The name of the invention: fluid catalytic cracking catalyst test equipment
Technical field
[0001]
　The present invention relates to a test apparatus for fluid catalytic cracking catalyst of hydrocarbon oil. For more information, fluidized catalytic cracking pilot device further commercial fluid catalytic cracking unit (real device) and a very similar reaction results, not only the evaluation of the fluid catalytic cracking catalyst, withdrawn from the commercial fluid catalytic cracking unit It was a test apparatus of the applicable fluid catalytic cracking catalyst in evaluation and research and development of the catalyst.
Background technique
[0002]
　Fluid catalytic cracking process is a process for predominantly producing a gasoline from a hydrocarbon oil.
[0003]
　As the catalyst used in fluid catalytic cracking processes, for example, zeolite and a binder and kaolin, a filler such as alumina, it is known catalysts containing additives as necessary.
[0004]
　For example, Patent Document 1, (1) and alumina particles with a particle size 2 ~ 60 .mu.m containing a metal component and a phosphorus component selected from one or more alkaline earth metals and rare earth metals, (2) the crystalline aluminosilicate and zeolite, have been described (3) porous inorganic oxide matrix uniformly dispersed hydrocarbon catalytic cracking catalyst. According to this catalyst, metal resistance, high activity, has a selectivity, it is described that can suppress the formation of hydrogen and coke.
[0005]
　Patent Document 2, alumina, contain inorganic oxide matrix other than the crystalline aluminosilicate zeolite and alumina, fluid catalytic cracking catalyst composition of hydrocarbons each component containing a phosphorus atom are described. Using this catalyst cracking of heavy oil hydrocarbon excellent bottom (搭底 oil) Resolution of hydrogen, the amount of coke is low, it is described that the greater the gasoline and kerosene and gas oil fraction.
[0006]
　Patent Document 3, (1) a molecular sieve having an -Si-OH-Al- skeleton having a modified surface pores with a specific phosphoric acid salt, and (2) water-insoluble metal salt, and (3) phosphoric acid compound It is described raw material mixture of hydrothermal stability obtained by water evaporation porous molecular sieve catalyst comprising a. The catalyst, hydrothermal resistance is high, is described as improving gas olefin yield, selectivity.
[0007]
　Patent Document 4, the airflow calcined alumina, clay mainly composed of silica and alumina, the fine spherical particles by spray drying an aqueous slurry of the silica-based inorganic oxide precursors and mixtures consisting of crystalline aluminosilicate, an alkali metal after the content of the oxide was washed to be 1.0 wt% or less as oxide, method for producing a catalytic cracking catalyst for introducing the rare earth is described. The catalyst, when used in catalytic cracking of heavy hydrocarbon oils containing a large amount of metal, high cracking activity, show high gasoline selectivity, coke, small production of gas, yet is described as having a high hydrothermal resistance ing.
[0008]
　Patent Document 5, zeolite and a catalyst composition comprising an inorganic oxide matrix composed of the active matrix component and an inert matrix component, a fluid catalytic cracking catalyst of hydrocarbon oil obtained by mixing two or more, each catalyst composition, the content of the zeolite are different (although one of the catalyst composition, the content of the zeolite contains a 0) that a catalyst for fluidized catalytic cracking of a hydrocarbon oil which comprises There has been described. According to this catalyst, gasoline and middle distillate is obtained in high yield, also coke becomes low yield, and further, high resolution of the bottom, i.e., reducing the yield of the heavy fraction It has been described as it is.
[0009]
　Patent Document 6, a catalyst composition A comprising 10 to 30% by weight of silica based binder as zeolite and a binder, and a catalyst composition B containing 10 to 30% by weight of the aluminum compound binder as zeolite and a binder the weight of the catalyst composition the a W the a and the weight of the catalyst composition Bs W Bs as the weight ratio (W the a : W Bs ) is 10: 90-90: it was mixed in any proportion in the 10 range It describes a fluid catalytic cracking catalyst of hydrocarbon oil, characterized in that. According to this catalyst, gasoline and gas oil fractions obtained in a high yield, also coke becomes low yield, and further, high resolution of the bottom, i.e., it is possible to suppress the generation of the heavy fraction It has been described as.
[0010]
　To test these catalytic properties are known American Society for Testing and Materials (ASTM)) in defined ASTM-D3907 micro activity test method (MAT-) it has been commonly used. A schematic view of a micro activity test method is shown in Figure 3. In Figure 3, 31 is a catalyst layer of a fixed bed, the feedstock supply nozzles 32, through a feed oil feed pump, feed oil is inserted into the reactor together with the purge gas derived from the purge supply line 33 that. 35 is a heating furnace, 36 indicates a thermocouple. Such employing a micro activity test method, the activity of the catalyst withdrawn from a commercial catalytic cracking unit, to evaluate the selectivity or the like, have been used as an indicator of operation.
[0011]
　However, in the test results at the operating results and MAT in the commercial catalytic cracking unit, although roughly match the trends of the activity level, the yield of the activity level, various types of products, there is a case selectivity does not necessarily match It was. This is MAT a reaction apparatus of a fixed bed, feedstock hydrocarbon oil and the contact time of the catalyst is believed to significantly differ.
[0012]
　For example, the contact time in the commercial catalytic cracking unit, may vary depending on the raw material hydrocarbon oil of the type and the like, with respect to which the generally few seconds, and at approximately 50 ~ 120sec in MAT to be used. Moreover, the amount of the catalyst used is also very small and a few grams.
[0013]
　Therefore, by using the pilot plant fluidized bed imitating commercial catalytic cracking unit (actual device), sometimes testing of catalyst evaluation is performed. For example, FIG. 4 shows a schematic diagram of a pilot plant apparatus. In FIG. 4, 41 is the reaction tower bottom, 42 reaction tower top, 43 raw material oil supply line, the separator 44, 45 stripper, 46 lift line, 47 regeneration tower, 48 catalyst transport line, 49 catalyst trap, 50 product oil recovery tank, 51 fractionator, 52 denotes a product gas. Feedstock from line 43, the catalyst is introduced via line 48 to each reaction column bottom 41, after being catalytic cracking reaction, the product is distilled through 50-52.
[0014]
　However, in a test of a pilot plant, the active level, the yield and quality of various products (octane number, etc.), but the selectivity to roughly coincide with the commercial catalytic cracking unit (real device), the number is filling amount of the catalyst kg many, and, since it takes a long time, including such preparation test time, has a drawback that does not increase the test efficiency. In addition, there is a need for a large amount of expenses to the production and maintenance of the pilot plant.
[0015]
　Therefore, development of a new test device employing a fluidized bed has been desired.
[0016]
　Patent Document 7, the test device employing a small fluidized bed shown in FIG. 2 are disclosed. In Figure 2, the catalyst was packed in the catalytic fluidized bed reactor 21, the feed oil and the dispersion gas supply nozzle 22, the feedstock, such as supplying, from the catalyst fluidizing gas supply nozzle and line 23 and 23 ', fluidizing gas is supplied. 24 product gas, a discharge line for the flowing gas. And a heating furnace 25 provided on the outside of the reactor, a test apparatus which performs catalytic cracking reaction while detecting the temperature by thermocouple 26.
[0017]
　The present applicant has obtained a small test apparatus of Patent Document 7, were subjected to various tests. However, this apparatus, loading of the catalyst is a few grams, the contact time between the feedstock hydrocarbon oil is generally at 60 ~ ... 120 seconds, although the test efficiency is good, the deviation of the test results of the pilot plant is not necessarily small, thus , on the performance evaluation of the catalyst used in the actual apparatus, was not considered necessarily sufficient ones.
CITATION
Patent literature
[0018]
Patent Document 1: Japanese Equity No. 5-16908
Patent Document 2: Laid-Open Publication No. 8-173816
Patent Document 3: Unexamined Publication No. 2009-511245
Patent Document 4: JP Publication No. 60-193543
Patent Document 5: JP Publication No. 2010-110698
Patent Document 6: WO2009 No. / 145,311
Patent Document 7: USP6,069,012
Summary of the invention
Problems that the Invention is to Solve
[0019]
　The present inventors have, to solve such a problem, a result of intensive studies, in a small test apparatus, the interior isolated catalyst flow cell of the reaction vessel (6) (1) is provided, the catalyst in this cell filled, the catalyst and flow conditions while supplying the catalyst fluidizing gas from above, by supplying a reactant hydrocarbon oil from above the fluidized catalyst zone, the test was approximated with the test results of a pilot plant results obtained and we have completed the present invention have found it to be.
Means for Solving the Problems
[0020]
　Fluid catalytic cracking catalyst testing apparatus according to the present invention, the catalyst flow cell (1) therein, onto the catalyst flow cell (1), the reaction raw material supply nozzle (2) a catalyst fluidizing gas from the top feeding nozzle (3) is provided, it is characterized in that it consists reactor bottom to the product recovery line (5) is provided (6).
[0021]
　The a catalyst flow cell (1) is cylindrical, the inside diameter (D the I ) is in the range of 1 ~ 4 cm, height (T) is in the range of 2 ~ 14cm, height (T) and the inside diameter ( D the I ratio (T) / (D a) the I is in the range) is 1.1 to 7.0, it is preferable that the bottom portion of the cell is conical structure concave down.
[0022]
　The internal volume of the catalyst flow cell (1) is preferably in the range of 5 ~ 40ml.
[0023]
　Catalyst loading of the catalyst flow cell during the test (1) is preferably in the range of 1 ~ 20 g.
[0024]
　The range of the average particle diameter of 40 ~ 100 .mu.m of the catalyst, bulk density is preferably in the range of 0.5 ~ 1.1g / ml.
Effect of the invention
[0025]
　According to the present invention, the reaction result of further fluidized catalytic cracking pilot unit be small and very close to be commercial catalytic cracking unit can be obtained, evaluation of the fluid catalytic cracking catalyst, was withdrawn from a commercial catalytic cracking unit it is possible to provide a test apparatus for fluid catalytic cracking catalyst of hydrocarbon oils which can be suitably used for evaluation and research and development of the catalyst.
Brief description of the drawings
[0026]
[Figure 1] shows a schematic diagram of an embodiment of such a fluid catalytic cracking catalyst testing apparatus of the present invention.
[Figure 2] shows a schematic view of a miniature test equipment of the fluidized bed disclosed in Patent Document 7.
[3] a schematic view of defined ASTM-D3907 micro activity test apparatus in American Society for Testing and Materials (ASTM).
[Figure 4] shows a schematic diagram of a fluidized bed pilot plant simulating a commercial catalytic cracking unit.
DESCRIPTION OF THE INVENTION
[0027]
　The following describes a fluid catalytic cracking catalyst test apparatus according to the present invention.
Fluid catalytic cracking catalyst testing apparatus
　fluid catalytic cracking catalyst testing apparatus according to the present invention, the catalyst flow cell (1) therein, onto the catalyst flow cell (1), the reaction raw material supply nozzle from the top ( 2) a catalyst fluidizing gas nozzles (3) is provided, it is characterized in that it consists reactor bottom to the product recovery line (5) is provided (6).
[0028]
　A schematic diagram of one embodiment of a fluid catalytic cracking catalyst testing apparatus according to the present invention shown in FIG.
[0029]
　1, the catalyst flow cell 1, the reaction raw material supply nozzle 2, the raw material oil supply pump 2 ', a catalyst fluidizing gas feed nozzle 3, the catalyst for fluidized gas source 3', support 4 nozzle, the product recovery line 5, it comprises a reaction vessel 6, the heating furnace 7 and thermocouple 8,.
[0030]
　The catalyst flow cell (1)
　a predetermined catalytic cracking catalyst is inserted into the catalyst flow cell (1), the catalyst is fluidized, performs catalytic decomposition of the introduced hydrocarbon oil. Such catalysts flow cell (1) is cylindrical and has a bottom portion at the bottom. It is preferable that the bottom is a cone-like structure or semi-spherical structure of concave below. Such a structure, since the catalyst flow cell is the catalyst uniform flow state during the reaction as compared with the case prismatic or bottom is flat, improves the reproducibility of the catalytic cracking test results of a hydrocarbon oil and reaction results were very close and the pilot device is obtained.
[0031]
　The catalyst flow cell (1), the cell interior is placed so as to be sequestered from the reaction vessel interior.
[0032]
　By providing such a catalyst flow cell into the reaction vessel, gasoline yield, LPG yield, etc. coke yield, it is possible to obtain the test results of the same level measurement result of the pilot plant. Although the reason is not clear, as in Patent Document 7, instead of using the reaction vessel itself, by using a sequestered cell reaction vessel, it can quickly separate the product and the fluidized catalyst layer, the secondary reaction since the (side reaction may be referred to) can be suppressed and the present inventors consider.
[0033]
　Incidentally, such a jig or stopper for holding the catalyst flow cell is may be provided in such a cell outer surface and a bottom portion, whereby the catalyst flow cell (1) is installed at a predetermined position within the reaction vessel. From the cell upper catalyst flow, below the nozzle (2) and (3) to may be adapted suspended to a support (4).
[0034]
　The inner diameter of the cylindrical cell (D the I ) is 1 ~ 4cm, more preferably in the range of 1 ~ 3cm.
[0035]
　The inner diameter of the cylindrical cell (D the I the) is small, the flow state of the catalyst is deteriorated, the measurement accuracy, there are cases where reproducibility is insufficient. Inner diameter (D of the cylindrical cell I even) is too large, or because the mixed state of the catalyst and the hydrocarbon oil to deteriorate for the diffusion of the lateral direction of the raw material hydrocarbon oil becomes insufficient, the measurement accuracy decrease or, also tend to decompose becomes insufficient.
[0036]
　The height of the cylindrical cell (T) is 2 ~ 14cm, more preferably in the range of 3 ~ 12cm.
[0037]
　Here, the height of the cylindrical cell (T) and refers to the bottom of the cell to the top of the cell.
[0038]
　Those heights of the cylindrical cell (T) is low, the catalyst is insufficient height for uniformly flow, either because the mixed state of the raw material hydrocarbon oil and the catalyst is deteriorated, the measurement accuracy decreases or, also tend to decompose becomes insufficient.
[0039]
　Even if the height of the cylindrical cell (T) is too high, there is no problem in terms of testing, because the test apparatus is increased, the upper limit of the micro activity test method (MAT-) may be any this extent.
[0040]
　Moreover, said height (T) and said inner diameter (D the I ) the ratio of the (T) / (D the I ) 1.1 to 7.0 that further is in the range of 1.5 to 6.5 preferable.
[0041]
　The ratio (T) / (D the I the) is within the above range, uniform flow state of the catalyst is obtained, since the mixed state of the raw material hydrocarbon oil and the catalyst can be uniformly performed, the measurement accuracy It can be increased.
[0042]
　Further, the inner volume of the catalyst flow cell (1) is 5 of 5 ~ 40 ml, and more preferably in the range of 6 ~ 30ml.
[0043]
　When the inner volume of the catalyst flow cell (1) is in this range, because a small amount of a catalyst loading preferred pour state obtained, the reproducibility of the catalytic cracking test results of hydrocarbon oil is improved and reaction results were very close and the pilot device is obtained.
[0044]
　Loading of the catalyst of the catalyst flow cell (1) during the test, the internal volume of the catalyst flow cell (1), the particle size distribution of the catalyst, varies depending bulk density or the like of the catalyst, 1 ~ 20 g, more it is preferably in the range of 2 ~ 15g.
[0045]
　The small loading of catalyst, the catalyst is not uniform flow state is obtained for small, contact between the catalyst and the raw material hydrocarbon oil becomes uneven, moreover, to reduce the amount of raw material hydrocarbon oil recovery of the product is lowered because, tends to become insufficient test accuracy. Is too large, loading of the catalyst, since the most amount of feedstock hydrocarbon oil, the amount of gas product after the reaction is increased, with respect to the internal volume of the catalyst flow cell (1) may internal pressure of the reactor to become excessive increases rapidly, the flow state or become uneven, trouble prone, such that the product gas to the catalyst for fluidized gas feed nozzle (3) flows backward, the test accuracy it may become insufficient.
[0046]
　Incidentally, if you want to test further increase the filling amount of the catalyst, it is also possible to increase the size of the catalyst flow cell (1) in proportion to the amount of catalyst. The test apparatus of the present invention the test of catalysts used in commercial catalytic cracking unit, has been designed for development, average particle size 40 ~ 100 .mu.m of the catalyst, preferably a catalyst in the range of 50 ~ 80 .mu.m it is preferred.
[0047]
　When the average particle size of the catalyst is not in the above range, in order to suitable catalyst fluidized state can not be obtained, there is a case where the test accuracy becomes insufficient.
[0048]
　The average particle diameter of the catalyst, by dry micro mesh sieve method, is sieved with 20,30,45,60,75,90,105,150Myuemu, obtains the weight percent of each sample was classified, plotting cumulative weight% and, as the average particle size of 50% by weight value.
[0049]
　The bulk specific gravity of 0.5 ~ 1.1g / ml of the catalyst, more preferably in the range of 0.6-1.0.
[0050]
　Even if the bulk density of the catalyst is not within the range, for a suitable fluidized state can not be obtained, there is a case where the test accuracy becomes insufficient.
[0051]
　Bulk density of the catalyst is measured based on the UOP Method254-65.
[0052]
　As a specific measuring method, the catalyst was calcined for 2 hours at 600 ° C., cooled, poured until overflowing the catalyst 25ml cylinder, leveling spilled catalyst from the cylinder top surface horizontally, measure the weight of the catalyst, the following formula It is calculated by.
[0053]
　Bulk density (g / ml) = catalyst weight (g) / 25 (ml)
　It should be noted that the top of the catalyst flow cell (1), in order to prevent scattering of the catalyst, can be provided a filter, further It can also be used in combination with such as glass wool.
[0054]
　The reaction material feed nozzle (2)
　a nozzle for supplying a reactant to the catalyst flow cell (1) (2) is provided inside the cell. Such reaction material feed nozzle (2), the tip, in the catalyst flow cell (1), and is disposed so as to be able to flow the catalyst. In particular reactant feed nozzle (2), the catalyst flow cell (1) conical structure of the lower or when having a hemispherical structure, the tip of the nozzle at the center of such a structure is provided so as to be positioned it is preferred that.
[0055]
　The tip of the reaction raw material supply nozzle (2), if the center of the cone-shaped structure or hemispherical structure, and the contact of the catalyst and the raw material hydrocarbon oil becomes more uniform, high test accuracy.
[0056]
　Reactant the cross-sectional area of the distal end portion of the supply nozzle (2) is 0.1 ~ 4 mm 2 , still more 0.2 ~ 2 mm 2 is preferably in the range of.
[0057]
　When the cross-sectional area of ​​the distal end portion of the reaction material feed nozzle (2) is in this range, it can be supplied stably reactants, good test accuracy.
[0058]
　For such a reaction raw material supply (2), such as by a pump from the outside of the reaction raw material supply source, to introduce the reaction raw materials to the catalyst flow cell (2).
[0059]
　The catalyst fluidizing gas nozzles (3)
　together with the reaction material feed nozzle (2), a gas supply nozzle for the catalyst flow from the upper (3) is provided to the catalyst flow cell (1). The catalytic reaction, in order to flow the catalyst, usually, the gas for the catalyst flow is fed.
[0060]
　Such catalysts fluidizing gas nozzles (3) a catalyst, in order to increase the efficiency of contact with the feed oil, is provided so that the tip portion of the nozzle in the center of the bottom of the conical region or hemispherical region, is located it is preferred that.
[0061]
　Since the leading end portion of the catalyst fluidized gas feed nozzle (3) is to be in the conical region or hemispherical region, a suitable catalyst fluidized state is obtained, a good test accuracy.
[0062]
　Further, the reaction raw material supply nozzle (2) a catalyst fluidizing gas nozzles (3) is preferably provided in close proximity. When both are provided close, the catalyst became suitable fluidized state by the fluidizing gas is uniformly contacted with feedstock hydrocarbon oil, it is possible to obtain an excellent test accuracy.
[0063]
　Particularly in the present invention, using a double pipe, the nozzle and the reaction raw material supply nozzle inside the inner tube (2), outside the outer peripheral tube as a gas supply nozzle for catalyst flow (3), used those obtained by integrating it is preferred.
[0064]
　It shows an embodiment example of such a double pipe in FIG.
[0065]
　Such reaction material feed nozzle a double pipe (2), when used as a catalyst for fluidized gas feed nozzle (3), it is possible to supply the feedstock hydrocarbon oil to become a suitable fluidized state catalysts, good it is possible to obtain the Do not test accuracy. Additionally, fluidizing gas it is possible to obtain a good test accuracy also has the role of uniformly distributed and diffused feedstock hydrocarbon oils.
[0066]
　Incidentally, as a reaction raw material supply nozzle outer peripheral tube of the double tube (2), although the inner tube can also be used as the gas supply nozzle catalyst flow (3), in this case, the mixed state of the catalyst and the raw material hydrocarbon oil reduced, there is also a fact that the test accuracy becomes insufficient.
[0067]
　The above reaction material feed nozzle (2) and the gas supply nozzle catalyst flow (3) it can supply reactive material in a predetermined range, and can be appropriately designed to the catalyst in a uniform flow state .
[0068]
　Sectional area 0.2 ~ 8 mm at the tip portion of the catalyst fluidizing gas nozzles (3) 2 , more 0.4 ~ 4 mm 2 is preferably in the range of.
[0069]
　If the said range the cross-sectional area of ​​the distal end portion of the catalyst fluidizing gas nozzles (3), it can be a catalyst and uniform fluidized state, good test accuracy.
[0070]
　As the catalyst fluidizing gas, but an inert gas, in the apparatus of the present invention, nitrogen gas is preferred from the viewpoint of economy.
[0071]
　Support (4)
　The reaction raw material supply nozzle (2) a catalyst fluidizing gas nozzles (3) so as to be fixed in position the support (4) is provided.
[0072]
　By providing a support (4), maintaining the fluidized state of the catalyst constant, it is possible to keep constant even further supply position of the feed hydrocarbon oil is obtained excellent test accuracy.
[0073]
　Incidentally, the support of the catalyst flow cell (1) is not shown, may be provided as appropriate. For example, the nozzle (2) (3) can be provided with support in the form applying a catalyst flow cell (1).
[0074]
　Product withdrawal line (5)
　in the lower part of the reaction vessel (6), product withdrawal line (5) is provided. The product is distilled with the start of the catalyst flow cell reaction (gaseous products, liquid product) and a catalytic fluidizing gas is recovered from the product recovery line (5), is subjected to, such as composition analysis.
[0075]
　Reaction vessel (6)
　the reaction vessel (6) is primarily the catalyst flow cell (1), the reaction raw material supply nozzle (2), a catalyst fluidizing gas nozzles (3) and a support (4) enclosing includes a lower to the product recovery line (5). The size of the reaction vessel (6), together with the shape and the like can containing catalyst flow cell (1) described above is preferably a structure capable of uniformly heated by the heating furnace (7) provided outside.
[0076]
　Heating furnace (7), a temperature detector (8)
　a heating furnace cyclic (7) are provided to allow insertion of the reaction vessel (6) therein. Heating furnace (7) it is appropriately adjusted so as to maintain a predetermined reaction temperature. Is not particularly restricted but includes heating method, it is possible to employ well known, as the temperature detector, well known, such as normal thermocouple is used.
[0077]
　Next, a description will be given test method by the test apparatus of a fluid catalytic cracking catalyst of the present invention.
[0078]
　Catalyst
　As the catalyst, can be tested without any particularly limitation as long as fluid catalytic cracking catalyst of hydrocarbon oil. At this time, the average particle diameter, it is preferable that the bulk specific gravity in the range described above.
[0079]
　The catalyst, Patent Documents 5 and 6 is disclosed in the crystalline aluminosilicate zeolite, an inorganic oxide matrix component, binder, catalyst mixed slurry of such clay minerals obtained by spray-drying (sometimes referred to fresh catalyst) it may also be used, but (sometimes referred equilibrium catalyst) withdrawn catalyst from a commercial catalytic cracking unit or the like can be used.
[0080]
　For fresh catalyst, it is preferable to measure by quasi equilibrate hydrothermally treated in advance with approximately 650 ~ 850 ℃. Further, Ni contained in the equilibrium catalyst, V, and metal components such as Fe supported on a fresh catalyst, then can be measured by quasi-equilibrated. Although the case of the equilibrium catalyst is depending on the test purpose, usually, it is tested to remove the carbon content and heating firing.
[0081]
　Carbonized water vegetable oil (raw oil)
　feedstockとshi te ha, reduced-pressure steam leaving Qing oil, often-pressure steam leaving a residual oil, reduced-pressure steam leaving a residual oil, offアsu fu B A Hikaru Suites oil LITE Cytec ku Hikaruオtest suitable (LCO),ヘBldgーCytec ku Hikaruオtest suitable (HCO) thou ruいwa ko me cry raのmixing oil use wo su ru koとgaでki ru.
[0082]
　Test method
　First, the catalyst flow cell in the reaction vessel (6) (1) filled with a predetermined amount of the catalyst, then placed in the reaction furnace vessel (6) (7) inside, then fluidizing gas the supplied at a predetermined speed the catalyst in the catalyst flow cell (1) are fluidized and heated so that the temperature of the catalyst layer becomes a predetermined reaction temperature.
[0083]
　After heating, the reaction by supplying a predetermined time at a predetermined rate from the reaction raw material supply nozzle feed oil (2).
[0084]
　While the reaction, the product from the product withdrawal line provided in the lower part of the reaction vessel (6) (5) were collected, after the product gas and product oil was separated and quantified by a cooler which is cooled to -10 ℃ , product gas, to separate and quantify the individual components contained in the product oil.
[0085]
　Separation and quantification of gas components, for example gas chromatography (manufactured by Shimadzu Corporation: GC-20B-3S) with, separate hydrogen and hydrocarbons having 1 to 6 carbon atoms, quantified.
[0086]
　Separation and quantification of the produced oil is, by gas chromatography Gufi (manufactured by Shimadzu Corporation GC-2014), gasoline, LCO, the HCO separated and quantified.
Example
[0087]
　Will be further specifically described the present invention by examples and comparative examples, the present invention is not intended to be limited in any way by these examples.
[0088]
Example 1
　fluid catalytic cracking catalyst testing apparatus
　as a testing apparatus for fluid catalytic cracking catalyst has a structure shown in FIG. 1, the height of the reaction vessel 6 is 26cm, inner diameter 2.2 cm, cell 1 High Saga 7.7cm, inside diameter of 1.6cm, the bottom is on the cone, the cone angle was 45 ° from the vertical. The nozzle is a double pipe structure, the cross-sectional area of the distal end portion of the reaction material feed nozzle 2 is 1.1 mm 2 is sectional area of the distal end portion of the catalyst fluidizing gas supply nozzle 3, 2.4 mm 2 in there were. The nozzle tip, was used which was installed so that the site of the center of the conical bottom portion of the cell 1.
[0089]
　The shape of the catalyst flow cell is cylindrical, the inner diameter (D 1 ) is 1.6 cm, the height (T) is 7.7 cm, the inner volume 14.4 ml.
[0090]
　Fluid catalytic cracking catalyst
　as the catalyst, JGC Catalysts and Chemicals Ltd.: CVZ, the average particle diameter of 65 .mu.m, a bulk specific gravity of 0.77 g / ml, the zeolite content using 25 weight%.
[0091]
　Quasi balance of
　fluid catalytic cracking catalysts for (JGC Catalysts & Chemicals (Co., Ltd.): CVZ, average particle diameter = 65μm, the bulk specific gravity = 0.77g / ml, Zeon LITE content = 25% by weight) wo 600 ℃で1 time firing into shi ta after niッCHEMICALS Hikaruおyoびba na jiウRousseau gaそme cryぞme cry 3000ppm, 500ppmとNaru yo-u ni na fu Te nn acid niッke Hikaruおyoびna fu Te nn acid ba na jiウRousseauのSuites Hikaru Eito nn solution wo absorption sa se, after zuいで110 ℃でdried, 600 ℃で1.5 times firing into shi, tsuいで, 810 ℃で12 one woods processing time su chi shi, again firing time of 1 600 ℃でshi te into quasi-equilibrium of shi ta.
[0092]
　Response test
　The filled with a catalyst 4.8g was pseudo-equilibrated in catalyst flow cell (1) fluid catalytic cracking catalyst testing apparatus, N as a fluidizing gas 2 gas was supplied under the condition of 30 ml (STP) / min while fluidization on and the temperature was raised to 550 ° C.. Subsequently, the reaction was carried out (NO.1) under the following conditions.
[0093]
　Reaction (NO.1)
　raw material hydrocarbon oil as desulfurization atmospheric residue oil and (DSAR) desulfurization vacuum distillation gas oil (DSVGO) 1: supply 10 seconds mixed oil at 1 in the oil passing rate of 0.096g / sec did. At this time, the catalyst / feedstock hydrocarbon oil ratio (C / O): 5, space velocity (WHSV): 72Hr -1 , the reaction time is 10sec.
[0094]
　Along with the start of the reaction, the product than the product withdrawal line (5) were collected, then, raw material hydrocarbon oil supply after the end of the reaction raw material supply nozzle (2) to 30ml / min and,, catalyst flow for the gas supply nozzle (3 N under the condition of 30 ml / min in) 2 while supplying gas to recover the product remaining on the catalyst. Thereafter, the product gas and product oil was separated and quantified by a cooler which is cooled to -10 ° C., the product gas, and the respective components contained in the product oil was separated and quantified.
[0095]
　After completion of the reaction, the catalyst was removed from the catalyst flow cell (1), the remaining coke on the catalyst was determined by the carbon analyzer ((manufactured by Horiba, Ltd.) EMIA-321V). Conversion rate based on the separation and quantitative results, the yield of each component were determined on the basis of the provisions of the following.
[0096]
　Gasoline boiling range: 36-204 boiling range of ℃ light cycle oil (LCO): 204 boiling range of ~ 343 ℃ heavy cycle oil (HCO): 343 ℃ or higher
　conversion rate (weight%) = 100- (LCO weight% + HCO weight% ) (% by weight)
　reaction (NO.2)
　in the reaction (NO.1), the catalyst 5.76g filled, to supply 10 seconds raw material hydrocarbon oil in the oil passing rate of 0.096g / sec, catalyst / feedstock hydrocarbon oils ratio (C / O): 6, space velocity (WHSV): 57Hr -1 , except that the reaction time was 10sec conducting a reaction (NO.2) in the same manner, conversion, yield of each component I was asked.
[0097]
　Reaction (NO.3)
　reaction in (NO.1), the catalyst 6.72g filled, the raw material hydrocarbon oil was supplied for 10 seconds in the oil passing rate of 0.096g / sec, catalyst / feedstock hydrocarbon oil ratio ( C / O): 7, space velocity (WHSV): 49Hr -1 , except that the reaction time was 10sec conducting a reaction (NO.3) in the same manner, conversion to determine the yield of each component.
[0098]
　Reaction NO. 1-3 Results were plotted on a graph as the relationship between the yield of conversion vs each component, from the graph to obtain the yield of each component in the 68 wt% conversion, and the results are shown in Table. Also showed a difference between the yield of each component in the result of the following Reference Example 1 in Table.
[Reference Example 1]
fluid catalytic cracking catalyst testing apparatus
　pilot plant catalyst circulation reproduction method known in the prior art shown in Figure 4 (JGC Catalysts and Chemicals Ltd.: Midget-2) with the performance evaluation tests It was. The diameter of the reaction tower bottom (41) is a 1.28cm, the diameter of the reaction tower top portion (42) at the bottom thinnest 0.94cm, a top widest part 2.14cm, the total height of the reaction column is 81. It was 7cm.
[0099]
　Fluid catalytic cracking catalyst
　was used in the same manner as in Example 1 was pseudo-equilibrated catalyst.
[0100]
　Reaction test
　catalyst circulation fluidized catalytic cracking catalyst for test equipment (manufactured by JGC Catalysts & Chemicals (Ltd.): Midget-2) to charge the pseudo-equilibrated catalyst 2kg, while circulating the catalyst, desulfurization atmospheric pressure as a raw material hydrocarbon oil resid and (DSAR) and desulfurization vacuum distillation gas oil (DSVGO) 1: mixed oil was fed at a rate of 10g / min in 1. At this time, the temperature of 520 ℃ of reaction tower top, so that the temperature of the reaction tower bottom and 550 ℃, the temperature was adjusted with an electric heater.
[0101]
　The catalyst after the reaction stripper (45), through the lift line (46) is transferred to the regeneration tower (47), while supplying air at a temperature of 680 ° C., coke quantity on the regenerated catalyst is 0.05 wt% It was regenerated so as to be less. Regenerated catalyst was recycled to the reaction column.　
[0102]
　Reaction (NO.1)
　in the above-mentioned, the catalyst circulation amount of 50g / min, catalyst / feedstock hydrocarbon oil ratio (C / O): The reaction was carried out in five of the conditions.
[0103]
　After resulting product recovered divided into product gas and product oil in the fractionator cooled to -20 ° C., to separate and quantify the components.
[0104]
　Conversion, the yield of each component was determined in the same provisions as in Example 1.
[0105]
　Reaction (NO.2)
　in the above-mentioned, the catalyst circulation amount of 70g / min, catalyst / feedstock hydrocarbon oil ratio (C / O): the reaction was carried out the (NO.2) in 7 of the conditions.
[0106]
　The resulting product was similarly separated and quantified with the reaction (NO.1).
[0107]
　Reaction (NO.3)
　in the above-mentioned, the catalyst circulation amount of 80g / min, catalyst / feedstock hydrocarbon oil ratio (C / O): the reaction was carried out the (NO.3) in 8 of the conditions.
[0108]
　The resulting product was similarly separated and quantified with the reaction (NO.1).
[0109]
　Reaction NO. 1-3 Results were plotted on a graph as the relationship between the yield of conversion vs each component, from the graph to obtain the yield of each component in the 68 wt% conversion, and the results are shown in Table.
[Comparative Example 1]
　Test device of a fixed-bed catalytic cracking catalyst
　shown in Figure 3, the test device of the fixed-bed catalytic cracking catalyst (JGC Catalysts Chemicals Ltd.: ASTM-MAT) was used. ASTM-MAT-a, the inner diameter of the reactor 34 is 1.56cm, the height is 25.7cm, the cross-sectional area of the raw material oil supply nozzle 32 is 0.6 mm 2 is.
[0110]
　Fluid catalytic cracking catalyst
　was used in the same manner as in Example 1 was pseudo-equilibrated catalyst.
[0111]
　Response studies
　testing apparatus of the fixed-bed catalytic cracking catalyst (JGC Catalysts Chemicals Ltd.: ASTM-MAT) reactor lower portion packed glass wool, on which the catalyst 4g was pseudo-equilibrated in the same manner as in Example 1 filled, it was set stuffed with glass wool on it.
[0112]
　Reaction (NO.1)
　the reactor temperature of 550 ℃, the raw material hydrocarbon oil as desulfurization atmospheric residue oil and (DSAR) desulfurization vacuum distillation gas oil (DSVGO) 1: 1 the mixed oil in 0.0177g / It was supplied for 75 seconds in a sec of oil passing speed. At this time, the catalyst / feedstock hydrocarbon oil ratio (C / O): 3, space velocity (WHSV): 16Hr -1 , the reaction time is 75sec.
[0113]
　Along with the start of the reaction, the product recovery line and the product was recovered from, then, raw material hydrocarbon oil supply after the end of the N in the conditions of 30ml to the reaction raw material supply nozzle (32) 2 while supplying the gas, remained on the catalyst the product was recovered. Thereafter, the product gas and product oil was separated and quantified by a cooler which is cooled to -10 ° C., the product gas, and the respective components contained in the product oil was separated and quantified.
[0114]
　After completion of the reaction, the catalyst was removed from the catalyst flow cell (1), the remaining coke on the catalyst was determined by the carbon analyzer ((manufactured by Horiba, Ltd.) EMIA-321V).
[0115]
　Conversion, the yield of each component was determined in the same provisions as in Example 1.
[0116]
　Reaction (NO.2)
　in the reaction (NO.1), oil flow rate of the raw material hydrocarbon oil and 64.4 seconds, the supply time remains 0.0177g / sec, catalyst / feedstock hydrocarbon oil ratio (C / O): 3.5, reaction time: except that the 64.4sec performs reaction (NO.2) in the same manner, conversion to determine the yield of each component.
[0117]
　Reaction (NO.3)
　in the reaction (NO.1), oil flow rate of the raw material hydrocarbon oil and 56.4 seconds, the supply time remains 0.0177g / sec, catalyst / feedstock hydrocarbon oil ratio (C / O): 4, reaction time: except that the 56.4sec performs reaction (NO.3) in the same manner, conversion to determine the yield of each component.
[0118]
　Reaction NO. 1-3 Results were plotted on a graph as the relationship between the yield of conversion vs each component, from the graph to obtain the yield of each component in the 68 wt% conversion, and the results are shown in Table. Further, the difference between the yield of each component in the result of Reference Example 1 are shown in Table.
[0119]
　[Comparative Example 2]
　fluid catalytic cracking catalyst test apparatus
　is shown in Figure 2, the test apparatus of the fluid catalytic cracking catalyst were used: (Kayser manufactured by ACE-MAT, model R +) a.
[0120]
　Such a bottom inner diameter of the reactor 21 is 1.58cm, the upper inner diameter is 2.29cm, the total height is 38.4cm, the raw material supply section divided area of the raw material oil and dispersing gas supply nozzle 22 0.2Mm 2 , dispersion use gas supply unit divided area 1.8Mm 2 was.
[0121]
　Fluid catalytic cracking catalyst
　was used in the same manner as in Example 1 was pseudo-equilibrated catalyst.
[0122]
　The reaction test
　fluid catalytic testing apparatus cracking catalyst (Kayser Co.: ACE-MAT, model R +) filled with a catalyst 9g was pseudo-equilibrated in the same manner as in Example 1 reactor, subjected to reaction under the following conditions It was.
[0123]
　Reaction (NO.1)
　the reactor temperature of 550 ℃, the raw material hydrocarbon oil as desulfurization atmospheric residue (DSAR) and the desulfurization vacuum distillation gas oil (DSVGO) 1: 1 were mixed in oil was 0.02g / It was supplied for 120 seconds in a sec of oil passing speed. At this time, the catalyst / feedstock hydrocarbon oil ratio (C / O): 3.75, space velocity (WHSV): 8Hr -1 , the reaction time is 120sec.
[0124]
　Together with the start of the reaction, the product from the product recovery line (24) is recovered, then the raw material hydrocarbon oil feed closes N 2 and the gas is supplied to recover the product on the catalyst. After recovered product was separated and quantified product gas and product oil at cooler cooled to -15 ° C., the product gas, and the respective components contained in the product oil was separated and quantified. Then, the temperature was raised reactor to 700 ℃ in an air atmosphere, while burning the remaining coke on the catalyst, to quantify the coke in carbon analyzer (Servomex Inc. 1440D).
[0125]
　Conversion, the yield of each component was determined in the same provisions as in Example 1.
[0126]
　Reaction (NO.2)
　reaction in (NO.1), oil flow rate of the raw material hydrocarbon oil is a supply time with 90 seconds left of 0.02g / sec, catalyst / feedstock hydrocarbon oil ratio (C / O) : 5, reaction time: except that the 90sec performs reaction (NO.2) in the same manner, conversion to determine the yield of each component.
[0127]
　Reaction (NO.3)
　reaction in (NO.1), oil flow rate of the raw material hydrocarbon oil is a supply time with 75 seconds left of 0.02g / sec, catalyst / feedstock hydrocarbon oil ratio (C / O) : 6, reaction time: except that the 75sec performs reaction (NO.3) in the same manner, conversion to determine the yield of each component.
[0128]
　Reaction NO. 1-3 Results were plotted on a graph as the relationship between the yield of conversion vs each component, from the graph to obtain the yield of each component in the 68 wt% conversion, and the results are shown in Table. Further, the difference between the yield of each component in the result of Reference Example 1 are shown in Table.
[0129]
[Table 1]

[0130]
　From the results of the above Examples, the test device in Example 1, a small difference between the test results of Reference Example 1 of the pilot test apparatus, and pilot testing device, it was found that almost the same results are shown. On the other hand, in Comparative Example 2 was used a test device of Patent Document. 7, LPG, a difference between the test results of Reference Example 1 in gasoline yield had increased.
Industrial applicability
[0131]
　By employing a test device of the present invention can be carried out in a commercial catalytic cracking unit, evaluation of the fluid catalytic cracking catalyst, the evaluation of the withdrawn catalyst from a commercial catalytic cracking unit in a small test apparatus. For this reason, it is a test device can contribute significantly to the research and development of the catalytic cracking catalyst.
Description of the code
[0132]
1 catalyst flow cell
2 reaction raw material supply nozzle
2 'raw material oil supply pump
3 catalyst flow for the gas supply nozzle
3' catalyst for fluidized gas supply source
4 support for the nozzle
5 product recovery line
6 reaction vessel
7 heating furnace
8 thermocouple (temperature detector)
21 reactor (catalyst fluidized bed)
22 raw materials oil and dispersing gas supply nozzle
23 catalyst flow for the gas supply nozzle
23 'catalyst flow for the gas supply line
24 product recovery line
25 heating furnace
26 thermocouple (temperature detector)
31 catalyst layer (fixed bed)
32 raw material oil supply nozzle
32 'raw material oil supply pump
33 purge gas supply line
34 the reactor
35 heating furnace
36 thermocouple (temperature detector)
41 reaction tower bottom
42 reaction tower top
43 feedstock supply line
44 separator
45 stripper
46 lift line
47 regeneration tower
48 catalyst transport line
49 catalyst trap
50 product oil recovery tank
51 fractionator
52 product gas

The scope of the claims
[Claim 1]
　A catalyst flow cell (1) therein, onto the catalyst flow cell (1), the reaction raw material supply nozzle (2) from the top with the catalyst fluidizing gas nozzles (3) are provided, the product in the lower part recovery line (5) fluid catalytic cracking catalyst testing apparatus characterized in that it consists of the reaction vessel (6) provided.
[Claim 2]
　The a catalyst flow cell (1) is cylindrical, the inside diameter (D the I ) is in the range of 1 ~ 4 cm, height (T) is in the range of 2 ~ 14cm, height (T) and the inside diameter ( D the I ) the ratio of (T) / (D the I claims) is in the range from 1.1 to 7.0, the bottom of the cell is characterized by a conical structure or hemispherical structure concave down fluid catalytic cracking catalyst test apparatus according to claim 1.
[Claim 3]
　Fluid catalytic cracking catalyst testing apparatus according to claim 1 or 2, characterized in that the internal volume of the catalyst flow cell (1) is in the range of 5 of 5 ~ 40 ml
[Claim 4]
　Fluid catalytic cracking catalyst testing apparatus according to any one of claims 1 to 3, catalyst loading of the catalyst flow cell during the test (1) is characterized in that in the range of 1 ~ 20 g.
[Claim 5]
　The average particle size of the catalyst is in the range of 40 ~ 100μm, fluid catalytic cracking catalyst testing apparatus according to claim 4, bulk density characterized in that the range of 0.5 ~ 1.1g / ml.