KR102073116B1 - One-pot process of producing C10+ compound from ethylene - Google Patents

Abstract

The present invention relates to a method for producing C_(8-16) heavy oil using a reactor which continuously conducts ethylene oligomerization, additional oligomerization of an ethylene oligomer, isomerization and aromatization at a temperature (T_0) selected in a range higher than 200°C and lower than 300°C. The present invention also relates to a method of manufacturing aviation-grade fuel.

Description

One-pot process of producing C10 + compound from ethylene

The present invention relates to C _8-16 heavy oil using a reactor in which ethylene oligomerization and further oligomerization, isomerization and aromatization of ethylene oligomers are carried out continuously at a temperature (T ₀ ) selected in the range above 200 ° C and below 300 ° C. It relates to a method for producing and a method for producing aviation fuel.

As the volume of air traffic increases rapidly, the entry and exit of international aircraft increases, and as a result, the interest in the emission of gas around the airport and its management is increasing. In particular, the global aviation industry accounts for 2% of the total GHG emissions. Therefore, the aviation sector needs to minimize GHG emissions.

Aviation oils must meet the demanding conditions of having a high energy density without freezing at high altitudes, and therefore, in order to secure properties suitable for these aviation oils, they have at least 8 carbon atoms (C ₈₊ ), more specifically at least 10 carbon atoms (C). those having a composition distribution of ₁₀₊₎ are preferred.

On the other hand, in connection with the depletion of petroleum resources, a method of synthesizing the aviation oil through oligomerization and / or isomerization of light olefins such as ethylene can be considered. Conventional methods for producing aviation fuels from light olefins include preparing ethylene oligomers through dimerization or oligomerization of light olefins and further oligomerizing, isomerizing and aromaticizing the ethylene oligomers to produce heavy oils. It consists of two or more steps to include. The heavy oil thus produced may be finally converted to aviation fuel grade raw materials through subsequent processes such as hydrogenation and / or distillation. In order to improve the efficiency and yield of the reaction, a method of synthesizing even heavy oil through a single process through a continuous oligomerization reaction of ethylene without going through a multi-step reaction has been sought.

On the other hand, there are two types of catalysts for the light olefin oligomerization reaction, ethylene can be oligomerized using a nickel-containing catalyst, and C ₃ or more olefins can be oligomerized using an acid catalyst. The oligomerization reaction using the acid can be carried out at a high temperature, and thus, zeolite or the like, which is a stable solid acid catalyst at a high temperature, can be used. However, since the selectivity for the oligomerization reaction is not constant when the reaction is carried out at such a high temperature, it is accompanied by isomerization, disproportionation, aromatization, cracking, and the like. The yield of the product is not constant, there is a disadvantage that a large amount of coke (coke) occurs.

For example, conventional heavy oil production methods for preparing aviation fuels have been used to produce C _8-16 heavy oil through oligomerization of ethylene by a single stage catalyst, but extend to C ₁₀₊ hydrocarbon compounds. In addition to low selectivity, C ₁₀₊ hydrocarbon compounds can be produced at high temperatures, but under these conditions, the C ₁₀₊ hydrocarbon compound, which is a product, is not easily separated / recovered and adheres to the surface of the catalyst. There is a problem of diminishing (Vasile Hulea et al., J. Catal., 2004, 225: 213-222).

On the other hand, in the case of using a zeolite catalyst which is a solid acid catalyst, although stable at high temperature, the reaction occurs only when the reaction temperature is increased to a predetermined level or more, so there is a disadvantage in that it is not energy economical.

We have worked diligently to uncover catalyst combinations and / or reaction conditions that can efficiently produce C ₁₀₊ compounds capable of providing aviation fuel from ethylene using a single reactor process at relatively low reaction temperatures. As a result, the nickel-containing solid acid catalyst layer for ethylene oligomerization reaction on the top; And at the bottom through the same reactor process filled with the two catalyst beds while feeding gaseous ethylene from the reactor packed with a zeolite catalyst layer for olefin oligomerization, isomerization and aromatization reaction to the top, i.e., under the same reaction conditions It was confirmed that heavy oil having a high ethylene conversion and a markedly increased C ₁₀₊ compound content in the product can be obtained in the liquid phase by a typical oligomerization reaction, thereby completing the present invention.

As one aspect for achieving the above object, the present invention

In a reactor in which ethylene oligomerization reactions and further oligomerization, isomerization and aromatization reactions of ethylene oligomers are carried out continuously at a temperature (T ₀ ) selected in the range above 200 ° C. and below 300 ° C.,

80% or more by weight of a compound having 10 or more carbon atoms (C ₁₀₊ ) and a compound having 20 or more carbon atoms (C ₂₀₊ ) based on a compound having 8 or more (C ₈₊ ) carbon atoms. In the method of manufacturing the product containing 25 weight% or more and 40 weight% or less,

The reactor is

The reactant inlet is formed at the top, the outlet is formed at the bottom,

At the top with a first catalyst layer filled to a thickness to form a product containing less than 25% by weight of a C ₁₀₊ compound from a gaseous ethylene containing reactant at a selected reaction temperature T ₀ ;

By further oligomerization, isomerization and aromatization of the product formed in the first catalyst layer at a selected reaction temperature T ₀ , a liquid product containing more than 31% by weight of C ₁₀₊ compound and 20% or more by weight of cyclic compound is obtained. In the lower portion of the first catalyst layer having a second catalyst layer filled with the thickness to be produced,

The ethylene-containing gas reactant is injected at a predetermined pressure from the reactant inlet at the top of the reactor to sequentially pass through the first catalyst layer and the second catalyst layer, react with the catalyst contained therein, and convert the product into a mixture of gas and liquid, thereby discharging the lower outlet. Is discharged through

The first catalyst in the first catalyst layer and the second catalyst in the second catalyst layer

i) the temperature at which the ethylene conversion in the ethylene oligomerization reaction of the first catalyst is maintained at 85% or more is greater than 200 ° C and less than 300 ° C;

ii) at a selected reaction temperature T _0, in the product of the ethylene oligomerization reaction by the ratio of the C ₁₀₊ compound in the product of the ethylene oligomerization reaction by the first catalyst layer <a combination of the same amount of the first catalyst layer and the second catalyst layer Conditions that are proportions of C ₁₀₊ compounds;

iii) conditions of ethylene conversion of the ethylene oligomerization reaction by the first catalyst> ethylene conversion of the ethylene oligomerization reaction by the second catalyst at the selected reaction temperature T ₀ ;

iv) the reaction temperature (T ₁ ) representing the maximum ethylene conversion in the ethylene oligomerization reaction with the first catalyst <the reaction temperature (T ₂ ) representing the maximum ethylene conversion in the ethylene oligomerization reaction with the second catalyst; And

v) selected reaction temperature T ₀ <the condition that the reaction temperature T ₂ indicating the maximum ethylene conversion in the ethylene oligomerization reaction by the second catalyst; selected to satisfy, C _8-16 heavy oil production method

To provide.

The reaction may be performed using a batch process or a continuous process, and the catalyst used therein may be used as a solid powder itself or in a slurry state containing an organic solvent such as dodecane, but is not limited thereto. For example, the process may be performed through a continuous process using a catalyst layer in a solid powder state or through a batch process using a catalyst layer in a slurry state dispersed in a dodecane solvent, but is not limited thereto.

In the method for preparing C _8-16 heavy oil of the present invention, at the selected reaction temperature T ₀ , the second catalyst may not be able to perform the oligomerization reaction of ethylene.

On the other hand, the first catalyst used in the process for producing C _8-16 heavy oil of the present invention may contain nickel which serves as an initiator of the ethylene oligomerization reaction at the selected reaction temperature T ₀ .

In the method for preparing C _8-16 heavy oil using the unification reactor process of the present invention, the first catalyst layer and the second catalyst layer have a mass ratio of 1: 9 to 9: 1, specifically, a mass ratio of 3: 7 to 7: 3. It may be configured as, but is not limited thereto.

Process for preparing a compound C ₈₊ Further, C ₁₀₊ compounds which may be used in air paid fuel from a conventional ethylene is then by the oligomerization of ethylene to prepare a C _4-8 compound to produce more compounds of high carbon number by an additional step A multi-step method was used. Alternatively, in the case of a single process using a nickel-containing catalyst known as an ethylene oligomerization catalyst, the selectivity to the C ₈₊ compound is low, or when the reaction temperature is increased to improve the reaction, the reaction efficiency itself is lowered. . On the other hand, when using a zeolite which is a stable catalyst at a high temperature, the reaction does not start smoothly, there is a disadvantage that the reaction occurs only at high temperatures.

Thus, the present invention is based on the discovery of an optimal catalyst combination and a single reactor process conditions for the production of expensive hydrocarbon compounds from ethylene through two or more reactions using two or more catalysts, which can be performed in one step under the same conditions. do. In particular, the present invention is characterized by a design process that can produce a heavy oil and the selectivities to higher efficiency at a relatively low temperature for an energy efficient process and a C ₈₊ compound addition, C ₁₀₊ compounds.

For example, the manufacturing method may be performed under a pressure of 5 to 30 bar, but is not limited thereto.

For example, the reactant ethylene in the preparation method of the present invention may be provided as a mixed gas with nitrogen which is an inert gas. For example, the mixing ratio may be ethylene: nitrogen = 1: 1 to 5: 1, but is not limited thereto.

The liquid product produced in the preparation method of the present invention may contain more than 31% and less than 38% of compounds having 10 or more carbon atoms (C ₁₀₊ ).

In addition, the liquid product may contain 20 to 70% by weight of an unsaturated or saturated cyclic compound in the total liquid product.

The first catalyst used in the preparation method of the present invention comprises silica and alumina in a weight ratio of 10:90 to 90:10, or specifically, in a weight ratio of 10:90 to 50:50, and includes the total weight of the first catalyst. Nickel may be contained in an amount of 1 to 10% by weight, specifically 2 to 7% by weight.

On the other hand, the second catalyst may contain silica and alumina in a molar ratio of 3: 1 to 100: 1.

Specifically, the first catalyst used in the preparation method of the present invention includes silica and alumina in a weight ratio of 10:90 to 90:10, and a catalyst containing 1 to 10 wt% nickel based on the total weight of the first catalyst. The second catalyst may contain silica and alumina in a molar ratio of 3: 1 to 100: 1. More specifically, the first catalyst used in the preparation method of the present invention includes silica and alumina in a weight ratio of 25:75 to 40:60, and contains 2 to 5 wt% nickel based on the total weight of the first catalyst. The second catalyst may contain silica and alumina in a molar ratio of 20: 1 to 25: 1, but is not limited thereto.

On the other hand, the manufacturing method of the present invention may further include a pretreatment step of activating the catalyst by heating to 500 to 600 ℃ while flowing an inert gas prior to the reaction, but is not limited thereto. The additional process may simultaneously activate the first catalyst and the second catalyst.

In another aspect, the present invention

In a reactor in which ethylene oligomerization reactions and further oligomerization, isomerization and aromatization reactions of ethylene oligomers are carried out continuously at a temperature (T ₀ ) selected in the range above 200 ° C. and below 300 ° C.,

From an ethylene-containing gas of at least 90% ethylene conversion, the method comprising producing a product containing C ₁₀₊ compounds 80 weight% or more, the C ₂₀₊ compounds up to 40% by weight at least 25% by weight of the C ₈₊ compound;

Cooling the product from the previous step and removing the gas to produce C _8-16 heavy oil; And

Converting the C _8-16 heavy oil obtained from the previous step to a aviation fuel by performing a hydrogenation process, a distillation process, or both,

The reactor for performing the first step is

The reactant inlet is formed at the top, the outlet is formed at the bottom,

At the top with a first catalyst layer filled to a thickness to form a product containing less than 25% by weight of a C ₁₀₊ compound from a gaseous ethylene containing reactant at a selected reaction temperature T ₀ ;

By further oligomerization, isomerization and aromatization of the product formed in the first catalyst layer at a selected reaction temperature T ₀ , a liquid product containing more than 31% by weight of C ₁₀₊ compound and 20% or more by weight of cyclic compound is obtained. In the lower portion of the first catalyst layer having a second catalyst layer filled with the thickness to be produced,

The ethylene-containing gas reactant is injected at a predetermined pressure from the reactant inlet at the top of the reactor to sequentially pass through the first catalyst layer and the second catalyst layer, react with the catalyst contained therein, and convert the product into a mixture of gas and liquid, thereby discharging the lower outlet. Is discharged through

The first catalyst in the first catalyst layer and the second catalyst in the second catalyst layer

i) the temperature at which the ethylene conversion in the ethylene oligomerization reaction of the first catalyst is maintained at 85% or more is greater than 200 ° C and less than 300 ° C;

ii) at a selected reaction temperature T _0, in the product of the ethylene oligomerization reaction by the ratio of the C ₁₀₊ compound in the product of the ethylene oligomerization reaction by the first catalyst layer <a combination of the same amount of the first catalyst layer and the second catalyst layer Conditions that are proportions of C ₁₀₊ compounds;

iii) conditions of ethylene conversion of the ethylene oligomerization reaction by the first catalyst> ethylene conversion of the ethylene oligomerization reaction by the second catalyst at the selected reaction temperature T ₀ ;

iv) the reaction temperature (T ₁ ) representing the maximum ethylene conversion in the ethylene oligomerization reaction with the first catalyst <the reaction temperature (T ₂ ) representing the maximum ethylene conversion in the ethylene oligomerization reaction with the second catalyst; And

v) selected reaction temperature T ₀ <the _{condition of} reaction temperature T ₂ representing the maximum ethylene conversion in the ethylene oligomerization reaction by the second catalyst;

To provide.

As described above, the second catalyst used in the method for preparing aviation fueled fuel of the present invention is selected at reaction temperature T ₀ , the second catalyst does not perform oligomerization reaction of ethylene, and the first catalyst is selected reaction temperature T It may contain nickel which serves as an initiator of the ethylene oligomerization reaction at _zero .

As used herein, the term "jet fuel" is a material used as a fuel for aircraft operation, also called aviation turbine fuel (ATF), is a colorless or straw-colored liquid. Unlike fuels used in automobiles, they are used at low temperatures and require special requirements. It is advantageous to have a low freezing point and a high density, high specific energy and high energy density so that it can travel a long distance from the low temperature by a single fuel. For example, jet oils of jet A-1 and jet class A, which are commonly used at present, have a flash point of 38 ° C. and an autoignition temperature of 210 ° C. Furthermore, it has a freezing point of -47 ° C for Jet A-1 and -40 ° C for Jet A-1. In order to meet the above conditions, aviation oil usually contains an aromatic compound in a predetermined content of 25% by volume or less. Therefore, in the case of aviation oil produced from biomass or the like, petroleum-based aromatic compounds may be added to satisfy the quality standards by supplementing the insufficient aromatics. However, the aviation oil of the present invention is produced from C _8-16 heavy oil containing a certain amount or more of aromatic compounds by the above-described method, and therefore does not require mixing with petroleum aviation oil.

Specifically, the method of manufacturing the aviation fuel class of the present invention may further include the step of distilling. For example, the product produced by oligomerization of light olefins with the catalyst according to the invention may be a mixture of hydrocarbon compounds having a series of carbon atoms rather than a single compound. Therefore, in order to produce only a hydrocarbon compound having a desired carbon number, it is possible to further purify and recover only the hydrocarbon compound having a desired carbon number by further distilling before or after the hydrogenation step.

The aviation fuel may further include additives such as antioxidants, antistatic agents, corrosion inhibitors, fuel system icing inhibitors, biocides or metal deactivators. It may include.

In accordance with the present invention, a combination of catalysts and / or reaction conditions are employed to efficiently produce C ₁₀₊ compounds capable of providing aviation fuel from ethylene in a single reactor process at relatively low reaction temperatures, with the ethylene oligomer at the top When the reaction was sequentially carried out through the same reactor process, i.e. under the same reaction conditions, while supplying gaseous ethylene from the top to the reactor sequentially filled with the nickel-containing solid acid catalyst layer for the polymerization reaction and the zeolite catalyst layer for the hydrocarbon isomerization reaction at the bottom, the ethylene conversion was decreased. Heavy oils with high and significantly increased C ₁₀₊ compound content in the product can be obtained in the liquid phase.

1 is a diagram schematically showing a conventional ethylene oligomerization process and a one-pot process for preparing a C ₁₀₊ compound by ethylene oligomerization followed by an oligomerization reaction of an olefin according to the present invention. .
Figure 2 is a diagram showing the selectivity of the product according to the ethylene conversion and carbon number according to the ethylene oligomerization reaction when using a 4% by weight Ni / Siral-30 catalyst. The reaction was carried out using 1 g of catalyst at 10 bar pressure at 0.375 / h space velocity (WHSV), flowing ethylene gas at a flow rate of 5 mL / min, (1) 200 ° C., (2) 250 ° C., (3) 300 ° C, and (4) 350 ° C.
3 is a diagram showing the selectivity of the product according to the ethylene conversion and carbon number according to the ethylene oligomerization reaction when using the H-ZSM-5 catalyst. The reaction was carried out using 1 g of catalyst at 10 bar pressure at 0.375 / h space velocity (WHSV), with ethylene gas flowing at a flow rate of 5 mL / min, (1) 250 ° C., (2) 300 ° C., And (3) at 350 ° C.
FIG. 4 shows the selectivity of the product according to ethylene conversion and carbon number in the ethylene oligomerization and subsequent olefin oligomerization reaction for a single reactor process using 4 wt% Ni / Siral-30 catalyst layer and H-ZSM-5 catalyst layer simultaneously It is also. The reaction was carried out at (1) 200 ° C., (2) 250 ° C., and (3) 300 ° C. with ethylene gas flowing at a flow rate of 5 mL / min under 10 bar pressure using 1 g each and a total of 2 g catalyst. Was performed in.
5 is a diagram showing the results of SIMDIS-GC (simulated distillation gas chromatography) analysis using the liquid product obtained after the ethylene oligomerization reaction.
6 is a diagram showing the GC / MS results for the liquid product obtained after the ethylene oligomerization and aromatization reaction according to the single reactor process when using a 4% by weight Ni / Siral-30 catalyst.
FIG. 7 is a diagram showing GC / MS results of the liquid product obtained after ethylene oligomerization and aromatization according to a single reactor process when using H-ZSM-5 catalyst.
FIG. 8 shows GC / MS results for the liquid product obtained after ethylene oligomerization and subsequent olefin oligomerization reaction for a single reactor process using 4 wt% Ni / Siral-30 catalyst layer and H-ZSM-5 catalyst layer simultaneously It is also.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by these examples.

Comparative example  One: Ni Of Siral  Ethylene by Single Reactor Process with Catalyst Oligomerization  reaction

As shown in (2) of FIG. 1, 4 weights in a fixed bed reactor having a tubular shape (length (L) 300 mm, outer diameter (OD) 9.6 mm and inner diameter (ID) 7.5 mm) made of stainless steel 1 g of% Ni / Siral-30 catalyst was charged to carry out an ethylene oligomerization reaction by a single reactor process. In the center of the reactor was provided with a sieve to fix the catalyst bed. The catalyst was compressed into a pellet press and sieved to collect particles having a diameter of 150 to 250 μm. The catalytic reaction was allowed to be carried out while the reactants flowed in contact with the catalyst in the direction of gravity. In addition, the reactor was equipped with a thermocouple (thermocouple) to check the temperature inside the reactor, it was possible to maintain the set temperature during the reaction.

Prior to the reaction, the nitrogen was heated at a rate of 5 ° C./min up to 550 ° C. while flowing nitrogen at a flow rate of 55 cc / min at room temperature and atmospheric pressure, and maintained at 550 ° C. for 8 hours, followed by continued flow of nitrogen to reach the reaction temperature. The catalyst charged in the reactor was activated while left until it was left. The pressure in the reactor was adjusted to be fixed at 10 bar using a back pressure regulator located at the outlet side of the reactor. The reactant ethylene was fed in a gaseous state with nitrogen as an inert gas. The reactor was controlled to flow through the reactor at a flow rate of 2 cc / min nitrogen and 5 cc / min ethylene using a mass flow controller (MFC).

The liquid phase in the product is collected in a condenser at -5 ° C through a circulator at the bottom of the reactor, and sampled therefrom to provide a gas with a FID DHA column (RTX-5 DHA5% diphenyl 5 m + RTX-100 DHA 100 m). Analysis was carried out for 210 minutes through gas chromatography (YL 6500 GC). Unreacted products and products not collected in the condenser are gaseous and TCD column (Carboxene 1000, 5 ft) and FID column (alumina bond / NaSO4, 50 m × 0.53 mm × 10 μm) every 16 hours every 2 hours after the start of the reaction. It was analyzed in real time by gas chromatography (gas chromatography, YL 6500GC).

The reaction was carried out by adjusting the reaction temperature to 200, 250, 300 and 350 ° C., respectively, and the ethylene conversion over time and the content of the product C _n (n = 2, 4 to 18) compound were measured, and the results are shown. 2 is shown.

As shown in FIG. 2, when the ethylene oligomerization reaction using a Ni / Siral-30 catalyst alone was performed, the reaction efficiency was confirmed according to the reaction temperature while increasing the reaction temperature at an interval of 50 ° C. from 200 ° C. to 350 ° C. When the reaction efficiency increased with the increase of, the reaction rate decreased when the reaction temperature increased above 300 ° C. Further, the ethylene conversion rate was highest at a reaction temperature of 250 ℃, the ratio of C ₁₀₊ compounds of the product was only 22%.

Comparative example  2: H- ZSM Ethylene Oligomerization Reaction by Single Reactor Process When Using -5 Catalyst

Ethylene oligomerization was carried out in the same manner as in Comparative Example 1 except for using H-ZSM-5 catalyst (Si / Al ₂ = 23) instead of Ni / Siral-30 catalyst.

The reaction was carried out by adjusting the reaction temperature to 250, 300 and 350 ° C., respectively, and the ethylene conversion over time and the content of the product C _n (n = 2, 4 to 18) compound were measured, and the result is shown in FIG. 3. Indicated.

As shown in FIG. 3, in the ethylene oligomerization reaction using H-ZSM-5 catalyst alone, a liquid product was produced only at a high reaction temperature of 300 ° C. or higher, and at 250 ° C., no liquid product was produced. There was also no conversion to C ₄₊ compound.

Example  One: Ni Of Siral  Catalyst and H- ZSM Ethylene by Single Reactor Process with -5 Catalyst Oligomerization  reaction

Ethylene was prepared in the same manner as in Comparative Example 1, except that 1 g Ni / Siral-30 catalyst and 1 g H-ZSM-5 catalyst were continuously charged instead of 1 g Ni / Siral-30 catalyst. The oligomerization reaction was carried out.

The reaction was carried out by adjusting the reaction temperature to 200, 250 and 300 ° C., respectively, and the ethylene conversion over time and the content of the product C _n (n = 2, 4 to 18) compound were measured, and the result is shown in FIG. 4. Indicated.

4, the conversion rate of ethylene in the reaction at 200 ℃ is of but only a maximum of 55%, as the reaction temperature increased to 250 ℃ ethylene conversion was significantly increased to more than 95%, the product C ₁₀₊ compounds The proportion of was also improved to more than 35%.

Experimental Example  1: Analysis of Liquid Products

The liquid products obtained from Comparative Examples 1 and 2, and Example 1 were analyzed based on ASTM D7500 method using SIMDIS-GC (simulated distillation GC, Agilent), and the C _10-24 of the dual aviation oil can be used. The content was measured and the results are shown in FIG. 5.

As shown in FIG. 5, when only the H-ZSM-5 catalyst was used, the liquid product was formed and analyzed only when the reaction temperature was 300 ° C. or higher. This is due to the absence of nickel, which serves as an initiator of the ethylene oligomerization reaction, suggesting that at low temperatures below 300 ° C., the H-ZSM-5 catalyst, Bronsted acid alone, does not show good activity in the ethylene oligomerization reaction. .

In addition, the collected liquid product was analyzed by FID of GC (Younglin 6500 GC) equipped with a capillary column (Rtx-100-DHA) to calculate the proportion of the double C ₁₀₊ compound, and the results are shown in Table 1 below. Shown in

Reaction temperature (℃) 200 250 300 350 % Product distribution C _2-9 C ₁₀₊ C _2-9 C ₁₀₊ C _2-9 C ₁₀₊ C _2-9 C ₁₀₊ catalyst Ni / Siral 83 17 78 22 79 21 73 27 H-ZSM-5 - - NA NA 45 55 45 55 Ni / Siral
+ H-ZSM-5 69 31 65 35 62 38 - -

Furthermore, the collected liquid product is analyzed based on ASTM D7500 method using SIMDIS-GC to subdivide C ₈₊ compounds into C _8-9 , C _10-19 and C ₂₀₊ compounds to calculate the content thereof. The results are shown in Table 2 below.

Reaction temperature (℃) 200 250 300 350 % Product distribution
C _8-9 C _10-19 C ₂₀₊ C _8-9 C _10-19 C ₂₀₊ C _8-9 C _10-19 C ₂₀₊ C _8-9 C _10-19 C ₂₀₊ catalyst Ni / Siral 23 67 10 0 84 16 17 69 14 17 71 12 H-ZSM-5 - - - NA NA NA 17 73 10 11 80 9 Ni / Siral
+ H-ZSM-5 8 63 29 11 59 30 13 70 17 - - -

Finally, the collected liquid product is analyzed by Agilent 6890N GC / 5973N Mass selective detector (GC / MS) to measure the ratio of aromatic and cyclic compounds in hydrocarbon compounds, and the results are shown in FIGS. Table 3 shows.

Other HCs / aromatic + cyclic HCs Reaction temperature (℃) 200 250 300 350 Ni / Siral 99.1 / 0.9 93/7 60/40 54/46 H-ZSM-5 - NA 33/67 7/93 Ni / Siral + H-ZSM-5 99.8 / 0.2 64/36 13/87 -

Claims (11)

In a reactor in which ethylene oligomerization reactions and further oligomerization, isomerization and aromatization reactions of ethylene oligomers are carried out continuously at a temperature (T ₀ ) selected in the range above 200 ° C. and below 300 ° C.,
80% or more by weight of a compound having 10 or more carbon atoms (C ₁₀₊ ) and a compound having 20 or more carbon atoms (C ₂₀₊ ) based on a compound having 8 or more (C ₈₊ ) carbon atoms. In the method of manufacturing the product containing 25 weight% or more and 40 weight% or less,
The reactor is
The reactant inlet is formed at the top, the outlet is formed at the bottom,
At the top with a first catalyst layer filled to a thickness to form a product containing less than 25% by weight of a C ₁₀₊ compound from a gaseous ethylene containing reactant at a selected reaction temperature T ₀ ;
By further oligomerization, isomerization and aromatization of the product formed in the first catalyst layer at a selected reaction temperature T ₀ , a liquid product containing more than 31% by weight of C ₁₀₊ compound and 20% or more by weight of cyclic compound is obtained. In the lower portion of the first catalyst layer having a second catalyst layer filled with the thickness to be produced,
The ethylene-containing gas reactant is injected at a predetermined pressure from the reactant inlet at the top of the reactor to sequentially pass through the first catalyst layer and the second catalyst layer, react with the catalyst contained therein, and convert the product into a mixture of gas and liquid, thereby discharging the lower outlet. Is discharged through
The first catalyst in the first catalyst layer is a Ni / Siral-30 catalyst containing 1 to 10% by weight of nickel with respect to the total weight of the first catalyst,
The second catalyst in the second catalyst layer is an H-ZSM-5 catalyst containing silica and alumina in a molar ratio of 3: 1 to 100: 1,
C _8-16 Process for preparing heavy oil.
The method of claim 1,
In the selected reaction temperature T _0, the second catalyst is characterized not perform oligomerization reaction of ethylene, method for producing a C _8-16 heavy oil.
The method of claim 1,
The first catalyst is characterized by a method of producing a C _8-16 heavy oil containing nickel that functions as an initiator of the ethylene oligomerization reaction at the selected reaction temperature T _0.
The method of claim 1,
The method of producing a C _8-16 wherein the heavy oil liquid product is to contain a saturated or unsaturated cyclic compounds from 20 to 70% by weight of the total liquid product.
delete delete delete The method of claim 1,
The method of preparing a C _8-16 heavy oil further comprising a pretreatment step of activating the catalyst by heating to 500 to 600 ℃ while flowing an inert gas prior to the reaction.
In a reactor in which ethylene oligomerization reactions and further oligomerization, isomerization and aromatization reactions of ethylene oligomers are carried out continuously at a temperature (T ₀ ) selected in the range above 200 ° C. and below 300 ° C.,
From an ethylene-containing gas of at least 90% ethylene conversion, the method comprising producing a product containing C ₁₀₊ compounds 80 weight% or more, the C ₂₀₊ compounds up to 40% by weight at least 25% by weight of the C ₈₊ compound;
Cooling the product from the previous step and removing the gas to produce C _8-16 heavy oil; And
Converting the C _8-16 heavy oil obtained from the previous step to a aviation fuel by performing a hydrogenation process, a distillation process, or both,
The reactor for performing the first step is
The reactant inlet is formed at the top, the outlet is formed at the bottom,
At the top with a first catalyst layer filled to a thickness to form a product containing less than 25 weight percent C ₁₀₊ compound from a gaseous ethylene containing reactant at a selected reaction temperature T ₀ ;
By further oligomerization, isomerization and aromatization of the product formed in the first catalyst layer at a selected reaction temperature T ₀ , a liquid product containing more than 31% by weight of C ₁₀₊ compound and 20% or more by weight of cyclic compound is obtained. In the lower portion of the first catalyst layer having a second catalyst layer filled with the thickness to be produced,
The ethylene-containing gas reactant is injected at a predetermined pressure from the reactant inlet at the top of the reactor to sequentially pass through the first catalyst layer and the second catalyst layer, react with the catalyst contained therein, and convert the product into a mixture of gas and liquid, thereby discharging the lower outlet. Is discharged through
The first catalyst in the first catalyst layer is a Ni / Siral-30 catalyst containing 1 to 10% by weight of nickel with respect to the total weight of the first catalyst,
The second catalyst in the second catalyst layer is an H-ZSM-5 catalyst containing silica and alumina in a molar ratio of 3: 1 to 100: 1,
Method of producing aviation fuel.
The method of claim 9,
At a selected reaction temperature T ₀ , the second catalyst is characterized in that it does not perform the oligomerization reaction of ethylene.
The method of claim 9,
The first catalyst is characterized in that it contains nickel, which serves as an initiator of the ethylene oligomerization reaction at a selected reaction temperature T ₀ .

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