydrocarbons).

Since the liquid catalyst is a heavy aromatic mixture, in the synthesis gas conversion reaction, the liquid medium is not decomposed into light fractions, and the reaction in the present invention is still in the form of crystalline zeolite present as a catalyst component. Selectivity is exhibited, and virtually no hydrocarbons with boiling points above 200°C are produced from synthesis gas.For these two reasons, hydrocarbons produced from synthesis gas can be easily separated from the liquid medium due to the difference in boiling point. can.

Furthermore, there is no need to replenish or withdraw the liquid medium during the long reaction period, which simplifies the process and makes it an economical process.

In the present invention carried out in a suspended bed reactor, the hot spots and temperature runaway in parts of the catalyst bed that are often experienced in fixed beds can be avoided due to the easy removal of the reaction heat.
It is possible to operate at a uniform temperature across the entire layer. For this reason,
Since the methane reaction, which tends to proceed at high temperatures, and the secondary decomposition of generated hydrocarbons in the gasoline boiling point range can be suppressed to a lower level than in the fixed bed reactor', hydrocarbons in the gasoline boiling point range can be obtained in high yield. Furthermore, in fixed bed reactions, coke usually adheres to the catalyst surface as the reaction progresses, reducing activity. However, in the present invention, since the liquid medium is a heavy aromatic, the coke is dissolved and removed by the liquid medium in its precursor, so the coke that causes a decrease in catalyst activity is removed. The surprising effect was that almost no adhesion occurred and the catalyst maintained stable activity for a long period of time.

Next, the present invention will be explained in more detail.

Synthesis gas, which is a raw material for the reaction, is not particularly limited, and usually has a molar ratio of H210'O of 0.5 or more, and is heated to a temperature of 200 to 450°C, preferably 250 to 350°C, with the catalyst slurry.
Temperature in °C, below 100 kg/tyi', preferably 10-50 kg/crl pressure, 100-10,0
00h, preferably 500-2,000h GH8
Contact is made under the condition of V. At this time, the gas fluid consisting of light hydrocarbons and inorganic gas separated by the high-pressure separator can be recycled to the reactor inlet. The recycled gas ratio is 0.1 to 100% by volume to the raw material synthesis gas. Preferably it is 0.5-10. The catalyst is a composite catalyst consisting of a metal or/and metal oxide having catalytic activity to hydrogenate carbon monoxide and crystalline zeolite, and can be broadly classified into Fe, Co, and Ru, which promote the Tropsch synthesis reaction. Cu, which promotes the composite catalysis or methanol synthesis reaction of one or more metals or metal oxides and crystalline zeolite, such as
Zn.

It is a composite catalyst of one or more metals or metal oxides such as Or or Pd and crystalline zeolite. Here, the content of the metal having catalytic activity for hydrogenating carbon oxide in the catalyst is 0.1 to 15 wt% as metal in the case of a supported catalyst, and 5 to 5 D wt% as metal oxide in the case of an oxide catalyst. Crystalline zeolite is usually a three-dimensional network structure in which silica and alumina share oxygen, and the ratio of oxygen atoms to the total of aluminum and silicon atoms is 2.
The negative electricity of the i 02 tetrahedron is an alkali metal cation,
In particular, it refers to crystalline aluminosilicates which are balanced with sodium, potassium or, in some cases, organic nitrogen cations. In addition, some or all of the aluminum may contain other metals, such as iron (Japanese Patent Application Laid-open No. 5S-7619Q'), chromium (
JP 55-115785), vanadium (West German patent 2851651), bismuth (JP 57-196)
718), lanthanum (% 10684/1984, 194757/1982), cerium (106/1982)
84. JP-A-58-194737), borosilicate (JP-A-58-194737)
3-55500,.

JP-A-55-76825), titanium (JP-A-57-1O)
It also includes crystalline silicates synthesized by substitution with trivalent metals such as 6a4). Generally, crystalline zeolites exist in large numbers in nature, but they can also be produced synthetically, and either of these can be used.

In addition, crystalline zeolite has a specific uniform pore size depending on the way oxygen atoms are bonded due to its crystal structure.As small pore size zeolite with a pore size of about 5λ, there are erionite, offretite, and ferrierite. Faujasite type zeolite or Y zeolite or mordenite is used as a large pore size zeolite with a pore size of about 91 mm, and ZSM-s (Japanese Patent Publication Publication No. 46
-10064), ZSM-11 (Special Publication No. 53-23280) with a silica to aluminum ratio of 12 or more, ZSM
-12 (Special Public Sho 5w2-16079), ZSM -21
(Special Publication No. 50-54598), ZSM-s s (U.S. Patent Application No. 528061, November 29, 1974)
, zsM, -3a (U.S. Patent No. 5C8060,
In addition to ZSM series zeolites developed by Mopil Oil Co., Ltd., such as 29E+ (November 1974), iron silicate developed by Shell International Research Co., Ltd. (Japanese Patent Application Laid-open No. 53-76199), and even though the manufacturing method is different, ZSM-'s type high silica crystalline zeolite whose X-ray diffraction pattern is similar to ZEIM-5, and zeolite in which part or all of the alumina of the above zeolite is replaced with other trivalent metals, such as boron silicate. (JP 53-55500), bismuth silicate (
JP-A-57-196y 1'a), tantalum silicate and cerium silicate (JP-A-57-1068)
4, Japanese Unexamined Patent Publication No. 58-194737).

In the reaction using a catalyst composite with a small pore olide with a pore size of about 51, the hydrocarbons produced are linear paraffins, olefins, or carbon atoms with a molecular size of about 5λ or less due to the shape selectivity of zeolite. When the hydrocarbon is a light hydrocarbon having 5 or less, lower olefins such as ethylene, propylene, butylene, etc., which are useful as petrochemical raw materials, can be obtained. Furthermore, if necessary, these lower olefins can be easily converted to hydrocarbons in the gasoline boiling point range by known methods such as alkylation, disproportionation, and dikeification.

A melting medium composed of medium pore size zeolite having a pore size of 5 to 9λ is the most preferred zeolite for obtaining hydrocarbons in the gasoline boiling point range in high yield.

When trying to obtain mainly aromatic hydrocarbons from hydrocarbons,
In addition to silica sources, alumina sources, and alkali sources, tetrapropylammonium salts (ZBM-5 from Mopil Oil Co., Ltd., specified as equity 11146-10064, as well as JP-A-51-67298
Zeta 3 of IC21, etc.), organic amines (JP-A-50-545'9B, JP-A-54-99799)
etc.), alcohol amines (48i-Kaisho 54-107
499, etc.), diglycolamine (JP-A-56-92)
The silica to alumina ratio obtained by carrying out a hydrothermal synthesis reaction in the presence of any one of 114') or its precursor is 12 to
100 crystalline aluminosilicate can be preferably used. In addition, when it is intended to mainly obtain olefin hydrocarbons from hydrocarbons, it is preferable to use a crystalline transition metal silicate containing substantially no aluminum, which is synthesized by adding a trivalent metal source in place of the alumina source described above. Can be used. A catalyst composed of large-pore zeolite with a pore diameter of about 9A produces not only hydrocarbons below the Ganlin boiling point range, but also kerosene and gas oil fractions, so if it is necessary to co-produce them. selected. In order to use any crystalline zeolite in the conversion reaction of the present invention, it is preferable that at least 50% of the cations are exchanged with hydrogen ions, rare earth ions, etc., and acidic sites are discovered.

Next, a description will be given of the liquid medium that is essential for preparing the catalyst slurry used in the present invention. That is, the heavy aromatic hydrocarbon oil used here is obtained by hydrodesulfurization treatment of heavy cycle oil produced as a by-product in a catalytic cracking unit known as a gasoline production process in an oil refinery. It is obtained by further dewaxing followed by dewaxing. The catalytic cracking process usually involves straight-run heavy gas oil with a boiling point of 250 to 400°C obtained by atmospheric distillation of crude oil;
Or the boiling point obtained by distilling heavy oil under reduced pressure is 350-550
℃ vacuum gas oil or their hydrodesulfurization equipment (l'li
Using the desulfurized oil obtained by reducing the yellow content and nitrogen content as the raw material, it is heated at 450 to 550°C (D temperature, 10 kg / J G
- Below] This is a process for obtaining a gasoline base material with a high octane number by contacting it in a fluidized state with a powdered catalyst consisting of one or more of pressure tezeolite, silica alumina, and alumina. Under the above conditions, 60 to 80 vot% of the feedstock oil undergoes decomposition and is separated into dry gas, LPG, and a fraction having a boiling point of naphtha or higher. Subsequently, the fraction with a boiling point of naphtha or higher is converted into naphtha with a boiling point of about 200°C or less, or a distillate with a boiling point of about 200 to 30°C in a distillation column.
Light cycle oil (Lco) at 0°C, boiling point approximately 500~
400℃ heavy cycle oil and residual oil (slurry oil)
separated into This heavy cycle oil, whose internal boiling point is approximately the same as that of the feedstock oil, is generally recycled to the reaction tower except for a portion that is extracted as a product.

The present inventors believe that this heavy cycle oil has already been treated at high temperatures under a crystalline zeolite-based catalyst, so it has high thermal stability at high temperatures, and is also stable under the zeolite-containing catalyst used in the present invention. We focused on the fact that the scales present in the catalyst, as well as the boiling point range and viscosity, have favorable properties as a liquid medium in which the catalyst is suspended. In other words, a typical heavy cycle oil has a specific gravity (15/4℃) of 069 to 1.0.50℃, a kinematic viscosity of 15 to 1 centistokes, and a pour point of +20 to -10℃.
, boiling point range 250-400°C, sulfur content 0.1-2. O
It exhibits properties with a nitrogen content of 0.01 to 0.5 wt%.

However, as can be seen from this property, there are large amounts of sulfur and nitrogen that poison the catalyst, and even if these poisoning substances are in trace amounts, they can affect the metal components of the catalyst used in the present invention. It is poisonous and must be removed before it can be used as a liquid medium. The removal method is not particularly limited, but a hydrodesulfurization treatment commonly used in industry can be used.

Hydrodesulfurization treatment involves treating heavy cycle oil in the presence of a customary hydrodesulfurization catalyst such as cobalt-molybdenum-alumina or nickel-fisted molybdenum-alumina.
0℃ storage, 20-150 kg/JG (D pressure,
LH8V O, 1~10h1 Hydrogen to oil ratio 50~1000
0 Nm”/ by contacting with the condition of /+ row b,
Sulfur content 0.5 wt% or less, nitrogen content 0.1 wt%
% or less, preferably sulfur content (L 1 wt% or less, crab content 0.05 wt% or less. If the desulfurized heavy cycle oil is subsequently subjected to catalytic dewaxing treatment, it becomes a more preferable liquid medium. Even if it is used as a liquid medium without catalytic dewaxing treatment, the catalytic activity will not be impaired.
At the beginning of the reaction, the paraffin contained in the desulfurized heavy cycle oil is decomposed by the crystalline zeolite catalyst component, resulting in a decrease in the liquid medium. Therefore, the desulfurized heavy cycle oil must be subjected to hydrodesulfurization after catalysis. You can also do it.

Catalytic dewaxing treatment is used to improve the pour point of ZSM 75
This reaction uses medium-pore zeolite, such as zeolite, as a catalyst, which can selectively decompose only the wax content. Already industrialized methods include Mopil Oil's MDDW method using ZSM-5 zeolite, and the British method using mordenite zeolite.・There is a wax removal method by Petroleum. In addition, among the crystalline zeolites that can be used in the present invention, the pore size is 5.
This can also be achieved by using a crystalline zeolite with a medium pore diameter of ~9λ as a catalyst. The reaction conditions for catalytic dewaxing vary depending on the type of catalyst, but are usually at a temperature of 250 to 400°C and a
Pressure below 00kg/JG, LHEIV 0.1~10
Do this with h-”.

Although the obtained wax-treated oil can be used as a liquid medium as it is, it is preferable to remove the fraction with a boiling point of 300° C. or lower produced by decomposition of the wax component by distillation.

The liquid medium thus obtained is mixed with a catalyst and subjected to the reaction in a slurry state. The mixing ratio of the catalyst is 5 to 50 wt% in concentration in the slurry, and the catalyst is 50 μm in advance.
m or less and then mixed or/and mixed with a liquid medium and then ground to a size of 50 μm or less, preferably 5 μm
The following is preferable.

Hereinafter, the present invention 2 will be specifically explained using Examples, but the present invention is not limited to the following unless it exceeds the gist thereof.

Preparation of crystalline zeolite Crystalline zeolite was produced as follows. Water glass, lanthanum chloride, water 36 Nano・L a203・ao
stol・160 mouth H, O molar ratio was prepared, an appropriate amount of hydrochloric acid was added to this, the pH of the above mixture was adjusted to around 9, and then tri-n propylamine, n Bropylbromide and methyl ethyl ketone were added in an amount 20 times the number of moles of L a20j, mixed well, and poured into a 1 ton stainless steel autogel. The above mixture was stirred at about 50 rpm and reacted at 100°C for 1 day, then at 1'70°C for 3 days. The composition of the obtained crystal, excluding organic compounds, expressed in dehydrated form, was 80,810 g of Na2O@La2O3. This is called crystalline lanthanum silicate.

Next, add silica sol, sodium aluminate, caustic soda, and water to 10 Na2O5At20i1 @46s102
The mixture was prepared to have a molar ratio of '11300H20, and diglycolamine was added as an organic compound to 18 times the number of moles of At20s, mixed well, and the mixture was charged into a 1 ton stainless steel autoclave. The above mixture was reacted at 160° C. for 3 days under autogenous pressure while stirring at about 590 rpm.

As a result of chemical analysis, the white fine crystals obtained were found to have Na1.
8 vrt%, NO, B wt%, and the silica to alumina molar ratio was 27. This is called DGA zeolite.

These two high-silica zeolites were then washed with water and subjected to ion exchange treatment under the plate in order to convert them into acid forms. First, 550℃,
The organic nitrogen cations were removed by firing for 5 hours. Next, it was immersed in 1N hydrochloric acid and treated at 80°C for 7 days, washed with ion-exchanged water until the pH of the washing water reached 6, dried at 110°C for 12 hours, and finally the crystalline form of the hydrogen ion type was obtained. Obtained zeolite.

Preparation of catalyst The catalyst was manufactured as follows. After washing the precipitated iron obtained by adding aqueous ammonia to an aqueous ferric nitrate solution with ion-exchanged water, the weight ratio of iron oxide to crystalline zeolite was 1:1.
The preparation of crystalline zeolite was shown to be mixed with crystalline lanthanum silicate. The mixture was dried at 130°C, impregnated with an aqueous ruthenium trichloride solution containing 1 wt% of ruthenium, dried at 130°C for 3 hours, and then calcined at 500°C for 3 hours to serve as a catalyst.

This is called STG-1.

In addition, a catalyst prepared in exactly the same manner except that DGA zeolite shown in the preparation of crystalline zeolite was used instead of crystalline lanthanum silicate was used as EITG-2.

In addition, 5T is a catalyst made by mechanically mixing BA13F's zinc and chromium-based methanol synthesis catalyst and crystalline lanthanum silicate at a weight ratio of 1:1, with a particle size of 50 μm or less.
( ) -5.

In addition, after mixing vanadium oxide and crystalline lanthanum silicate in a weight ratio of 1=1, the ruthenium content is 1
Impregnated with a ruthenium trichloride aqueous solution in an amount of wt%,
A powder catalyst of 50 μm or less obtained by drying at 130° C. for 3 hours is referred to as STG-4.

Preparation of the liquid medium The suspension was prepared as follows. Heavy cycle oil with the properties shown in Table 1 was collected from a catalytic cracker using desulfurized vacuum gas oil as feedstock, and was pre-sulfurized using Ketjen's KF702 cobalt-molybdenum-alumina hydrodesulfurization catalyst (the hydrodesulfurization catalyst was desulfurized). When the catalyst is subjected to a reaction, it is necessary to sulfurize the metal components in the catalyst, and this operation is called preparatory flow.

That is, unless cobalt and molybdenum in the catalyst are sulfurized, their desulfurization activity is low and undesirable side reactions such as decomposition occur. For this reason, preliminary sulfurization is performed to change the metal components into sulfides and obtain the best activity. ), 380℃, 45 kg/tyl G
, LH8V=1 h-'.

The treatment was performed at a hydrogen to oil ratio of 50 () In3/kl.

Next, a part of the desulfurized oil was mixed and molded with the above-mentioned hydrogen-type DGA zeolite in a weight ratio of 1:1 using boehmite alumina gel as a matrix, and then calcined at 550°C. 9/cm”G%LH8
V = 1.5 h-”, hydrogen to oil ratio 20ONm” /
Catalytic dewaxing treatment was carried out under the conditions of kl. Subsequently, the dewaxed oil was separated into fractions with a boiling point below 300°C and above 300°C in a distillation apparatus, and the fraction with a boiling point above 300°C was used as a liquid medium.

Table 2 shows the properties of the desulfurized oil and the desulfurized and dewaxed oil.

Table 1 Specific properties of raw material heavy cycle oil Gravity (15/4℃) 0.9833 Kinematic viscosity (cat
50°C) 5.769 Pour point (°C) -1-15 Sulfur content (wt) 1.09 Nitrogen content (wt%) 0. os Distillation properties IBP 277℃ 10% 505℃ 30% 315℃ 50% 324℃ 70% 352℃ 90% 346℃ EP 358℃ Table 2 Desulfurization heavy cycle oil Desulfurization dewaxing heavy cycle oil specific gravity (
15/4℃) 0.9451 0.9921 Sulfur content (w
t%) [1,0140,02 Nitrogen content (wt%) a0
0 & a01 Pour point (℃) +0.5 -57.5 Kinematic viscosity (cat 40℃) -1599 Composition (wt) Aromatic content 7 & 4 84.0 Non-aromatic content
23.9 1/i, 0 Note) The reason why desulfurization and dewaxing heavy cycle oil has more ps and 1 minute than desulfurization and dewaxing heavy cycle oil is that in addition to the fact that desulfurization and denitrification do not occur at all in the dewaxing treatment, This is because the wax content in the desulfurized oil is decomposed into heavy content, and as a result, S and N in the heavy content are concentrated.

In order to examine the influence of the sulfur content in the liquid medium on this I's catalyst, the reaction temperature was set at 360°C during the hydrodesulfurization process.
The sulfur content [107 it%] was carried out in the same manner except that the temperature was
A desulfurized heavy cycle oil was prepared.

Effect of 8 minutes in liquid medium The effect of sulfur content in liquid medium on STG-2 catalyst was investigated using a fixed bed flow actor.

Horse/Co raw material gas with a molar ratio of 2 was heated to 520°C and 20 to 9
/ ctl G, GH8V = 1000 h-”
(When contacted with 5TG-2 catalyst under D conditions, CO conversion rate was 9.
It was 1.5%. After that, heavy cycle oil with a sulfur content of 1.09 wt was heated at 320°C and 20 kg/m'G.
, LH,, SV = 1000 h"-" after passing through the oil for 2 hours under the flow of syngas, the catalyst activity was tested again under the same conditions, and as a result, the CO conversion rate decreased to 7%. Separately, similar experiments were conducted using desulfurized heavy cycle oil with different sulfur content, and as shown in Table 3, there was no decrease in activity. become.

Table 3 1.09 91.5 7 0.07 91.8 '89 0.014 90.6 B? Examples 1 and 2 The 5TG-1 catalyst 1902 prepared in the crystalline zeolite section was mixed into the liquid medium 530f with a sulfur content of 0.02 vt% prepared in the section of preparation of liquid medium, and the catalyst particle size was 5 on average.
After grinding until it becomes less than pm, the hole diameter is 30μ at the bottom.
A stainless steel M suspension bed reaction tube with a capacity of 1 t and equipped with a perforated plate of m2 was filled.

This slurry catalyst was pretreated using synthesis gas with a Hv/CO molar ratio of 2 at 300°C, normal pressure, and a gas flow rate of sOL/H for 6 hours, and then reacted using H2100 molar ratio of 2 or specific gravity synthesis gas as a raw material. Ta.

The reaction conditions and reaction results are shown in Table 4.
and H2 were converted to hydrocarbons with a high conversion rate, and particularly high yields of hydrocarbons in the gasoline boiling point range were obtained. Another major feature was that the catalyst bed maintained a uniform temperature throughout the reaction period, and there was no local heat generation that is seen in fixed bed reactors. Further, during the reaction period of 50 hours, there was almost no change in the height of the slurry layer, and as a result of measuring the weight of the slurry catalyst taken out after the reaction, 95% of the liquid medium was recovered. Therefore, it can be seen that the liquid mass of the present invention can be used in a suspended bed reaction without impairing the performance of the catalyst used in the reaction applied to the present invention, and without being decomposed itself.

Table 4 Example 3 The results were obtained when the reaction was carried out in exactly the same manner as in Example 2, except that the desulfurized heavy cycle oil prepared in the liquid medium preparation section was used and the 9 o'clock speed was changed. It is also shown in Table 4.

Since the liquid medium used here has not been subjected to the wax treatment, the wax content is decomposed by the zeolite component in the STG-1 catalyst under the reaction conditions, producing by-products hydrocarbons below the gasoline boiling point range. A decrease in the level of the liquid medium in the reaction tube was observed over about 10 hours from the start of the reaction. However, after that, there was no change in the catalyst layer level, and as in the case of the actual flow side 25, a uniform reaction temperature was maintained, and only the conversion reaction from synthesis gas to hydrocarbons proceeded effectively.

After the reaction was completed, the liquid medium was recovered and the recovery rate was 83 wt%. Therefore, desulfurized heavy cycle oil can also be used as the liquid medium of the present invention without impairing the catalytic activity, although there is some loss due to decomposition at the beginning of use.

Example 4 STG prepared in the catalyst preparation section was added to the liquid medium 400f with a sulfur content of 0.02 wt% produced in the liquid medium preparation section.
Example 4 is the result of carrying out a synthesis gas conversion reaction using a slurry catalyst obtained by mixing 110f of -2 catalysts and pulverizing the catalyst until the catalyst particle size became 5 μm or less on average. The experimental equipment and method were the same as in Example 2, and the reaction results are shown in Table 5 below. Even in this method, there was almost no decrease in catalyst activity or change in the height of the catalyst slurry layer during the 24-hour reaction time, and the recovery rate of the liquid medium after the reaction was 96.
%Met.

Example 5 In Example 4, the slurry catalyst obtained using the STG-3 catalyst shown in the section of catalyst preparation was filled into the STG-2 catalyst, and the synthesis of I(2/co molar ratio 2) Using a gas, the reaction was carried out under the conditions of a reaction temperature of 380°C, a reaction pressure of 40 kg/c, ?a, and a space-time velocity of 1oo (z/catalyst z-h). The results are shown in Table 5 as Example 5.Here The liquid medium used did not poison the methanol synthesis catalyst component consisting of zinc and chromium, and during the reaction period, the entire layer of the catalyst slurry maintained a uniform temperature distribution of ±5°C and exhibited stable activity. In addition, even at a relatively high temperature of 380° C., there was almost no loss in capacity due to decomposition of the liquid medium itself, and the recovery rate after the reaction was 96 Wt.

Table 5 Example 6 In Example 5, 5TG-4 was used instead of STG-3 catalyst.
All of the reactions were carried out under the same conditions using a catalyst at a reaction temperature of 28 clos, and the results are also listed as Example 6 in Table 5 above. In this case as well, high CO conversion and CO conversion were obtained, the yield of gasoline fraction reached 74.2 wt%, and there was no abnormal heat generation in the catalyst slurry layer, allowing stable operation.

Among agents: 1) Akira Agent Ryo Hagi Hara -

Claims (1)

[Claims] In a method for producing hydrocarbons by contacting a composite catalyst of a metal or/and metal oxide and crystalline zeolite with catalytic activity for hydrogenating carbon monoxide with synthesis gas, a heavy cycle is generated as a by-product in the catalytic cracking process. A method for producing hydrocarbons, which comprises suspending the catalyst in a liquid medium such as a heavy aromatic hydrocarbon mixture obtained by hydrodesulfurizing oil, and bringing synthesis gas into contact with the suspension. .