JPWO2015141624A1 - Catalyst test equipment for fluid catalytic cracking - Google Patents

Abstract

The reaction results are very close to those of a pilot device for fluid catalytic cracking and a commercial fluid catalytic cracking device (actual device). Evaluation of fluid catalytic cracking catalyst, evaluation and research of catalyst extracted from commercial fluid catalytic cracking device A catalyst testing device for hydrocarbon oil fluid catalytic cracking applicable to development is provided. Inside the catalyst flow cell (1), the catalyst flow cell (1) is provided with a reaction raw material supply nozzle (2) and a catalyst flow gas supply nozzle (3) from above, and a product at the bottom. A catalyst test apparatus for fluid catalytic cracking comprising a reaction vessel (6) provided with a recovery line (5).

Description

  The present invention relates to a test apparatus for a catalyst for fluid catalytic cracking of hydrocarbon oil. Specifically, the reaction results are very close to those of a pilot device for fluid catalytic cracking and further to a commercial fluid catalytic cracking device (actual device). In addition to evaluating the catalyst for fluid catalytic cracking, it is extracted from the commercial fluid catalytic cracking device. The present invention relates to a test apparatus for fluid catalytic cracking catalysts applicable to the evaluation and research and development of new catalysts.

  The fluid catalytic cracking process is a process for producing gasoline mainly from hydrocarbon oils.

  As a catalyst used in the fluid catalytic cracking process, for example, a catalyst containing a zeolite, a binder, a filler such as kaolin and alumina, and an additive as required is known.

  For example, Patent Document 1 discloses (1) alumina particles having a particle diameter of 2 to 60 μm containing a metal component selected from one or more of alkaline earth metals and rare earth metals and a phosphorus component, and (2) crystalline aluminosilicate. A catalyst for catalytic cracking of hydrocarbons in which (3) zeolite is uniformly dispersed in a porous inorganic oxide matrix is described. It is described that this catalyst has metal resistance, high activity, and selectivity and can suppress generation of hydrogen and coke.

  Patent Document 2 describes a catalyst composition for fluid catalytic cracking of hydrocarbons containing an alumina, a crystalline aluminosilicate zeolite, and an inorganic oxide matrix other than alumina, each component containing a phosphorus atom. It is described that when this catalyst is used for the catalytic cracking of heavy oil hydrocarbons, the bottom (bottom oil) resolution is excellent, the amount of hydrogen and coke produced is low, and the gasoline and kerosene oil fractions increase.

  In Patent Document 3, (1) a molecular sieve having a -Si-OH-Al- skeleton whose surface pores are modified with a specific phosphate, (2) a water-insoluble metal salt, (3) a phosphate compound, A hydrothermally stable porous molecular sieve catalyst obtained by evaporating water from a raw material mixture containing is described. This catalyst is described as having high hydrothermal resistance and improving gas olefin yield and selectivity.

  Patent Document 4 discloses fine spherical particles obtained by spray-drying an aqueous slurry of a mixture of air-flow calcined alumina, clay containing silica and alumina as a main component, a precursor of a silica-based inorganic oxide and crystalline aluminosilicate, and an alkali metal. It describes a method for producing a catalytic cracking catalyst in which a rare earth is introduced after washing so that the oxide content is 1.0% by mass or less as an oxide. It is described that when this catalyst is used for catalytic cracking of heavy hydrocarbon oils containing a large amount of metal, it exhibits high cracking activity, high gasoline selectivity, low production of coke and gas, and high hydrothermal resistance. ing.

  Patent Document 5 discloses a catalyst for fluid catalytic cracking of hydrocarbon oil obtained by mixing two or more catalyst compositions containing zeolite and an inorganic oxide matrix composed of an active matrix component and an inert matrix component, Each catalyst composition has a different zeolite content (however, one catalyst composition includes a case where the zeolite content is 0), and a catalyst for fluid catalytic cracking of hydrocarbon oil, Is described. According to this catalyst, gasoline and middle distillate can be obtained in high yield, coke can be produced in low yield, and further, bottom resolution can be increased, that is, the yield of heavy fraction can be lowered. It is stated that you can.

Patent Document 6 discloses a catalyst composition A containing 10 to 30% by mass of a silica-based binder as a zeolite and a binder, and a catalyst composition B containing 10 to 30% by mass of an aluminum compound binder as a zeolite and a binder. The mass of catalyst composition A is W _A and the mass of catalyst composition B is W _B , and the mass ratio (W _A : W _B ) is mixed at an arbitrary ratio within the range of 10:90 to 90:10. A catalyst for fluid catalytic cracking of hydrocarbon oils is described. According to this catalyst, gasoline and light oil fractions can be obtained in high yield, coke can be produced in low yield, and bottom resolution can be increased, that is, production of heavy fractions can be suppressed. It is described.

  In order to test such catalytic properties, ASTM-D3907's microactivity test method (MAT) defined by the American Society for Testing and Materials (ASTM) is known and commonly used. A schematic diagram of such a microactivity test method is shown in FIG. In FIG. 3, 31 is a fixed bed catalyst layer, and the raw material oil is inserted into the reactor together with the purge gas led out from the purge supply line 33 via the raw material oil supply nozzle 32 and the raw material oil supply pump. The Reference numeral 35 denotes a heating furnace, and 36 denotes a thermocouple. Employing such a microactivity test method, the activity, selectivity and the like of a catalyst extracted from a commercial catalytic cracking apparatus are evaluated and used as an operation index.

  However, although the activity results in the commercial catalytic cracking unit and the test results in the MAT generally agree with the trend in activity level, the activity level, yield of various products, and selectivity may not always match. It was. This is thought to be because MAT is a fixed bed reactor and the contact time between the raw hydrocarbon oil and the catalyst is greatly different.

  For example, although the contact time in a commercial catalytic cracking apparatus varies depending on the type of raw material hydrocarbon oil used, it is approximately several seconds, whereas in MAT, it is approximately 50 to 120 seconds. In addition, the amount of catalyst used is very small at several grams.

  Therefore, a catalyst evaluation test may be performed using a fluidized bed pilot plant simulating a commercial catalytic cracking apparatus (actual apparatus). For example, FIG. 4 shows a schematic diagram of a pilot plant apparatus. In FIG. 4, 41 is the bottom of the reaction tower, 42 is the top of the reaction tower, 43 is the feed oil supply line, 44 is the separator, 45 is the stripper, 46 is the lift line, 47 is the regeneration tower, 48 is the catalyst transport line, and 49 is the catalyst. A trap, 50 is a generated oil recovery tank, 51 is a fractionator, and 52 is a generated gas. The feedstock oil is introduced from the line 43 and the catalyst is introduced from the line 48 to the reaction tower bottom 41, and after catalytic cracking reaction, the product is distilled through 50 to 52.

  However, in the pilot plant test, the activity level, yield and quality of various products (octane number, etc.), and selectivity are almost the same as those of commercial catalytic cracking equipment (actual equipment), but the catalyst charge is several kg. In addition, there is a disadvantage that the test efficiency does not increase because a long test time including preparation is required. In addition, the production and maintenance of the pilot plant is expensive.

  Therefore, development of a new test apparatus employing a fluidized bed has been desired.

  Patent Document 7 discloses a test apparatus employing a small fluidized bed shown in FIG. In FIG. 2, the catalyst is packed into the catalyst fluidized bed reactor 21, feedstock oil and the like are supplied from the feedstock 22 for the feedstock oil and dispersed gas, and from the feed gas supply nozzles and lines for the catalyst flow 23 and 23 ′, Flowing gas is supplied. Reference numeral 24 denotes a discharge line for product gas and fluid gas. And it is a test apparatus which performs catalytic cracking reaction, detecting temperature with the thermocouple 26 in the heating furnace 25 provided in the reactor exterior.

  Therefore, the present applicant obtained the small test apparatus of Patent Document 7 and conducted various tests. However, this apparatus has a catalyst filling amount of several grams and a contact time with the raw material hydrocarbon oil of about 60 to 120 seconds, and the test efficiency is good, but the deviation from the test result of the pilot plant is not necessarily small. In terms of the performance evaluation of the catalyst used in the actual apparatus, it was not necessarily sufficient.

Japanese Patent Publication No. 5-16908 JP-A-8-173816 Special table 2009-511245 gazette JP-A-60-193543 JP 2010-110698 A WO2009 / 145311 USP 6,069,012

  As a result of intensive studies to solve such problems, the present inventors have provided a catalyst flow cell (1) isolated inside the reaction vessel (6) in a small test apparatus, and the catalyst is placed in this cell. Filling and supplying the catalyst flow gas from the upper part to make the catalyst in a fluid state, and supplying the reaction raw material hydrocarbon oil from the upper part to the flow catalyst area, the test result approximate to the test result in the pilot plant is obtained. As a result, the present invention has been completed.

  A catalyst test apparatus for fluid catalytic cracking according to the present invention comprises a catalyst flow cell (1) inside, a catalyst flow cell (1), a reaction raw material supply nozzle (2) from above, and a catalyst flow gas. It is characterized by comprising a reaction vessel (6) provided with a supply nozzle (3) and provided with a product recovery line (5) at the bottom.

The catalyst flow cell (1) is cylindrical, the inner diameter (D _I ) is in the range of 1 to 4 cm, the height (T) is in the range of 2 to 14 cm, the height (T) and the inner diameter ( D _I) the ratio of (T) / (D _I) is in the range of 1.1 to 7.0, it is preferable the bottom of the cell is conical structure concave down.

  The internal volume of the catalyst flow cell (1) is preferably in the range of 5 to 40 ml.

  The catalyst filling amount of the catalyst flow cell (1) during the test is preferably in the range of 1 to 20 g.

  The average particle diameter of the catalyst is preferably in the range of 40 to 100 μm, and the bulk specific gravity is preferably in the range of 0.5 to 1.1 g / ml.

  According to the present invention, a reaction result very close to that of a pilot device for fluid catalytic cracking or a commercial catalytic cracking device can be obtained even if it is small, and the catalyst for fluid catalytic cracking is evaluated and extracted from the commercial catalytic cracking device. It is possible to provide a test apparatus for a catalyst for fluid catalytic cracking of hydrocarbon oil, which can be suitably used for catalyst evaluation and research and development.

The schematic diagram of the one aspect | mode of the catalyst test apparatus for fluid catalytic cracking concerning this invention is shown. The schematic diagram of the small test apparatus of the fluidized bed disclosed by patent document 7 is shown. The schematic diagram of the micro-activity test apparatus of ASTM-D3907 prescribed | regulated to the American Society for Materials Testing (ASTM) is shown. The schematic diagram of the pilot plant of the fluidized bed which imitated the commercial catalytic cracking apparatus is shown.

Hereinafter, the fluid catalytic cracking catalyst test apparatus according to the present invention will be described.
A catalytic test apparatus for fluid catalytic cracking according to the present invention includes a catalyst flow cell (1) inside the catalyst flow cell (1), and a reaction raw material supply nozzle from above ( 2) and a gas supply nozzle (3) for catalyst flow, and a reaction vessel (6) provided with a product recovery line (5) at the bottom.

  A schematic diagram of one embodiment of a fluid catalytic cracking catalyst test apparatus according to the present invention is shown in FIG.

  FIG. 1 shows a catalyst flow cell 1, a reaction raw material supply nozzle 2, a raw material oil supply pump 2 ', a catalyst flow gas supply nozzle 3, a catalyst flow gas supply source 3', a nozzle support 4, and a product recovery line. 5, a reaction vessel 6, a heating furnace 7, and a thermocouple 8 are provided.

Catalyst flow cell (1)
A predetermined catalytic cracking catalyst is inserted into the catalyst flow cell (1), and the catalyst is flowed to perform catalytic cracking of the introduced hydrocarbon oil. The catalyst flow cell (1) is cylindrical and has a bottom at the bottom. The bottom is preferably a concave conical or hemispherical structure. Such a structure improves the reproducibility of the catalytic cracking test results for hydrocarbon oils, because the catalyst during the reaction is in a more uniform flow state than when the catalyst flow cell is prismatic or has a flat bottom. In addition, a reaction result very close to that of the pilot device can be obtained.

  The catalyst flow cell (1) is placed so that the inside of the cell can be isolated from the inside of the reaction vessel.

  By providing such a catalyst flow cell inside the reaction vessel, it is possible to obtain measurement results at the same level as the pilot plant test results in terms of gasoline yield, LPG yield, coke yield, and the like. Although the reason is not clear, as in Patent Document 7, the reaction vessel itself is not used, but by using a cell isolated from the reaction vessel, the product and the fluidized catalyst layer can be quickly separated, and the secondary reaction The present inventors think that it is possible to suppress (sometimes referred to as a side reaction).

  Note that a jig, a stopper, or the like for holding the catalyst flow cell may be provided on the outer surface or bottom of the cell, whereby the catalyst flow cell (1) is installed at a predetermined position in the reaction vessel. The upper part of the cell for catalyst flow may be suspended from the nozzles (2) and (3) or the support (4) described later.

The inner diameter (D _I ) of the cylindrical cell is preferably in the range of 1 to 4 cm, more preferably 1 to 3 cm.

If the inner diameter (D _I ) of the cylindrical cell is small, the flow state of the catalyst is deteriorated, and the measurement accuracy and reproducibility may be insufficient. Even if the inner diameter (D _I ) of the cylindrical cell is too large, the mixing accuracy of the catalyst and hydrocarbon oil deteriorates due to insufficient lateral diffusion of the raw hydrocarbon oil. It tends to decrease or the decomposition becomes insufficient.

  Also, the height (T) of the cylindrical cell is preferably in the range of 2 to 14 cm, more preferably 3 to 12 cm.

  Here, the height (T) of the cylindrical cell means from the bottom of the cell to the top of the cell.

  If the height (T) of the cylindrical cell is low, the height for the uniform flow of the catalyst becomes insufficient, and the mixed state of the raw hydrocarbon oil and the catalyst deteriorates. Also, there is a tendency for decomposition to be insufficient.

  Even if the height (T) of the cylindrical cell is too high, there is no problem in testing, but since the test apparatus becomes large, the upper limit of the microactivity test method (MAT) may be about this level.

Further, the ratio (T) / (D _I ) between the height (T) and the inner diameter (D _I ) is in the range of 1.1 to 7.0, more preferably 1.5 to 6.5. preferable.

When the ratio (T) / (D _I ) is within the above range, a uniform flow state of the catalyst can be obtained, and the mixed state of the raw material hydrocarbon oil and the catalyst can be uniformly performed. Can be high.

  The internal volume of the catalyst flow cell (1) is preferably in the range of 5 to 40 ml, more preferably 6 to 30 ml.

  If the internal volume of the catalyst flow cell (1) is in the above range, a suitable flow state can be obtained even with a small amount of catalyst charge, so the reproducibility of the catalytic cracking test result of hydrocarbon oil is improved. In addition, a reaction result very close to that of the pilot device can be obtained.

  The amount of catalyst in the catalyst flow cell (1) during the test varies depending on the internal volume of the catalyst flow cell (1), the particle size distribution of the catalyst, the bulk density of the catalyst, etc., but 1 to 20 g, It is preferable that it exists in the range of 2-15g.

  When the amount of the catalyst is small, a uniform flow state cannot be obtained because the catalyst is small, the contact between the catalyst and the raw hydrocarbon oil becomes uneven, and the amount of the raw hydrocarbon oil used is reduced. For this reason, the product recovery rate tends to decrease, and the test accuracy tends to be insufficient. Even if the amount of the catalyst is too large, the amount of raw material hydrocarbon oil used is also increased, resulting in an increase in the amount of gas product generated after the reaction, and with respect to the internal volume of the catalyst flow cell (1) described above. Since the internal pressure of the reaction vessel may increase rapidly due to excess, problems such as non-uniform flow conditions and backflow of product gas to the catalyst flow gas supply nozzle (3) are likely to occur, and test accuracy is improved. It may be insufficient.

  In addition, when it is desired to further increase the catalyst filling amount, the size of the catalyst flow cell (1) can be increased in proportion to the catalyst amount. The test apparatus of the present invention is designed for the purpose of testing and developing a catalyst used in a commercial catalytic cracking apparatus, and the catalyst has an average particle diameter of 40 to 100 μm, preferably 50 to 80 μm. It is preferable.

  If the average particle diameter of the catalyst is not within the above range, a suitable catalyst flow state cannot be obtained, and the test accuracy may be insufficient.

  The average particle diameter of the above catalyst was sieved at 20, 30, 45, 60, 75, 90, 105, and 150 μm by a dry micromesh sieve method, and the weight percent of each classified sample was determined, and the cumulative weight percent was plotted. The 50% by weight value is defined as the average particle size.

  The bulk specific gravity of the catalyst is preferably in the range of 0.5 to 1.1 g / ml, more preferably 0.6 to 1.0.

  Even when the bulk specific gravity of the catalyst is not within the above range, the test accuracy may be insufficient because a suitable flow state cannot be obtained.

  The bulk specific gravity of the catalyst is measured based on UOP Method 254-65.

  As a specific measurement method, the catalyst is calcined at 600 ° C. for 2 hours, cooled, poured into a 25 ml cylinder until the catalyst overflows, the overflowed catalyst is horizontally ground from the cylinder upper surface, and the weight of the catalyst is measured. Calculated by

Bulk specific gravity (g / ml) = catalyst weight (g) / 25 (ml)
In addition, a filter can be provided at the uppermost part of the catalyst flow cell (1) to prevent the catalyst from scattering, and it can be used in combination with glass wool or the like.

Reaction raw material supply nozzle (2)
A nozzle (2) for supplying the reaction raw material to the catalyst flow cell (1) is provided inside the cell. The reaction raw material supply nozzle (2) is installed so that the tip thereof can flow in the catalyst flow cell (1) and the catalyst. In particular, when the reaction raw material supply nozzle (2) has a conical structure or a hemispherical structure at the lower part of the catalyst flow cell (1), the nozzle is provided so that the tip of the nozzle is positioned at the center of the structure. It is preferable.

  If the tip of the reaction raw material supply nozzle (2) is at the center of the conical or hemispherical structure, the contact between the catalyst and the raw material hydrocarbon oil becomes more uniform, and the test accuracy is high.

The cross-sectional area of the tip of the reaction raw material supply nozzle (2) is preferably in the range of 0.1 to ⁴ mm ² , more preferably 0.2 to ² mm ² .

  When the cross-sectional area of the tip of the reaction raw material supply nozzle (2) is in the above range, the reaction raw material can be stably supplied and good test accuracy can be obtained.

  In the reaction raw material supply (2), the reaction raw material is introduced into the catalyst flow cell (2) from an external reaction raw material supply source by a pump or the like.

Gas supply nozzle for catalyst flow (3)
A catalyst flow gas supply nozzle (3) from above is provided in the catalyst flow cell (1) together with the reaction raw material supply nozzle (2). In the catalytic reaction, a gas for catalyst flow is usually supplied to flow the catalyst.

  The catalyst flow gas supply nozzle (3) is provided so that the tip of the nozzle is located at the center of the lower conical region or hemispherical region in order to increase the contact efficiency with the catalyst and the raw material oil. It is preferable.

  When the tip of the catalyst flow gas supply nozzle (3) is in a conical region or a hemispherical region, a suitable catalyst flow state can be obtained, so that good test accuracy can be obtained.

  The reaction raw material supply nozzle (2) and the catalyst flow gas supply nozzle (3) are preferably provided close to each other. When both are provided close to each other, the catalyst that has been in a suitable fluidized state by the fluidizing gas uniformly contacts the raw material hydrocarbon oil, so that good test accuracy can be obtained.

  In particular, in the present invention, a double pipe is used, and an inner inner nozzle is used as a reaction raw material supply nozzle (2), and an outer outer pipe is used as a catalyst flow gas supply nozzle (3). It is preferable.

  FIG. 1 shows an example of such a double pipe.

  When such a double pipe is used as the reaction raw material supply nozzle (2) and the gas flow nozzle for catalyst flow (3), it is possible to supply the raw material hydrocarbon oil to the catalyst in a suitable flow state, which is good. Test accuracy can be obtained. Further, the fluidizing gas also has a role of uniformly dispersing and diffusing the raw material hydrocarbon oil, so that good test accuracy can be obtained.

  The outer pipe of the double pipe can be used as the reaction raw material supply nozzle (2), and the inner pipe can be used as the gas flow supply nozzle for catalyst flow (3), but in this case, the mixed state of the catalyst and the raw material hydrocarbon oil is The test accuracy may be insufficient.

  The reaction raw material supply nozzle (2) and the catalyst flow gas supply nozzle (3) can be appropriately designed and used so that a predetermined range of reaction raw material can be supplied and the catalyst can be in a uniform flow state. .

Sectional area of the distal end portion of the catalyst fluidizing gas supply nozzle (3) is 0.2~8mm ^2, more preferably in the range of 0.4~4mm ^2.

  If the cross-sectional area of the tip of the catalyst flow gas supply nozzle (3) is within the above range, the catalyst can be made to be in a uniform flow state, and good test accuracy can be obtained.

  Note that an inert gas is used as the catalyst flow gas. In the apparatus of the present invention, nitrogen gas is recommended from the viewpoint of economy.

Support (4)
A support (4) is provided so that the reaction raw material supply nozzle (2) and the catalyst flow gas supply nozzle (3) can be fixed at predetermined positions.

  By providing the support (4), the flow state of the catalyst can be kept constant, and the feed position of the raw hydrocarbon oil can be kept constant, so that excellent test accuracy can be obtained.

  A support for the catalyst flow cell (1) is not shown, but can be provided as appropriate. For example, a support in the form of hanging the catalyst flow cell (1) on the nozzles (2) and (3) can be provided.

Product recovery line (5)
A product recovery line (5) is provided at the lower part of the reaction vessel (6). The product (gaseous product, liquid product) and catalyst flow gas that are distilled at the start of the reaction in the catalyst flow cell are recovered from the product recovery line (5) and used for composition analysis and the like.

Reaction vessel (6)
The reaction vessel (6) mainly contains the above-described catalyst flow cell (1), reaction raw material supply nozzle (2), catalyst flow gas supply nozzle (3) and support (4), and a product at the bottom. It has a recovery line (5). The size, shape, and the like of the reaction vessel (6) are preferably such that the catalyst flow cell (1) can be contained and heated uniformly by a heating furnace (7) provided outside.

Heating furnace (7), temperature detector (8)
An annular heating furnace (7) is provided so that the reaction vessel (6) can be inserted therein. The heating furnace (7) is appropriately adjusted so as to maintain a predetermined reaction temperature. The heating method is not particularly limited, and a well-known one can be adopted. As the temperature detector, a well-known one such as a thermocouple is usually used.

  Next, a test method using the test apparatus for the fluid catalytic cracking catalyst of the present invention will be described.

The catalyst catalyst can be tested without particular limitation as long as it is a catalyst for fluid catalytic cracking of hydrocarbon oil. At this time, it is preferable that an average particle diameter and bulk specific gravity exist in the above-mentioned range.

  The catalyst is obtained by spray-drying a mixed slurry of crystalline aluminosilicate zeolite, inorganic oxide matrix component, binder, clay mineral and the like disclosed in Patent Documents 5 and 6 (sometimes referred to as a fresh catalyst). A catalyst extracted from a commercial catalytic cracking apparatus (sometimes referred to as an equilibrium catalyst) or the like can also be used.

  In the case of a fresh catalyst, it is preferable to measure by hydrothermally treating in advance at approximately 650 to 850 ° C. and making it quasi-equilibrium. It is also possible to carry out measurement by supporting a metal component such as Ni, V, Fe, etc. contained in the equilibrium catalyst on a fresh catalyst and then quasi-equilibrium. In the case of an equilibrium catalyst, although it depends on the purpose of the test, it is usually tested by heating and baking to remove carbon.

Hydrocarbon oil (raw oil)
As the raw material oil, vacuum distillation light oil, atmospheric distillation residual oil, vacuum distillation residual oil, deasphalted oil, light cycle oil (LCO), heavy cycle oil (HCO), or a mixed oil thereof can be used.

Test method First, the catalyst flow cell (1) in the reaction vessel (6) is filled with a predetermined amount of catalyst, then the reaction vessel (6) is placed in the heating furnace (7), and then the flow gas Is supplied at a predetermined speed to fluidize the catalyst in the catalyst flow cell (1), and the temperature of the catalyst layer is raised to a predetermined reaction temperature.

  After the temperature rise, the raw material oil is supplied from the reaction raw material supply nozzle (2) at a predetermined speed for a predetermined time to be reacted.

  While reacting, the product is recovered from the product recovery line (5) provided at the bottom of the reaction vessel (6), and the product gas and product oil are separated and quantified with a cooler cooled to -10 ° C. , Separating and quantifying each component contained in the product gas and product oil.

  Separation and quantification of gas components are performed by, for example, separating and quantifying hydrogen and hydrocarbons having 1 to 6 carbon atoms by gas chromatography (manufactured by Shimadzu Corporation: GC-20B-3S).

  Separation and quantification of the product oil are performed by separating and quantifying gasoline, LCO, and HCO by gas chromatography (GC-2014, manufactured by Shimadzu Corporation).

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited at all by these Examples.

[Example 1]
Catalyst test apparatus for fluid catalytic cracking The catalyst test apparatus for fluid catalytic cracking has the structure shown in FIG. 1, with the reaction vessel 6 having a height of 26 cm, an inner diameter of 2.2 cm, and the cell 1 having a height of 7.7 cm. The inner diameter was 1.6 cm, the bottom was on a cone, and the cone angle was 45 ° from the perpendicular. The nozzle has a double tube structure, the cross-sectional area of the tip of the reaction raw material supply nozzle 2 is 1.1 mm ² , and the cross-sectional area of the tip of the catalyst flow gas supply nozzle 3 is 2.4 mm ² . there were. The nozzle tip used was the one installed so as to be the central part of the cone bottom of the cell 1.

The catalyst flow cell has a cylindrical shape, an inner diameter (D ₁ ) of 1.6 cm, a height (T) of 7.7 cm, and an internal volume of 14.4 ml.

As a catalyst catalyst for fluid catalytic cracking , JGC Catalysts & Chemicals Co., Ltd. product: CVZ, an average particle diameter of 65 μm, a bulk specific gravity of 0.77 g / ml, and a zeolite content of 25% by weight were used.

Pseudo-equilibrium fluidized catalytic cracking catalyst (manufactured by JGC Catalysts & Chemicals Co., Ltd .: CVZ, average particle size = 65 μm, bulk specific gravity = 0.77 g / ml, zeolite content = 25 wt%) was calcined at 600 ° C. for 1 hour. Thereafter, a toluene solution of nickel naphthenate and vanadium naphthenate was absorbed so that nickel and vanadium would be 3000 ppm and 500 ppm, respectively, then dried at 110 ° C., calcined at 600 ° C. for 1.5 hours, and then at 810 ° C. Steam treatment was performed for 12 hours, and quasi-equilibrium was obtained by firing again at 600 ° C. for 1 hour.

Reaction test The catalyst flow cell (1) of the fluid catalytic cracking catalyst test apparatus is filled with 4.8 g of the pseudo-equilibrium catalyst, and N ₂ gas is supplied as a fluidizing gas at a rate of 30 ml (STP) / min. The temperature was raised to 550 ° C. while fluidizing. Then, the reaction (NO. 1) was performed under the following conditions.

Reaction (NO.1)
An oil obtained by mixing desulfurized atmospheric residual oil (DSAR) and desulfurized vacuum distilled light oil (DSVGO) at a ratio of 1: 1 as a raw material hydrocarbon oil was supplied at an oil feed rate of 0.096 g / sec for 10 seconds. At this time, catalyst / raw material hydrocarbon oil ratio (C / O): 5, space velocity (WHSV): 72 hr ⁻¹ , and reaction time is 10 sec.

At the start of the reaction, the product is recovered from the product recovery line (5). Then, after the supply of the raw material hydrocarbon oil is completed, the reaction raw material supply nozzle (2) is 30 ml / min and the catalyst flow gas supply nozzle (3 The product remaining on the catalyst was recovered while supplying N ₂ gas at a rate of 30 ml / min. Thereafter, the produced gas and the produced oil were separated and quantified with a cooler cooled to −10 ° C., and then each component contained in the produced gas and the produced oil was separated and quantified.

  After completion of the reaction, the catalyst was taken out from the catalyst flow cell (1), and the coke remaining on the catalyst was quantified with a carbon analyzer (EMIA-321V manufactured by Horiba, Ltd.). Based on the separation / quantification results, the conversion rate and the yield of each component were determined based on the following rules.

Boiling range of gasoline: 36 to 204 ° C. Boiling range of light cycle oil (LCO): 204 to 343 ° C. Boiling range of heavy cycle oil (HCO): 343 ° C. or more Conversion (wt%) = 100− (LCO wt% + HCO wt%) )(weight%)
Reaction (NO.2)
In the reaction (NO.1), 5.76 g of the catalyst was charged, and the raw material hydrocarbon oil was supplied at an oil passing rate of 0.096 g / sec for 10 seconds, and the catalyst / raw material hydrocarbon oil ratio (C / O): 6 , Space velocity (WHSV): 57 hr ⁻¹ , reaction (NO. 2) was carried out in the same manner except that the reaction time was 10 sec, and the conversion rate and the yield of each component were determined.

Reaction (NO.3)
In the reaction (NO. 1), 6.72 g of catalyst was charged, and raw material hydrocarbon oil was supplied at an oil passing rate of 0.096 g / sec for 10 seconds, and the catalyst / raw material hydrocarbon oil ratio (C / O): 7 , Space velocity (WHSV): 49 hr ⁻¹ , reaction (NO. 3) was carried out in the same manner except that the reaction time was 10 sec, and the conversion rate and the yield of each component were determined.

Reaction NO. The results of 1 to 3 were plotted on a graph as the relationship between the conversion rate vs. the yield of each component, and the yield of each component at a conversion rate of 68% by weight was determined from the graph, and the results are shown in the table. Moreover, the difference with the yield of each component in the result of the following reference example 1 was shown in the table | surface.
[Reference Example 1]
Catalyst test apparatus for fluid catalytic cracking A performance evaluation test was conducted using a conventionally known catalyst circulation regeneration pilot plant (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Midget-2) shown in FIG. The diameter of the bottom of the reaction tower (41) is 1.28 cm, the diameter of the top of the reaction tower (42) is 0.94 cm at the bottom detail and 2.14 cm at the top thickest part, and the total height of the reaction tower is 81.cm. It was 7 cm.

Fluid catalytic cracking catalyst A catalyst equilibrated in the same manner as in Example 1 was used.

Reaction test catalyst circulation type catalyst test device for fluid catalytic cracking (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Midget-2) was charged with 2 kg of quasi-equilibrium catalyst, and while circulating the catalyst, desulfurized atmospheric pressure as raw material hydrocarbon oil The oil which mixed residual oil (DSAR) and desulfurization vacuum distillation light oil (DSVGO) by 1: 1 was supplied at the speed | rate of 10 g / min. At this time, the temperature was adjusted with an electric heater so that the temperature at the top of the reaction tower was 520 ° C. and the temperature at the bottom of the reaction tower was 550 ° C.

  After the reaction, the catalyst passes through the stripper (45) and the lift line (46) and is transferred to the regeneration tower (47). While supplying air at a temperature of 680 ° C., the amount of coke on the regenerated catalyst is 0.05% by mass. Played back to be as follows. The regenerated catalyst was circulated through the reaction tower.

Reaction (NO.1)
In the above, the reaction was carried out under conditions of a catalyst circulation rate of 50 g / min and a catalyst / raw material hydrocarbon oil ratio (C / O): 5.

  The resulting product was recovered by separating it into product oil and product gas with a fractionator cooled to −20 ° C., and then each component was separated and quantified.

  The conversion rate and the yield of each component were determined according to the same rules as in Example 1.

Reaction (NO.2)
In the above, the reaction (NO. 2) was performed under the conditions of a catalyst circulation rate of 70 g / min and a catalyst / raw material hydrocarbon oil ratio (C / O): 7.

  The obtained product was separated and quantified in the same manner as in the reaction (NO. 1).

Reaction (NO.3)
In the above, the reaction (NO. 3) was performed under the conditions of a catalyst circulation rate of 80 g / min and a catalyst / raw material hydrocarbon oil ratio (C / O): 8.

  The obtained product was separated and quantified in the same manner as in the reaction (NO. 1).

Reaction NO. The results of 1 to 3 were plotted on a graph as the relationship between the conversion rate vs. the yield of each component, and the yield of each component at a conversion rate of 68% by weight was determined from the graph, and the results are shown in the table.
[Comparative Example 1]
Fixed-bed catalytic cracking catalyst test apparatus A fixed-bed catalytic cracking catalyst test apparatus (manufactured by JGC Catalysts & Chemicals Co., Ltd .: ASTM-MAT) shown in FIG. 3 was used. ASTM-MAT has an inner diameter of the reactor 34 of 1.56 cm and a height of 25.7 cm, and the cross-sectional area of the feed oil supply nozzle 32 is 0.6 mm ² .

Fluid catalytic cracking catalyst A catalyst equilibrated in the same manner as in Example 1 was used.

Reaction test Fixed bed catalytic cracking catalyst test equipment (manufactured by JGC Catalysts & Chemicals Co., Ltd .: ASTM-MAT) was filled with glass wool at the bottom of the reactor, and 4 g of the catalyst quasi-equilibrated in the same manner as in Example 1 was added thereto. Filled and set with glass wool on it.

Reaction (NO.1)
The temperature in the reactor was set to 550 ° C., and an oil obtained by mixing desulfurized atmospheric residual oil (DSAR) and desulfurized vacuum distilled gas oil (DSVGO) at 1: 1 as a raw material hydrocarbon oil at an oil feed rate of 0.0177 g / sec. Feeded for 75 seconds. At this time, the catalyst / raw material hydrocarbon oil ratio (C / O): 3, the space velocity (WHSV): 16 hr ⁻¹ , and the reaction time is 75 sec.

At the start of the reaction, the product was recovered from the product recovery line, and then after the feed of the raw material hydrocarbon oil was completed, N ₂ gas was supplied to the reaction raw material feed nozzle (32) under the condition of 30 ml and remained on the catalyst. The product was recovered. Thereafter, the produced gas and the produced oil were separated and quantified with a cooler cooled to −10 ° C., and then each component contained in the produced gas and the produced oil was separated and quantified.

  After completion of the reaction, the catalyst was taken out from the catalyst flow cell (1), and the coke remaining on the catalyst was quantified with a carbon analyzer (EMIA-321V manufactured by Horiba, Ltd.).

  The conversion rate and the yield of each component were determined according to the same rules as in Example 1.

Reaction (NO.2)
In the reaction (NO. 1), the feed rate of the raw hydrocarbon oil remains 0.0177 g / sec, the feed time is 64.4 seconds, and the catalyst / raw hydrocarbon oil ratio (C / O): 3.5 The reaction (NO. 2) was carried out in the same manner except that the reaction time was 64.4 sec, and the conversion rate and the yield of each component were determined.

Reaction (NO.3)
In the reaction (NO. 1), the feed rate of the raw hydrocarbon oil remains 0.0177 g / sec, the feed time is 56.4 seconds, the catalyst / raw hydrocarbon oil ratio (C / O): 4, the reaction The reaction (NO. 3) was carried out in the same manner except that the time was 56.4 sec, and the conversion rate and the yield of each component were determined.

  Reaction NO. The results of 1 to 3 were plotted on a graph as the relationship between the conversion rate vs. the yield of each component, and the yield of each component at a conversion rate of 68% by weight was determined from the graph, and the results are shown in the table. Moreover, the difference with the yield of each component in the result of the reference example 1 is shown in the table.

[Comparative Example 2]
Catalyst test apparatus for fluid catalytic cracking The catalyst test apparatus for fluid catalytic cracking (made by Kayser: ACE-MAT, model R +) shown in FIG. 2 was used.

The reactor 21 has a lower inner diameter of 1.58 cm, an upper inner diameter of 2.29 cm and an overall height of 38.4 cm. The raw material supply partial cross-sectional area of the raw material oil and the gas supply nozzle 22 for dispersion is 0.2 mm ² The working gas supply partial cross-sectional area was 1.8 mm ² .

Fluid catalytic cracking catalyst A catalyst equilibrated in the same manner as in Example 1 was used.

Reaction test The catalyst of the fluid catalytic cracking test equipment (Kayser: ACE-MAT, model R +) was charged with 9 g of the pseudo-equilibrium catalyst as in Example 1 and reacted under the following conditions. It was.

Reaction (NO.1)
The temperature in the reactor was set to 550 ° C., and an oil obtained by mixing desulfurized atmospheric residual oil (DSAR) and desulfurized vacuum distilled light oil (DSVGO) at a ratio of 1: 1 as a raw material hydrocarbon oil at a feed rate of 0.02 g / sec. Feeded for 120 seconds. At this time, the catalyst / raw material hydrocarbon oil ratio (C / O): 3.75, the space velocity (WHSV): 8 hr ⁻¹ , and the reaction time is 120 sec.

Along with the start of the reaction, the product was recovered from the product recovery line (24). Then, after the supply of the raw hydrocarbon oil was completed, N ₂ gas was supplied to recover the product on the catalyst. The recovered product was separated and quantified into product gas and product oil with a cooler cooled to −15 ° C., and then each component contained in the product gas and product oil was separated and quantified. Thereafter, the temperature of the reactor was raised to 700 ° C. in an air atmosphere, and the coke was quantified with a carbon analyzer (1440D manufactured by Servomex) while burning the coke remaining in the catalyst.

  The conversion rate and the yield of each component were determined according to the same rules as in Example 1.

Reaction (NO.2)
In the reaction (NO. 1), the feed rate of the raw hydrocarbon oil remains at 0.02 g / sec, the feed time is 90 seconds, the catalyst / raw hydrocarbon oil ratio (C / O): 5, and the reaction time: The reaction (NO. 2) was conducted in the same manner except that the period was 90 sec, and the conversion rate and the yield of each component were determined.

Reaction (NO.3)
In the reaction (NO. 1), the feed rate of the raw hydrocarbon oil remains at 0.02 g / sec, the feed time is 75 seconds, the catalyst / raw hydrocarbon oil ratio (C / O): 6, and the reaction time: The reaction (NO.3) was carried out in the same manner except for 75 sec, and the conversion rate and the yield of each component were determined.

  Reaction NO. The results of 1 to 3 were plotted on a graph as the relationship between the conversion rate vs. the yield of each component, and the yield of each component at a conversion rate of 68% by weight was determined from the graph, and the results are shown in the table. Moreover, the difference with the yield of each component in the result of the reference example 1 is shown in the table.

  From the results of the above examples, it was found that the test apparatus of Example 1 had a small difference from the test result of Reference Example 1 of the pilot test apparatus, and showed almost the same results as the pilot test apparatus. On the other hand, in the comparative example 2 using the test apparatus of patent document 7, the difference with the test result of the reference example 1 was large by LPG and a gasoline production rate.

  If the test apparatus of this invention is employ | adopted, the evaluation of the catalyst for fluid catalytic cracking in a commercial catalytic cracking apparatus and the evaluation of the catalyst extracted from the commercial catalytic cracking apparatus can be performed with a small scale test apparatus. For this reason, it is a test apparatus that can greatly contribute to the research and development of catalytic cracking catalysts.

1 Catalyst flow cell
2 Reaction material supply nozzle
2 'feed oil supply pump
3 Gas supply nozzle for catalyst flow
3 'Gas supply source for catalyst flow
4 Nozzle support
5 Product recovery line
6 Reaction vessel
7 Heating furnace
8 Thermocouple (Temperature detector)
21 reactor (catalyst fluidized bed)
22 Feed oil and gas supply nozzle for dispersion
23 Gas supply nozzle for catalyst flow
23 'Gas flow line for catalyst flow
24 Product recovery line
25 Heating furnace
26 Thermocouple (Temperature detector)
31 Catalyst layer (fixed bed)
32 Feed oil supply nozzle
32 'feed oil supply pump
33 Purge gas supply line
34 reactor
35 Heating furnace
36 Thermocouple (Temperature detector)
41 Bottom of reaction tower
42 Top of reaction tower
43 Raw oil supply line
44 Separator
45 Stripper
46 Lift line
47 Regeneration tower
48 Catalyst transport line
49 Catalyst trap
50 Oil recovery tank
51 Fractionator
52 Product gas

Claims (5)

  Inside the catalyst flow cell (1), the catalyst flow cell (1) is provided with a reaction raw material supply nozzle (2) and a catalyst flow gas supply nozzle (3) from above, and a product at the bottom. A catalyst test apparatus for fluid catalytic cracking comprising a reaction vessel (6) provided with a recovery line (5). The catalyst flow cell (1) is cylindrical, the inner diameter (D _I ) is in the range of 1 to 4 cm, the height (T) is in the range of 2 to 14 cm, the height (T) and the inner diameter ( claims D _I) the ratio of (T) / (D _I) is in the range of 1.1 to 7.0, the bottom of the cell is characterized by a conical structure or hemispherical structure concave down Item 4. The catalytic test apparatus for fluid catalytic cracking according to Item 1.   The catalytic test apparatus for fluid catalytic cracking according to claim 1 or 2, characterized in that the internal volume of the catalyst flow cell (1) is in the range of 5 to 40 ml.   The catalyst test apparatus for fluid catalytic cracking according to any one of claims 1 to 3, wherein the catalyst filling amount of the catalyst flow cell (1) during the test is in the range of 1 to 20 g.   The catalyst test apparatus for fluid catalytic cracking according to claim 4, wherein the average particle diameter of the catalyst is in the range of 40 to 100 µm and the bulk specific gravity is in the range of 0.5 to 1.1 g / ml.

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