2000.M2.1.

R&D on Catalyst for Catalytic Cracking of Heavy Oil With High Metal and High Residual Carbon Content
(High residual carbon catalytic cracking group) Sodegaura No. 404 laboratory Toshio Ito, Motoo Tanaka, Tomoyuki Sumiyoshi, Yoshifumi Hiramatsu

1.

Contents of Empirical Research

Special petroleum laws have been repealed; competition with overseas petroleum companies has become fierce, and in order to beat the competition in the petroleum industry, stepped-up efficiency at refineries and development of new technologies have become urgent necessities. Greater efficiency and new technologies are also required at RFCC facilities. Attention is now being focused on treatment of coarse feedstock (low-priced feedstock which could not be treated up to the present) containing large amounts of residual carbon believed to be metals and coke precursors, and on treatment of RFCC feedstock in which metals, residual carbon and sulfur have increased in the course of continuous treatment over two years with direct desulfurization units. When useful FCC gasoline and LCO are obtained from this coarse RFCC feedstock, the economy of RFCC equipment improves, the range of crude oil selection at refineries expands, and international competitiveness is strengthened. It is suspected that in the future, crude oil will be heavy and large quantities of coke will be produced, but in obtaining FCC gasoline and LCO, the volume of CO2 discharged from RFCC equipment regenerator tower can be drastically reduced by using catalyst that produces little coke. This approach would also contribute to the prevention of global warming. In light of these conditions, the objective of the present research is to develop an RFCC catalyst which exhibits the following performance in the RFCC process when desulfurized heavy oil has been passed through, and it is assumed that this oil is a mixture of Arabian heavy and Rutawi containing 15ppm or more of metal and 5wt% or more of residual carbon. FCC gasoline + LCO Coke 64wt% or more 8wt% or below

Other objectives include greater operational efficiency in the RFCC process, reduced volumes of CO2 generation, and countermeasures against global warming. 1.1 Search for and improvement of highly active catalysts With RFCC catalyst, feedstock containing heavy fraction and large quantities of sulfur and metals such as V or Ni must be processed so that the yield of FCC gasoline and LCO is 64wt% or more and the coke yield is 8wt% or less. For this purpose, studies have been done on globular alumina, which is believed to generate little coke, to be used as a substitute for the conventional needle alumina, and catalyst comprised of globular alumina combined with substances of different properties and ingredients have been trial-produced and examined.

1.1.1 Evaluation of catalyst in which the volumes of globular alumina and zeolite were increased With the aim of improving catalytic reactivity, catalyst was fabricated in which the volumes of both globular alumina and zeolite were increased, and catalyst reactions were evaluated. 1.1.2 Evaluation of the activity of catalyst in which globular alumina are combined with regular alumina To improve catalytic reactivity even further, catalyst was fabricated in which globular alumina was combined with regular alumina, and catalyst reactions were evaluated. 1.1.3 Impact of zeolite additive With the aim of increasing the yield of FCC gasoline and LCO even further, the volume of zeolite additive added to catalyst was increased over the conventional amounts, and catalyst reactions were evaluated. 1.2 Investigation of the factors affecting catalyst activity With the aim of attaining high yields of FCC gasoline and LCO, the relationships between catalyst pore distribution, acid volume and catalytic activity were investigated. The relationships between catalyst OH base, distribution of alumina in catalyst, and reaction results were also investigated. 1.2.1 Investigation of catalytic pore distribution In examining catalyst structure, the inter-relationships among the following were studied: meso-pore (intermediate pore) positions, catalytic meso-pore and macro pore distributions, which are believed to be effective in FCC gasoline and LCO production, pore capacity and reactivity. 1.2.2 Investigation of catalyst acid volume Among catalysts yielding outstanding reaction results, the relationship between acid volume and reaction results was investigated. 1.2.3 Investigation of catalyst OH base The relationships between catalyst reaction results and OH base strength, which is related to catalyst acid strength, were investigated. 1.3 Examination of catalyst industrial production methods Industrial production methods were investigated in order to establish a method for production, on industrial scale, of catalyst developed on the laboratory scale. In the investigation of industrial production methods, attention was focused on catalyst composition and on uniformity in catalyst structure during production testing and on stability during catalyst spray drying. Stability during the catalyst washing process was also considered. 1.4 Determination of catalyst practical performance Metal resistance, hydrothermal resistance and wear resistance of manufactured and tested catalyst were investigated in consideration of use of the catalyst in practical equipment.

2.

Results of empirical research and analysis thereof

2.1 Search for and improvement of highly active catalyst 2.1.1 valuation of catalyst in which the volumes of globular alumina and zeolite were increased In commercial catalyst , as shown in Figure 2.1-1, because there are few meso-pores, primary cracked oil produced by cracking of heavy feedstock stagnates in the pores and coke is generated. Consequently, in order to curtail coke formation and have FCC gasoline + LCO produced, in the catalyst targeted for development, also shown in the Figure, it is important to increase meso-pores of uniform size so that primary cracked oil, which can be produced by cracking feedstock, can be quickly cracked into gasoline and LCO without stagnating in the pores. As shown in Figure 2.1-2, these meso-pores produce uniform grains. This production can take place because when grains agglutinate, cavities which can produce uniform grains also become uniform.

Coke
Meso-pore

Commercial catalyst
Macropore Meso-pore

Development target catalyst

Macropore Primary cracked oil

Gasoline

Feedstock Primary cracked oil Gasoline

Feedstock

LCO

Figure 2.1-1

Comparative outline of pore structure of development target catalyst and commercial catalyst

Commercial catalyst Silica Needle lumina

Development target catalyst Silica Alumina Globular alumina

Meso-pore

Meso-pore

Non-uniform pores
Figure 2.1-2

Development target Catalyst Meso-pore Uniform pore

Outline of preparation of alumina having uniform meso-pores

For this reason, catalyst manufacture takes place in which globular alumina containing uniform grain size is used. Using I4-05 catalyst, developed in 1998, as a reference for comparison, percentages of increases in globular alumina and zeolite are presented in Table 2.1-1.

Table 2.1-1 Volumes of added globular alumina and zeolite Item/ Catalyst Globular alumina (wt%) Zeolite (wt%) I4-05 Standard Standard I4-10 +10 +3 I4-11 +7 +5 I4-12 +9 +6

The activity of the newly prepared catalyst was evaluated by means of the microactivity test (MAT). Prior to activity evaluation, vanadium and nickel were added to the catalyst, and it was subjected to steaming and to pseudo-equilibrium treatment. The properties of the feedstock used in activity evaluation are given in Table 2.1-2. The feedstock used satisfies the property requirements ultimately targeted.

Table 2.1-2 Properties of feedstock used in evaluation of catalyst activity Item/ Feedstock Density (15%) Sulfur component (wt%) Residual carbon component (wt%) Metal component (ppm) Reaction evaluation feedstock 0.936 0.51 5.9 15

The results of evaluation of catalyst reactions are shown in Figure 2.1-3. It was found that when three times as much globular alumina, as opposed to zeolite, has been added to I4-10 catalyst, the final targets, namely FCC gasoline + LCO yield of 64wt% or more and coke yield of 8wt% or less, are satisfied. It was also found that I4-10 catalyst yields better results that the nventional I4-05 catalyst. The mechanism behind this pattern is believed to be as follows. When the volume of globular alumina added to catalyst is increased, meso-pores (intermediate pores) increase; and when the feedstock (heavy oil) undergoes adequate primary cracking in the pores, the yields of FCC gasoline and LCO increased because the primary cracked oil, produced in large volume in the meso-pores, is cracked smoothly with zeolite, which has been increased. The reason that the coke yield increases only slightly even though the FCC gasoline + LCO yield has been increased is that the feedstock is cracked smoothly in the meso-pores, which have increased, and primary cracked oil does not stagnate inside the pores.

FCC gasoline + LCO (wt%)

70 65 64 60 55 50 -10
Target value

10

: I4-10
Target value

Coke (wt%)

8 6 4

:I4-11 : I4-12 :I4-05

-5 Standard +5

+10

+15

2 -10

-5 Standard +5

+10

+15

Conversion rate (wt%)

Conversion rate (wt%)

Figure 2.1-3

Evaluations of reactions with catalysts of increased globular alumina and zeolite

2.1.2 Evaluation of the activity of catalyst in which globular alumina are combined with regular alumina With the aim of further improving catalyst activity, studies were done on combinations of globular alumina and regular alumina. Percentages of added globular alumina and regular alumina are shown in Table 2.1-3.

Table 2.1-3 Percentages of globular alumina and regular alumina added to catalyst Alumina type / catalyst Globular alumina (wt%) Regular alumina (wt%) Commercial catalyst 0 Standard I4-13 catalyst 12 +5 I4-14 catalyst 6 +11

The results of evaluations of reactions are shown in Figure 2.1-4. It was found that as the percentage of globular alumina increases, the yield of FCC gasoline + LCO escalates and the coke yield declines. We see that when the volume of added globular alumina is 12wt%, the target values are satisfied. One reason for this is ascribed to the fact that feedstock is cracked smoothly by meso-pores, which are created by globular alumina, so that results are improved. With large volumes of regular alumina, uniform meso-pores cannot be easily formed among catalyst pores, the feedstock does not disseminate smoothly, and reaction results decline. And when regular alumina is used, it is believed that because the pores are small, L acid in alumina increases relatively, which results in overcracking by acid; coke yield escalates and the yield of FCC gasoline + LCO drops to a low level.

FCC gasoline + LCO (wt%)

70 65 64 60 55 50 -10 -5 +5 +10 +15

Target value

10
Target value

8
Coke (wt%)

: I4-13 : I4-14 : Cmmercial

catalyst

6 4 2 -10 -5 +5 +10 +15

Standard

Standard

Conversion rate (wt%)

Conversion rate (wt%)

Figure 2.1-4

Evaluations of reactions with catalysts in which globular alumina and regular alumina are combined

2.1.3 Impact of zeolite additive With the aim of further increasing the yield of FCC gasoline and LCO, studies were undertaken in which the volume of zeolite added to catalyst was increased over the conventional level. Volumes of zeolite added to catalyst are presented in Table 2.1-4.

Table 2.1-4 Volumes of zeolite added to catalyst Item / Catalyst name Zeolite volume (wt%) I4-13 catalyst Standard I4-18 catalyst +10

The results of evaluations of catalyst reactions are given in Figure 2.1-5. We can see that when the volume of zeolite added is increased 10wt%, the yield of FCC gasoline and LCO drops and coke yield increases. Because zeolite has been increased 10wt%, FCC gasoline and other light, primary products are overcracked. Concurrently, opportunities for direct cracking of feedstock by zeolite increase because of the large volume of zeolite added to the catalyst, the yield of FCC gasoline and LCO drops, and coke yield increases.

FCC gasoline + LCO (wt%)

70
Coke (wt%)

12 10 8 6 4 -5
Standard

65 64 60 55 50

Target value

Target value

:I4-13 :I4-18

+5

+10

+15

-10

-5

Standard

+5

+10

+15

Conversion rate (wt%)

Conversion rate (wt%)

Figure 2.1-5

Impact of added zeolite volume on reaction results

2.2 Investigation of the factors affecting catalyst activity 2.2.1 Investigation of catalytic pore distribution The impact of pore distribution on the results of catalytic reactions was investigated. The pore distribution of a typical developed catalyst is illustrated in Figure 2.2-1. It was found that catalysts having meso-pores, which are intermediate pores in the vicinity of 100, produce favorable results.

Log differential pore capacity (ml/g)

Developed catalyst Commercial catalyst

10

100

1000

10000

100000

Pore diameter ()
Figure 2.2-1 Pore distribution in developed catalyst

Table 2.2-1 shows the percentages of pore capacity in I4-10 catalyst, which produced the best reaction results, and in catalysts on the market with pore sizes ranging from 40 ~ 400, 400 ~ 2000 and 2000 ~ 18000. As indicated under reaction results in section 2.1, it was found that developed catalyst of high FCC gasoline + LCO yield had extensive meso-pore capacity between 40 and 400.

Table 2.2-1 Distributions of pore diameter in developed catalyst and commercial catalyst Pore capacity percentage/ Catalyst name 40 400 (%) 400 2000 (%) 2000 18000 (%) 26 38 36 33 40 27 29 36 35 I4-05 catalyst I4-10 catalyst I4-13 catalyst Commercial catalyst 21 47 32

2.2.2 Investigation of catalyst acid volume In order to investigate the factors behind catalytic activity, the acid volume of developed catalyst was measured by ammonia adsorption heat, and the results are given in Figure 2.2-2. In light of these results and the results of a search for and improvement of catalyst as discussed in section 2.1, no clear relationship between acid volume and yield of FCC gasoline + LCO, or coke yield, could be recognized. However, in view of the fact that the greatest volume of adsorption heat is in the I4-10 catalyst, which produces the highest yield of FCC gasoline + LCO, it is evident that acid must be added to catalyst to some extent in order to improve upon a yield of 64wt% or more for FCC gasoline + LCO.

NH3 adsorption heat volume (kJ/mol)

200 180 160 140 120 100 80 60 40 20 0 0 200 400 600

NH3 adsorption volume (10-6mol/g)

I4-05 I4-10 I4-13 Commercial Catalyst

800

1000

Figure 2.2.2

Measurements of ammonia adsorption heat in catalyst

2.2.3 Investigation of catalyst OH base Since it is suspected that numerous OH bases are included in catalysts that have large quantities of solid acid, catalyst OH bases were determined by IR measurements. Measurements of OH bases by IR in the I4-10 catalyst, which produced favorable results, are presented in Figure 2.2-3. In the figure, a number of OH base peaks originating from solid acid or water can be observed, and the peak near 3600 cm-1, which is believed to be a solid acid OH base, is also high.

1.7 1.6 1.5 Absorb 1.4 1.3 1.2 1.1 1 0.9 0.8 0.7 4000

3800

3600

3400

3200

3000

2800

Wave number (cm-1)

Figure 2.2-3

Measurements of OH base by IR of I4-10 catalyst

In addition to I4-10 catalyst, OH base measurements were taken for a number of other catalysts of outstanding reactivity, and Table 2.2-2 presents the results of comparisons of peak strength near 3600 cm-1. From these results, plus the results of evaluations of catalyst reactions, it was learned that there is not much of a correlation between OH base strength and reaction results. It is suspected that pore distribution has a strong impact on reaction results. However, in view of the fact that the OH base peak strength is highest for I4-10 catalyst, which produces the best reaction results, although results are the same as measurements by ammonia adsorption heat mentioned earlier, it was discovered that OH base, which is a solid acid, is required to some extent in addition to pore distribution in order to improve still further the yield of FCC gasoline + LCO.

Table 2.2-2 Strength of OH base in developed catalyst I4-05 catalyst OH base strength (-) 0.115 I4-10 catalyst 0.156 I4-13 catalyst 0.028 Commercial catalyst 0.135

2.2.4 Examination of alumina distribution in catalyst An investigation was undertaken to discover how alumina becomes distributed in catalyst when globular alumina has been added. Measurements by EPMA of alumina distribution in catalyst revealed that large alumina clusters are distributed more widely in I4-10 catalyst to which globular alumina has been added than in commercial catalyst. In catalyst of high reactivity, it is suspected that large clusters of globular alumina are scattered widely and that pores effective in reactions are formed. 2.3 Examination of catalyst industrial production methods Industrial production methods were investigated in order to establish a method for production, on industrial scale, of catalyst developed on the laboratory scale. In the investigation of industrial production methods, attention was focused on catalyst composition and on uniformity in catalyst structure during production testing, and on stability during catalyst spray drying. Stability during the catalyst washing process was also considered. 2.3.1 Examination of catalyst composition and catalyst structure An investigation was made to determine if catalyst could be produced on an industrial scale without problems and according to specifications. As a result of the catalyst search, I4-10 catalyst, which yielded the best results, was used as a basis in testing of catalyst production. Catalyst specifications and the composition and property values of manufactured and tested catalyst are shown in Table 2.3-1. The specifications and property values of this catalyst fall within the permissible range of variance from specifications, and it was found that there were no problems with catalyst composition or structural uniformity at the time of production testing.

Table 2.3-1 Composition and properties of test produced catalyst Specification Composition TiO2 (wt%) RE 2O3 (wt%) Na2O (wt%) Al2O3 (wt%) Ignition loss (wt%) 2 Physical property surface area (m /g) 2 Matrix surface area (m /g) 2 Zeolite surface area (m /g) Apparent bulk density (g/ml) Pore capacity (g/ml) Mean grain size (m) Test produced catalyst

Standard Standard Standard Standard Standard Standard Standard Standard Standard Standard Standard

+0.1 +0.2 -0.08 +1.5 -1.2 -4 -10 +14 +0.04 +0.01 +2

2.3.2 Examination of catalyst bulk density and stability in grain size during spray drying If conditions change during spray drying of catalyst, cavities are created in the catalyst and catalyst grain sizes become disparate. When large cavities are produced in the catalyst and grain sizes become disparate, the catalyst becomes weak in mechanical strength, and the flow condition of catalyst in practical equipment becomes poor, which in turn adversely affects reaction results. Accordingly, an investigation was made to ascertain the possibility of production stable in terms of apparent bulk density and grain diameter. Temporal changes in apparent bulk density and grain diameter of catalyst during catalyst test production are presented in Table 2.3-2. At each stage of test production, changes were within permissible limits, and it was concluded that during spray drying, catalyst physical properties are stable and there are no problems.

Table 2.3-2 Temporal changes in apparent bulk density and in grain diameter during catalyst test production Early term Middle term Late term Apparent bulk density (ml/g) Standard Standard Standard -0.01 Standard Standard -0.02 Standard -0.02 80 m or less (wt%) Standard Standard Standard +1.4 Standard -3.7 Standard -0.5 Standard -1.9

2.3.3 Examination of stability during catalyst washing Upon completion of spray drying of catalyst, the catalyst must be washed and poisonous ingredients in catalyst, Na2O and SO4, must be removed. Unless such impurities are below a threshold value, during catalyst application they will react with zeolite or matrix, which are active ingredients, producing a drop in catalyst activity. For this reason, temporal changes in the concentrations of these impurities during catalyst washing were investigated. The temporal changes in Na2O and SO4 during washing are presented in Table 2.3-3. Throughout all catalyst production testing, changes in both Na2O and SO4 were below the reference value, and it was concluded that there are no problems in washing out the impurities.

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Table 2.3-3 Temporal changes in Na 2O and SO4 during catalyst washing Early term Middle term Late term Na2O (wt%) Standard -0.05 Standard -0.08 Standard -0.05 SO4 (wt%) Standard -0.19 Standard -0.23 Standard -0.17

2.4 Determination of catalyst practical performance Metal resistance, hydrothermal resistance and wear resistance of produced and tested catalyst were investigated in consideration of use of the catalyst in practical equipment. 2.4.1 Metal resistance When catalyst is used in practical equipment, V and Ni in feedstock accumulate on catalyst due to catalyst reaction and reproduction, and the catalyst is gradually poisoned. When the metal resistance of catalyst is low, the catalyst rapidly deteriorates and reaction output declines. Accordingly, two types of catalyst were produced in which the quantities of V and Ni retained in each were varied; the catalysts were then subjected to steaming and the metal resistance of each was examined through evaluations of catalyst reactions. The results of evaluations of metal resistance in test-produced catalyst are given in Figure 2.4-1. These results indicated that the drop in reaction output, as opposed to V and Ni poisoning, was slight in the test-produced catalyst, and that the metal resistance of the test-produced catalyst is high in comparison to commercial catalyst.

Standard

Conversion rate (wt%)

+20

Test-produced catalyst
Standard

+10

Standard

Commercial catalyst
2,000 3,000 V + Ni (ppm) 4,000 5,000

1,000

Figure 2.4-1

Metal resistance of test-produced catalyst

2.4.2 Hydrothermal resistance In the regeneration tower of practical equipment, coke produced on catalyst by reactions is burnt; the reproduction tower becomes high in temperature; hydrogen included in the coke is burnt, and a vapor ambient is created. When the hydrothermal resistance of catalyst is low, the catalyst structure is destroyed in a high-temperature, vapor ambient and surface area declines, causing reactivity to drop so that targeted output can no longer be attained. For this reason, hydrothermal resistance is required in catalyst so it can withstand a high-temperature vapor ambient.

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In order to determine the hydrothermal resistance of the test-produced catalyst, the catalyst was subjected to steaming at the high temperatures of 773C or 732C, and its reactivity was then evaluated. The results of this evaluation are shown in Figure 2.4-2. It was found that the hydrothermal resistance of the test-produced catalyst is superior to that of commercial catalyst, and that there are no problems.

Standard

+20

Conversion rate (wt%)

Test-produced catalyst
Standard

+10
Commercial catalyst
Standard

720

730

740

750

760

770

780

Treatment temperature (C)

Figure 2.4-2 Hydrothermal resistance of test-produced catalyst

2.4.3 Wear resistance In the equipment, RFCC is circulated between the reaction tower and regeneration tower and wear is produced by collisions between the catalyst and equipment and by collisions among catalyst grains. When catalyst wear is extensive, large volumes of catalyst are introduced into the equipment, which makes for poor economy. Accordingly, the wear resistance of the test-produced catalyst was measured. To measure wear resistance, a fixed quantity of catalyst was filled into a cylindrical container, air was introduced from the bottom of the container at close to the speed of sound so that the catalyst grains would flow violently and collide; the catalyst was thus pulverized into powder form and powder scattering from the top of the cylinder was collected, and its volume measured. The results of this wear resistance test are presented in Table 2.4-1. It was found that the test-produced catalyst presents no problems in wear resistance, since the scattered volume of test-produced catalyst was less than that of commercial catalyst.

Table 2.4-1 Measurements of wear resistance in test-produced catalyst Catalyst scattering volume (wt%/30h) Test-produced catalyst 3 Commercial catalyst 4

3.

Results of Empirical Research

3.1 Search for and improvement of highly active catalyst With the aim of increasing the yield of FCC gasoline + LCO and decreasing coke yield, various studies were done on zeolite and globular alumina, which causes meso- pores (intermediate pores) to form in catalyst. As a result, it was found that at bench plant the developed catalyst satisfied the target values of the present research. 12

3.2 Investigation of the factors affecting catalyst activity Various factors affecting catalyst activity, including catalyst pore distribution, acid volume, OH base and alumina distribution, were investigated for the purpose of escalating catalyst reaction output. It was discovered that favorable reaction results are obtained from catalyst having many meso-pores, that is, intermediate pores in the vicinity of 100. It was also found that high yields of FCC gasoline + LCO are obtained from catalyst having a meso-pore capacity of between 40 ~ 400. Another finding is that the catalysts producing favorable reaction results are ones that have large clusters of alumina spread widely throughout which cause pores to form that are effective in reactions. 3.3 Examination of catalyst industrial production methods Studies were done on catalyst composition and structure, on stability during spray drying and on stability during washing, all items of concern in industrial manufacture of catalyst, and it was found that there were no problems in any instance. 3.4 Determination of catalyst practical performance Studies were done, in practical terms, on the metal resistance, hydrothermal resistance and wear resistance of developed catalyst, and it was found that in every instance, the results were better than with commercial catalyst and that no problems were encountered.

4.

Synopsis

In the present R&D on catalyst for catalytic cracking of heavy oil containing high levels of metal and residual carbon, studies were done on catalyst manufacture on an industrial scale, and as a result of evaluations of reactions, using bench equipment, it was found that catalytic performance reached targeted values. To gain a more solid evaluation of developed catalyst in the future, short-term evaluations will be made of applicability, using practical equipment, in relation to catalyst stripability (removal of produced oil adhering to catalyst), which cannot be evaluated easily with laboratory equipment, and catalyst service life. In reference to final targets, the applicability of catalyst obtained in studies of industrial manufacturing methods will be evaluated, the factors affecting activity will be investigated and other steps will be taken to advance the development of catalysts.

Copyright 2000 Petroleum Energy Center all rights reserved.

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