CA2412923C - Catalytic hydrogenation process utilizing multi-stage ebullated bed reactors - Google Patents
Catalytic hydrogenation process utilizing multi-stage ebullated bed reactors Download PDFInfo
- Publication number
- CA2412923C CA2412923C CA002412923A CA2412923A CA2412923C CA 2412923 C CA2412923 C CA 2412923C CA 002412923 A CA002412923 A CA 002412923A CA 2412923 A CA2412923 A CA 2412923A CA 2412923 C CA2412923 C CA 2412923C
- Authority
- CA
- Canada
- Prior art keywords
- reactor
- stage
- liquid
- catalyst
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for catalytic multi-stage hydrogenation of heavy hydrocarbonaceous feedstocks using catalytic ebullated bed reactors, operated at generally the same reaction conditions. In the process, the feedstock is reacted with hydrogen in a first stage catalytic ebullated bed reactor at operating conditions of 700-850 ~F temperature, 800-3000 psi hydrogen partial pressure at the reactor outlet, 0.2-2.0 V,/hr/V, liquid hourly space velocity, catalyst space velocity of 0.03-0.33 bbl/day per pound of fresh catalyst and at reduced superficial gas velocity of 0.02-0.3 ft/sec in each reactor, so as to provide increased percentage liquid volume and reduced gas hold-up in each reactor. The first stage reactor effluent liquid portion is fed into the second stage reactor. The second stage reactor effluent is phase separated and fractionated to produce lower boiling liquid products. A vacuum bottoms fraction normally boiling above about 650 ~F and preferably above 900 ~F is recycled back to the first stage reactor.
Description
CATALYTIC HYDROGENATION PROCESS UTILIZING MULTI-STAGE
EBULLATED BED REACTORS
BACKGROUND OF INVENTION
This invention pertains to improved catalytic hydrogenation of heavy hydrocarbonaceous feedstocks utilizing catalytic multi-stage ebullated bed reactors for producing desired lower boiling hydrocarbon liquid products. It pertains particularly to such catalytic multi-stage hydrogenation processes having increased catalyst loading and liquid volume together with reduced gas hold-up in each reactor, and thereby provides improved performance efficiency for the processes.
In conventional catalytic hydrogenation processes for heavy hydrocarbon feedstocks utilizing multi-stage ebullated bed reactors, the hydrogen gas recycle rate in each reactor is usually kept relatively high to assure that excess hydrogen gas exists in the catalyst bed to provide the necessary chemical hydrogenation reactions with the feedstock. However, such excess hydrogen flow requires relatively high superficial gas velocities in the reactor(s), which results in less available volume for the reacting liquid and increased gas hold-up in the reactor. Because the feedstock hydrogenation and hydrocracking reactions occur predominantly in the liquid phase, this conventional practice has the result of undesirably reducing the percentage of feedstock liquid being exposed to and reacted with the catalyst in the reactor, and undesirably reduces process performance. Also, for known catalytic ebullated bed type reactors which utilize internal gas/liquid separation devices, the volume of catalyst in a particular size reactor is undesirably limited.
Many prior art patents have been directed to various improvements in catalytic hydrogenation processes for heavy hydrocarbon feedstocks utilizing catalytic ebullated bed reactors, and have disclosed various operational parameters for such reactors. For example, U.S. Patent No. 3,183,180 to Schuman et al., U.S.
EBULLATED BED REACTORS
BACKGROUND OF INVENTION
This invention pertains to improved catalytic hydrogenation of heavy hydrocarbonaceous feedstocks utilizing catalytic multi-stage ebullated bed reactors for producing desired lower boiling hydrocarbon liquid products. It pertains particularly to such catalytic multi-stage hydrogenation processes having increased catalyst loading and liquid volume together with reduced gas hold-up in each reactor, and thereby provides improved performance efficiency for the processes.
In conventional catalytic hydrogenation processes for heavy hydrocarbon feedstocks utilizing multi-stage ebullated bed reactors, the hydrogen gas recycle rate in each reactor is usually kept relatively high to assure that excess hydrogen gas exists in the catalyst bed to provide the necessary chemical hydrogenation reactions with the feedstock. However, such excess hydrogen flow requires relatively high superficial gas velocities in the reactor(s), which results in less available volume for the reacting liquid and increased gas hold-up in the reactor. Because the feedstock hydrogenation and hydrocracking reactions occur predominantly in the liquid phase, this conventional practice has the result of undesirably reducing the percentage of feedstock liquid being exposed to and reacted with the catalyst in the reactor, and undesirably reduces process performance. Also, for known catalytic ebullated bed type reactors which utilize internal gas/liquid separation devices, the volume of catalyst in a particular size reactor is undesirably limited.
Many prior art patents have been directed to various improvements in catalytic hydrogenation processes for heavy hydrocarbon feedstocks utilizing catalytic ebullated bed reactors, and have disclosed various operational parameters for such reactors. For example, U.S. Patent No. 3,183,180 to Schuman et al., U.S.
4,217,206 and U.S. 4,427,535 to Nongbri et al disclose hydrogenation of petroleum residua using catalytic single stage ebullated bed reactors having internal gas/liquid separation, and U.S. 4,576,710 to Nongbri et al and U.S.
4,853,111 to MacArthur et al disclose use of such catalytic two-stage reactors.
Other prior art patents have disclosed hydrogenation process improvements utilizing catalyses having various compositions and pore structures, and specific reaction conditions based on characteristics of the feedstocks. However, a need still remains for providing a comprehensive improved catalytic multi-stage ebullated bed reactor system which is capable of producing improved hydrogenation process performance efficiencies.
SUMMARY OF INVENTION
This invention provides an improved catalytic multi-stage hydrogenation process for treating heavy hydrocarbonaceous feedstocks and producing desired lower boiling hydrocarbon liquid products with enhanced process performance. For this improved hydrogenation process, we have discovered that a more efficient catalytic multi-stage ebullated bed reactor system having improved performance results can be achieved by maximizing the catalyst loading and also providing increased reactor liquid residence time in each reactor, by utilizing reduced catalyst space velocity and reduced superficial gas velocity which are maintained within desired critical ranges in each reactor. These process improvements result in desirably increasing the liquid hold-up volume percent and reducing excessive gas hold-up volume percent in each of the reactors.
These desirable reaction results are accomplished by providing such increased volume percent of particulate catalyst and lower catalyst space velocities in each reactor by utilizing an external gas/liquid separator, in combination with utilizing lower superficial upward gas velocities and reduced gas hold-up in each reactor, while providing a desired outlet hydrogen partial pressure and desired level of hydrogenation or hydroconversion as selected for any particular feedstock.
4,853,111 to MacArthur et al disclose use of such catalytic two-stage reactors.
Other prior art patents have disclosed hydrogenation process improvements utilizing catalyses having various compositions and pore structures, and specific reaction conditions based on characteristics of the feedstocks. However, a need still remains for providing a comprehensive improved catalytic multi-stage ebullated bed reactor system which is capable of producing improved hydrogenation process performance efficiencies.
SUMMARY OF INVENTION
This invention provides an improved catalytic multi-stage hydrogenation process for treating heavy hydrocarbonaceous feedstocks and producing desired lower boiling hydrocarbon liquid products with enhanced process performance. For this improved hydrogenation process, we have discovered that a more efficient catalytic multi-stage ebullated bed reactor system having improved performance results can be achieved by maximizing the catalyst loading and also providing increased reactor liquid residence time in each reactor, by utilizing reduced catalyst space velocity and reduced superficial gas velocity which are maintained within desired critical ranges in each reactor. These process improvements result in desirably increasing the liquid hold-up volume percent and reducing excessive gas hold-up volume percent in each of the reactors.
These desirable reaction results are accomplished by providing such increased volume percent of particulate catalyst and lower catalyst space velocities in each reactor by utilizing an external gas/liquid separator, in combination with utilizing lower superficial upward gas velocities and reduced gas hold-up in each reactor, while providing a desired outlet hydrogen partial pressure and desired level of hydrogenation or hydroconversion as selected for any particular feedstock.
For this invention, the catalytic ebullated bed reactor construction arrangement for the first stage reactor does not include an internal gas/liquid separation device, but instead utilizes an efficient external gas/liquid separator.
Utilizing such external gas/liquid separation results in an increased volume of particulate catalyst being provided in a particular size reactor and reduces the catalyst space velocity, which is defined as the volumetric rate of feedstock processed per unit weight of fresh catalyst in the reactor. For such commercial size reactors having outside diameter of 12-14 ft. and a height of 50-60 ft., a vertical distance of 5-10 ft. should be maintained between the ebullated bed maximum expansion level and the reactor outlet conduit, so as to avoid any carryover of catalyst from the reactor. Also, operating conditions for each of the two-staged catalytic ebullated bed reactors are selected so that the upward superficial gas velocity is maintained within a desired critical range, and the gas hold-up volume percentage in each reactor is beneficially reduced, which consequently permits more reactor liquid to be in contact with the catalyst bed, so that the reactor performance as well as the overall process performance results are enhanced.
This invention is useful for processing heavy hydrocarbonaceous feedstocks and providing overall hydroconversions in the range of 50-100 vol.% to produce desired lower boiling hydrocarbon liquid products.
Therefore, to summarise, the present invention concerns a process for catalytic multi-stage ebullated bed hydrogenation of heavy hydrocarbonaceous feedstocks for producing lower boiling hydrocarbon liquids and gases, the process comprising:
(a) feeding a heavy hydrocarbonaceous liquid feedstock together with hydrogen gas into a first stage catalytic ebullated bed reactor at liquid space velocity of 0.2 - 2.0 volume of feed per hour per volume of reactor (Vf/hrNr,) and at catalyst space velocity of 0.03 - 0.33 bbl/day/lb catalyst, providing upward superficial gas velocity of 0.02-0.30 ft/sec while maintaining reaction temperatures of 700-850 F, and 800-3,000 psi hydrogen partial pressure at the reactor outlet, and producing a first stage reactor effluent material;
3a (b) phase separating the first stage effluent material into a gas portion and a first liquid portion, and passing the first liquid portion to a second stage catalytic ebullated bed reactor maintained at the reaction conditions similar to those of step (a), and producing a second stage reactor effluent material;
(c) phase separating the second stage effluent material into a gas and a second liquid portion;
(d) fractionating said second liquid portion to produce a medium-boiling hydrocarbon liquid fraction product having normal boiling range of 400-650 F and a vacuum bottoms fraction material having a normal boiling point above about 650 F; and (e) recycling said vacuum bottoms fraction material directly to said first stage catalytic ebullated bed reactor to provide a recycle volume ratio of the vacuum bottoms material to fresh feedstock of 0-1.0/1, so as to achieve between 50 and 100 vol.% conversion of the 975 F+ fraction in the feedstock to lower-boiling hydrocarbon liquid and producing increased yields of said medium-boiling hydrocarbon liquid product.
The invention also concerns a process for catalytic multi-stage ebullated bed hydrogenation of heavy hydrocarbonaceous feedstocks and for producing lower boiling hydrocarbon liquids and gases, the process comprising:
(a) feeding a heavy hydrocarbonaceous liquid feedstock containing 50-90 vol.% 975 F+ residua together with hydrogen gas into a first stage catalytic ebullated bed reactor at liquid space velocity of 0.2-2.0 volume of feed per hour per volume of reactor (Vf/hrNr,) and at catalyst space velocity of 0.03-0.33 bbl/day/Ib catalyst, providing upward superficial gas velocity of 0.02-0.25 ft/sec while maintaining reaction temperatures of 700-850 F, and 800-3,000 psi hydrogen partial pressure at the reactor outlet, and producing a first stage reactor effluent material containing gas and liquid portions;
3b (b) phase separating the first stage effluent material into a gas portion and a first liquid portion, and passing the first liquid portion on to a second stage catalytic ebullated bed reactor maintained at the reaction conditions of step (a), and producing a second stage reactor effluent material;
(c) phase separating the second stage effluent material into gas and a second liquid portion, and withdrawing the second liquid portion;
(d) fractionating said second liquid portion to produce a medium boiling hydrocarbon liquid fraction product having normal boiling range of 400-650 F, a vacuum gas oil having a normal boiling range of 650-950 F, and a vacuum bottoms material having a normal boiling temperature above about 950 F; and (e) recycling said vacuum bottoms fraction material directly back to said first stage catalytic ebullated bed reactor to provide a recycle volume ratio of the vacuum bottoms material to fresh feedstock of 0-0.7/1, so as to achieve 50-100 vol.% conversion of the 975 F+ fraction in the feedstock to lower boiling hydrocarbon liquid and producing increased yields of said medium-boiling hydrocarbon liquid product containing low sulfur and nitrogen.
The broad and preferred characteristics for the hydrocarbonaceous feedstocks and the reactor broad and preferred operating condition ranges for which this invention is useful are provided in Table 1 below:
FEEDSTOCK AND REACTOR OPERATING CONDITIONS
Condition Broad Preferred Feedstock Residua Content, vol.% 975 F+ 30 - 100 50 - 90 Feedstock CCR*, wt.% 1- 50 10 - 40 Feedstock Nickel plus Vanadium, Wppm Up to 1,000 100 - 800 Reactor LHSV**, hr 1(per Reactor Stage) 0.2 - 2.0 0.4 - 1.2 Reactor Temperature, F 700 - 850 750 - 840 Reactor Total Pressure, Psig 1,000 - 4,000 1,500 - 3,000 Reactor Outlet Hydrogen Partial Pressure, Psi 800 - 3,000 1,000 - 2,500 Reactor Superficial Gas Velocity, fps 0.02 - 0.30 0.025 - 0.20 Catalyst Space Velocity, BPD/Lb (per Stage) 0.03 - 0.33 0.04 - 0.20 Catalyst Replacement Rate, Lb/Bbl (per Stage)0.05 - 0.5 0.1 - 0.4 Catalyst Bed Expansion, % 25 - 75 35 - 50 Vacuum Bottoms Recycle Rate, Vr/Vfeed 0-1 0.2 - 0.7 Cutpoint of Vacuum Bottoms Recycle, F 650+ 900+ , * CCR = Conradson carbon residue.
** LHSV = Liquid hourly space velocity in each reactor, as defined as volumetric fresh feed rate divided by reactor total volume.
In the process, the fresh feedstock together with hydrogen are introduced into a first stage catalytic ebuiiated bed reactor, which does not contain an internal gas/liquid phase separator device. The catalyst bed is expanded by 25-75 percent above its settled level by the upflowing liquid and gas streams, and is maintained within the broad operating conditions of 700-850 F temperature, 800-3,000 psig hydrogen partial pressure at the reactor outlet, liquid hourly space velocity of 0.20-2.0 volume fresh feed per hour per volume of reactor (Vf/hrNr) and at catalyst space velocity of 0.03 - 0.33 barrel feed per day per pound fresh catalyst in the reactor. Because of the lower catalyst space velocity and superficial gas velocity being utilized in the reactor, the reacting liquid votume percentage is increased and gas hold-up volume is desirably reduced.
The first stage reactor usually hydroconverts 30-95 vol.% of the fresh heavy feedstock and any recycled residua material to a lower boiling hydrocarbon effluent material.
The first stage reactor effluent material is phase separated in an external gas/liquid separator, a gas fraction is removed, and a sufficient portion of the remaining liquid is recycled to the reactor to maintain the desired 25-75%
catalyst bed expansion therein. The remaining liquid fraction is passed together with additional hydrogen to a second stage catalytic ebullated bed type reactor.
The second stage ebullated bed reactor is operated similarly to the first stage reactor and typically is maintained at 0-50 F, lower temperature in the broad range of 700-850 F (370-455 C) and 0.20-2.0 (Vf/hrNr) space velocity, so as to effectively further hydragenate the remaining unconverted residual material therein. The second stage reactor usually further hydroconverts 30-95 vol.% of the remaining residua feed material to lower boiling hydrocarbon materials.
From the second stage reactor, the effluent material is passed to various gas/liquid separation and distillation steps, from which gases and low-boiling hydrocarbon liquid product and distillation vacuum bottoms fraction materials are removed. If desired for achieving higher percentage conversion of the feedstock, a portion of the vacuum bottoms fraction material boiling above at least 650 F
(343 C) temperature and preferably boiling above about 900 F(482 C) can be recycled back to the first stage catalytic reactor inlet at a recycle volume ratio to the fresh feedstock of 0-1.0/1, and preferably at 0.2-0.7/1 recycle ratio for further hydroconversion reactions therein.
Particulate catalyst materials which are useful in this hydrogenation process may contain 2-25 wt.% percent total active metals selected from the metals group consisting of cadmium, chromium, cobalt, iron, molybdenum, nickel, tin, tungsten, and mixtures thereof deposited on a support material selected from the group consisting of alumina, silica and combinations thereof. Also, catalysts having the same characteristics may be used in both the first stage and second stage reactors, or each reactor may use catalysts having different characteristics. Useful particulate catalysts will be in the form of beads, extrudates or spheres and have broad and preferred characteristics as shown in Table 2 below:
USEFUL CATALYST CHARACTERISTICS
Catalyst Characteristic Broad Preferred Particle Diameter, in. 0.025-0.083 0.030-0.065 Particle Diameter, mm 0.63-2.1 0.75-1.65 Bulk Density, lb/ft3 25-50 30-45 Particle Crush Strength, lb/mm 1.8 min. 2.0 min.
Total Active Metals Content, wt.% 2-25 5-20 Total Pore Volume, cm2/gm* 0.30-1.50 0.40-1.20 Total Surface Area, m2/gm 100-400 150-350 Average Pore Diameter, Angstrom** 50-350 80-250 * Determined by mercury penetration method at 60,000 psi pressure.
** Average pore diameter calculated by ADP = 4 Pore Volume x 104 Surface Area Catalysts having unimodal, bimodal and trimodal pore size distributions are useful in this process. Preferred catalyses should contain 5-20 wt.% total active metals consisting of combinations of cobalt, molybdenum and nickel deposited on an alumina support material.
This improved process for catalytic multi-stage hydrogenation of heavy hydrocarbonaceous feedstocks advantageously provides enhanced performance results by utilizing increased catalyst loading and liquid volume percent together with reduced gas hold-up in each of the multiple staged reactors with external gas/liquid separation. Such enhanced performance efficiency is manifested principally by providing better utilisation of the reactor volume for any particular desired hydroconversion result. This process is generally useful for catalytic hydrogenation and hydroconversion of heavy petroleum crudes, topped crudes, and vacuum residua, bitumen from tar sands, for coal hydrogenation and liquefaction, and for catalytic co-processing coal/oil blends to produce lower boiling, higher value hydrocarbon liquid products.
BRIEF DESCRIPTION OF DRAWINGS
This invention will be described further with the aid of the following drawings, in which:
Fig. 1 is a schematic flow diagram of an improved catalytic two-stage hydrogenation process for heavy hydrocarbonaceous feedstocks for producing desired lower-boiling liquid and gas products according to the invention;
Fig. 2 is a graph generally showing the typical general relationship between catalyst space velocity for a catalytic ebullated bed reactor and feedstock hydrodesulfurization results for the reactor;
Fig. 3 is a graph of experimental data generally showing the relationship between superficial gas velocity in a catalytic ebullated bed reactor and gas hold-up volume percentage in the reactor for various superficial liquid velocities;
and Fig. 4 is a graph generally showing the effect of reactor gas hold-up volume percent on hydrodesulfurization results particularly in a second stage catalytic reactor.
DESCRIPTION OF INVENTION
The present invention is now described in more detail for a hydrogenation process utilizing an improved catalytic two-stage ebullated bed reaction system for treating heavy hydrocarbon feedstocks. For the process as shown by Figure 1, a pressurized heavy hydrocarbon feedstock such as petroleum vacuum residua containing 30-100 vol.% 975 F+ residua and preferably 50-90 vol.% is provided at 10 and combined with hydrogen at 12. A heavy vacuum bottoms recycle liquid can be added at 13, and the combined stream at 14 is pressurized and fed through flow distributor la upwardly into first stage catalytic ebullated bed reactor 16 containing ebullated bed 18. The total feedstock to reactor 16 consists of the fresh hydrocarbon feed material at 10 plus any recycled vacuum bottoms material at 13. The recycle volume ratio of the vacuum bottoms material to the fresh oil feedstock is in the range of 0-1.0/1, and preferably is 0.2-0.7/1 recycle ratio, with the higher recycle ratios being used for achieving higher overall percentage conversion of the feedstock residua.
The first stage reactor 16 contains an ebullated bed 18 of particulate supported type catalyst having the form of beads, extrudates, spheres, etc., and is maintained within the range of broad and preferred operating conditions as shown in Table 1 above. The physical level of catalyst at 18a in the reactor is higher than for typical ebullated-bed reactors. This is because the usual internal recycle cup device which occupies a significant portion of reactor height, is not provided for separating the reactor liquid and vapor portions within the reactor 16. Instead, an external or interstage phase separator 20 is provided between the first and second stage catalytic reactors to effectively separate the reactor liquid and vapor effluent portions. Removal of the usual internal recycle cup separator results in more catalyst and a higher level for the expanded catalyst bed in the reactor and desirably provides for a lower catalyst space velocity, which contributes to the higher levels of performance for the reactors. A
vertical height distance "h" of 5 -10 ft. is maintained between the maximum bed expansion lever and the inlet of reactor outlet conduit 19 to prevent carryover of catalyst particles from the expanded bed 18.
From first stage reactor 16, overhead effluent stream 19 is withdrawn and passed to the external phase separator 20. From separator 20, a vapor stream 21 is removed and passed to gas purification section 42. Also, a liquid stream is withdrawn, and a sufficient flow is recirculated through conduit 24 by ebuilating pump 25 back to the reactor 16 to expand the catalyst bed 18 by the desired 25-75 percent above its normal settled bed height. For the first stage reactor 16, particulate catalyst material is added at connection 17 at the desired replacement rate, and can be used catalyst withdrawn from second stage reactor 30 at connection 36, and usually treated at unit 38 as desired to remove undesired particulate fines, etc. at 37. Fresh make-up catalyst can be added to catalyst bed 18 as needed at connection 17a, and an equivalent amount of spent catalyst is withdrawn from catalyst bed 18 at connection 17b.
The typical general relationship between reactor catalyst space velocity and reactor performance results is illustrated in Figure 2, which shows the effect of lower catalyst space velocities on hydrodesulfurization performance for ebullated-bed reactors having equal total volumes, hydrocarbon feedrates, reaction temperatures and catalyst replacement rates. Figure 2 clearly shows the improvement in first stage reactor desulfurization performance provided by lower catalyst space velocities, resulting mainly from use of an external gas/liquid separation device instead of the usual internal separation device and for nominal residue conversion levels between about 65 and 90 vol.%. The hydrocarbon liquid feedstock and hydrogen both react in contact with the catalyst in the reactor ebullated bed to form lower boiling components which have lower contaminant levels than the feedstock.
The hydrogen gas provided at 12 to the first stage reactor 16 is mainly recycled unreacted hydrogen having purity in the range of 85-95 vol. percent and some essentially pure make-up hydrogen as needed. For this improved process, the hydrogen feed rate to the first stage reactor and to the subsequent staged reactors is established at a minimum required level, which provides at each reactor outlet a required hydrogen partial pressure which is determined based on characteristics for a particular feedstock, the catalyst characteristics, the desired level of reaction severity, and the product quality objectives.
Typically, the required hydrogen feed rate to a catalytic reactor is expressed as a multiple of the quantity of hydrogen chemically consumed in the reactor, and such hydrogen rate is usually in the range of 2.0 to 5.0 times the chemical hydrogen consumption therein. Minimizing hydrogen gas feed rate in the catalytic ebullated-bed reactor(s) results in lower gas hold-up of hydrogen and hydrocarbon vapor evolved therein, and provides longer liquid residence time and enhanced liquid phase kinetics at the catalyst surface. The longer reactor liquid residence time is explained by the following relationship:
Reactor Liquid Residence Time = Volume of Reactor Occupied by Liguid *
Liquid Hourly Space Velocity **
10 * Reactor volume occupied by Liquid = Volume total - Volume occupied by Gas -Volume occupied by solid (catalyst) ** Volumetric rate of fresh liquid feed divided by reactor total volume The volume percent of hydrogen gas hold-up in the catalytic ebullated-bed reactor including hydrocarbon vapors generated therein, is primarily related to the reactor superficial gas velocity, with increased upward superficial gas velocity resulting in an increased gas hold-up volume percentage in the reactor.
Experimental data showing this relationship between the upward superficial gas velocity and gas hold-up volume percent in catalytic ebullated-bed reactors is shown in Figure 3. The measured gas hold-up volume percent in the reactor is shown as a function of the reactor superficial gas velocity at three different levels of reactor liquid upward superficial velocity. The superficial gas velocity for up flowing hydrogen gas clearly has the primary effect on gas hold-up volume in the reactor, with a secondary effect being due to different superficial liquid upward velocities for the feed liquid in the reactor Regarding the need for providing a sufficient quantity of reactant hydrogen gas in the reactor for desired chemical consumption therein, recent laboratory studies at gas hold-up percentages less than about 5-10 vol.% have clearly shown that this is a sufficient hydrogen quantity. Gas hold-up in excess of about -5 vol.% has usually been a consequence of scale-up of small size experimental catalytic ebullated-bed reactors to commercial size reactors (i.e., for taller reactors having lower length/diameter ratios than for slender laboratory scale reactors), and result in a less efficient reaction system because the liquid residence times and gas hold-up volumes are usually adversely affected. The present invention advantageously minimises this excessive hydrogen gas and hydrocarbon vapor hold-up volume percentage in the reactor, so as to provide the enhanced reaction kinetics and higher overall levels of process performance for the reactor system.
This relationship of catalytic reactor performance such as percent hydroconversion, hydrodesulfurization, etc. of the heavy hydrocarbon feedstock to the percentage of gas hold-up in an ebullated bed reactor is further illustrated in Figure 4. This comparison was made for catalytic ebullated bed reactors having equal total volumes, hydrocarbon feedrates, reaction temperatures and catalyst replacement rates. The results indicate that for reduced gas hold-up in a second stage reactor, the hydrodesulfurization results are significantly increased for various overall hydroconversion levels of 65 vol.% and 90 vol.% for the feedstock.
As mentioned above, the first stage reactor effluent stream 19 is passed to the interstage separator 20, which has two main functions: (a) to provide an ebullating recycle liquid stream back to the first stage reactor with minimal gas entrainment, and (b) to provide a liquid feed stream to the second stage reactor having a minimal vapor content. The effect of the function (b) is reduced gas hold-up in the second stage reactor and the same reaction benefits as described for the first stage reactor. The liquid feed to the second stage reactor 30 contains the unconverted residue from the original feedstock, and hydroconversion fractions which normally boil above about 600 F (316 C).
Recycled hydrogen, together with fresh make-up hydrogen at 45 is added as stream 32 to the second stage reactor 30, the hydrogen gas rate being selected stream 32 to the second stage reactor 30, the hydrogen gas rate being selected so as to result in a minimal hydrogen partial pressure at the reactor 30 outlet as needed to meet processing and product objectives as described above. Relative to typical hydrogen gas rates previously used, the gas rate provided at 32 to the second stage reactor 30 for this invention is substantially lower. This results in lower gas hold-up volume percentages in the reactor, greater liquid residence time, and a more efficient reactor system. In this situation, the gas hold-up is reduced from about 27 to 12 vol. percent, which results in an improvement in second stage desulfurization results from 65 to 70 wt.% based on the fresh feedstock.
Also from the external phase separator 20, a liquid portion 26 from the liquid stream 22 provides liquid feed material upwardly through flow distributor 27 into ebullated bed 28 of the second stage catalytic ebullated bed reactor 30. The catalyst bed 28 is expanded by 25-75% above its settled height by the upflowing gas and liquid therein. Reactor liquid is withdrawn from an internal phase separator 33 through conduit 34 to recycle pump 35, and is reintroduced upwardly through the flow distributor 27 into the ebullated bed 28 to maintain the desired catalyst bed expansion therein.
The second stage catalytic reactor 30 with ebullated catalyst bed 28 is operated within the broad and preferred conditions as shown in Table 1 above, and maximises resid hydrogenation reactions which occur therein. The second stage reaction temperature is preferably 0-50 F lower than that of the first stage reactor. Recycle and fresh hydrogen is provided at 32 to the second stage reactor 30, so that a minimal but adequate level of hydrogen partial pressure of 1,000-2,500 psi is maintained at the reactor 30 outlet.
The catalyst particles in ebullated beds 18 and 28 have a relatively narrow size range for uniform bed expansion under controlled upward liquid and gas flow conditions. While the useful catalyst size range is between 0.025 and 0.083 inch effective diameter, including beads, extrudates, or spheres, the catalyst size is reactor, the density of the catalyst particles, and the lifting effect of the upflowing liquid and hydrogen gas are important factors in providing the desired 25-75 percent expansion and operation of the catalyst beds. If desired, used particulate catalyst may be withdrawn from the second stage reactor bed 28 at connection 36 and fresh catalyst is added at connection 36a as needed to maintain the desired catalyst volume and catalytic activity therein. This used catalyst withdrawn at 36, which has relatively low metal contaminant concentration, can be passed to a treatment unit 38 where it is washed and screened to remove undesired fines at 37, and the recovered catalyst at 39 can provide used catalyst addition at 17 to the first stage reactor bed 18, together with any fresh make-up catalyst added at connection 17a as needed. From the second stage reactor 30, an effluent stream is removed at 31 and passed to a phase separator 40. From separator 40, a hydrogen-containing gas stream 41 is passed to the gas purification section 42 for removal of contaminants such as C02, H2S, and NH3 at vent 43. Purified hydrogen at 44 is recycled back to each catalytic reactor 16 and 30 as desired as the hydrogen streams 12 and 32 respectively, while fresh hydrogen is added at 45 as needed.
Also from the separator 40, a liquid fraction 46 is withdrawn, pressure reduced at 47 to 0-100 psig, and is introduced into fractionation tower unit 48. A
gaseous product stream is removed at 49 and a light hydrocarbon liquid product normally boiling between 400-650 F is withdrawn at 50. A bottoms nominal 650 F+
fraction is withdrawn at 52, reheated at heater 53, and passed to vacuum distillation step at 54. A vacuum gas oil liquid product is removed overhead at 55. Vacuum bottoms stream 56, which has been hydrogenated in the second stage catalyst reactor 30, can be recycled back as stream 13 to the first stage catalytic reactor 16. The recycle volume ratio for vacuum bottoms stream 56 to fresh feed at 10 can be 0-1.0/1, and preferably should be 0.2-0.7/1 for achieving hydroconversion of the feedstock exceeding about 70 vol. percent. It is pointed out that by utilizing this two stage catalytic hydroconversion process, the thermal reactions and catalytic activity in each stage reactor can be effectively matched reactions and catalytic activity in each stage reactor can be effectively matched and enhanced. The remaining unconverted vacuum bottoms material not being recycled at 13 is withdrawn at 57 as a net product.
This invention will now be described further by use of the following example, which is intended to be illustrative only and should not be construed as limiting the scope of the invention.
Example To demonstrate the process advantages of this invention, analyses of four commercial ebullated-bed reactor cases have been developed and are presented below. The basis for these comparative cases is the catalytic two-stage ebullated bed reactor processing of a typical Arabian light/heavy vacuum residual feedstock and providing 65 and 90 vol.% hydroconversion of the 1050 F+ vacuum residua fraction and with a high percentage level of desulfurization. The vacuum residual feedstock has inspection analyses as shown in Table 3 below.
FEEDSTOCK ANALYSES
Characteristic Value Residue Content (1050 F+), vol.% 92 Gravity, API 4.7 Sulfur, wt.% 5.3 Conradson Carbon Residue, wt.% 24.6 Nickel plus Vanadium, Wppm 222 Two conventional process base cases No. 1 and 3 which do not incorporate features of the present invention and two improvement cases No. 2 and 4 which the process performance advantages of the invention. The cases No. 1 and 2 comparisons are both for a moderate 65 vol.% overall hydroconversion of the 1050 F+ vacuum residua fraction, and the cases No. 3 and 4 comparisons are both for a high 90 vol.% overall hydroconversion of the residua fraction to lower boiling hydrocarbon products. These examples are based on actual laboratory and commercial data at either identical or similar reaction and operating conditions, including the feedstock and catalyst characteristics. The operating conditions for the four comparison cases are provided in Table 4 below.
Case No. 1 2 3 4 Desired Overall Conversion, V% 65 65 90 90 First Stage Reactor LHSV, V/hrN 0.60 0.60 0.60 0.60 Reactor Temperature, F 814 814 844 844 Catalyst SV, BPD/Lb 0.106 0.085 0.127 0.108 Catalyst Replacement Rate, Lb/Bbl 0.123 0.123 0.175 0.175 Superficial Gas Velocity, Ft/Sec 0.114 0.105 0.107 0.096 Reactor Gas Hold-Up, V% 20.1 18.5 18.9 16.9 Hydrogen Chemical Consumption, SCF/Bbl 758 869 1147 1114 Inlet Circulation Rate, X Consumption 3.6 3.0 3.1 2.7 Inlet Purity, vol.% 94.9 92.0 96.1 92.0 Partial Pressure Inlet, Psia 2505 2505 2505 2505 Partial Pressure Outlet, Psia 2415 2046 2166 1967 Second Stage Reactor LHSV, V/hrN 0.60 0.60 0.60 0.60 Reactor Temperature, F 814 814 844 844 Catalyst SV, BPD/Lb 0.106 0.106 0.127 0.127 Catalyst Replacement Rate, Lb/BbI 0.123 0.123 0.175 0.175 Superficial Gas Velocity, Ft/Sec 0.153 0.069 0.144 0.079 Reactor Gas Hold-Up. vol.% 26.9 12.1 25.4 13.9 Hydrogen Chemical Consumption, SCF/Bbl 512 481 733 806 Inlet Circulation Rate, X Consumption 2.1 3.0 2.0 2.7 Inlet Purity, vol.% 85.3 92.0 92.0 92.0 Partial Pressure Inlet, Psia 2206 2355 2180 2480 Partial Pressure Outlet, Psia 1964 1963 1949 1958 For the base cases No. 1 and 3, the catalytic ebullated-bed two-stage reactors are operated at typical pre-invention conditions including a high feed rate of hydrogen entering the first stage reactor, the upward ebullation liquid flow being provided from an internally located recycle cup or gas/liquid separator, and with cell of the first stage reactor effluent material (vapor + liquid) being passed directly to the catalytic second stage reactor. The superficial gas velocities in the first and second staged reactors are about 0.11 and 0.15 ft/s respectively, and result in undesirably large gas hold-up volumes of 18-20 vol.% and 25-27 vol.
%
respectively in the first and second staged reactors. For the two improvement Cases No. 2 and 4, the improved results for the present invention utilizing the same reactor total volume and liquid hourly space velocity as for the respective base Cases No. 1 and 3 are demonstrated. For the first stage reactor, the catalyst volume is increased and the catalyst space velocity is decreased by 20 percent due to elimination of the internal recycle cup or gas/liquid separator from the reactor upper portion. The first stage gas hold-up volume is reduced by 8-11 percent primarily because a lower hydrogen gas circulation rate and a lower hydrogen partial pressure at the reactor outlet are utilized.
More significantly, in the second stage reactor the gas hold-up volume is reduced by 45-55 percent. This reduction in second stage gas hold-up volume percentage is due to the use of interstage gas/liquid separation, and the use of a reduced minimal hydrogen gas recirculation rate. This reduction in the second stage reactor gas hold-up volume becomes available for providing increased reactor liquid volume and increases the effective liquid residence time in the second stage reactor by 20-30 percent. The comparative process performance for hydroconversion and desulfurization for the Cases No. 1 and 2. and for Cases No. 3 and 4 are shown in Table 5 below.
PROCESS COMPARATIVE PERFORMANCES
Difference Difference Case No. -1 -2 1-2 -3 -4 3--4 First Stage Reactor 1050 F+ Conversion, vol.% 45.8 44.5 -1.3 73.0 72.5 -0.5 Desulfurization, M.% 70.0 70.4 +0.4 63.2 65.0 +1.8 Second Stage Reactor 1050 F+ Conversion, vol.% 35.4 41.4 +6.0 63.0 68.7 +5.7 Desulfurization, wt.% 65.1 69.9 +4.8 53.3 58.9 +5.6 Overail Results 1050 F+ Conversion, vol.% 65.0 67.5 +2.5 90.0 91.4 +1.4 Desulfurization, wt.% 89.5 91.1 +1.6 82.8 85.6 +2.8 It is noted that the level of first stage reactor residue conversion for the comparative cases shows a slight decrease due to higher solids hold-up.
However, first stage desulfurization is increased slightly due to the higher catalyst loading and lower gas hold-up volume percentage in the reactor. Also, as a primary result of the significantly lower gas hold-up in the second stage reactor, i.e. from 26.9 to 12.1 vol.%, at moderate 65% conversion and from 25.4 to 13.9 vol.% at the hiaher 90% conversion, the process overall percent hydroconversion is increased from 65 to 67.5 vol.% for the moderate 65 vol.%
conversion cases, and from 90.0 to 91.4 vol.% for the high 90 vol.% conversion case. The increase in overall desulfurization from 89.5 to 91.1 wt.% in the moderate conversion cases and from 82.8 to 85.6 md.% in the high conversion cases is a direct result of the increase in the second stage desulfurization.
It should be noted that the moderate 65 vol.% conversion cases utilized a particulate catalyst having a unimodal pore size distribution, and the high conversion cases utilized a catalyst having a bi-modal pore size distribution which results in a somewhat lower desulfurization level.
Although this invention has been described broadly and also in terms of preferred embodiments, it will be understood that modifications and variations can be made to the process which are all within the basic scope of the invention as defined by the following claims.
Utilizing such external gas/liquid separation results in an increased volume of particulate catalyst being provided in a particular size reactor and reduces the catalyst space velocity, which is defined as the volumetric rate of feedstock processed per unit weight of fresh catalyst in the reactor. For such commercial size reactors having outside diameter of 12-14 ft. and a height of 50-60 ft., a vertical distance of 5-10 ft. should be maintained between the ebullated bed maximum expansion level and the reactor outlet conduit, so as to avoid any carryover of catalyst from the reactor. Also, operating conditions for each of the two-staged catalytic ebullated bed reactors are selected so that the upward superficial gas velocity is maintained within a desired critical range, and the gas hold-up volume percentage in each reactor is beneficially reduced, which consequently permits more reactor liquid to be in contact with the catalyst bed, so that the reactor performance as well as the overall process performance results are enhanced.
This invention is useful for processing heavy hydrocarbonaceous feedstocks and providing overall hydroconversions in the range of 50-100 vol.% to produce desired lower boiling hydrocarbon liquid products.
Therefore, to summarise, the present invention concerns a process for catalytic multi-stage ebullated bed hydrogenation of heavy hydrocarbonaceous feedstocks for producing lower boiling hydrocarbon liquids and gases, the process comprising:
(a) feeding a heavy hydrocarbonaceous liquid feedstock together with hydrogen gas into a first stage catalytic ebullated bed reactor at liquid space velocity of 0.2 - 2.0 volume of feed per hour per volume of reactor (Vf/hrNr,) and at catalyst space velocity of 0.03 - 0.33 bbl/day/lb catalyst, providing upward superficial gas velocity of 0.02-0.30 ft/sec while maintaining reaction temperatures of 700-850 F, and 800-3,000 psi hydrogen partial pressure at the reactor outlet, and producing a first stage reactor effluent material;
3a (b) phase separating the first stage effluent material into a gas portion and a first liquid portion, and passing the first liquid portion to a second stage catalytic ebullated bed reactor maintained at the reaction conditions similar to those of step (a), and producing a second stage reactor effluent material;
(c) phase separating the second stage effluent material into a gas and a second liquid portion;
(d) fractionating said second liquid portion to produce a medium-boiling hydrocarbon liquid fraction product having normal boiling range of 400-650 F and a vacuum bottoms fraction material having a normal boiling point above about 650 F; and (e) recycling said vacuum bottoms fraction material directly to said first stage catalytic ebullated bed reactor to provide a recycle volume ratio of the vacuum bottoms material to fresh feedstock of 0-1.0/1, so as to achieve between 50 and 100 vol.% conversion of the 975 F+ fraction in the feedstock to lower-boiling hydrocarbon liquid and producing increased yields of said medium-boiling hydrocarbon liquid product.
The invention also concerns a process for catalytic multi-stage ebullated bed hydrogenation of heavy hydrocarbonaceous feedstocks and for producing lower boiling hydrocarbon liquids and gases, the process comprising:
(a) feeding a heavy hydrocarbonaceous liquid feedstock containing 50-90 vol.% 975 F+ residua together with hydrogen gas into a first stage catalytic ebullated bed reactor at liquid space velocity of 0.2-2.0 volume of feed per hour per volume of reactor (Vf/hrNr,) and at catalyst space velocity of 0.03-0.33 bbl/day/Ib catalyst, providing upward superficial gas velocity of 0.02-0.25 ft/sec while maintaining reaction temperatures of 700-850 F, and 800-3,000 psi hydrogen partial pressure at the reactor outlet, and producing a first stage reactor effluent material containing gas and liquid portions;
3b (b) phase separating the first stage effluent material into a gas portion and a first liquid portion, and passing the first liquid portion on to a second stage catalytic ebullated bed reactor maintained at the reaction conditions of step (a), and producing a second stage reactor effluent material;
(c) phase separating the second stage effluent material into gas and a second liquid portion, and withdrawing the second liquid portion;
(d) fractionating said second liquid portion to produce a medium boiling hydrocarbon liquid fraction product having normal boiling range of 400-650 F, a vacuum gas oil having a normal boiling range of 650-950 F, and a vacuum bottoms material having a normal boiling temperature above about 950 F; and (e) recycling said vacuum bottoms fraction material directly back to said first stage catalytic ebullated bed reactor to provide a recycle volume ratio of the vacuum bottoms material to fresh feedstock of 0-0.7/1, so as to achieve 50-100 vol.% conversion of the 975 F+ fraction in the feedstock to lower boiling hydrocarbon liquid and producing increased yields of said medium-boiling hydrocarbon liquid product containing low sulfur and nitrogen.
The broad and preferred characteristics for the hydrocarbonaceous feedstocks and the reactor broad and preferred operating condition ranges for which this invention is useful are provided in Table 1 below:
FEEDSTOCK AND REACTOR OPERATING CONDITIONS
Condition Broad Preferred Feedstock Residua Content, vol.% 975 F+ 30 - 100 50 - 90 Feedstock CCR*, wt.% 1- 50 10 - 40 Feedstock Nickel plus Vanadium, Wppm Up to 1,000 100 - 800 Reactor LHSV**, hr 1(per Reactor Stage) 0.2 - 2.0 0.4 - 1.2 Reactor Temperature, F 700 - 850 750 - 840 Reactor Total Pressure, Psig 1,000 - 4,000 1,500 - 3,000 Reactor Outlet Hydrogen Partial Pressure, Psi 800 - 3,000 1,000 - 2,500 Reactor Superficial Gas Velocity, fps 0.02 - 0.30 0.025 - 0.20 Catalyst Space Velocity, BPD/Lb (per Stage) 0.03 - 0.33 0.04 - 0.20 Catalyst Replacement Rate, Lb/Bbl (per Stage)0.05 - 0.5 0.1 - 0.4 Catalyst Bed Expansion, % 25 - 75 35 - 50 Vacuum Bottoms Recycle Rate, Vr/Vfeed 0-1 0.2 - 0.7 Cutpoint of Vacuum Bottoms Recycle, F 650+ 900+ , * CCR = Conradson carbon residue.
** LHSV = Liquid hourly space velocity in each reactor, as defined as volumetric fresh feed rate divided by reactor total volume.
In the process, the fresh feedstock together with hydrogen are introduced into a first stage catalytic ebuiiated bed reactor, which does not contain an internal gas/liquid phase separator device. The catalyst bed is expanded by 25-75 percent above its settled level by the upflowing liquid and gas streams, and is maintained within the broad operating conditions of 700-850 F temperature, 800-3,000 psig hydrogen partial pressure at the reactor outlet, liquid hourly space velocity of 0.20-2.0 volume fresh feed per hour per volume of reactor (Vf/hrNr) and at catalyst space velocity of 0.03 - 0.33 barrel feed per day per pound fresh catalyst in the reactor. Because of the lower catalyst space velocity and superficial gas velocity being utilized in the reactor, the reacting liquid votume percentage is increased and gas hold-up volume is desirably reduced.
The first stage reactor usually hydroconverts 30-95 vol.% of the fresh heavy feedstock and any recycled residua material to a lower boiling hydrocarbon effluent material.
The first stage reactor effluent material is phase separated in an external gas/liquid separator, a gas fraction is removed, and a sufficient portion of the remaining liquid is recycled to the reactor to maintain the desired 25-75%
catalyst bed expansion therein. The remaining liquid fraction is passed together with additional hydrogen to a second stage catalytic ebullated bed type reactor.
The second stage ebullated bed reactor is operated similarly to the first stage reactor and typically is maintained at 0-50 F, lower temperature in the broad range of 700-850 F (370-455 C) and 0.20-2.0 (Vf/hrNr) space velocity, so as to effectively further hydragenate the remaining unconverted residual material therein. The second stage reactor usually further hydroconverts 30-95 vol.% of the remaining residua feed material to lower boiling hydrocarbon materials.
From the second stage reactor, the effluent material is passed to various gas/liquid separation and distillation steps, from which gases and low-boiling hydrocarbon liquid product and distillation vacuum bottoms fraction materials are removed. If desired for achieving higher percentage conversion of the feedstock, a portion of the vacuum bottoms fraction material boiling above at least 650 F
(343 C) temperature and preferably boiling above about 900 F(482 C) can be recycled back to the first stage catalytic reactor inlet at a recycle volume ratio to the fresh feedstock of 0-1.0/1, and preferably at 0.2-0.7/1 recycle ratio for further hydroconversion reactions therein.
Particulate catalyst materials which are useful in this hydrogenation process may contain 2-25 wt.% percent total active metals selected from the metals group consisting of cadmium, chromium, cobalt, iron, molybdenum, nickel, tin, tungsten, and mixtures thereof deposited on a support material selected from the group consisting of alumina, silica and combinations thereof. Also, catalysts having the same characteristics may be used in both the first stage and second stage reactors, or each reactor may use catalysts having different characteristics. Useful particulate catalysts will be in the form of beads, extrudates or spheres and have broad and preferred characteristics as shown in Table 2 below:
USEFUL CATALYST CHARACTERISTICS
Catalyst Characteristic Broad Preferred Particle Diameter, in. 0.025-0.083 0.030-0.065 Particle Diameter, mm 0.63-2.1 0.75-1.65 Bulk Density, lb/ft3 25-50 30-45 Particle Crush Strength, lb/mm 1.8 min. 2.0 min.
Total Active Metals Content, wt.% 2-25 5-20 Total Pore Volume, cm2/gm* 0.30-1.50 0.40-1.20 Total Surface Area, m2/gm 100-400 150-350 Average Pore Diameter, Angstrom** 50-350 80-250 * Determined by mercury penetration method at 60,000 psi pressure.
** Average pore diameter calculated by ADP = 4 Pore Volume x 104 Surface Area Catalysts having unimodal, bimodal and trimodal pore size distributions are useful in this process. Preferred catalyses should contain 5-20 wt.% total active metals consisting of combinations of cobalt, molybdenum and nickel deposited on an alumina support material.
This improved process for catalytic multi-stage hydrogenation of heavy hydrocarbonaceous feedstocks advantageously provides enhanced performance results by utilizing increased catalyst loading and liquid volume percent together with reduced gas hold-up in each of the multiple staged reactors with external gas/liquid separation. Such enhanced performance efficiency is manifested principally by providing better utilisation of the reactor volume for any particular desired hydroconversion result. This process is generally useful for catalytic hydrogenation and hydroconversion of heavy petroleum crudes, topped crudes, and vacuum residua, bitumen from tar sands, for coal hydrogenation and liquefaction, and for catalytic co-processing coal/oil blends to produce lower boiling, higher value hydrocarbon liquid products.
BRIEF DESCRIPTION OF DRAWINGS
This invention will be described further with the aid of the following drawings, in which:
Fig. 1 is a schematic flow diagram of an improved catalytic two-stage hydrogenation process for heavy hydrocarbonaceous feedstocks for producing desired lower-boiling liquid and gas products according to the invention;
Fig. 2 is a graph generally showing the typical general relationship between catalyst space velocity for a catalytic ebullated bed reactor and feedstock hydrodesulfurization results for the reactor;
Fig. 3 is a graph of experimental data generally showing the relationship between superficial gas velocity in a catalytic ebullated bed reactor and gas hold-up volume percentage in the reactor for various superficial liquid velocities;
and Fig. 4 is a graph generally showing the effect of reactor gas hold-up volume percent on hydrodesulfurization results particularly in a second stage catalytic reactor.
DESCRIPTION OF INVENTION
The present invention is now described in more detail for a hydrogenation process utilizing an improved catalytic two-stage ebullated bed reaction system for treating heavy hydrocarbon feedstocks. For the process as shown by Figure 1, a pressurized heavy hydrocarbon feedstock such as petroleum vacuum residua containing 30-100 vol.% 975 F+ residua and preferably 50-90 vol.% is provided at 10 and combined with hydrogen at 12. A heavy vacuum bottoms recycle liquid can be added at 13, and the combined stream at 14 is pressurized and fed through flow distributor la upwardly into first stage catalytic ebullated bed reactor 16 containing ebullated bed 18. The total feedstock to reactor 16 consists of the fresh hydrocarbon feed material at 10 plus any recycled vacuum bottoms material at 13. The recycle volume ratio of the vacuum bottoms material to the fresh oil feedstock is in the range of 0-1.0/1, and preferably is 0.2-0.7/1 recycle ratio, with the higher recycle ratios being used for achieving higher overall percentage conversion of the feedstock residua.
The first stage reactor 16 contains an ebullated bed 18 of particulate supported type catalyst having the form of beads, extrudates, spheres, etc., and is maintained within the range of broad and preferred operating conditions as shown in Table 1 above. The physical level of catalyst at 18a in the reactor is higher than for typical ebullated-bed reactors. This is because the usual internal recycle cup device which occupies a significant portion of reactor height, is not provided for separating the reactor liquid and vapor portions within the reactor 16. Instead, an external or interstage phase separator 20 is provided between the first and second stage catalytic reactors to effectively separate the reactor liquid and vapor effluent portions. Removal of the usual internal recycle cup separator results in more catalyst and a higher level for the expanded catalyst bed in the reactor and desirably provides for a lower catalyst space velocity, which contributes to the higher levels of performance for the reactors. A
vertical height distance "h" of 5 -10 ft. is maintained between the maximum bed expansion lever and the inlet of reactor outlet conduit 19 to prevent carryover of catalyst particles from the expanded bed 18.
From first stage reactor 16, overhead effluent stream 19 is withdrawn and passed to the external phase separator 20. From separator 20, a vapor stream 21 is removed and passed to gas purification section 42. Also, a liquid stream is withdrawn, and a sufficient flow is recirculated through conduit 24 by ebuilating pump 25 back to the reactor 16 to expand the catalyst bed 18 by the desired 25-75 percent above its normal settled bed height. For the first stage reactor 16, particulate catalyst material is added at connection 17 at the desired replacement rate, and can be used catalyst withdrawn from second stage reactor 30 at connection 36, and usually treated at unit 38 as desired to remove undesired particulate fines, etc. at 37. Fresh make-up catalyst can be added to catalyst bed 18 as needed at connection 17a, and an equivalent amount of spent catalyst is withdrawn from catalyst bed 18 at connection 17b.
The typical general relationship between reactor catalyst space velocity and reactor performance results is illustrated in Figure 2, which shows the effect of lower catalyst space velocities on hydrodesulfurization performance for ebullated-bed reactors having equal total volumes, hydrocarbon feedrates, reaction temperatures and catalyst replacement rates. Figure 2 clearly shows the improvement in first stage reactor desulfurization performance provided by lower catalyst space velocities, resulting mainly from use of an external gas/liquid separation device instead of the usual internal separation device and for nominal residue conversion levels between about 65 and 90 vol.%. The hydrocarbon liquid feedstock and hydrogen both react in contact with the catalyst in the reactor ebullated bed to form lower boiling components which have lower contaminant levels than the feedstock.
The hydrogen gas provided at 12 to the first stage reactor 16 is mainly recycled unreacted hydrogen having purity in the range of 85-95 vol. percent and some essentially pure make-up hydrogen as needed. For this improved process, the hydrogen feed rate to the first stage reactor and to the subsequent staged reactors is established at a minimum required level, which provides at each reactor outlet a required hydrogen partial pressure which is determined based on characteristics for a particular feedstock, the catalyst characteristics, the desired level of reaction severity, and the product quality objectives.
Typically, the required hydrogen feed rate to a catalytic reactor is expressed as a multiple of the quantity of hydrogen chemically consumed in the reactor, and such hydrogen rate is usually in the range of 2.0 to 5.0 times the chemical hydrogen consumption therein. Minimizing hydrogen gas feed rate in the catalytic ebullated-bed reactor(s) results in lower gas hold-up of hydrogen and hydrocarbon vapor evolved therein, and provides longer liquid residence time and enhanced liquid phase kinetics at the catalyst surface. The longer reactor liquid residence time is explained by the following relationship:
Reactor Liquid Residence Time = Volume of Reactor Occupied by Liguid *
Liquid Hourly Space Velocity **
10 * Reactor volume occupied by Liquid = Volume total - Volume occupied by Gas -Volume occupied by solid (catalyst) ** Volumetric rate of fresh liquid feed divided by reactor total volume The volume percent of hydrogen gas hold-up in the catalytic ebullated-bed reactor including hydrocarbon vapors generated therein, is primarily related to the reactor superficial gas velocity, with increased upward superficial gas velocity resulting in an increased gas hold-up volume percentage in the reactor.
Experimental data showing this relationship between the upward superficial gas velocity and gas hold-up volume percent in catalytic ebullated-bed reactors is shown in Figure 3. The measured gas hold-up volume percent in the reactor is shown as a function of the reactor superficial gas velocity at three different levels of reactor liquid upward superficial velocity. The superficial gas velocity for up flowing hydrogen gas clearly has the primary effect on gas hold-up volume in the reactor, with a secondary effect being due to different superficial liquid upward velocities for the feed liquid in the reactor Regarding the need for providing a sufficient quantity of reactant hydrogen gas in the reactor for desired chemical consumption therein, recent laboratory studies at gas hold-up percentages less than about 5-10 vol.% have clearly shown that this is a sufficient hydrogen quantity. Gas hold-up in excess of about -5 vol.% has usually been a consequence of scale-up of small size experimental catalytic ebullated-bed reactors to commercial size reactors (i.e., for taller reactors having lower length/diameter ratios than for slender laboratory scale reactors), and result in a less efficient reaction system because the liquid residence times and gas hold-up volumes are usually adversely affected. The present invention advantageously minimises this excessive hydrogen gas and hydrocarbon vapor hold-up volume percentage in the reactor, so as to provide the enhanced reaction kinetics and higher overall levels of process performance for the reactor system.
This relationship of catalytic reactor performance such as percent hydroconversion, hydrodesulfurization, etc. of the heavy hydrocarbon feedstock to the percentage of gas hold-up in an ebullated bed reactor is further illustrated in Figure 4. This comparison was made for catalytic ebullated bed reactors having equal total volumes, hydrocarbon feedrates, reaction temperatures and catalyst replacement rates. The results indicate that for reduced gas hold-up in a second stage reactor, the hydrodesulfurization results are significantly increased for various overall hydroconversion levels of 65 vol.% and 90 vol.% for the feedstock.
As mentioned above, the first stage reactor effluent stream 19 is passed to the interstage separator 20, which has two main functions: (a) to provide an ebullating recycle liquid stream back to the first stage reactor with minimal gas entrainment, and (b) to provide a liquid feed stream to the second stage reactor having a minimal vapor content. The effect of the function (b) is reduced gas hold-up in the second stage reactor and the same reaction benefits as described for the first stage reactor. The liquid feed to the second stage reactor 30 contains the unconverted residue from the original feedstock, and hydroconversion fractions which normally boil above about 600 F (316 C).
Recycled hydrogen, together with fresh make-up hydrogen at 45 is added as stream 32 to the second stage reactor 30, the hydrogen gas rate being selected stream 32 to the second stage reactor 30, the hydrogen gas rate being selected so as to result in a minimal hydrogen partial pressure at the reactor 30 outlet as needed to meet processing and product objectives as described above. Relative to typical hydrogen gas rates previously used, the gas rate provided at 32 to the second stage reactor 30 for this invention is substantially lower. This results in lower gas hold-up volume percentages in the reactor, greater liquid residence time, and a more efficient reactor system. In this situation, the gas hold-up is reduced from about 27 to 12 vol. percent, which results in an improvement in second stage desulfurization results from 65 to 70 wt.% based on the fresh feedstock.
Also from the external phase separator 20, a liquid portion 26 from the liquid stream 22 provides liquid feed material upwardly through flow distributor 27 into ebullated bed 28 of the second stage catalytic ebullated bed reactor 30. The catalyst bed 28 is expanded by 25-75% above its settled height by the upflowing gas and liquid therein. Reactor liquid is withdrawn from an internal phase separator 33 through conduit 34 to recycle pump 35, and is reintroduced upwardly through the flow distributor 27 into the ebullated bed 28 to maintain the desired catalyst bed expansion therein.
The second stage catalytic reactor 30 with ebullated catalyst bed 28 is operated within the broad and preferred conditions as shown in Table 1 above, and maximises resid hydrogenation reactions which occur therein. The second stage reaction temperature is preferably 0-50 F lower than that of the first stage reactor. Recycle and fresh hydrogen is provided at 32 to the second stage reactor 30, so that a minimal but adequate level of hydrogen partial pressure of 1,000-2,500 psi is maintained at the reactor 30 outlet.
The catalyst particles in ebullated beds 18 and 28 have a relatively narrow size range for uniform bed expansion under controlled upward liquid and gas flow conditions. While the useful catalyst size range is between 0.025 and 0.083 inch effective diameter, including beads, extrudates, or spheres, the catalyst size is reactor, the density of the catalyst particles, and the lifting effect of the upflowing liquid and hydrogen gas are important factors in providing the desired 25-75 percent expansion and operation of the catalyst beds. If desired, used particulate catalyst may be withdrawn from the second stage reactor bed 28 at connection 36 and fresh catalyst is added at connection 36a as needed to maintain the desired catalyst volume and catalytic activity therein. This used catalyst withdrawn at 36, which has relatively low metal contaminant concentration, can be passed to a treatment unit 38 where it is washed and screened to remove undesired fines at 37, and the recovered catalyst at 39 can provide used catalyst addition at 17 to the first stage reactor bed 18, together with any fresh make-up catalyst added at connection 17a as needed. From the second stage reactor 30, an effluent stream is removed at 31 and passed to a phase separator 40. From separator 40, a hydrogen-containing gas stream 41 is passed to the gas purification section 42 for removal of contaminants such as C02, H2S, and NH3 at vent 43. Purified hydrogen at 44 is recycled back to each catalytic reactor 16 and 30 as desired as the hydrogen streams 12 and 32 respectively, while fresh hydrogen is added at 45 as needed.
Also from the separator 40, a liquid fraction 46 is withdrawn, pressure reduced at 47 to 0-100 psig, and is introduced into fractionation tower unit 48. A
gaseous product stream is removed at 49 and a light hydrocarbon liquid product normally boiling between 400-650 F is withdrawn at 50. A bottoms nominal 650 F+
fraction is withdrawn at 52, reheated at heater 53, and passed to vacuum distillation step at 54. A vacuum gas oil liquid product is removed overhead at 55. Vacuum bottoms stream 56, which has been hydrogenated in the second stage catalyst reactor 30, can be recycled back as stream 13 to the first stage catalytic reactor 16. The recycle volume ratio for vacuum bottoms stream 56 to fresh feed at 10 can be 0-1.0/1, and preferably should be 0.2-0.7/1 for achieving hydroconversion of the feedstock exceeding about 70 vol. percent. It is pointed out that by utilizing this two stage catalytic hydroconversion process, the thermal reactions and catalytic activity in each stage reactor can be effectively matched reactions and catalytic activity in each stage reactor can be effectively matched and enhanced. The remaining unconverted vacuum bottoms material not being recycled at 13 is withdrawn at 57 as a net product.
This invention will now be described further by use of the following example, which is intended to be illustrative only and should not be construed as limiting the scope of the invention.
Example To demonstrate the process advantages of this invention, analyses of four commercial ebullated-bed reactor cases have been developed and are presented below. The basis for these comparative cases is the catalytic two-stage ebullated bed reactor processing of a typical Arabian light/heavy vacuum residual feedstock and providing 65 and 90 vol.% hydroconversion of the 1050 F+ vacuum residua fraction and with a high percentage level of desulfurization. The vacuum residual feedstock has inspection analyses as shown in Table 3 below.
FEEDSTOCK ANALYSES
Characteristic Value Residue Content (1050 F+), vol.% 92 Gravity, API 4.7 Sulfur, wt.% 5.3 Conradson Carbon Residue, wt.% 24.6 Nickel plus Vanadium, Wppm 222 Two conventional process base cases No. 1 and 3 which do not incorporate features of the present invention and two improvement cases No. 2 and 4 which the process performance advantages of the invention. The cases No. 1 and 2 comparisons are both for a moderate 65 vol.% overall hydroconversion of the 1050 F+ vacuum residua fraction, and the cases No. 3 and 4 comparisons are both for a high 90 vol.% overall hydroconversion of the residua fraction to lower boiling hydrocarbon products. These examples are based on actual laboratory and commercial data at either identical or similar reaction and operating conditions, including the feedstock and catalyst characteristics. The operating conditions for the four comparison cases are provided in Table 4 below.
Case No. 1 2 3 4 Desired Overall Conversion, V% 65 65 90 90 First Stage Reactor LHSV, V/hrN 0.60 0.60 0.60 0.60 Reactor Temperature, F 814 814 844 844 Catalyst SV, BPD/Lb 0.106 0.085 0.127 0.108 Catalyst Replacement Rate, Lb/Bbl 0.123 0.123 0.175 0.175 Superficial Gas Velocity, Ft/Sec 0.114 0.105 0.107 0.096 Reactor Gas Hold-Up, V% 20.1 18.5 18.9 16.9 Hydrogen Chemical Consumption, SCF/Bbl 758 869 1147 1114 Inlet Circulation Rate, X Consumption 3.6 3.0 3.1 2.7 Inlet Purity, vol.% 94.9 92.0 96.1 92.0 Partial Pressure Inlet, Psia 2505 2505 2505 2505 Partial Pressure Outlet, Psia 2415 2046 2166 1967 Second Stage Reactor LHSV, V/hrN 0.60 0.60 0.60 0.60 Reactor Temperature, F 814 814 844 844 Catalyst SV, BPD/Lb 0.106 0.106 0.127 0.127 Catalyst Replacement Rate, Lb/BbI 0.123 0.123 0.175 0.175 Superficial Gas Velocity, Ft/Sec 0.153 0.069 0.144 0.079 Reactor Gas Hold-Up. vol.% 26.9 12.1 25.4 13.9 Hydrogen Chemical Consumption, SCF/Bbl 512 481 733 806 Inlet Circulation Rate, X Consumption 2.1 3.0 2.0 2.7 Inlet Purity, vol.% 85.3 92.0 92.0 92.0 Partial Pressure Inlet, Psia 2206 2355 2180 2480 Partial Pressure Outlet, Psia 1964 1963 1949 1958 For the base cases No. 1 and 3, the catalytic ebullated-bed two-stage reactors are operated at typical pre-invention conditions including a high feed rate of hydrogen entering the first stage reactor, the upward ebullation liquid flow being provided from an internally located recycle cup or gas/liquid separator, and with cell of the first stage reactor effluent material (vapor + liquid) being passed directly to the catalytic second stage reactor. The superficial gas velocities in the first and second staged reactors are about 0.11 and 0.15 ft/s respectively, and result in undesirably large gas hold-up volumes of 18-20 vol.% and 25-27 vol.
%
respectively in the first and second staged reactors. For the two improvement Cases No. 2 and 4, the improved results for the present invention utilizing the same reactor total volume and liquid hourly space velocity as for the respective base Cases No. 1 and 3 are demonstrated. For the first stage reactor, the catalyst volume is increased and the catalyst space velocity is decreased by 20 percent due to elimination of the internal recycle cup or gas/liquid separator from the reactor upper portion. The first stage gas hold-up volume is reduced by 8-11 percent primarily because a lower hydrogen gas circulation rate and a lower hydrogen partial pressure at the reactor outlet are utilized.
More significantly, in the second stage reactor the gas hold-up volume is reduced by 45-55 percent. This reduction in second stage gas hold-up volume percentage is due to the use of interstage gas/liquid separation, and the use of a reduced minimal hydrogen gas recirculation rate. This reduction in the second stage reactor gas hold-up volume becomes available for providing increased reactor liquid volume and increases the effective liquid residence time in the second stage reactor by 20-30 percent. The comparative process performance for hydroconversion and desulfurization for the Cases No. 1 and 2. and for Cases No. 3 and 4 are shown in Table 5 below.
PROCESS COMPARATIVE PERFORMANCES
Difference Difference Case No. -1 -2 1-2 -3 -4 3--4 First Stage Reactor 1050 F+ Conversion, vol.% 45.8 44.5 -1.3 73.0 72.5 -0.5 Desulfurization, M.% 70.0 70.4 +0.4 63.2 65.0 +1.8 Second Stage Reactor 1050 F+ Conversion, vol.% 35.4 41.4 +6.0 63.0 68.7 +5.7 Desulfurization, wt.% 65.1 69.9 +4.8 53.3 58.9 +5.6 Overail Results 1050 F+ Conversion, vol.% 65.0 67.5 +2.5 90.0 91.4 +1.4 Desulfurization, wt.% 89.5 91.1 +1.6 82.8 85.6 +2.8 It is noted that the level of first stage reactor residue conversion for the comparative cases shows a slight decrease due to higher solids hold-up.
However, first stage desulfurization is increased slightly due to the higher catalyst loading and lower gas hold-up volume percentage in the reactor. Also, as a primary result of the significantly lower gas hold-up in the second stage reactor, i.e. from 26.9 to 12.1 vol.%, at moderate 65% conversion and from 25.4 to 13.9 vol.% at the hiaher 90% conversion, the process overall percent hydroconversion is increased from 65 to 67.5 vol.% for the moderate 65 vol.%
conversion cases, and from 90.0 to 91.4 vol.% for the high 90 vol.% conversion case. The increase in overall desulfurization from 89.5 to 91.1 wt.% in the moderate conversion cases and from 82.8 to 85.6 md.% in the high conversion cases is a direct result of the increase in the second stage desulfurization.
It should be noted that the moderate 65 vol.% conversion cases utilized a particulate catalyst having a unimodal pore size distribution, and the high conversion cases utilized a catalyst having a bi-modal pore size distribution which results in a somewhat lower desulfurization level.
Although this invention has been described broadly and also in terms of preferred embodiments, it will be understood that modifications and variations can be made to the process which are all within the basic scope of the invention as defined by the following claims.
Claims (18)
1. A process for catalytic multi-stage ebullated bed hydrogenation of heavy hydrocarbonaceous feedstocks for producing lower boiling hydrocarbon liquids and gases, the process comprising:
(a) feeding a heavy hydrocarbonaceous liquid feedstock together with hydrogen gas into a first stage catalytic ebullated bed reactor at liquid space velocity of 0.2 - 2.0 volume of feed per hour per volume of reactor (V f/hr/Vr,) and at catalyst space velocity of 0.03 - 0.33 bbl/day/lb catalyst, providing upward superficial gas velocity of 0.02-0.30 ft/sec while maintaining reaction temperatures of 700-850°F, and 800-3,000 psi hydrogen partial pressure at the reactor outlet, and producing a first stage reactor effluent material;
(b) phase separating the first stage effluent material into a gas portion and a first liquid portion, and passing the first liquid portion to a second stage catalytic ebullated bed reactor maintained at the reaction conditions similar to those of step (a), and producing a second stage reactor effluent material;
(c) phase separating the second stage effluent material into a gas and a second liquid portion;
(d) fractionating said second liquid portion to produce a medium-boiling hydrocarbon liquid fraction product having normal boiling range of 400-650°F and a vacuum bottoms fraction material having a normal boiling point above about 650°F; and (e) recycling said vacuum bottoms fraction material directly to said first stage catalytic ebullated bed reactor to provide a recycle volume ratio of the vacuum bottoms material to fresh feedstock of 0-1.0/1, so as to achieve between 50 and 100 vol.% conversion of the 975°F+ fraction in the feedstock to lower-boiling hydrocarbon liquid and producing increased yields of said medium-boiling hydrocarbon liquid product.
(a) feeding a heavy hydrocarbonaceous liquid feedstock together with hydrogen gas into a first stage catalytic ebullated bed reactor at liquid space velocity of 0.2 - 2.0 volume of feed per hour per volume of reactor (V f/hr/Vr,) and at catalyst space velocity of 0.03 - 0.33 bbl/day/lb catalyst, providing upward superficial gas velocity of 0.02-0.30 ft/sec while maintaining reaction temperatures of 700-850°F, and 800-3,000 psi hydrogen partial pressure at the reactor outlet, and producing a first stage reactor effluent material;
(b) phase separating the first stage effluent material into a gas portion and a first liquid portion, and passing the first liquid portion to a second stage catalytic ebullated bed reactor maintained at the reaction conditions similar to those of step (a), and producing a second stage reactor effluent material;
(c) phase separating the second stage effluent material into a gas and a second liquid portion;
(d) fractionating said second liquid portion to produce a medium-boiling hydrocarbon liquid fraction product having normal boiling range of 400-650°F and a vacuum bottoms fraction material having a normal boiling point above about 650°F; and (e) recycling said vacuum bottoms fraction material directly to said first stage catalytic ebullated bed reactor to provide a recycle volume ratio of the vacuum bottoms material to fresh feedstock of 0-1.0/1, so as to achieve between 50 and 100 vol.% conversion of the 975°F+ fraction in the feedstock to lower-boiling hydrocarbon liquid and producing increased yields of said medium-boiling hydrocarbon liquid product.
2. A hydrogenation process according to claim 1, wherein said first stage reaction conditions are 750-840°F temperature, 1,000-2,500 psig hydrogen partial pressure at the reactor outlet, 0.40-1.2 V f/Hr/Vr, liquid space velocity and 0.04-0.20 Bbl/day/lb. catalyst space velocity.
3. A hydrogenation process according to claim 1, wherein said second stage reaction conditions are 750-840°F temperature, 1,000-2,500 psig hydrogen partial pressure at the reactor outlet 0.40-1.2 V f/Hr/Vr, liquid space velocity, and 0.04-0.20 Bbl/day/lb. catalyst space velocity.
4. A hydrogenation process according to claim 2, wherein the reactor superficial gas velocity is 0.025-0.20 ft./sec and gas hold-up volume percent is minimized.
5. A hydrogenation process according to claim 3, wherein the reactor superficial gas velocity is 0.025-0.20 ft/sec. and the gas hold-up volume percent in the reactor is minimized.
6. A hydrogenation process, according to claim 1, wherein a height distance of 5-10 ft. is maintained in the first stage catalytic reactor between the ebullated bed upper lever and the reactor outlet connection.
7. A hydrogenation process according to claim 1, wherein said recycled vacuum bottoms material has a normal boiling point above about 900°F
and is recycled to the first stage reactor at a volume ratio of vacuum bottoms material to fresh feed of 0-1.0/1 to achieve 65-90 vol.% conversion of the feedstock to lower-boiling hydrocarbon liquid products.
and is recycled to the first stage reactor at a volume ratio of vacuum bottoms material to fresh feed of 0-1.0/1 to achieve 65-90 vol.% conversion of the feedstock to lower-boiling hydrocarbon liquid products.
8. A hydrogenation process according to claim 1, wherein the volume ratio of vacuum bottoms material recycled to said first stage reactor to the fresh feedstock being fed to said first stage reactor is about 0.2/1-0.7/1.
9. A hydrogenation process according to claim 1, wherein the catalyst used in said first stage and second stage reactors contains 2-25 wt.% total active metals and has total pore volume of 0.30-1.50 cc/gm, total surface area of 100-400m2/gm and average pore diameter of at least 50 angstrom units.
10. A hydrogenation process according to claim 1, wherein the catalyst used in the first stage and second stage reactors has total pore volume of 0.40-1.20 cc/gm, total surface area of 150-350 m2/gm and average pore diameter of 80-250 angstrom units.
11. A hydrogenation process according to claim 1, wherein the catalyst used in said second stage catalytic reactor contains 5-20 wt.% cobalt-molybdenum on alumina support material.
12. A hydrogenation process according to claim 1, wherein the catalyst used in said second stage catalytic reactor contains 5-20 wt.% nickel-molybdenum on alumina support material.
13. A hydrogenation process according to claim 1, wherein used catalyst is withdrawn from said second stage catalytic reactor and passed to said first stage catalytic reactor as the catalyst addition therein, and fresh catalyst replacement rate of 0.05-0.50 pound catalyst per barrel of the fresh feedstock is provided to said second stage reactor.
14. A hydrogenation process according to claim 1, wherein the feedstock is petroleum residua material having 30-100 vol.% normally boiling above 975°F
and containing 5-50 wt.% Conradson Carbon Residue (CCR) and up to 1,000 wppm total metals.
and containing 5-50 wt.% Conradson Carbon Residue (CCR) and up to 1,000 wppm total metals.
15. A hydrogenation process according to claim 1, wherein the feedstock is bitumen derived from tar sands.
16. A process for catalytic multi-stage ebullated bed hydrogenation of heavy hydrocarbonaceous feedstocks and for producing lower boiling hydrocarbon liquids and gases, the process comprising:
(a) feeding a heavy hydrocarbonaceous liquid feedstock containing 50-90 vol.% 975°F+ residua together with hydrogen gas into a first stage catalytic ebullated bed reactor at liquid space velocity of 0.2-2.0 volume of feed per hour per volume of reactor (V f/hr/Vr,) and at catalyst space velocity of 0.03-0.33 bbl/day/lb catalyst, providing upward superficial gas velocity of 0.02-0.25 ft/sec while maintaining reaction temperatures of 700-850°F, and 800-3,000 psi hydrogen partial pressure at the reactor outlet, and producing a first stage reactor effluent material containing gas and liquid portions;
(b) phase separating the first stage effluent material into a gas portion and a first liquid portion, and passing the first liquid portion on to a second stage catalytic ebullated bed reactor maintained at the reaction conditions of step (a), and producing a second stage reactor effluent material;
(c) phase separating the second stage effluent material into gas and a second liquid portion, and withdrawing the second liquid portion;
(d) fractionating said second liquid portion to produce a medium boiling hydrocarbon liquid fraction product having normal boiling range of 400-650°F, a vacuum gas oil having a normal boiling range of 650-950°F, and a vacuum bottoms material having a normal boiling temperature above about 950°F; and (e) recycling said vacuum bottoms fraction material directly back to said first stage catalytic ebullated bed reactor to provide a recycle volume ratio of the vacuum bottoms material to fresh feedstock of 0-0.7/1, so as to achieve 50-100 vol.% conversion of the 975°F+ fraction in the feedstock to lower boiling hydrocarbon liquid and producing increased yields of said medium-boiling hydrocarbon liquid product containing low sulfur and nitrogen.
(a) feeding a heavy hydrocarbonaceous liquid feedstock containing 50-90 vol.% 975°F+ residua together with hydrogen gas into a first stage catalytic ebullated bed reactor at liquid space velocity of 0.2-2.0 volume of feed per hour per volume of reactor (V f/hr/Vr,) and at catalyst space velocity of 0.03-0.33 bbl/day/lb catalyst, providing upward superficial gas velocity of 0.02-0.25 ft/sec while maintaining reaction temperatures of 700-850°F, and 800-3,000 psi hydrogen partial pressure at the reactor outlet, and producing a first stage reactor effluent material containing gas and liquid portions;
(b) phase separating the first stage effluent material into a gas portion and a first liquid portion, and passing the first liquid portion on to a second stage catalytic ebullated bed reactor maintained at the reaction conditions of step (a), and producing a second stage reactor effluent material;
(c) phase separating the second stage effluent material into gas and a second liquid portion, and withdrawing the second liquid portion;
(d) fractionating said second liquid portion to produce a medium boiling hydrocarbon liquid fraction product having normal boiling range of 400-650°F, a vacuum gas oil having a normal boiling range of 650-950°F, and a vacuum bottoms material having a normal boiling temperature above about 950°F; and (e) recycling said vacuum bottoms fraction material directly back to said first stage catalytic ebullated bed reactor to provide a recycle volume ratio of the vacuum bottoms material to fresh feedstock of 0-0.7/1, so as to achieve 50-100 vol.% conversion of the 975°F+ fraction in the feedstock to lower boiling hydrocarbon liquid and producing increased yields of said medium-boiling hydrocarbon liquid product containing low sulfur and nitrogen.
17. The process of claim 16, wherein the effluent material removed from at least the first stage catalytic reactor is phase separated external to the reactor.
18. A process according to claim 16 or 17, wherein:
- said reaction temperature in step a) is from 750 to 840°F;
- said hydrogen partial pressure is 1000-2,500 psi;
- said liquid space velocity is from 0.4 to 1.2 V f/hr/Vr;
- said catalyst space velocity is from 0.04 - 0.20 bdl/day/lb catalyst ; and - said superficial gas velocity is from 0.025 to 0.20 ft/sec.
- said reaction temperature in step a) is from 750 to 840°F;
- said hydrogen partial pressure is 1000-2,500 psi;
- said liquid space velocity is from 0.4 to 1.2 V f/hr/Vr;
- said catalyst space velocity is from 0.04 - 0.20 bdl/day/lb catalyst ; and - said superficial gas velocity is from 0.025 to 0.20 ft/sec.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2000/005628 WO2001098436A1 (en) | 2000-06-19 | 2000-06-19 | Catalytic hydrogenation process utilizing multi-stage ebullated bed reactors |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2412923A1 CA2412923A1 (en) | 2001-12-27 |
| CA2412923C true CA2412923C (en) | 2008-10-07 |
Family
ID=8163992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002412923A Expired - Lifetime CA2412923C (en) | 2000-06-19 | 2000-06-19 | Catalytic hydrogenation process utilizing multi-stage ebullated bed reactors |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1299507B1 (en) |
| JP (1) | JP4834875B2 (en) |
| CA (1) | CA2412923C (en) |
| DE (1) | DE60025350T2 (en) |
| MX (1) | MXPA02012003A (en) |
| WO (1) | WO2001098436A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2234710A2 (en) | 2007-11-28 | 2010-10-06 | Saudi Arabian Oil Company | Process for catalytic hydrotreating of sour crude oils |
| US7938953B2 (en) * | 2008-05-20 | 2011-05-10 | Institute Francais Du Petrole | Selective heavy gas oil recycle for optimal integration of heavy oil conversion and vacuum gas oil treating |
| US7938952B2 (en) * | 2008-05-20 | 2011-05-10 | Institute Francais Du Petrole | Process for multistage residue hydroconversion integrated with straight-run and conversion gasoils hydroconversion steps |
| US8372267B2 (en) | 2008-07-14 | 2013-02-12 | Saudi Arabian Oil Company | Process for the sequential hydroconversion and hydrodesulfurization of whole crude oil |
| US9260671B2 (en) | 2008-07-14 | 2016-02-16 | Saudi Arabian Oil Company | Process for the treatment of heavy oils using light hydrocarbon components as a diluent |
| EP2445997B1 (en) | 2009-06-22 | 2021-03-24 | Saudi Arabian Oil Company | Demetalizing and desulfurizing virgin crude oil for delayed coking |
| CN103857771B (en) * | 2011-07-29 | 2016-06-01 | 沙特阿拉伯石油公司 | For the ebullated bed method of the raw material containing the hydrogen dissolved |
| ITMI20130131A1 (en) * | 2013-01-30 | 2014-07-31 | Luigi Patron | IMPROVED PRODUCTIVITY PROCESS FOR THE CONVERSION OF HEAVY OILS |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3322665A (en) * | 1965-05-18 | 1967-05-30 | Hydrocarbon Research Inc | High conversion hydrogenation of heavy gas oil |
| US4457831A (en) * | 1982-08-18 | 1984-07-03 | Hri, Inc. | Two-stage catalytic hydroconversion of hydrocarbon feedstocks using resid recycle |
| JPS61287438A (en) * | 1985-06-14 | 1986-12-17 | Mitsubishi Heavy Ind Ltd | Dispersing device for three phase fluidized bed reactor |
| JPS627436A (en) * | 1985-07-03 | 1987-01-14 | Mitsubishi Heavy Ind Ltd | Dispersing mechanism of three-phase fluidized reactor |
| US4765882A (en) * | 1986-04-30 | 1988-08-23 | Exxon Research And Engineering Company | Hydroconversion process |
| ZA961830B (en) * | 1995-03-16 | 1997-10-31 | Inst Francais Du Petrole | Catalytic hydroconversion process for heavy petroleum feedstocks. |
-
2000
- 2000-06-19 MX MXPA02012003A patent/MXPA02012003A/en active IP Right Grant
- 2000-06-19 JP JP2002504387A patent/JP4834875B2/en not_active Expired - Lifetime
- 2000-06-19 EP EP00936894A patent/EP1299507B1/en not_active Expired - Lifetime
- 2000-06-19 CA CA002412923A patent/CA2412923C/en not_active Expired - Lifetime
- 2000-06-19 WO PCT/EP2000/005628 patent/WO2001098436A1/en active IP Right Grant
- 2000-06-19 DE DE60025350T patent/DE60025350T2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| MXPA02012003A (en) | 2003-05-27 |
| EP1299507B1 (en) | 2006-01-04 |
| JP2004515568A (en) | 2004-05-27 |
| WO2001098436A1 (en) | 2001-12-27 |
| DE60025350T2 (en) | 2006-07-13 |
| JP4834875B2 (en) | 2011-12-14 |
| DE60025350D1 (en) | 2006-03-30 |
| EP1299507A1 (en) | 2003-04-09 |
| CA2412923A1 (en) | 2001-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6270654B1 (en) | Catalytic hydrogenation process utilizing multi-stage ebullated bed reactors | |
| US4457831A (en) | Two-stage catalytic hydroconversion of hydrocarbon feedstocks using resid recycle | |
| US5925238A (en) | Catalytic multi-stage hydrodesulfurization of metals-containing petroleum residua with cascading of rejuvenated catalyst | |
| US6190542B1 (en) | Catalytic multi-stage process for hydroconversion and refining hydrocarbon feeds | |
| US4853111A (en) | Two-stage co-processing of coal/oil feedstocks | |
| EP0732389B1 (en) | Complete catalytic hydroconversion process for heavy petroleum feedstocks | |
| US4576710A (en) | Catalyst desulfurization of petroleum residua feedstocks | |
| US4427535A (en) | Selective operating conditions for high conversion of special petroleum feedstocks | |
| US6841062B2 (en) | Crude oil desulfurization | |
| CN102037101B (en) | Process for multistage residue hydroconversion integrated with straight-run and conversion gasoils hydroconversion steps | |
| RU2722644C1 (en) | Multistage hydrocracking of still residue | |
| EP1840190B1 (en) | Process and installation for conversion of heavy petroleum fractions in a boiling bed with integrated production of middle distillates with a very low sulfur content | |
| US8926824B2 (en) | Process for the conversion of residue integrating moving-bed technology and ebullating-bed technology | |
| US4762607A (en) | Hydroconversion process with combined temperature and feed staging | |
| US6200462B1 (en) | Process for reverse gas flow in hydroprocessing reactor systems | |
| US5522983A (en) | Hydrocarbon hydroconversion process | |
| KR101696017B1 (en) | Multistage resid hydrocracking | |
| US4478705A (en) | Hydroconversion process for hydrocarbon liquids using supercritical vapor extraction of liquid fractions | |
| AU761961B2 (en) | Integrated hydroconversion process with reverse hydrogen flow | |
| CN101724453A (en) | Hydrogenation method of heavy hydrocarbon multi-segment fluidized bed | |
| CA2412923C (en) | Catalytic hydrogenation process utilizing multi-stage ebullated bed reactors | |
| KR20030090677A (en) | Two stage hydrocracking process | |
| US3975259A (en) | Hydrodesulfurization of liquid hydrocarbon utilizing a suspended catalyst particle of less than 10 microns | |
| US3207688A (en) | Hydrocracking process in two stages employing finely divided catalyst particles | |
| CA1238005A (en) | Multi-stage catalytic process for high conversion of heavy hydrocarbon liquid feedstocks |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request |