o-EPA United States Industrial Environmental Research EPA-600/7-78-119 Environmental Protection Laboratory June 1978 Agency Research Triangle Park MC 27711 Demetallization Catalyst Tests on Heavy Residual Oils Interagency Energy/Environment R&D Program Report ------- RESEARCH REPORTING SERIES Research reports of the Office of Research and Development, U.S. Environmental Protection Agency, have been grouped into nine series. These nine broad cate- gories were established to facilitate further development and application of en- vironmental technology. Elimination of traditional grouping was consciously planned to foster technology transfer and a maximum interface in related fields. The nine series are: 1. Environmental Health Effects Research 2. Environmental Protection Technology 3. Ecological Research 4. Environmental Monitoring 5. Socioeconomic Environmental Studies 6. Scientific and Technical Assessment Reports (STAR) 7. Interagency Energy-Environment Research and Development 8. “Special” Reports 9. Miscellaneous Reports This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT RESEARCH AND DEVELOPMENT series. Reports in this series result from the effort funded under the 17-agency Federal Energy/Environment Research and Development Program. These studies relate to EPA’s mission to protect the public health and welfare from adverse effects of pollutants associated with energy sys- tems. The goal of the Program is to assure the rapid development of domestic energy supplies in an environmentally-compatible manner by providing the nec- essary environmental data and control technology. Investigations include analy- ses of the transport of energy-related pollutants and their health and ecological effects; assessments of, and development of, control technologies for energy systems; and integrated assessments of a wide range of energy-related environ- mental issues. REVIEW NOTICE This report has been reviewed by the participating Federal Agencies, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the Government. nor does mention of trade names or commercial products constitute endorsement or recommendation for use. This document is available to the public through the National Technical Informa- tion Service, Springfield, Virginia 22161. ------- EPA-600/7-78-119 June 1978 Demetallization Catalyst Tests on Heavy Residual Oils by V.V. Manshilin, Yu K. Vail, B.A. Lipkind, and A.V. Agafonov All Union Scientific Research Institute of Oil Refining, VNIINP Moscow 111116 Aviamotornaya St 6 USSR MMKhP Main Directorate of the USSR Hydrometeorological Service and P. Maruhnic and G Nongbri Hydrocarbon Research, Inc. New York and Puritan Avenues Lawrenceville, New Jersey 08648 Contract No. 68-02-0293 Program Element No. EHE623A and William J. Rhodes Industrial Environmental Research Laboratory Office of Energy, Minerals, and Industry U.S. Environmental Protection Agency Research Triangle Park, N.C. 27711 Prepared for U.S. ENVIRONMENTAL PROTECTION AGENCY Office of Research and Development Washington, DC 20460 ------- ABSTRACT A cooperative project between the USA and USSR was undertaken to exchange technology on the demetallization step of an overall pro- cess to produce low sulfur fuel oil from heavy petroleum residua. This joint project was initiated so that each country could learn the state of the art in the other country. Catalysts and petroleum residua feedstocks were exchanged and tests carried out by each country using its own equipment and operating procedures. The results of the tests were exchanged and discussed at meetings held in the USSR and the USA. In this report, all tests using USA catalyst have been described by the United States and all tests using USSR catalyst have been described by the USSR, and each country describes its equipment and operating procedures used in carrying out the tests. Included for each aging test are graphs showing degree of demetallization and desulfurization and the rate of catalyst deactivation. Fresh and used catalyst analyses are presented along with detailed run sumaries and product inspections. Results showed that each country’s molybdenum impregnated catalyst exhibited about equal demetallization capability while the USA catalyst exhibited higher desulfurization capability during demetallization. Sections of this report collaborated on and reported jointly in- clude the sumary, introduction and conclusions. Each country considered the project mutually beneficial. ii ------- TABLE OF CONTENTS Page Section No . Abstract ii List of Figures iv List of Tables viii 1.0 Introduction 1 2.0 Conclusions 2 3.0 Feedstocks 3 L 4 .O Tests Conducted 5.0 Description of Catalysts 8 5.1 USSR Catalyst 8 5.2 USA Catalysts 8 6.0 Description of Units and Test Methods l 4 6.1 USSR 1k 6.2 USA 18 7.0 Discussion of Results 21 7.1 Tests on USSR Catalyst 21 7.2 Tests on USA Catalysts 39 7.2.1 Used Catalyst Analyses 51 7.2.2 Pore Size Distribution 51 8.0 References 60 9.0 Appendices 61 9.1 Tests Reported by USSR 61 9.2 Tests Reported by USA 69 II I ------- LIST OF FIGURES Figure Page No. No . Fresh USSR T—3 Catalyst 2 Porogram of Fresh USA Demetallization Catalyst (1 Mo) HRI No. 3634 12 3 Porogram of Fresh USA Demetallization Catalyst (0 Mo) HRI No. 3309 13 4 Diagram of the USSR Pilot Equipment 5 Schematic Drawing of the USSR Reactor 16 6 USA Unit Flow Diagram 19 7 Schematic Drawing of the USA Reactor 20 8 Variation of Vanadium Removal with Mid-Hours on Stream During the Demetallization of Tia Juana and Rornashkin Vacuum Resids over USSR Catalyst (T-3) - Runs made in the USSR 24 9 Variation of Vanadium Removal with Mid-Hours on Stream During the Demetallization of Gach Saran Vacuum Resid over USSR catalyst(t3) — Run made in the USSR 25 10 Variation of Vanadium Removal with Mid—Hours on Stream During the Demetallization of Tia Juana Vacuum Resid over USSR Catalyst (T-3) - Run made in the USA 27 11 Variation of Vanadium Removal with Mid-Hours on Stream During the Demetallization of Tia Juana Vacuum Resid over USSR Catalyst (T-3) - Run made in the USA 27 12 Desulfurization Obtained During Demetallization of Tia Juana Vacuum Resid over USSR Catalyst (T—3) - Run made in the USSR 28 iv ------- LIST OF FIGURES (Continued ) Figure Page No. No . 13 Desulfurization Obtained During the Demetalfl- zation of Romashkin Vacuum Resid over USSR Catalyst (T-3) - Run made in the USSR 29 Desulfurization Obtained During the Demetalli- zation of Gach Saran Vacuum Resid over USSR Catalyst (1—3) - Run made in the USSR 30 15 Desulfurization Obtained During the Demetalli- zation of Tia Juana Vacuum Resid over USSR Catalyst (1—3) - Run made in the USSR 31 16 Desulfurization Obtained During Demetallization of Romashkin Vacuum Resid over USSR Catalyst (T-3) - Run made in the USA 32 Comparison of Porograms of New and Used(T-3) Catalyst after Operating on Tia Juana Vacuem Resid 34 18 Comparison of Porograms of New and Used(T-3) Catalyst after Operating on Romashkin Vacuum Resid 35 19 Comparison of Porograms of New and Used (1-3) Catalyst after Operating on Gach Saran Vacuum Resid 36 20 Comparison of Porograms of Fresh USSR Catalyst (T-3) and Used Catalyst after Operating on ha Juana Vacuum Resid - Run made in the USA 37 21 ComparisonofPorograms of Fresh USSR Catalyst (T—3) and Used Catalyst after Operating on Romashkin Vacuum Resid - Run made in the USA 38 22 Variation of Vanadium Removal with Mid—Hours on Stream During the Demetallization of Romashkin Vacuum Resid over USA Catalyst (1 Mo) - Run made in the USA 42 V ------- LIST OF FIGURES (Continued ) Figure Page No. No . 23 Desulfurization Obtained During the Demetal- lization of Romashkin Vacuum Resid over USA Catalyst (1 Mo) - Run made in the USA 43 24 Variation of Vanadium Removal with Mid-Hours on Stream During the Demetallization of Romashkin Vacuum Resid over USA Catalyst (1 Mo) - Run made in the USSR 44 25 Desulfurization Obtained During the Demetal- lization of Romashkin Vacuum Resid over USA Catalyst (1 Mo) — Run made in the USSR 45 26 Variation of Vanadium Removal with Mid—Hours on Stream During the Demetallization of Romashkin Atmospheric Resid over USA Catalyst (1 Mo) - Run made in the USA 47 27 Desulfurization Obtained During Demetallization of Roniashkin Atmospheric Resid over USA Catalyst (1 ? Mo) - Run made in the USA 48 28 Variaiton of Vanadium Removal with Mid—Hours on Stream During the Demetallization of Romashkin Atmospheric Resid over USA Catalyst (0 Mo) - Run made in the USSR 49 29 Desulfurization Obtained During the Demetalli- zation of Romashkin Atmospheric Resid over USA Catalyst (0 Mo) - Run made in the USSR 50 30 Variaitor. of Vanadium Removal with Mid-Hours on St 4 ream During the Demetallization of Tia Juana Vacuum Resid over USA Catalyst (1 Mo)— Run made in the USSR 52 31 Desulfurization Obtained During the Demetalli- zation of ha Juana Vacuum Resid over USA Catalyst (1 Mo) - Run made in the USSR 53 vi ------- L)ST OF FiGURES (Continued ) Figure Page No. No . 32 Comparison of Porograms of Fresh USA Catalyst (1 Mo) and Used Catalyst after Operating on Romashkin (USSR) Atmospheric Resid - Run made in the USA 55 33 Comparison of Porograms of Fresh USA Catalyst (I Mo) and Used Catalyst after Operating on Rornashkin (USSR) Vacuum Resid - Run made in the USA 56 3L Comparison of Porograms of Fresh USA Catalyst (0 Mo) and Used Catalyst after Operating on Rocnashkin (USSR) Atmospheric Resid - Run made in the USSR 57 35 Comparison of Porograms of Fresh USA Catalyst (1 Mo) and Used Catalyst after Operating on (USSR) Vacuum Resid - Run made in the USSR 36 Comparison of Porograms of Fresh USA Catalyst (1 ? Mo) and Used Catalyst after Operating on ha Juana Vacuum Resid — Run made in the USSR 59 VI I ------- LIST OF TABLES Table Page No. No . Feedstock Analyses 5 2 Demetallization Tests Carried Out in USSR 6 3 Dernetallization Tests Carried Out in USA 7 4 Properties of USSR Catalyst 9 5 Properties of USA Catalyst 11 6 Results on USSR Demetallization Catalyst Tests Made in Both Countries 22 7 Characteristics of Used USSR Demetallization Catalyst (T—3) 33 8 Results on USA Demetallization Catalysts Tests Made in Both Countries 1 +0 9 Analyses on USA Catalyst From Aging Tests Made in USA and USSR 54 10 Demetallization Run Summary of Tia Juana Vacuum Resid over USA Catalyst (1 Mo) - Run made in USSR 62 11 Demetallization Run Summary of Romashkin Vacuum Resid over USA Catalyst (1 Mo) - Run made in USSR 63 12 Demetallization Run Summery of Tia Juana Vacuum Resid over USSR Catalyst (1 Mo) - Run made in USSR 64 13 Demetallization Run Summary of Romashkin Atmospheric Resid over USA Catalyst (I Mo) - Run made in USSR 65 Demetallization Run Summary of Gach Saran Vacuum Resid over USSR Catalyst - Run made in USSR 66 Viii ------- LIST OF TABLES (Continued ) Table Page No. No . 15 Demetallization Run Summary of Romashkin Vacuum Resid over USSR Catalyst - Run made in USSR 67 16 Demetallization Run Summary of Romashkin Atmospheric Resid over USSR Catalyst - Run made in USSR 68 Demetallization Run Summary of Roniashkin Vacuum Resid over USSR Catalyst - Run made in USA 70 18 Demetallization Run Summary of Tia Juana Vacuum Resid over USSR Catalyst — Run Made in USA 71 19 Demetallization Run Summary of Romashkin Atmospheric Resid over USA Catalyst (1 Mo) - Run made in USA 72 20 Demetallization Run Summary of Rornashkin Vacuum Resid over USA Catalyst (1 ° Mo) - Run made in USA 73 ix ------- 1.0 INTRODUCTION Air pollution with oxides of sulfur from burning high sulfur fuel oils is of universal concern. Fuel oils containing l sulfur or less are produced commercially by catalytic hydrodesulfurization of low metals petroleum residua. Production of low sulfur fuel oils from heavy petroleum residua containing large concentrations of metals, mainly vanadium and nickel, is economically unattractive because of the rapid deactivation of the hydrodesulfurization cata- lysts due to metals deposition. By removing the bulk of the metals from heavy residua prior to desulfurization, the overall economics can be improved and best use can be made of this petroleum fraction. Industrial experience in the use of desulfurization equipment for atmospheric residua in a fixed bed operation has shown that when the metals content in the feed is greater than 100 ppm, demetal- lization of the feed is first required. Therefore, careful salt removal from the feed to a level of 3-5 mg/l is necessary. To increase the effective life of desulfurization catalysts at the present time, there are various methods used to pretreat the feed- stock based on methods to remove asphaltenes and metalorganic com- plexes related to them with hydrocarbon solvents (processes of I%Dobenu, Domex”, the firms Shell, Finn, etc.). The disadvantages of these processes are the reduction of the fuel oil output to 75—855 of the feed and the problem of utilizing the salt removal res idua. One method of reducing the metals concentration is by pretreating the resid over a relatively cheap scavenger catalyst prior to final sulfur reduction over the more expensive desulfurization catalyst. The overall resid desulfurizatjon then becomes more attractive economically. The present cooperative project between the USA and the USSR had as its objective an exchange of technology in the field of demetal- lization of heavy petroleum residua in a scheme to produce low sulfur fuel oil, in order for each country to gain knowledge of the state of the art in the other country. At a meeting in 197L held in the USA, a program to meet this objec- tive was agreed upon. After an exchange of materials consisting of dernetallization catalysts (independently developed by each country) and feedstocks of atmospheric and vacuum residua, tests ------- were carried out by each country on these materials at similar operating conditions using its own equipment and procedures. At the conclusion of the tests, product and used catalyst samples were exchanged to afford comparison of results. In a preliminary report, each side sumarized the results of tests it conducted. At meetings in June 1976 in the USSR and January 1977 in the USA, reports were exchanged, discussed and translations clarified. At the June meeting, agreement was reached on the format for a final report. All tests using USA catalyst would be described by the USA and all tests using USSR catalyst would be described by the USSR, regardless of which country con- ducted the tests. Each country would also describe its catalyst, test units and operating procedures, and materials supplied. Parts of the final report to be reported jointly would include the suninary, introduction, feedstock analyses, and conclusions. To further carry out the objective of the project, the USSR dele- gation, on their visit to the USA, was afforded on—site inspections of test units actually used iii conducting test runs on the project as well as an inspection of laboratory facilities and the equipment used for the tests. The USA delegation, on their visit to the USSR, was afforded inspection of test units similar to those used for the test runs. The delegation also inspected laboratory facilities and equipment. 2.0 CONCLUSIONS The objective of the cooperative project between the USA and USSR was realized in that each country had an opportunity to evaluate technology in the other country pertaining to the dernetailization of heavy petroleum residua in the course of producing low sulfur fuel oil. Each side was afforded on-site inspections of experi- mental test units and laboratory facilities. Generally, the results of the experimental work showed the two molybdenum impregnated demetallization catalysts to be about equal in their capacity to reduce vanadium content of petroleum residua while the USA catalyst exhibited consistently higher desulfurization capability during demetallization. 2 ------- The series of comparative tests conducted in both countries on Soviet vacuum resid using the American catalyst showed that results obtained in the USA differ slightly from those obtained in the USSR. The data showed that in the demetallizatiort of Romashkin vacuum resid in tests conducted in the USA, the US catalyst achieved a higher degree of vanadium removal, greater depth of desulfurization, and a lower rate of catalyst deactivation than in analogous tests conducted in the USSR. In cooperative tests with vacuum resids from the heavy crude oils of ha Juana and Gach Saran for both US and USSR.catalysts, similar results were obtained in both countries. These differences in the demetallization of Romashkin vacuum resid may be attributed to differences in test equipment and/or method of operation. The project was carried out in a spirit of cooperation. The meet- ings held in each country were conducted in a friendly, business- like manner, and each host country showed every courtesy and hospitality to the other’s delegations. 3.0 FEEDSTOCKS Comparative tests of catalysts were carried out using atmospheric and vacuum residua from Romashkin petroleum, ha Juana vacuum resid from Venezuela and Gach Saran vacuum resid from Iran. Tia Juana vacuum resid used by both countries on this project was supplied by the USA. This feed originated in the Lake Maracaibo area of Venezuela and was obtained from the Creole Petroleum Corporation, a subsidiary of Exxon. The 1973 production of ha Juana crude was 120-million barrels, equivalent to 36-million barrels of vacuum residua, with estimated crude reserves of l,702—million barrels. Gach Saran vacuum resid used by the USSR was also supplied by the USA. Gach Saran crude originates in the Persian/Arabian Gulf in Iran. In 1973, the production of Gach Saran crude was 324-million barrels, equivalent to 75—million barrels of vacuum resid, with an estimated reserve of 8 ,1k0-million barrels. The vacuum resid feed used on this project was obtained from Kashima Oil Company of Japan. 3 ------- ha Juana vacuum resid is heavier than the Romashkin vacuum resid from the Soviet Union. The density is higher than 1.0 g/cm 3 . The coking capacity is above 20.0, and it has approximately the same sulfur content as the Romashkin vacuum resid, but contains much larger amounts of asphaltenes (12.9 and 9.4, as compared to 6.5? for the Romashkin vacuum resid). There is a much higher metals content in ha Juana vacuum resid, 666 ppm (V = 588 ppm and Ni = 78 ppm) and Gach Saran vacuum resid, 469 ppm (V = 324 ppm and Ni = 145 ppm) compared to 323 ppm (V = 242 ppm and Ni = 81 ppm) in the omashkin vacuum resid. Romashkin vacuum resid and Romashkin atmospheric resid used on this project were supplied by the USSR. Table 1 lists the inspections on these four feeds. The analyses are the average values obtained from analyses carried out by each country. In calculating and reporting results of tests made in the USA, values from inspections made on the same batch of feedstock as fed to the unit were used rather than average values. The difference in vanadium content of USSR vacuum resid as reported by the USA and the USSR may be due to variation in feed composition which might explain differences in test results obtained in each country. 4.0 TESTS CONDUCTED In accordance with the Protocol of December 13, 1974, Appendix 3, A-7, both countries agreed to conduct two types of demetallization catalyst tests. The first were called screening tests, and their purpose was to determine whether results in each country could be accurately reproduced in the other country. Tests of the second type were called aging tests, and their purpose was to obtain data on demetallization using different feeds and catalysts so that each country could study the state of the art in this field in the other country and also determine the advantages and disadvantages of each combination of feed and catalysts. After an exchange of feeds and catalysts, each side carried out the screening and aging tests in accordance with the schedule presented in Tables 2 and 3. 4 ------- Table 1. FEEDSTOCK ANALYSES Romashk in Atm. Resid 0.9616 (15.7) 2.71 0.27 8.8 1 36 48 281 48 0.926 2.2 1+ 52 1 . 000 3.35 * Analyses performed by USSR only Analyses performed by USA only Romashk in Vac. Resid 1.001 ( .9) 3.08 0.49 16.0 236 81 379 6.9 0.948 2.45 93. 1 1.010 3.25 Tia Juana Vac. Resid 1.012 (8.3) 2.95 0.48 20.7 588 78 1+27 (8oo) 3.2 0.946 (18.1) 2.31 96.8 1.014 (8.0) 3.05 *Gach Saran Vac. Resid 1.0176 (7.6) 3.29 0.60 20.9 324 145 8.0 0.91+33 (18.5) 2.00 92.0 1.0369 (5.0) 3.40 0 Density, g/cm ( API) Sulfur, W Nitrogen Total, W *Coke, W (Conradson C) Vanadium, ppm Nickel, ppm **IBP—°C (°F) Vol. * (IBP—500°C) Density, g/cm 3 (°API) Sulfur, U * Vol. ? (500°C+) Density, g/cm 3 (°API) Sulfur, U Notes: (538) (21.3) (10.0) (711+) (17.8) (8.6) 5 ------- Table 2. DEMETALLIZATION TESTS CARRIED OUT IN THE USSR I. Screening Tests Lasting 100-150 Hours Run Number 2 Catalyst USA l Mo USA 1 Mo Feed Tia Juana Vac. Resid Gach Saran Vac. Resid II. Aging Tests Lasting 500 Hours Run Number 2 3 4 5 6 7 8 Catalyst USA l Mo USA l Mo USSR (o.7 Mo) USA (o Mo) USSR (o.7 Mo) USSR (0.7 Mo) USSR (o.fl Mo) USA (l Mo) Feed Tia Juana Vac. Resid USSR Vac. Resid Tia Juana Vac. Resid USSR Atm. Resid Gach Saran Vac. Resid USSR Vac. Resid USSR Atm. Resid USSR Atm. Resid 6 ------- Table 3. DEMETALLIZATION TESTS CARRIED OUT IN THE USA I. Screening Tests Lasting 100—150 Hours Run Number Catalyst USSR (O.72 Mo) Feed USSR Atm. Resid. II Aging Tests Lasting 500 Hours Run Number 2 3 4 Catalyst USSR (o.7 Mo) USSR (0.7 Mo) USA (l Mo) USA (l Mo) USSR Vac. Tia Juana USSR Atm. USSR Vac. Feed Resid Vac. Resid Resid Resid 7 ------- 5.0 DESCRIPTION OF CATALYSTS 5.1 USSR Catalyst The physical—chemical properties of the recent T-3 catalyst of the Soviet Union and its poromeric characteristics are given in Table 4 and Figure 1. The 1-3 catalyst has a low bulk density of 0.52 g/cm 3 , a high sur- face area of 235 M 2 /g, and contains 0.7* Mo. Figure 1 gives a curve showing the distribution of the pore radii in the new T-3 catalyst. The catalyst has a polydispersed structure, with pores having a radius from 30—50 — 51.6*, from 50-100 ° - 21.4*, from 100-500 - 7.9*, and above 500 - 19.1*, and above 5000 A - 13.4*. 5.2 USA Catalysts Two aging demetallization tests made in the USA and two tests made in the USSR used the catalyst developed by KRI. This catalyst, activated bauxite impregnated with one weight percent molybdenum and designated as HRI 3634, was part of a comercial run made by the Minerals and Chemical Division of Engelhard Corporation. One other test made in the USSR used unpromoted activated bauxite (0* Mo), designated as HRI 3309, which was also obtained from Engeihard Corporation. Table 5 lists the chemical and physical characteristics of the two catalysts and Figure 2 and Figure 3 give the respective pore size distribution curves. In the course of earlier development work carried out on the de- metallizaton catalyst, the one weight percent molybdenum level impregnation was chosen after evaluations were made on 0.5, 1.0, and 2.0 weight percent molybdenum preparations. The 0.5* Mo catalyst was inferior with respect to the level of demetallization and desulfurization as compared to the 2.0* Mo catalyst, while the 2.0* Mo catalyst did not exhibit significant superiority over the 1.0* Mo catalyst. 8 ------- Table 4. PROPERTIES OF USSR CATALYST USSR Catalyst with Indices O.7? Mo Type of Catalyst Activated Bauxite Compacted Bulk Density, g/cm 3 0.52 Surface Area, M 2 /g (based on toluene) 235 Volume of Pores, cm 3 /g 0.51 Average Pore Radius, 44.0 Fractional Composition, MM — W 0.8 4.28 0.63 56.0 Less than 0.5 38.8 Strength Index, kg/mm 0.95 9 ------- 0.6 0.5 0 ) E oJ Q) E r oO.3 0• > 0 0.2 0.1 100000 Pore Radius (Angstroms) / 30000 10000 5000 1001) 500 100 50 30 Figure 1. FRESH USSR 1-3 CATALYST ------- Table 5. PROPERTIES OF USA CATALYSTS l Mo O Mo HRI Number 3634 3309 Molybdenum, W 1.06 0 Volatile Matter, W 2.0 2.0 Compacted Bulk Density, g/cm 3 0.978 1.04 Surfac€. Area, M 2 /g (B.E.T. Nitrogen) 195.6 175 Pore Volume, cm 3 /g 0.317 0.225 Particle Size Range, W 0.84/0.59 mm (20/30 Mesh) 52.4 45.3 0.59/0.42 mr (30/40 Mesh) 30.7 31.8 0.42/0.297 mm (40/50 Mesh) 16.9 22.9 11 ------- I I I I I I I I NJ -. 0 D 0 0 0 o o 0 Pore Dameter (Angstroms) 0.1+ — I U E 0 — NJ 0 0.3 0.2 — 0.1 0.0 0 0 0 0 NJ — o o o D o o 0 I % fl 0 0 0 NJ 0 0 0 0 0 0 % fl 0 0 I I NJ — 0 0 o 0 0 CD Figure 2. POROGRAM OF FRESH USA DEMETALLIZATION CATALYST Q° Mo) HRI NO. 3 j ------- I I I I ¼fl 0 0 0 Pore Diameter (Angstronis) E U a) E 0 ‘JJ a) L 0 0 0.3 0.2 0.1 0.0 NJ - C D 0 C D D C D 0 0 0 0 0 CD 0 0 NJ — 0 o 0 0 o 0 NJ CD C D 0 C 0 0 U, 0 C D NJ 0 0 CD 0 Lfl L.J 0 0 Figure 3. POROGRAM OF FRESH USA DEMETALL ZATION CATALYST (o Mo) HRI NO. 3309 ------- 6.0 DESCRIPTION OF UNITS AND TEST METHODS 6.1 USSR All tests were carried out in fixe bed bench scale units, the reactor having a catalyst volume of 200 cm . The direction of feed oil was upflow. Figures 4 and 5 present schematic diagrams of the unit and reactor. The preheated feed was mixed with preheated hydrogen containing gas and fed to the bottom of the reactor. After leaving the reactor the liquid products, together with the hydrogen containing gas, were cooled and fed to the high pressure separator. From here, hydrogen sulfide was removed from the hydrogen containing gas and recycled. The liquid products were fed to the low pressure separator from which it was periodically removed and measured. The reactor was fabricated from a tube having the following dimensions: External diameter - 50 mm Internal diameter - 28 mm Length - 800 mm A housing for three thermocouples was located in the center of the reactor. Two hundred milliliters of catalyst werecharged to the reactor on a layer of ceramics of a similar particle size. A layer of ceramics was also placed on top of the catalyst bed. The startup procedure was as follows: (a) Nitrogen purge under one third, one—half and one working pressure. (b) Purging of the system with hydrogen and preliminary drying of the catalyst by circulating hydrogen containing gas at 500 normal liters per liter (nl/l) (2841 SCF/Bbl) with gradual increase in temperature of 50°C (122°F) per hour. When a temperature of 300°C (572°F) was reached, it was held for 2 hours. The feed was then introduced and the temperature gradually increased at 50°C per hour up to a temperature of 370°C (698°F). 14 ------- Fiqure 1 • DIAGRAM OF THE USSR PILOT EQUIPMENT - “a Pump Liquid Product Sample Line 4- ------- Output of Reaction Products I ,2,3 Thermocouples Input of Feed + Hydrogen Containing Gas External Diameter - 58 mm Internal Diameter - 28 mm External Thermocouple Rousing Diameter - 10 mm Internal Diameter of Feed Input - 5 mm Operational Conditions: P = 200 Atm. t = L 5 j0 C Fi gure 5. SCHEMATIC DRAWING OF THE USSR REACTOR 16 ------- (c) Presulfiding of the catalyst was carried out at a temperature of 370°C (698°F) for 18 hours using a virgin 350-500°C fraction gas oil (containing a moderate amount of sulfur) at a liquid feed rate of 1000 nI/i (5612 SCF/Bbl). Then the temperature was increased up to a given level. (d) The test was then initiated and the run data taken six hours after startup. According to the Protocol of December 13, 1974, conditions of the tests were carried out at a hydrogen pressure of lL+0 atmospheres, a temperature of 400°C (725°F), liquid space velocity of I Hrl for atmospheric residua and a temperature of 420°C (788°F) and liquid space velocity of 0.75 Hr1 for vacuum residua. The circulation of the gas-containing hydrogen was maintained in all the experiments at a level of 1000 nl/l (5612 SCF/Bbl) on feed. Each test lasted 500 hours. The hydrogenation product which was periodically removed from the low pressure separator was subsequently analyzed (once every 24 hours): (a) Density determination, g/cm 3 (b) Fractionation under vacuum (according to Bogdanov) Cc) Determination of sulfur content, W Cd) Conradson carbon determination, W The used catalyst, after discharge from the reactor, must be washed for two hours in a Soxhiet device with benzene and the following are determined: (a) Bulk weight, g/cm 3 (b) Specific surface, M 2 /g (c) Pore volume, crn 3 /g Cd) Content of carbon and hydrogen (e) Content of nickel and vanadium (f) Sulfur content 17 ------- Results of the used catalyst are given in this report (Tables 7 and 8). Preliminary experiments showed that in the case of demetallization on catalysts-adsorbents, the demetallization kinetics (with respect to removal of vanadium) may be adequately described by the following first order equation: Mf ln—= K — M mV p where Mf and is the content of vanadium in the feed and the hydro- genation product in ppm; K is the demetallization rate constant; and m V is the volumetric rate of feed supply, in HR1 The deactivation rate of the demetallization catalyst was determined by the change in the demetallization constant as a function of catalyst mid hours on stream. To compare the desulfurization activity of the catalysts, graphs were drawn showing degree of desulfurization versus operational t i me. 6.2 USA All demetallization runs were carried out in continuous, downf low fixed bed reactor systems. A schematic diagram is shown in Figure 6. The reactor, fabricated of 1-1/2-inch (38 mm) 0.D. by one-inch (25.4 mm) I.D. stainless steel tubing, has a catalyst bed length of approximately sixteen inches (406 mm). A drawing of the reactor tube is shown in Figure 7. The volume (loose) of catalyst charged to the reactor was 200 cm 3 . Provision was made for an internal thermocouple which was positioned in the center of the catalyst bed approximately midway between the top and bottom. Heat to the reactor was supplied by a lead bath. The melted charge stock was pumped to reactor pressure with a meter- ing pump, mixed with hydrogen makeup gas, and fed to the top of the reactor. The hydrogen concentration of the makeup gas was 100* and no recycle of the exit gases was employed. In the reactor, the feed was contacted with the catalyst. The mixed vapor and liquid product from the reactor was cooled and passed to a hgh pressure receiver from which gas was sampled, metered, ar d vented. The net product ------- HYDROGEN THERMOCOUPLES LIQUID PRODUCT TO FLARE KNOCKOUT PUMP Figure 6. USA UNIT FLOW DIAGRAM ------- INLET OUTLET — 29 1/2” DRILL & TAP FOR 1” THREAD DETAIL “A” DETAIL “B” F;gure 7. SCHEMATIC DRAWING OF THE USA REACTOR 6 /2” / CATALYST BED LEVEL TC OF REACTOR 20 ------- was let down in pressure and passed to a low pressure receiver from which gas was sampled periodically, metered, and vented. The liquid product was collected and weighed periodically. Upon completion of a run, the catalyst was removed from the reactor for inspection and/or analysis. Three essentially identical units, 115, 148, and 184 were used for these runs. A standard startup procedure was used to condition the catalyst at lower temperature for a short period of time. The startup procedure was as follows: 1B,2 Period I A Etc . Temperature, (°F) °C (750)400 (775)415 (790)420 (790)420 Pressure, (psig) atm. (2050)140 (2050)140 (2050)140 (2050)140 Hydrogen Rate, (SCF/Bbi) ni/i (4000)712 (4000)712 (4000)712 (4000)712 Liquid Space Velocity, Vo/Hr/Vr Constant Time on Temperature, Hours 4 4 1 Continue At Conditions For operation at 400°C, the temperature for the first four hours was held at 370°C then increased to 400°c and held for the duration of the run. Gas samples from the highpressure receiver were analyzed twice weekly on a mass spectrometer, Du Pont Model 2l-103C. Daily inspections of the liquid product included: density by hydrometer, atmospheric distillation to 550°F (288°C), sulfur analyses on the 550°F+ fraction by Leco induction furnace method ASTM D-1552, and metals analysis for vanadium and nickel by atomic absorption Perkin Elmer Model 303. Besides the daily inspections, about twice weekly sulfur analyses were made on the initial to 550 F (288°C) fraction and appropriate corrections made on total product sulfur. Prior to analyzing used catalysts, the oil was first removed by benzene extraction in a Soxhiet extractor, then analyzed for carbon, sulfur, vanadium, and nickel. Metals and sulfur were analyzed using the same equipment as for liquid products while carbon was analyzed by high temperature combustion in oxygen using Perkin Elmer Model 240 elemental analyzer. Pore size distribution curves were obtained by mercury intrusion on Aminco’s 60,000 psi (4083 atm.) Porosimeter. 7.0 DISCUSSION OF RESULTS 7.1 Tests on USSR Catalyst Table 6 gives the results of tests on the T—3 catalyst for Romashkin atmospheric and vacuum residua, ha Juana vacuum resid, and Gach Saran vacuum resid carried out in the USSR and USA. 21 ------- TABLE 6. RESULTS ON USSR DEMETALLIZATION CATALYST TESTS MADE IN BOTH COUNTRIES Catalyst USSR (o.7 Mo) Feed USSR Vac. Resid USSR Vac. Resid Tia Juana Vac. Resid ha Juana Vac. Resid Gach Saran Vac. Resid USSR Atm. Resid Testing Country USA USSR USA USSR USSR USSR Hours On Stream 24 471 48 480 96 469 48 480 48 480 48 480 Product F ”) N.) Density, Gravity, 0 g/cm 3 °AP I .973 14.0 2.53 47 34 Sulfur, W ° Vanadium, ppm Nickel, ppm 0.97 1 14.2 2.58 4c 414 0.982 12.6 2.45 40 25 0.979 13.0 2.59 51 32 0.984 12.8 2.32 208 57 0.98 1 12.7 2.32 234 57 0.986 12.0 2.26 190 30 0.982 12.6 2.20 228 34 0.98 1 12.7 2.57 43 46 0.991 11.3 2.51 60 49 0.946 18.1 2.04 26 17 0.949 17.6 2.15 30 22 ------- An analysis of the results obtained confirms the preliminary data in- dicating that there was generally good reproducibility of results (except in one case) carried out on identical catalysts and feed in different countries. Figures 8 and 9 give the deactivation of the T-3 catalyst versus time on stream for different types of feedstocks. There is a difference between the degree of vanadium removal in the T-3 catalyst when pro- cessing Tia Juana vacuum resid and Romashkin vacuum resid. After 500 hours, the residual content of vanadium in the product when processing Tia Juana Vacuum resid was 223-228 ppm during tests of the USSR catalyst. This corresponds to a demetallization degree of about 62 percent. in the demetallization of Romashkin vacuum resid, it was about 44-51 ppm or 80 percent. The chemical composition of the feed and the properties of the metal- organic compounds had a great influence upon the demetallization rate constant of the feedstock. Although the content of vanadium in ha Juana vacuum resid was approximately 2.5 times greater than in Romashkin vacuum resid (as may be seen from Figures 8, 9, 10 and 11)the demetallization rate constant was approximately 1.5 times lower than for Romashkin vacuum resid. It must be noted that for all types of feeds studied, the degree of nickel removal was much lower than the degree of vanadium removal (see Appendix). On T—3 catalyst tests, the degree of desulfurization on all types of feeds varied from 17 to 27 percent which cooresporids to a residual sulfur content of 2.2 percent in the product at the end of the run using Tia Juana vacuum resid and 2.6 percent sulfur for Romashkin vacuum resid (see Figures 12, 13, 14, 15 and 16). The deactivation of the catalyst is a result of the cracking reactions taking place at the same time as the reactions of demetallization and desulfurization and deposition of coke in the catalyst pores. There- fore, to predict the stable operations of the catalyst and the poten- tial of its adsorption metal capacity, the characteristics of the used catalyst are of great importance in terms of their content of coke deposits and metal deposits, as well as on the volume of the pores (porograms) and specific surface. Table 7 gives the characteristics of the used 1—3 catalyst after operations using different types of feeds, and Figures 17, 18, 19, 20 and 21 give the curves for the pore radius distribution. In accordance with the recommendations of the USA the pore volumes and the specific surfaces for the used catalyst were corrected with respect to a new catalyst to make a comparison of the data. The following formula was used: 23 ------- Tia Juana V.R. Roniashkin V.R . Run Conditions Feed Composition 24 72 120 168 216 26 4 312 360 408 456 504 MID-HOURS ON STREAM > 0 E 0 E - > 0.75 Figure 8. VARIATION OF VAN ADIUM REMOVAL WITH MiD-HOURS ON STREAM DURING THE ROMASHKIN VACUUM DEMETALLIZATIOU OF hA JUANA AND RESIDS OVER USSR CATALYST (T-3) MADE IN THE USSR RUNS 140 420 Density, g/cm 3 Sulfur, W % 1.028 2.95 1.001 3.13 Hydrogen. Pressure, Atm. Temperature, °C Vanadium, ppm Nickel, ppm 588 78 242 81 Liquid Space V/Hr/V Velocity, I0 8 6 5 , 0 0 i 00 i i ‘ ‘ ‘ ‘ I 0 I 0o I I I I I 1 85 80 70 60 .E 50 J 3.00 0 4.J 0 0 L a- E -u Co to > 0 0 2 o 0 0000000000 I I I - _A __ _ I _ I I I I I 0 00 I I I I I I I I _ 1 __ . _ .I I ------- Feed Composition Run Conditions Density, glcm 3 1.0176 Hydrogen Pressure, Atm. 140 Sulfur, W °‘ 5.29 Temperature,’°C 1420 Vanadium, ppm 32 4 Liquid Space Velocity, V/Hr/V 0.75 Nickel, ppm 145 10: I t I , i i 90 8 85 0 o 0 OA 0 0 o o °‘j °“e - 6 0 0 00 70 5 0 0 co 0 0 60 L O 0 0 L i 0 50 E Q) F”, E— 3 40 ° ‘ -I -’ -o c-o 2 30 >C (0 > _L I L ( I I I i i I I i I I I I I I I I 24 72 120 168 216 264 312 360 408 4 6 o4 MID-HOURS ON STREAM Figure 9. VARIATION OF VANADIUM REMOVAL WITH MID1IOURS ON STREAM DURIN — THE DEMETALLIZAT ION OF GACH SARAN VACUUM RESID OVER USSR CATALYST (1-3) RUN MADE IN THE USSR ------- Feed Composition Operating Conditions Density, g/cm 3 1.012 Hydrogen Pressure,Atm. l40 Sulfur, W ? 2.95 Temperature, 0 C 20 Vanadium, ppm 588 Liquid Space Velocity, Nickel, ppm 78 V/Hr/V 0.75 (V 5 I I I I I I I I I L 80 L O 7° . 6O I j _________________ I 1 —1 50 48 q6 144 192 240 288 336 384 432 480 MID-HOURS ON STREAM Figure 10. VARIATION OF VANADIUM REMOVAL WITH MID-HOURS ON STREAM DURING THE DEMETALLIZATION OF 114 JUANA VACUUM PESID OVER USSR CATALYST (T-3) RUN MADE IN THE USA ------- Density, glcm 3 Sulfur, W Vanadium, ppm Nickel, ppm Run Conditions Hydrogen Pressure, Atm. Temperature, 0 C Liquid Space Velocity, V/Hr/V l +0 1+20 0.75 OF VANADIUM REMOVAL WITH MID-HOURS ON STREAM DURING THE DEMETALLIZATION OF ROMASHKIN VACUUM RESID OVER USSR CATALYST (T- T , RUN MADE IN THE USA Feed Composition 0.001 3.09 236 81 F. ’, —4 0) 0) U- E C (U > 4-, U 0 L C E C (0 10 — 9-.- 8— 7— 6— 5— It— 3— 2_ ‘I — Figure 11. I I I I I I I I I__i 88 • I84 e.G.., J . -8o I F I I I ii 1144 192 240 298 336 381+ 1+32 480 (0 > 0 E 0 ) a: E (0 C CU 4-, C 0) U L 4) a- 1+8 96 VARIATION ------- Feed Composition Run Conditions Density, 9/cm 3 1.028 Hydrogen Pressure, Atm. 1 o Sulfur, W 2.95 Temperature, °C 2O Vanadium, ppm 588 LiquId Space Velocity, V/Hr/V 0.75 Nickel, ppm 78 > 0 E cl) - 30 0 0 L 0000000 0000000000 20 CO U) 4 -J c i) 0 L c i ) a- I I I I I —1 148 96 1144 192 2140 288 336 3814 1432 480 528 MID-HOURS ON STREAM Figure 12. DESULFURIZATION OBTAINED DURING DEMETALLIZATION OF TIA JUANA VACUUM R ID OVER USSR CATALYST (T-3) RUN MADE IN THE USSR ------- Feed Composition Run Conditions Density, 9/cm 3 1 .001 Hydrogen Pressure, Atm. l +0 Sulfur, W 3.13 Temperature, 0 C 420 Vanadium, ppm 2 +2 Liquid Space Velocity, V/Hr/V 0.75 Nickel, ppm 81 — (U > 0 E a) 30 1 ooo o ° 0000 20 0o0o 000000 V) C 10 L a) I I F I 1+8 96 11+1+ 192 21+0 288 332 381+ 432 480 501+ MID-HOURS ON STREAM Figure 13. DESULFURIZATION OBTAINED DURING THE DEMETALLIZATION OFROMASHKIN VACUUM RESID OVER USSR CATALYST (1-3) RUN MADE IN THE USSR ------- Feed Composition Run Conditions Density, g/cm 3 1.0176 Hydrogen Pressure, Atm. 1110 Sulfur, W 3.29 Temperature, °C 1 e2 0 Vanadium, ppm 3211 Liquid Space Velocity, V/Hr/V 0.75 Nickel, ppm l 45 hO - (t > 30 0 0 I T°T°T°T°T°T°T°T° 101 148 96 11+t 1 192 2140 288 332 3814 432 480 5011 MID-HOURS ON STREAM Figure 14. DESULFURIZATION OBTAINED DURING THE DEMETALLIZATION OF GACH SARAN VACUUM RESID RUN MADE IN THE USSR ------- Hydrogen Pressure, Atm. 0 Temperature, C Liquid Space Velocity, V/Hr/V (U > 70 U) 60 504 14 Q 30 10 U) 0 Feed Composition Density, 9/cm 3 1.0)2 Sulfur, W 2.95 Vanadium, ppm 588 Nickel, ppm Operating Condi tions 1110 1 120 0.75 II: I I I I I I I 1 18 96 11411 192 240 2 8 — 3 2 3 i 4 2 48 bo MID-HOURS ON STREAM fI ure 15. DESULFURIZATION OBTAINED DURING THE DEMETALLIZATION OF hA JIJANA VACUUM RESID OVER USSR CATALYST (1-3) RUN MADE IN THE USA ------- Feed Composition Run Conditions Density, 9/cm 3 1.00) Hydrogen Pressure, Atm. 140 Sulfur, W ° c 3.09 Temperature, °C 420 Vanadium, ppm 236 Liquid Space Velocity, Nickel, ppm RI V/Hr/V 0.75 5 I I L — > 0 — E U) L - 0 U) 3 ‘4- — L CQ (I , C 2 _ i0 ‘4.- %_ U) U U) • * I. .•O ..•. —10 1 — 0 100 200 300 400 500 HID-HOURS ON STREAM Fiqur 16. DESULFURIZATION OBTAINED DURING DEMETALLIZATION OF ROMASHK1N VACUUM RFSID OVER USSR CATALYST (T-3) RUN MADE IN THE USA ------- Table 7. CHARACTERISTICS OF USED USSR DEMETALLIZATION CATALYST (1-3 ) 0.754 (2.14) 1.137 0.141 99. 5 12.91 12.04 8.0 1.8 0.0458 0.0056 0.0095 0.0047 0.0397 0.0511 0.746 (2.12) 1.17 0. 199 62.6 14.40 13.5 9.5 3.69 Pore Volume, cm 3 /g 0. 0698 0.0048 0.0161 0.02 15 0. 0654 0.0213 Vacuum Resid of Romashkin Petrol eum 0.869 (2.47) 0.930 0.229 49.6 12.29 9.57 6.43 2.21 0.0338 0.0212 0. 0109 0. 0040 0. 0319 0.1276 Indices Feed Tia Juana Vacuum Resid Gach-Saran Vacuum Resid Catalyst Age, 11 3 /kg (Bbl/Lb) Bulk Density, g/cm 3 Volume of Pores, g/cm 3 Specific Surface, M 2 /g Carbon Content, W * Sulfur Content, W * ‘ Vanadium Content, W * Nickel Content, W * Distribution of PoreRadius, Angstroms 30-50 X 50-100 100-500 500-1000 1000-5000 5000 Characteristics of used catalyst are given after 600 hour run. ------- I $ I I I I 100000 30000 10000 5000 1000 500 100 50 30 Pore Radius (Angstrorns) Figure 17 - COMPARISON OF POROGRAMS OF NEW AND USED (T-3) CATALYST AFTER OPERATING ON hA JUANA VACUUM RESID E U E 0 > L 0 0 0.6 0.5 0.3 0.2 0.1 1. New 1-3 Catalyst 2. 1-3 After Operating On Tia Juana Vacuum Resid ------- 0. I I I I 100000 30000 10000 5000 1000 300 100 50 30 Pore Radius (Angstroms) 0. 0.L+ E 0 a) E 0 > a) L 0 C- 1. 0.3 2. Hew T-3CatalySt 0.2 1-3 After Operating On Romashkin Vacuum Resid 0.1 Figure 18. COMPARISON OF POROGRAMS OF NEW AND USED 1-3 CATALYST AFTER OPERATING ONROMASHKIN VACUUM RESID ------- I I I 0.6 0.5 I. New 1-3 Catalyst Oi 2. 1-3 After Operatinq On Gach Sar n Vacuum Resid E C’ 0.2 0. 1 - - I 100000 30000 10000 5000 1000 500 100 50 30 Pore Radius (Anystroms) Figure 19. COMPARISON OF POROGRAMS OF NEW AND USED T3 CATALYST AFTER OPERATING ON GACH SARAN VACUUM RESID ------- I I IL E o 0.14 LU z 1 0 > LU C 100000 30000 PORE RADIUS (ANGSTROMS) Figure 20. COMPARISON OF POROGRAMS OF FRESH USSR CATALYST (1-3) AND USED CATALYST AFTER OPERATING ON TIA JUANA VACUUM RESID RUN MADE IN THE USA I I 2. Fresh USSR Catalyst (T-3) Used Catalyst 10000 5000 1000 500 100 50 30 ------- E ° 0.4 w z -J 0 > 0.2 (Li 0 0 100000 PORE RADIUS (ANGSTROMS) Fhiure 21. COMPARISON OF POROGRAMS OF FRESH USSR CATALYST (1-3) AND USED CATALYST AFTER OPERATING ONROMASHKINVACUIJM RESID RUN MADE IN THE USA I I Fresh USSR Catalyst (1-3) Used Catalyst 2. I I I I I I.._._. 1 30000 10000 5000 1000 500 100 50 30 ------- cm 3 /g of new catalysts = l.OO—E + 1/2 Es x crn 3 lg of used catalyst F 1 — is the weight portion of vanadium, nickel and carbon for the used catalyst; and F 5 — is the weight portion of sulfur for the used catalyst. It may be seen from Table 7 that the carbon content in the catalyst is approximately the same for processing different types of feeds. On the other hand, the pore volume for a used T-3 catalyst during demetallization of ha Juana vacuum resid is approximately 1.5 less than for Romashkin vacuum resid. A comparison of the porograrns for a new and used 1-3 catalyst when processing ha Juana vacuum resid and Romashkin vacuum resid shows changes in every case. The portion of pores with a radius less than 100 decreases greatly, and to a lesser extent the pore portion changes from 100 to 1000 A and there is a great increase in the portion of pores above 1000 (see Figures 13, 14, and 15). The appendix to this report gives the detailed characteristics of the hydrogenation products obtained during the operating period for all types of feeds. 7.2 Tests on USA Catalysts Table 8 presents a summary of results achieved from tests made in each country using the USA catalysts on various feedstocks. There follows a discussion of each test conducted and a presentation of graphs showing vanadium removal versus mid—hours on stream, and the desulfurization achieved during demetallization. Used catalyst analyses and evaluations are also given along with pore size distribution curves. Test Carried Out In USA Catalyst: USA 1 ? Mo (HRI 3634) Feed: USSR Vacuum Resid (Gudron) This aging dernetallization test was carried out in Run 184-202 at a hydrogen pressure of 140 atm., temperature of 420°C and liquid space velocity of 0.75 V/Hr/V for a duration of 474 hours on stream until it was voluntarily shutdown. No operating difficulties were 39 ------- Table 8. RESULTS ON USA DEMETALLIZATION CATALYST TESTS MADE IN BOTH COUNTRIES Catalyst USA (I? Mo) USA (l Mo) USA (l? Mo) USA (O Mo) USA (l Mo) USA (l c Mo) Feed USSR Vac. Resid USSR Vac. Resid USSR Atm. Resid USSR Atm. Resid ha Juana Vac. Resid USSR Atm. Resid Testing Country USA USSR USA USSR USSR USSR Hours On Stream 43 1474 138 5014 45 1477 48 5014 1i8 504 148 480 Prod u c t Density, g/cm 3 0.9335 0.9554 0.9636 0.9760 0.9328 0.91402 0.9490 0.9433 0.9791 0.9810 0.935 0.939 Gravity, °API 20.1 16. 6 15.3 13.5 20.2 19.0 17.6 18.5 13.0 12.7 19.8 19.2 Sulfur, W 0.92 1.49 1.29 2.38 1.16 1.50 2.38 2.16 2.01 1.98 1.38 1.87 Vanadium, ppm 17 35 1t3 68 20 28 71 50 195 290 22 35 Nickel, ppm 23 31 38 64 114 23 25 19 37 58 14 14 ------- experienced during this test. The catalyst dumped freely from the reactor. Demetallization and desulfurization data obtained from this test are summarized in Figures 22 and 23, respectively. In these figures the vanadium and sulfur data are expressed as the ratio of vanadium or sulfur in the product versus mid-hours on stream. The mid-hours on stream is used because it represents the middle age of a 214 hour product period on which the analyses were conducted. In this test vanadium removal started at about 9O level and dropped to about 8o after 60 hours gradually to 82 at the end of the test. Desulfurization obtained in this ranged from 69 at the beginning and dropped to 56 at the end of the test. Average demetallization achieved was 84% vanadium removal and the average desulfurization during the demetallization test was 61.5% sulfur removal producing a product oil containing 1.26 W % sulfur and 31 ppm vanadium. Average values for sulfur and vanadium in the products were calculated by an arithmetic average of values obtained during the life of the test. Test Carried Out in USSR Catalyst: USA 1 % Mo (HRI 3634) Feed: USSR Vacuum Resid (Gudron) This test made in the USSR corresponds to the test made in the USA as Run 1814—202. It was carried out at a total pressure of 150 atm. (approximately 140 atm. hydrogen partial pressure), temperature of 420°C and liquid space velocity of 0.75 V/Hr/V. Demetallization and desulfurization data obtained are summarized in Figures 213 and 25, respectively. In these figures the vanadium and sulfur data are plotted as ratios of vanadium or sulfur in the feed to vanadium or sulfur in the product against mid—hours on stream. In this run vanadium removal started at 83% and dropped to 682 at the end of the run. Desulfurizaiton started at about 60% and dropped to 23% at 350 hours and remained at this level until the end of the run. The average demetallization achieved was 72% vanadium removal and the average desulfurization during the demetallization test was 34% sulfur removal producing a product oil containing 2.01 W % sulfur and 63 ppm vanadium. The feed and product analyses used in the above calculations were supplied by the USSR. 41 ------- CATALYST: USA ( I rio) FIRI NO. 36311 FEED: USSR VACUUM RESID RUN: 1814 -202 FEED COMPOSITION OPERATING CONDITIONS Density,g/cm 3 1.00614 Hydro jen Pressure, Atm. 11+0 Sulfur, W 3.27 Temperature, °C 1420 Vanadium, ppm 198 Liquid Space Velocity, V/Hr/V: 0.75 Nickel, ppm 80 20 I I I 1 1 U 4 )0 U.. L 9O C JO —C E 8 (0 86 _ 6 (0 > (0 0 - • • 83 oc CE 80 > L 4) 75 - 3 I I 0 100 200 300 1+00 500 Mid-Hours On Stream Figure 22. VARIATION OF VANADIUM REMOVAL WITH MID-HOURS 011 STREAM DURING THE DEMETALLIZATION OF ROMASHKIN VACUUM RESID OVER USA CATALYST (1 Mo) RUN MADE IN THE USA ------- CATALYST: USA (1 Mo) HRI MO. 3631+ FEED: USSR VACUUtI RESID RUN: 18’+-202 FEED COMPOSITION OPERATING CONDITIONS Density g/cm 3 1.0061+ hydrogen Pressure, Atm. 11+0 Sulfur, W ; 3.27 Temperature, °C 420 Vanadium, ppm 198 Liquid Space Velocity, V/Hr/V: 0.75 Nickel, ppm 80 6. I I I 5’ L 14 9- IS . 67 > 0) 3. 75 CE 60 L 5 4)0 ) 2 C a. L 50 4) a. U -. L — D 4- ‘I ) 1— I I I 0 100 200 300 1+00 500 Mid-Flours On Stream Figure 23. OES(JLFURIZATION OBTAINED DURING THE DEMETALLIZATION OFROMASHKIN VACUUM RESID OVER USA CATALYST (i Mo) RUN MADE IN THE USA ------- CATALYST: USA (1 plo) HRI NO. 363 4 FEED: USSR VACUUM RESID FEED COMPOSITIOII OPERATIH(’ 1 CONDITIONS Density,g/Cm 3 1.0005 Hydrogen Pressure, Atm. IL 0 Sulfur, W 2 3.03 Temperature, °C Vanadium, ppm 229 Liquid Space Velocity, V/Hr/V: 0.75 Nftkel, ppm 80 E 6- - Ro (0 (0 5- 0 U 75 - E -D 67 U L -- U. L 3_ 3- C —c 2.. (0 cr0 (oc > (0 > • I I I I 0 100 200 300 400 500 tiid-Hours On Stream Figure 21+. VARIATION OF VANADIUM REMOVAL WITH MID-HOURS ON STREAM DURING THE DEMETALLIZATION OF ROMASHKIN VACUUM RESID OVER USA CATALYST (1° Mo) RUN MADE IN THE USSR ------- CATALYST: USA (I Mo) HRI NO. 363 i FEED: USSR VACUUM RESID FEED COMPOSITION OPERATING CONDITIONS Density, 9/cm 3 1.0005 Hydrogen Pressure, Atm. 140 Sulfur, 11 3.03 Temperature, °C 420 Vanadium, ppm 229 Liquid Space Velocity, V/IIrfV: 0.75 Nickel, ppm 80 6- i I I 5.. 4.. -w U 3-. (4 O L L 4- 2.. 4 .-L > — . . —- c E QJQ) . . . • • • • • • •-20 1- 0 100 200 300 4oo 500 Mid-Hours On Stream Figure 25. DESULFURIZATION OBTAINED DURING THE DEMETALLIZATION OF ROMASHKIN VACUUM RESID OVER USA CATALYST (l0/ M6) RUN MADE IN THE USSR ------- Results obtained by the USSR showed a lower level of vanadium removal and higher deactivation slope. There is no apparent explanation for this difference. Difference in initial startup of the unit, if any, may have caused this difference in the results. Test Carried Out in USA Catalyst: USA 1 Mo (HRI 3634) Feed: USSR Atmospheric Resid (Mazut) This test was carried out in Run 184-203 at 140 atm hydrogen pressure, temperature of 400°C and liquid space velocity of 1.0 V/Hr/V. The average demetallization achieved was 78 vanadium removal and the average desulfurization was 5l sulfur removal producing a product oil containing 1.42 W sulfur and 29 ppm vanadium. Figure 26 shows the catalyst deactivation slope of vanadium removal and Figure 27 shows the sulfur removal slope during the demetallization test. Test Carried Out in USSR Catalyst: USA O Mo (HRI 3309) Feed: USSR Atmospheric Resid (Mazut) This test was carried out at a total pressure of 150 atm, temperature of 400°C and a liquid space velocity of 1.00 V/Hr/V. The average demetallization achieved during this test was 64 vana- dium remcval and the average sulfur removal was l6 producing a product oil containing 2.27 W sulfur and 50 ppm vanadium. Figure 28 sh is the catalyst deactivation slope for vanadium removal and Figure 29 for sulfur removal. The catalyst deactivation slope shows that this catalyst improves with age in its capacity to remove vanadium from this particular feed indicating catalytic effect of deposited metals on the catalyst. This effect was not evident on sulfur removal. 46 ------- CATALYST: USA (1 c Mo) I IRI NO. 3631+ FEED: USSR ATtIOSPIIERIC RESID RUN: 18 1 +_2o3 FEED COIIPOSITION OPERATING CONDITIONS Density, g/cm 3 0.9652 Hydrogen Pressure, Atm. 1140 Sulfur, W 2.88 Temperature, °C 1+00 Vanadium, ppm 130 Liquid Space Velocity, V/Hr/V: 1.0 Nickel, ppm 145 8 i i E 7.. 0 186 Q)C 6 S • —183 > > 0 0 • •• • • • • • • • • _I80 — C c4) a) a 14. —175° L a) 0 - (0 - cm 3•. mc 2 - I 0 100 200 300 1+00 500 Mid-Hours On Stream Figure 26. VARIATION OF VANADIUM REMOVAL WITh M1D-HOITflS 09 STREAM DURING THE DEMETALLIZATI0NJ ROMASHKIN ATMOSPHERIC RESID OVER USA CATALYST (1% Mo) RUN MADE IN THE USA ------- CATALYST: USA (I 2 Mo) HRI tl0. 3631. FEED: USSR ATHOSPHERIC RESID RUN: 1814—203 FEED COIIPOSITIOIi OPERATIUG CONDITIONS Density, g/cm 3 0.9652 Hydrogen Pressure, Atm. 140 Sulfur, W 2.83 Temperature, °C 1400 Vanadium, ppm 130 Liquid Space Velocity, V/ I lr/V: 1.0 Nickel, ppm 45 6- i I 5- 0 3 L 0 )0 4— L L • —6 0:,_ 2-- • •S. L • ••••••• 50 > I GJ0.) 4- I ° I33 a. ‘1, I — I I I I 0 100 200 301) 4oo 500 Mid-Hours On Stream Figure 27. DESULFURIZATION OBTAINED DURING DEMETALLIZATION OF ROMASHKIN ATMOSPHERIC RESID OVER USA CATALYST (1 Mo) RUN MADE IN USA ------- CATALYST: USA (0 2 Mo) HRI HO. 3309 FEED: USSR ATMOSPHERIC RESID FEED COMPOSITION OPERATING CONDITIONS Density, g/cm 3 0.96 16 Hydrogen Pressure, Atm. 140 Sulfur, W 2.71 Temperature, °c 400 Vanadium, ppm 136 Liquid Space Velocity, V/Hr/V: 1.0 Nickel, ppm 1 9 6 I 5. E ‘.0 ‘ U > )O 3. . • 7(Ufl3 U. L 0 - • • , 4o E a)c E 2-. vU OL 0 . ( C — 0 100 200 300 400 500 Mid-Hours On Stream Figure 28. VARIATION OF VANADIUM REMOVAL WITH MID-HOURS ON STREAM DURING THE DEMETALLIZATION OF ROMASI-IKIN ATMOSPHERIC RESID OVER USA CATALYST (o Mo) RUN MADE IN THE USSR ------- CATALYST: USA (0 Mo) HRI NO. 3309 FEED: USSR ATMOSPHERIC RESID FEED COtIPOSITION OPERATING CONDITIONS Density, 9/cm 3 0.9616 Hydrogen Pressure, Atm. Sulfur, W 2.71 Temperature, °C 1400 Vanadium, ppm 136 Liquid Space Velocity, V/Ilr/V: 1.0 Nickel, ppm 149 6 i 5. 0 J 4 U a) -D U L 3 L c 33 —C 50 L 2-. > CE (I ) L ••. •I•• • I I I I 0 100 200 300 400 500 Mid-Hours On Stream Figure 29. DESULFURIZATION OBTAINED DURING THE DEMETALLIZATION OF ROMASHKIN ATMOSPHERIC RESID OVER USA CATALYST (0 Mo) RUN MADE IN THE USSR ------- Test Carried Out in USSR Catalyst: USA l Mo (HRI 3634) Feed: Tia Juana Vacuum Resid This test was carried out at a total pressure of 150 atmospheres, temperature of 420°C and a liquid space velocity of 0.75 V/Hr/V. The average demetallization achieved during this test was 6o° vanadium removal and the average desulfurization during demetal- lization was 35 sulfur removal producing a product oil containing 1.93 W sulfur and 239 ppm vanadium. Figure 30 sho s the catalyst deactivation slope of vanadium removal and Figure 31 shows the sulfur removal during demetallization. 7.2.1 Used Catalyst Analyses The results of used catalyst analyses are sumarized in Table 9. The fairly low carbon levels on all used catalysts indicate no coking problems were encountered during the tests. On the only two comparable tests made in both countries, that is USA l Mo catalyst on USSR vacuum resid, the loss in surface area and total pore volume was greater on the catalyst from the test made in the USSR than in the USA. Since the demetallizatior, in the USA test was greater (84? versus 72 vanadium removal) and the desulfurization was also deeper (62 versus 34 ), at the same operating conditions, the differences might be attributed to methods of operation and/or differences in test equipment. Figures 32, 33, 34, 35, and 36 present the pore size distribution curves on the used catalysts which are compared to the fresh catalysts used. 7.2.2 Pore Size Distribution Determinations and Interpretation Pore size distributions on all catalysts were determined using Aminco’s Model J5-7125D 60,000 psi (1+083 atm.) mercury intrusion porosimeter. The range of pore sizes which can be measured using this instrument is from 30 to about 180,000 in diameter. The upper range corres- ponds to 10 psi (0.68 atm.), the pressure needed to fill with mercury the interstitial voids between catalyst particles. A correction was made before reporting results by subtracting the volume of mercury intruded at 10 psi (0.68 atm.) from the total volume of mercury in- truded into the catalyst sample. 51 ------- CATALYST: USA (1 Mo) IIRI MO. 3634 FEED: hA JUANA VACUUM RESID FEED COMPOSITION OPERATIMG CONDITIOFIS Density, q/cm 3 1.038 Hydrogen Pressure, Atm. 140 Sulfur, W 2.95 Temperature, °C 420 Vanadium, ppm 589 Liquid Space Velocity, V/hrIV: 0.75 Nickel, ppm 78 6. I I I I 5 1 75 E 0 0 • I. •-67 ‘ a)-t 3 S •. 6o LL S ••. S S 550 1’ E E 2 I .. a) .33 (0 - :, (0 >1• I I I 0 tOO 200 300 400 500 Mid-Hours On Stream Figure 30. VARIATION OF VANADIUM REMOVAL WITH MID-HOURS ON STREAM DURING THE DEMETALLIZATION OF hA JUANA VACUUM RESID OVER USA CATALYST (1 Mo) RUN MADE IN THE USSR ------- CATALYST: USA (1 % Mo) 1 -IRI NO. 3631k FEED: TIA JUANA VACUUN RESID FEED COMPOSITION ________________ OPERATING CONDITIONS Density, g/cm 3 1.038 Hydrogen Pressure, Atm. 1140 Sulfur, W 2.95 Temperature, °C 1420 Vanadium, ppm 589 Liquid Space Velocity, V/Hr/V: 0.75 Nickel, ppm 78 6 ‘.ri 5 ‘4 U -D 00 3 L L 4- C — C 2 (1) (0 > 4 . Q ‘4- • CE —4- U Q ci 3 0) a- I — I I I I I 0 100 200 300 ‘ 4O() 500 Mid-Hours On Stream Figure 31. DESLJLFURIZATION OBTAINED DURING THE DEMETALLIZATION OF hA JUANA VACUUM RESID OVER USA CATALYST (1 °‘ Mo) RUN MADE IN THE USSR ------- Table 9. ANALYSES ON USA CATALYST FROM AGING TESTS MADE IN USA AND.USSR Country Making Test Catalyst Identifi ion Fresh (0 Mo) URI 3309 Fresh (l Mo) HRI 36314 USA l Mo 184-203 USA I° Mo l81+ -202 USSR 0 l; Mo HRI 3817 USSR I Mo HRI 3816 USSR I Mo HRI 3815 Carbon Sulfur Feed W W USSR Atm. Resid 8.92 USSR Vac. Resid 7.81 USSR Atm. Resld 7.69 USSR Vac. Resid 8.30 Tia Juana Vac. Res d 8.28 Vanadium Nickel C.B.D. ______ W g/cm 3 -- 1.0140 Surface Total Pore Area Volume M 2 /g __________ 1.05 1.2514 1145.7 1.52 1.306 66.2 0.67 1.140 112.3 0.83 1.256 146.3 0.59 1.390 32.1 175 0.225 0.317 Loss In Total Pore Volume 0.181 42.9 0.136 57.1 0.133 0.085 73.2 0.088 12.2 Temperature, °C (°F) Pressure, Atm. ,( sig) L,quid Space Velocity, Vo/Hr/Vr Atm. Resids 400 (752) 1140 (2050) 1.0 Vac. Resids 20 (790) 140 (2050) 0. 75 Note: Pore volume and surface area data were corrected to fresh catalyst basis. Pore volumes were also corrected for interstitial voids. (SEE TEXT) U, 3.31 6.43 5.30 7.93 8.89 -- - - 0.978 195.6 3.78 3.12 7.58 OPERATING CONDITIONS ------- U V E 0 > ‘U L 0 Q•!4 0.3 0.2 0.1 I I I I I I I I o 0 o 0 o 0 Pore Diameter (Anqstroms) Figure 32. COMPARISON OF POROGRAMS OF FRESH USA CATALYST (1 % Mo) AND USED CATALYST AFTER OPERATING 1. Fresh Catalyst (1 plo) 2. Used Catalyst 2 0.0 r : 0 0 C) 0 0 0 C) C) 0 0 0 0 0 0 —I 0 o o o 0 0 o 0 0 0 0 I I I I I I r1 0 0 C) C) 0 0 U, 0 0 ON ROMASHKIN (USSR) ATMOSPHERIC RESID RUN MADE IN THE USA ------- I I I I I I I E U E 0 > (1) L 0 ’ — 0 o 0 0 0 o 0 o 0 U - I 0 0 Fiqure 33. COMPARISON OF POROGRAMS OF FRESH USA CATALYST (1 Mo) AND USED CATALYST AFTER OPERATING 0.4 — j I 1. Fresh Catalyst (1 Mo) 2. Used Catalyst 0.3 — 0.2 0.1 2 0.0 F ’) — ‘-I, o 0 0 c o 0 •0 0 o 0 0 CD o CD C) I I I I I I F’) o 0 0 0 0 CD Pore Diameter (Angstroms) 0 0 N) — CD CD o 0 ON ROMASHKIN (USSR) VACUUM RESID RUN MADE IN THE USA ------- 0. I I I I I I I I 1. Fresh Catalyst (0 Mo) 2. Used Catalyst J, NJ — f1 NJ Q 0 0 • . - ‘. .. 0 0 0 0 o 0 0 0 0 0 c 0 0 0 0 Pore Diameter (Angstroms) Figure 3Z . COMPARISON OF POROGRAMS OF FRESH USA CATALYST (o ? Mo) AND USED CATALYST AFTER OPERATING C. -’ E U ‘1) E 0 > c i) L 0 0 0.3 0.2 0.1 0.0 2 0 0 0 0 C :, I I I I I C:, C D 0 0 0 0 0 0 I I ¼J1 0 0 NJ — o o 0 0 ‘.11 C.A) 0 0 ON ROMASHKIN (USSR) ATMOSPHERIC RESID RUN MADE IN THE USSR ------- I I I I Pore Diameter (Angstroms) I I I I Figure 35. COMPARISON OF POROGRAMS OF FRESH USA CATALYST (I Mo) AND USED CATALYST E U 4, 0 4, 0 a- I. Fresh Catalyst (I Mo) 0. 0.3 0.2 0.1 — 0.0 2. Used Catalyst % fl a, 2 NJ 0 0 0 0 0 0 0 0 0 0 U i 0 0 0 0 C 0 0 0 C 0 0 0 U i 0 0 0 NJ — o o Ui 0 C I I I I I I NJ — 0 0 0 0 Ui 0 0 AFTER OPERATING ON ROMASUKIN (ussR) VACUUM RESID RUN MADE IN THE USSR ------- cv E U 4) E 0 t_D 4) L 0 a- 0.z — I I 0.3 0.2 0.1 C) o 0 o 0 0 0 — o 0 C ) C) o 0 o 0 Figure 36. COMPARISON OF POROGRAMS OF FRESH USA CATALYST (1 ? Mo) AND USED CATALYST AFTER OPERATING I I I I 1. Fresh Cata’yst (1 Mo) 2. Used Catalyst 0.0 I I I I \ fl 0 0 0 C) 2 U, 0 C) 0 N J D -o 0 0 O 0 Pore Diameter (Angstroms) I I I I U, 0 0 NJ — 0 0 o o U, 0 0 ON hA JUANA VACUUM RESID RUN MADE IN THE USSR ------- Pore size and surface area data on used catalysts were corrected to fresh catalyst basis using the following relationship: cm 3 /g Fresh Catalyst = + x cm 3 lg Used Catalyst where F 1 = weight fraction of V, Ni, C on used catalyst F 5 = weight fraction sulfur on used catalyst 8.0 LIST OF REFERENCES 1. Oil & Gas Journal, 70, 31, pp. 98-100 (1972) 2. Bitumen—Tare-Asphalte—Pache, 1/2, c. 9—22, pp. 122—128 (1975) 60 ------- 9.0 APPENDICES 9.1 TESTS REPORTED BY USSR ------- Table O. DEMETALLIZATION RUN SUMMARY OF hA JUANA VACUUM RESID OVER USA CATALYST ( 1 ? Mo) RUN MADE IN THE USSR CataIys USA Omnetalll,atlon Catalyst (I 7. MO) URI Idt ’ntlficatlon Ho. 363 , Feed Source ha Juana ttacuum Re ld 0.n3Ity. 1.038 9/cm 3 Sulfur, 2.95 W 7. VanadIum/NIckel, ppm 589/78 Hours On Stream Operating tondit ions temperature, Pressure, Atm. Space Velocity, O/Hr/Vr Catalyst. 141, Cans. Catalyst, V. cm 3 Ll . jld Product Den l ty , q/cm 3 Sulfur, V ‘7 , Total Product 500°C Vanadium, ppm NIckel, ppm 1NP-3S0°C, V P. IBP-SO0°t, V 248 195 227 200 235 180 200 275 236 717 22 4 232 215 260 252 248 256 48 3/ 50 40 ‘.8 50 42 8 c2 35 58 42 39 58 51, 62 5 14.5 5 S 5 5 5 5 5 5 5 5 5 5 6 6 5 5.5 18 21 21 20 25 23 2 . 24 24 25 24 24 21, 23 21 22.5 22 2) 290 290 290 58 35 58 5 5 5 21 20.5 21.5 1420 420 1420 420 350 150 ISO 150 21, 148 72 96 120 144 168 192 216 2140 2614 288 312 336 360 381. 408 432 0 ’ 0.75 196 200 0.75 0.15 0.75 196 196 196 200 200 200 1420 1.20 1.20 1.20 420 1.20 1.20 420 420 1.20 420 1.20 420 420 ISO ISO ISO ISO ISO 150 ISO ISO ISO 150 ISO ISO ISO ISO 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.15 0.75 0.75 0.75 0.75 0.75 196 196 196 196 196 196 196 196 196 196 196 196 196 196 200 200 200 200 200 200 200 200 200 200 200 200 200 200 lop, “C 1456 4P’i 504 1.20 420 1420 ISO ISO ISO 0.75 0.75 0.75 196 196 196 200 200 200 2.08 34 2.21 82 0.9803 .9791 0.9819 .9780 .9182 .9/86 .9790 .9790 .9710 .9769 .9798 .9791 .9015 .9789 .9815 .9805 .9199 .9785 .9799 .9801 .9810 2.01 1.92 1.85 1.81. 1.90 1.87 1.86 1,91 1.86 1.87 194 1.83 1.93 1.95 1.93 1.99 1.97 1.37 1.29 1,37 1.30 1.39 1,40 1.35 1.50 1.38 1.40 1.41 I. 6 1.35 1.31 1.30 1,33 1.35 2.15 2.00 1.89 1.96 1,99 1.98 1.97 2.0$ 1.97 2.00 2.0’. 3.95 1.99 2.13 2.05 2.11 2.09 77 86 99 too too 87 III 95 100 79 89 8 ’. 97 78 97 90 106 1.99 1.99 1.98 3.37 I. )) 137 2.13 2.11 2,13 76 90 79 ------- Table 11. DEMETALLIZATION RUN SUMMARY OF ROMASHKIN VACUUM RESID OVER USA CATALYST (1 Mo) RUN MADE IN THE USSR Calyst: l iSA 04’n’etaIlI7atlon Catalyst (I % Mo) HAl hlentIfIcatI o No. 3634 Feed Sowcs. USSR Vacuum A,sld (Guironl DensIty, 1.0005 q/cm Sulfur, 3.03 U 3. VanadIum/Nickel, ppm 229/80 420 420 420 420 420 420 150 150 150 150 ISO ISO 420 420 420 150 ISO ISO Hours On Sjseam Oper at l ondlt.lons Temperature, “C 0’ froduct DensIty, g ./cm 3 9fl r lotal Product I BP-500°C 500°C 4 lAP. °C Vanadium. Isprn Nickel, ppm IBP-350°C, V % 1.23 0.76 1.42 86 1.29 1.45 .81 1.01 1.59 1.71 10 ’s 96 24 48 /2 96 120 144 168 192 216 240 26’i 288 312 6 360 384 408 1432 456 480 5014 420 420 1420 420 420 620 420 620 420 1420 1420 1420 Pressure, Atm. ISO ISO ISO 150 150 50 ISO ISO 150 ISO 150 ISO Space Velocity Vr,/Hr/Vr 0.15 0.15 0./5 0.75 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.15 0.75 0.75 Catalyst, U, Cars. 196 196 196 196 196 196 196 I 196 196 196 196 196 196 196 196 196 196 196 196 196 Catalyst. V. cm 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 0,9761 .9636 .9638 .9682 .9658 .9658 .9698 .9696 .9616 .9708 .9754 .9/50 .9754 .9750 .9758 .9173 .9775 .9716 .97814 .9754 .9760 2.42 1.91 2.53 106 2.38 .97 2.56 108 8 43 38 7 / 7 62 149 8 14’. 35 8 66 ‘.1 1 28 60 38 7 30 49 39 9 31, 73 41 8 29 65 142 8 30 66 58 8 29 72 61. 8 29 56 52 1 29 64 62 7 28 68 /2 7 27 80 /4 8 28 76 64 6 27 64 68 7 27 64 62 7 28 68 64 7 28 48 .99 I .66 96 .70 1.06 I .90 93 1.73 I .114 1.89 78 1.87 1.31 2.05 102 1.89 I .37 2.01 lot) .96 1.50 2.18 80 2.08 1.55 2.37 102 2 .09 1.60 2.31 92 2.16 I .66 2.38 95 2.28 .71 2.50 98 2.25 1.851 2.140 97 2.32 1.814 2.55 98 2.40 1.90 2.54 1014 2.41 I .98 2.63 los 2.49 .96 2.5/ 98 2 . 40 I .92 2. 89 IBP-500°C, V 9, 32.5 28 30 30 32 32 ------- Table 12. DEMETALLIZATION RUN SUMMARY OF hA JUANA VACUUM RESID OVER USSR CATALYST RUN MADE IN THE USSR 0 ’ Operating Cond ltioni P. 135 atm. 1.470°C V—o.85 Hr 24 48 72 96 120 i i14 168 192 216 240 264 288 312 336 360 386 608 632 656 480 504 0.9819 0.9863 0.9861 0.9196 0.9863 0.98 0.9782 0.97914 0.9183 0.9814 0.912 1 0.9806 0.9636 0.9825 0.9805 0.96 0.9624 0.9822 0.9822 0.9820 0.9818 2.36 2,26 2.23 2.18 2.19 2.28 2.25 2.25 2.13 2.15 2.11 2.11 2.26 2.21 2.16 2.26 2.20 2.21 2.20 2.21 2.16 1.12 1.90 1.76 1.75 1.82 1.85 1.73 1.82 1.77 1.76 1.69 1.71 1.88 1.77 1.91 1.91 1.80 1.78 1.79 1.85 1.83 2.56 2.62 2.141 2.33 2.37 2.35 2.37 2.35 2.30 2.29 2.25 2.23 2.35 2.60 2.30 2.31, 2.31 2.29 2.30 2.21 2,20 6.6 11.7 17.6 17.1 17.7 17.6 17.8 18.3 11.4 17.0 15.5 17.8 17.4 17.2 17.3 17.7 17.3 17.5 16.9 17.2 17.3 H4,Urs On Stre n Density, qfcm 3 Sulfur, U total Product I BP -500°C 500°Cu Conradson C, U Nitroqen, W 1, lap, °C l0 . °C Boiling Range, °C 1BP-350. V ‘I, 1DP-500. V % 180-350, V (, Vanadiun, ppm Nickel, ppm Demetal II zat Ion Rate Constant 0.39 0.33 0.38 0.35 0.37 0.38 0,314 ItO 90 97 92 98 80 83 98 96 84 94 94 86 112 92 112 100 93 88 89 tOO 423 4314 431 423 430 416 431 423 420 416 399 438 1451 442 441 445 445 1449 435 450 448 6.0 5.0 5.0 5.5 5.0 7.0 5.0 5.0 6.0 6.0 6.0 5.0 4.5 5.0 5.0 5.0 5.0 5.0 5.5 5.5 5.0 71.0 22.0 21.0 22.0 20.0 214.0 22.0 23.0 23.0 23.0 27.0 20.0 21.0 20.0 21.0 20.0 20.0 20.0 21.0 20.0 20.0 4. 3,5 3.5 4.0 3.5 5.0 6.0 4.0 5.0 14.5 14.5 14.o 3.5 4.0 4.0 4.0 4.0 14.0 4.5 4.0 14.0 188 168 180 174 170 115 114 190 215 228 223 29 30 29 29 30 29 52 34 35 0.89 0.98 0.93 0.955 0.955 0.9S5 0.89 0.80 0.75 0.77 ------- Table 13. DEMETALLIZATION RUN SUMMARY OF ROMASHKIN ATMOSPHERIC RESID OVER USA CATALYST (0 Mo) RUN MADE IN THE USSR Catalyst: USA OemetaIIIz ,ltIOn Catalyst (0 Mn) URI I Inot I Ilcat Inn P In. 3309 Feed Sou4ce: USSR At splu rlc R.sld (H.1?u%) D nsUy. 0 9616 q/r.n Sulfur. 7.7% Vsnjjltj ,n/NIckeI . 136/1*9 ppm Hours On SIrr.uo 21* 68 77 96 120 64 $68 197 716 240 768 788 112 336 360. 384 1408 1432 456 480 506 o n Ten p atUre, 1 1*00 1400 400 1400 400 1400 1400 1400 1400 1400 1400 *00 400 1*00 1400 1400 1400 1400 1400 $*00 400 Pr ccure, Atm. $50 $50 $50 $50 150 ISO 150 150 $50 ISO $50 ISO $50 150 150 ISO ISO 150 ISO ISO 150 Space VelocIty. Vo/lIr/Ar 1.0 1.0 1.0 .0 1.0 .0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 P.O 1.0 1.0 1.0 1.0 Catalyst. 14. t a*s. 208 208 208 208 208 206 208 208 208 208 208 208 208 208 208 208 208 208 208 208 208 Catalyst, V. rn 200 200 200 200 200 700 200 700 200 200 200 200 200 200 200 200 200 200 200 200 200 DenSity, q/r,n .91439 .91*90 .9 1*76 .91412 .9505 .91450 .9468 .91463 .91455 .9 14149 .9655 .9463 .9423 .9433 9669 .9475 .9669 .9469 .9439 .9633 Sulfur w V 0ot ,l Prrlt,ct 2.31 2.38 2. 1*0 2.36 2.29 2.40 2.30 2.21 2.26 2.26 2.29 2.40 7.38 2.15 2.08 2.22 2.19 2.19 2.11 2.17 2.16 lee, °C 96 II) $19 113 II? $09 115 126 98 13 14 106 V ar *ad lurn,pp*n 58 71 71 56 55 57 41 $45 41 38 31 35 86 69 52 1*6 65 66 50 Nlckel,ppm 22 25 24 23 20 23 20 70 9 19 $8 $7 26 24 21 2$ 2$ $9 $9 leP S0°t. V 8 6 8 8 7 7 8 8.5 7 6 8 IRP-500°C. V . 62 63 614 63 F .? 614 1414 6 1.5 62 61 6$ ------- Table 14. DEMETALLIZATION RUN SUMMARY OF GACH SARAN VACUUM RESID OVER USSR CATALYST RUN MADE IN THE USSR Operating Conditions P .135 atm. 1 . 420 °C V—O.75 Hr Hours On Strr ,,m 24 48 72 96 120 144 $68 192 216 240 264 288 312 336 360 384 408 432 456 480 504 Density. q/cm 0.9824 0.9808 0.9884 0.9820 0.9902 0.9856 0.9888 0.9890 0.9904 0.9902 0.9900 0.9894 0.9894 0.9894 0,9888 0.9928 0.9922 9.9916 0.9900 0.9910 0.9920 Sulfur, W Total Product 2.79 257 2.54 2.63 2.61 2.61 2.66 2.63 2.61 2.57 2.65 2.65 2.65 2.66 2.64 2.68 2.65 2,72 2.65 2.51 2.71 18P-500,°C 1.16 2.3 2.10 2.16 2.22 2.18 2.26 2.27 2.29 2.30 2.25 2.211 2.22 2.22 2.23 2.27 2.32 2.33 2.18 2.25 1.93 500, °C 2.119 2.81 2.69 2.71 2.68 2.65 2.69 2.69 2.72 2.70 2.70 2.67 2.75 2.60 2.75 2.75 2.10 2.82 2.68 2.65 2.80 Conradson C, I ‘I 15.8 17.3 $6.6 $7.0 16.9 15.8 $7.1 17.3 $7.1 $7.0 17.1 17.6 $7.3 17.7 $7.6 17.5 17.1 $7.0 $7.1 $7.7 17.4 NItrogen, W ‘I. 0.52 0.56 0.56 0.57 0.59 0.52 0.57 IBP, °C 85 115 80 04 88 75 100 84 84 84 90 96 92 91 76 84 90 80 60 $02 92 10%. °C 391 424 414 415 411 414 416 423 1123 411 416 416 1115 1116 416 422 411 410 381 410 417 Boiling R ingc,°C IBP-350, V 7, 8.0 6.0 7.0 7.0 7.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 8.0 6.0 6.0 lOP-SOn, V 7. 23.0 29.0 21.0 22.0 21.0 23.0 21.0 21.0 21.0 22.0 21.0 21.0 71.0 21.0 22.0 20.0 22.0 23.0 23.0 22.0 22.0 18 0-350,V ‘. 6.0 4.5 5.0 5.0 5.0 11.5 6.0 4.0 4.0 4.5 4.0 4.0 4.0 4.0 4.0 11.0 4.o 4.0 5.0 4.0 4.5 V.u’,adium. ppm 2 1 1 43 117 57 44 47 51 61 53 49 60 49 68 43 64 65 42 56 57 60 68 Nickel, ppm 314 111, 47 48 38 1,6 47 46 52 54 51 52 51 50 52 51 49 46 51 49 119 ------- Table 15. DEMETALLIZATION RUN SUMMARY OF ROMASHKIN VACUUM RESID OVER USSR CATALYST RUN MADE IN USSR Operating Conditions P— 135 ate. T—l 120°C. V—0.75 Hr 1 Hours On Stream 26 148 72 96 120 IkIi 168 192 216 2140 266 288 312 336 360 3814 408 432 1456 1180 5014 Oensity, q/cm 3 0.97117 0.9821 0.9813 0.9779 0.9775 0.9828 0.97014 0.9796 SuUur, H 2.6 4 2.45 2.110 2.31 2. 1i2 2.34 2.38 2.50 2.53 2.51 2.53 2.1.8 2.140 2.37 2.47 2.55 2.63 2.60 2.59 2.59 2.60 Conradson C, W % 12.9 13.1 1.37 12.6 12.’. 12.6 12.8 114.6 114.1 16.1 13.8 16.0 114.0 12.1 14.5 111.5 14.5 114.0 15.1 15.3 14.7 NItro er ., H 0.46 0.48 0.46 0.46 0.45 0.46 18P, °C 117 109 80 94 80 91 102 I I I iot, °c 372 )3 36 381 375 409 606 500 0 801 1mg Range, C 18P-350, V 4 8 8 9 9 8 7.0 1.0 1.0 IBP-500, V % 26 26 29 29 27 21.0 28.0 11.0 180-350, V Y. 5 6 6 6 5 5.0 5.0 4.0 Van. .,dlon.ppn 36 60 145 62 64 35 35 59 51 ‘ .6 35 44 51 49 NlckeI.ppm 18 25 27 23 21 18 20 29 31 26 24 31 32 31 ------- Table 16. DEMETALLIZATION RUN SUMMARY OF ROMASHKIN ATMOSPHERIC RESID OVER USSR CATALYST RUN MADE IN THE USSR Opera11nq Condltlori P.135 atm., t.1.O& (, V.1.0 Hr 1 Hours On Stream 24 48 72 96 120 11.11 168 192 216 21.0 261. 288 312 336 360 38’. 408 1.32 ‘.56 1.80 501. nsit , gitm 3 0.9412 0.9464 0.9464 0.948! 0.9487 0.946! 0.9489 0.9481 0.9502 0.91.87 0.9491 0.9478 0.948! 0.9500 0.9494 0.9486 0.9481 O.9 ’ .79 0.9485 0.9494 0.9492 Sulfur, W ) 2.04 7,Ql 2.36 2.30 2.28 2.33 2.22 2.16 2.21 2.27 2.33 2.31. 2.31. 2.22 2.20 2.16 2.21. 2.19 2.17 2.15 2.22 Conradson C, U 7.6 7.6 7.3 7.5 7.5 1.3 7.5 7.2 7.5 7.l 7.2 7.1 7.3 7.3 7.0 7,3 1.! 7.4 7.2 7.2 7.4 NItrogen, U 0.2g. 0.21. 0.23 0.21 0.24 ISP, °C 138 325 13o ItO 146 12’. 118 116 736 118 116 114 120 126 119 120 32! 116 118 122 120 ‘0%, °C 371 310 368 365 383 369 360 358 379 355 360 351 36? 369 361 364 361 360 359 366 365 SoIling Range, 0 C ISP-350, V 7.0 6.0 6.0 7.0 5.0 6.0 8.0 8.0 5.0 7.0 6.0 6.0 6.0 1.0 7.0 7.0 6.0 8.0 7.0 8.0 8.0 ISP-500, V % 61,0 59.0 60.0 60.0 53.0 60.0 63,0 60.0 53.0 61.0 61.0 64.0 62.0 60.0 61.0 62.0 60.0 61.0 61.0 60.0 60.0 180-350, V 6.5 s.s 5.0 6.0 4.5 5.5 7.0 1.0 6.5 6.5 5. 5.5 5.0 6.0 6.5 6.S 6.5 7.5 6.5 7.5 7.0 VanadIum, ppm 16 26 26 28 3! 27 Il 16 22 Il 23 20 13 24 28 21 24 30 311 30 32 NIckel, ppm 12 Il 20 20 22 IS 35 36 20 16 16 39 iS 20 20 22 20 21 23 22 23 ------- 9.2 TESTS REPORTED BY USA 69 ------- Table 17. DEMETALLIZATION RUN SUMMARY OF ROMASHKIN VACUUM RESID OVER USSR CATALYST RUN MADE IN THE USA Catalyst USSR T-3 (Oh Mo) Run Nunber 115-1250 Feed Ronashkln Vacqum Pesd Density, q/cm’ 1.006 11 Sulfur, W t 321 V snaalum/NickeI, ppm 98/80 Hours Or. Strean’ 14 38 62 86 110 13’ 158 182 206 230 2511 278 302 326 350 37 1k 398 422 1447 1471 !rating Condit ions lemperature, “C ‘42) 421 420 420 42) 1421 1420 42) 1120 42) 1470 1420 1,21 1420 420 42) 42) 1420 42) 420 “ .1 H 2 Pressure, Atm. 136 136 13€ 136 135 136 1314 136 136 136 136 136 136 13€ 136 135 136 136 136 136 Space Velocity V/Hr/V 0.75 0.15 0.82 0.74 0.76 0.74 0.76 0.1’I 0.75 0.80 0.75 0.77 0.74 0.70 0.82 0.83 0.80 0.15 0.711 0.75 liquid Product Density, q/c .n 3 0.9725 09806 0.9745 0.9705 0.9752 0.9725 0.9792 0.9772 0.9718 0.9738 0.98’sO 0.9732 0.9692 0.97)2 0.9738 0.9125 0.9705 0.9799 0.96920.9112 Sulfur, Id V 2.53 2.65 2.12 2.143 2.41 2.148 2.46 2.5) 2.5) 2.4) 2.57 2.54 2.57 2.48 2.64 2.27 2.57 2.60 2.57 2.58 lOP “C 232 182 199 199 193 196 202 199 192 $91 186 196 190 192 195 20) 2)5 182 200 191 Vanadium, ppm 147 30 3) 33 34 32 140 38 35 3/ 40 40 40 32 38 39 39 36 38 40 Nickel, ppm 3 1 s 38 43 42 42 44 43 43 40 4) 45 45 45 37 iii 44 414 39 38 39 lRP-288°C,Vt 4 6 6 7 7 6 6 6 6 6 7 8 7 8 6 6 5 7 6 6 ------- Table 18. DEMETALLIZATION RUN SUMMARY OF hA JUANA VACUUM RESID OVER USSR CATALYST RUN MADE IN THE USA Hours On Stream USSR T- (0.7* Ho) ha Juana Vacuum Resid Dersity. 5/cmi 10122 Sal fur. U 7 3. II Vanaror/ 4 liclrel. ppm 552//5 12 36 60 84 108 132 156 180 204 228 252 276 300 324 348 372 396 421 1445 469 ! L ng Conditions Temperature. “C 420 420 42) 421 42) 42) 42) 42) 42) 421 422 420 42) 42) 423 42) 42) 42) 1420 420 H 2 Pressure, Atm. 135 136 136 135 136 134 137 I I! 137 135 135 135 136 136 136 135 136 136 136 135 Space Velocity V/Hr/V 0.80 0.76 0.72 0.77 0.80 0.77 0./5 0.7) 0.84 0.82 0.76 0.614 0.85 0.67 0.90 0.71 0.80 0.75 0.69 liquid .! _‘ .! Density, u/cm 3 Sulfur. ‘1 3 I OP, °C Vanadium, ppm Nickel, IRP-288°C, V 7 0.91)2 0.9786 0.9792 0.9847 0.9871 , 0.9840 0.9765 0.9779 0.986) 0.9820 0.97145 0.9632 0.9786 0.9833 0.9813 0.9786 0.9792 0.9833 0.98680.99)3 2./3 2.62 2.143 2,37 2.32 2.36 2.36 2.38 2.32 2.36 2.35 2.40 2.28 2.5) 2.12 2.27 2.36 2.34 2.38 2.32 2146 20g. 2)) 205 2014 206 209 223 2)6 238 211 23) 193 195 200 196 204 201 211 196 222 222 2)0 208 22) 2)0 204 2)2 2)) 210 209 223 20) 240 203 235 2140 2)6 2141 2311 50 54 53 57 58 56 56 52 52 54 55 57 149 52 53 55 59 56 58 si 2 4 6 6 6 5 5 5 S 5 5 5 5 i 6 7 6 8 Catalyst: Run N,,mber 148-360 Feed: ------- Table 19. DEMETALLIZATION RUN SUMMARY OF ROMASHKIN ATMOSPHER$C RES D OVER USA CATALYST (1 Mo) RUN MADE IN THE USA Catalyst: USA Oemetalli atlon C.talyut (1% Mo) 178 g URI Identification No. 36314 182 cm 3 Run Number 1814-203 Feed Source: USSR Atmospheric Re,d (Mazut) Oensity . g/cis 09652 Sulfur. W 2.88 Vanadium/Nickel, ppm 130/1*5 Hours 0 Stream 20 145 69 93 ill 141 65 189 213 237 261 285 309 333 357 381 405 1*29 1451. 1.77 Operating Conditions Temperature, °C 1*00 400 400 400 1100 400 403 400 400 400 1400 399 399 1*00 400 400 400 400 400 400 H 2 Pressure, Atm. 140 140 1140 140 140 1110 139 140 139 138 138 139 138 139 140 11*0 1140 11*0 139 11*0 Space Velocity V/Hr/V 1.07 1.04 I II 1.13 1.09 1.11 1.09 1.03 1.13 1.11 1.06 1.05 1.08 1.08 1.06 1.06 1.03 1.02 1.08 1.05 roduc Density g/cm 3 .9303 .9328 .9334 .937 1 .93311 .9365 .9346 .9358 .9371 .9358 .93446 .9371 .9340 .9358 .931.0 .9377 .9352 .9334 .9352 .9402 Sulfur, 14 t 1.36 1.16 i.32 1.31 1.25 ,l4i4 1.30 1.31 1.55 1.37 1.42 1.43 1.53 1.48 1.55 1.51 l.54 1.42 1.59 1.50 181’, °C 188 237 2314 252 22’. 271 266 249 199 288 252 282 251. 215 199 202 189 177 200 169 Vanadium, ppm 22 20 26 25 25 27 28 29 42 35 30 30 30 29 29 29 29 28 29 28 Nickel, ppm Iii 14 6 21 21 22 21 20 2S 23 20 21 21 21 25 25 2 * 23 23 23 IBP-288°C .y 3 2 I I I I I 2 2 2 2 I 2 2 2 I 2 I 2 2 ------- Table 20. DEMETALLIZATION RUN SUMMARY OF ROMASHKIN VACUUM RESID OVER USA CATALYST (1 % Mo) RUN MADE IN THE USA Catalyst: USA Demetalllcatlon Catalyst (It Mo) 378 g HRI IdentiFication No. 363li 182 cm 3 Run Number: %8i. 2O2 Feed Source: USSR Vacuum Re id (Gudron) Density g/ce 3 3.00611 Sulfur, V 3.27 Vanadium/Nickel, ppm 398/60 Hours On Stream 39 43 61 91 115 139 163 187 211 235 259 283 307 331 354 378 1102 i26 1,50 474 -4 Operat ngCond t ions Temperature, °C 423 1421 418 421 12% 1121 423 1421 1121 1123 1121 1120 112% 42% 1123 42% 42% 421 42% 1121 Pressure, Atm. 331 l 4O 339 338 339 139 139 139 139 339 139 1111 1111 139 139 139 138 139 339 339 Space Velocity V/Hr/V 0.67 0.13 0.87 0.72 0.83 0.76 0.84 0.73 0.711 0.76 0.84 0.78 0.79 0.72 0.711 0.73 0.76 0.13 0.88 0.79 J uid_Product Density 9/cm 3 .3529 .3535 .9593 .9529 .9567 .9563 .9563 .9567 .9567 .9600 .9639 .9606 .9535 .9600 .95511 .9561 .9529 .9503 .9652 .9554 Sulfur, V 2 0.98 0.92 1.16 1.05 1.18 1.18 1.12 1.18 1.20 1.30 1.110 3.32 3.34 1.21 1.37 3.40 u.48 3.28 1.61 .49 laP, °C 390 49 1, I 377 376 Ill 369 165 I 9 204 382 3534 380 379 373 370 178 384 3734 382 Vanadium, ppm 20 37 28 25 28 21 30 30 33 30 43 38 32 32 37 39 39 33 36 35 Nickel ppm 22 23 30 29 32 34 34 30 31 30 35 33 29 29 32 33 32 28 33 33 IRP-2 8°C,V3 7 9 8 7 B 8 8 8 1 7 8 7 6 9 7 B 7 7 7 ------- TECHNICAL REPORT DATA (Please read Thun cfions on the reverse before co,npletingl iT PORT NO. 2. EPA-600/7-78-119 3. RECIP1ENTS ACCESSIOI* NO. 4.rrrLE AND SUBTITLE 5. REPORT DATE Demetallization Catalyst Tests on Heavy Residual OHs June 1978 6. PERFORMING ORGANIZATION CODE AumOR(S) y V. Manshi]in et al. (USSR), W. J. Rhodes (EPA, IERL-RTP), and P. Maruhnic and G. Nongbri ( y drocarbon Research) J.PERFORMING OROANIZAT!ON NAME AND ADDRESS 8. PERFORMING ORGANIZATION REPORT NO. 10. PROGRAM ELEMENT NO. Hydrocarbon Research, Inc. New York and Puritan Avenues EHE623A 11. CONTRACT/GRANT NO. Lawrenceville, New Jersey 08648 . 68-02-0293 12. SPONSORING AGENCY NAME AND ADDRESS EPA, Office of Research and Development Industrial Environmental Research Laboratory 13. TYPE OF 9EPORT ND PERIOD COVERED CODE Research Triangle Park, NC 27’lll EPA/600/13 15.SUPPLEMENTARY NOTES IERL-RTP coauthor/project officer is W.J. Rhodes, Mail Drop 61, 919/541-2851. The report gives results of a cooperative project between the U.S. and the USSR to exchange technology on the demetallization step of an overall process to pro- duce low sulfur fuel oil from heavy petroleum residua. Catalysts and petroleum residua feedstocks were exchanged and tests were carried out by each nation using its own equipment and operating procedures. Test results were exchanged and dis - cussed at meetings in both the USSR and the U.S. In this report, all tests using U. S. catalysts were described by the U.S. and all tests using USSR catalysts were des- cribed by the USSR. Each nation described its own test equipment and operating pro- cedures. Included for each aging test are graphs showing the degree of demetalli- zation and desulfurization and the rate of catalyst deactivation. Fresh and used cat- alyst analyses are presented, along with detailed run summaries and product inspec- tions. Each nation’s molybdenum-impregnated catalyst exhibited about equal demetal- ization capability; however, the U.S. catalyst exhibited higher desulfurization capa- bility during demetallization. Sections of this report collaborated on and reported jointly include the summary, introduction, and conclusions. The project was con- sidered mutually beneficial. 7. KEY WORDS AND DOCUMENT ANALYSIS DESCRIPTORS b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group Air Pollution Molybdenum Petroleum Products Testing Metals Vanadlium Desuiftirization Fuel Oil Residual Oils Air Pollution Control Stationary Sources Demetallization USSR l3B UG l4B llF , O7B 07A , 07D llH , 2lD Catalysis 18. DISTRIBUTION STATEMENT Unlimited _______________ 19. SECURITY CLASS (This Report) Unclassified 21. NO. OF PAGES 8 20. SECURITY CLASS (This page) Unclassified 22. PRICE EPA Form 2220.1 (9.73) r4r4 ------- |