CA1196877A - Coal hydrogenation process having increased solids retention in ebullated bed reactor - Google Patents
Coal hydrogenation process having increased solids retention in ebullated bed reactorInfo
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- CA1196877A CA1196877A CA000418157A CA418157A CA1196877A CA 1196877 A CA1196877 A CA 1196877A CA 000418157 A CA000418157 A CA 000418157A CA 418157 A CA418157 A CA 418157A CA 1196877 A CA1196877 A CA 1196877A
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- liquid
- reactor
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- coal
- baffle
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Classifications
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- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
- C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/0065—Separating solid material from the gas/liquid stream by impingement against stationary members
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
ABSTRACT
An improved reaction process and apparatus for the cata-lytic hydrogenation of coal to produce hydrocarbon liquid and gas products. In the process the concentration of unconverted coal solids in the reactor is increased by use of a coal solids deflecting means such as a baffle criti-cally located with the upper portion of the reactor upstream of the effluent stream withdrawal conduit opening. Such deflection means provides for an increased concentration and prolonged reaction of coal solids usually larger than about 30 microns in the reactor liquid to produce increased con-version and yield of hydrocarbon liquid products, and thereby reduces the need for liquid-solids separation downstream from the reaction step. The solids deflection means preferably comprises a solid baffle attached to the reactor effluent withdrawal conduit upstream of its opening, and is preferably made removable from the reactor upper end.
An improved reaction process and apparatus for the cata-lytic hydrogenation of coal to produce hydrocarbon liquid and gas products. In the process the concentration of unconverted coal solids in the reactor is increased by use of a coal solids deflecting means such as a baffle criti-cally located with the upper portion of the reactor upstream of the effluent stream withdrawal conduit opening. Such deflection means provides for an increased concentration and prolonged reaction of coal solids usually larger than about 30 microns in the reactor liquid to produce increased con-version and yield of hydrocarbon liquid products, and thereby reduces the need for liquid-solids separation downstream from the reaction step. The solids deflection means preferably comprises a solid baffle attached to the reactor effluent withdrawal conduit upstream of its opening, and is preferably made removable from the reactor upper end.
Description
H~ 72 :L~
~OAI. HYD~OG~NATION PROCESS HAV~NG IMCREASED SOLIDS
RE~ENTION IN EBULLATED BED REACTOR
BACKGROUND OF INVENTI0~l This invention pertains to improved catalytic hydrogena-tlon of coal to produce increased percentages of lo~-boiling hydrocarbon liquid products. It pertains particularly to coal hydrogenation processes using an upflow ebullated cata-lyst bed type reactor in which an increased percentage of unconverted coal solids is retained in the reactor for further conversion reaction therein, thereby producing increased percentages of light hydrocarbon liquid and gas products.
In conventional ebullated catalyst bed reaction pro-cesses for the hydroconversion of hydrocarbon feedstocks, as described in U. S. Patent No. 3,519,555 to Keith, et al, a reactor liquid concentration of a desired equilibrium pro-duct distribution is maintained as determined by the reac-tants and process conditions. A continuous reaction process exists with both internal and external recycled streams. In a conventional ebullated bed hydrogenation reaction process for coal, the reactor liquid solids concentration which usually comprises about equal amounts oE unconverted coal and ash may range from 10-25 W % fine particulate solids.
Such solids concentration in the reactor is usually main-tained by ~rovidinga liquid-solid separation step downstream of the reactor and recycling a liquid stream containing a reduced concentration of solids to the reactor, as generally taught by U. S. Patent 3,540,995 to Wolk, et al. However, it is desirable to increase the percent hydroconversion of coal solids and semi-solid materials in the reactor so as to , ~
~1'3t~ 7 provide for increased yields of light hydrocarbon liquid products by using basically simpler solids separation proce-dures within the reaction zone, and thereby minimize or possibly avoid the need for providing an e~ternal liquid-solids separation step in the process.
U. S. 3,188,286 to Van Driesen discloses a hydrocracking process for heavy hydrocarbon oils, whlch uses inclined wall mounted baffles or a cylindrical screen within an ebullated bed catalytic reactor to help retain particulate catalyst material within the reactor. Also, U.S, 3 677,71~ to Weber et al discloses use of a phase separation device located in the upper~portion of the ebullated bed catalyst reactor to help retain catalyst in the reactor. However, a procedure or means for desirably retaining ~ine unconverted coal solids within an ebullated bed catalytic reactor for achieving increased conversion of such coal solids to 'nydro-carbon liquid products has apparently not been previously disclosed or used.
SUMMARY OF INVENTION
The present invention provides an improved reaction pro-cess and apparatus for catalytic hydrogenation of coal to produce hydrocarbon liquld and gas products, wherein coal solids are selectively retained in the reactor liquid for prolonged hydrogenation reactions and improved conversion therein. Such increased retention of coal solids in the reactor is accomplished by deflecting solid coal particles larger than about 30 microns which rise with the upflowing liquid away from the opening jnto the effluent stream with-7'7 drawal conduit and back into the reactor liquid. Suchdeflecting of fine coal solids is accomplished by suitable deflection means critically positioned in the upper portion of the reactor vessel near and associated with the withdraw-al conduit. This solids deflection means, such as a baf~le, provides -for increased retention in the reactor of the larger particle size least reacted coal solids and semi-solids material for prolonged hydrogenation reaction at the reaction conditions. The retention of such solids having particle size usually larger than about 30 microns and pre-ferably within the range of 40~200 microns prolongs the residence -time and thus increases the hydrogena-tion reaction and percentage conversion of these heavy hydrocarbon materials to lower boiling components, such as light and medium hydrocarbon liquid and gas products.
By using this reactor system having solids deflection and retention means incorporated therein ~ the solids con-centration in the reactor slurry llquid is increased to exceed about 15 W % and may be increased up to about 30 W %
concentration or more in the liquid. Such higher solids concentration in the reactor results in 10 - 2~ W % more unconverted coal being retained in the reactor for ~urther reaction therein, and provides improved yields of light and medium liquid fraction products from the coal. A minor por-tion of the reactor recycled liquid containing larger size coal and ash particles is withdrawn from the reactor as needed to maintain the solids concentration in the reactor below an allowable level, such as about 30 W %.
Accordingly, this invention provides a significant increase in coal conversion reaction efficiency and increased throughput per unit reactor volume, D~SCXIPTION OF INVEMTIO~
____ In accordance with the invention, an ebullated bed catalyst reactor for coal hydrogenation is provided with a solids deflection baffle or retention device used within the reactor, and such baffle is critically located within the reactor upper portion to effect the increased solids con-centrations desired in the reactor liquid. The baffle is located so as to partially shield the inlet to the effluent withdrawal conduit from upflowing coal solids and thereby reduce the amount of particulate coal solids (unconverted coal and ash) entering the conduit with the combined efflu-ent liquid, and gas stream and selectively retain such solids in the slurry liquid being recycled through the ebullated catalyst bed.
The reactor deflection baf1e may be varied in position and shape. The reactor baffle can be made any shape, such as flat, curved downwardly, or conical-shaped, and is pre-ferably attached to and supported by the withdrawal conduit.
The baffle can be oriented within the reactor either hori-zontally or inclined with the horizontal plane at an angle between 0 to about 45. The deflection baffle angle should usualy not exceed about 45 with the horizontal, so that the larger upflowing particles will be deflected back downwardly into the reactor liquid. The center line distance between the withdrawal conduit lower end and the upper surface of the baffle should be at least equal to the conduit inside diameter and is preferably 1.2-10 times the conduit dia-meter. Also the baffle is sized relative to the inside diameter of the reactor withdrawal conduit so that the hor-izontal projection of the baffle area should exceed the in-7~7 side cross sectional area of the condui-t '~y about 2 to 2~
times the conduit area. These dimensional and area rela-tionships provide for selectively retaining in the reactor the desired increased concentration of unconverted coal solids for further reaction. If desiredJ the position of the solids deflection baffle in the reactor may be made variable for process control purposes.
This invention is particularly applicable to catalytic reaction systems having internal recycle of reactor liquid to provide the desired amount of expansion and ebulla-tion of the catalyst bed such as for H-Coal~ coal liquefaction pro-cesses. Reaction conditions maintained in the reactor should be within the broad range of 750-950F temperature and 1000-4000 psi hydrogen partial pressure. Coal feed rate or space velocity should be between about 5-60 pound/hr/ft3 reactor volume. The catalyst particle size used should be sufficiently large for it to be reliably retained in the ebullated bed and not be ~c-ar-~i~d--out--with the recycled liquid. The catalyst particles are usually larger than about 0.016 inch (400 microns) effective diameter~ and preferably are in the range of 0.020 to 0.0~5 inch diameter (500-1600 microns). Such increased upflow velocity of reactor liquid permits greater feedstream throughput to be achieved for a particular size reactor.
For such ebullated catalyst bed reactors using internal liquid recycle, the deflection baffle is also located suf-ficiently removed from the top of the liquid-gas separation device (recycle cup) so as to avoid any catalyst carryover from the ebullated bed into the recycle cup. Such catalyst carryover causes undesired recirculation of catalyst par-ticles through the liquid recycle pump, which not only causes increased attrition of the catalyst but can also cause serious erosion damage to the pump, The reactor hav-7~
ing deflectlon baffle means in its upper portion is usuallyand preferahly used for coal hydrogenation processes liti-lizing upflow or ebullated type catalyst beds. However~ the invention can also be advantageously used for coal hydroge-nation processes without an externally added catalyst, in which it is desired to maintain a high percentage of ash solids in the reaction zone for their catalytic effect on the hydroconversion reaction~
It is an additional feature of the invention that use of this deflection baffle arrangement for providing increased solids retention in the reactor permits selectively withdrawing a low solids concentration liquid effluent stream from the upper portion of the reactor, and also withdrawing a high solids concentration minor stream from the internal liquid recycle loop separately from the reactor upper effluent stream Because a portion of the liquid-solids separation for -the coal hydrogenation process occurs within the reactor, this arrangement thereby reduces the downstream liquid-solids separation requirements of the process. The high solids concentrations stream-can usually be successfully processed in a vacuum distillation step, and the heavy vacuum bottoms portion containing high con-centration of solids can be used either as fuel, or as feed for producing the hydrogen needed in the process.
If the reactor is operated at high feed rates or space velocities which results in more unconverted coal in the product streams, it may be necessary to remove some o~ the coal solids from the recycle liquid stream. Such solids removal may be accomplished in a solvent precipitation step instead of using expensive hydroclones for liquid-solids separation.
DESCRIP5'ION _ ~R~WIMGS
E'igure 1 is a schematlc diacJram showing the principal elements of a liquid phase catalytic reaction process for hydrogenating coal, using a reactor containing a solids deflection means.
Figure 2 shows a typical reactor containing a coni~cal-shaped solids deflection means.
Figure 3 shows a typical coal liquefaction process utilizing a reactor containing solids deflection means, and from which s-treams having varying solids concentration are withdrawn from the reactor for further processing.
Figure 4 is a graph showing the typical relationship between reactor liquid recycle flow rate and weight percent coal solids in the reactor liquid.
DESCRIPTION OF PREFERRED EMBODIMENTS
As shown in Figure 1, coal at 10, such as bituminous or sub-bituminous coal having an ash content of 5-12 W %, is usually ground, dried, and screened at 12, and is sized to substantial]y all pass 30 mesh screen (0.023 inch) and preferably is 40-32S mesh screen size (0.0165-0017 inch) U.S. Sieve Series. The particulate coal from conduit 13 is then slurried at 14 with a slurrying oil 15 to provide an oil/coal weight ratio ranging from about 1 to about 5. The resulting coal-oil slurry at 16 is pressurized at 18 to elevated pressure and is combined with a hydrogen-rich gas at 20. The coal-liquid-gas mixture is then heated at heater 21 and introduced through flow distributor 22 into the bottom of the upflow hydrogenation reactor 24 containing ebullated catalyst bed 25, usually having catalyst particle size of 0.020 to 0.065 inch (500-1600 microns).
The reactor 24 is adapted for providing a liquid-phase reaction of the coal gas and a particulate hydrogenation catalyst placed in random motion therein by the upflowing liquid. Reaction conditions are preferably maintained within the ranges of 780-900F temperature and 1500~3500 psi hydrogen partial pressure. Coal feed rate should preferably be about 10-40 pound/hr/ft3 reactor volume. The reactor liquid is preferably recycled internally downward through recycle cup 26 and downcomer conduit 27 to recycle pump 28 so as to maintain the desired extent of catalyst bed expan-sion in the reactor, such as about 10 to 100 percent over the bed settled height. Such reactor liquid recycle rate usually ranges between about 20-50 gallons per minute per ft2 reactor cross-sectional area. Fresh catalyst is added at connection 23a and used catalyst is withdrawn at 23b as needed to maintain the desired catalytic activity in the reactor.
As also shown in Figure 1, a deflection means such as baffle 30 is provided in -the vapor disengagement zone 26a located above liquid recycle cup 26. The baffle 30 is solid and oriented in such positlon so as to deflect upflowing coal solids downwardly/and thus partially shield the opening 32a to effluent withdrawal condult 32. Baffle 30 thereby provides for a partial separation of fine unconverted coal and ash solids from larger sized solids in the reactor, and thus selectively reduces the percentage of larger coal solids entering the withdrawal conduit 32 along with com-bined liquid and vapor portions. An increased concentration of fine unconverted coal and ash solids having particle size preferably within the range of about 40-300 microns is retained in the reactor liquid for further reaction therein.
~t~
~ne suitable deflec~or or baffle ~oni~Juration for thi.s invention includes a flat plate oriented at an angle with the horizontal of about 0 to 45 degrees, and usually haviny a horizontally projected area equal to about 2 to 20 times the cross-sectional area of the withdrawal conduit, as generally shown in Figure 1. ~affle 30 is preferably supported from conduit 32 by at least three structural rods 33, as is better shown in Figure 2. The conduit 32 and connçcted baffle 30 are preferably made removable from the upper end of reactor 24 through removable bolted flange 3~.
A catalytically reacted effluent stream containing combined hydrocarbon liquid and gas components is withdrawn through conduit 32, and passed to phase separator 36. A gaseous stream is removed at 37, and liquid -containing a minor concentration of fine solids is removed at 39. Also, if desired, a portion 29a of recycle liquid stream 29 containing increased concentration of coal and ash solids can be withdrawn from the reactor for separate processing.
Another suitable deflection baffle configuration is conical-shaped baffle 3~ as shown in Fiqure 2, with the cone apex oriented upwardly and centrally aligned with the effluent conduit 32. The baffle conical surfaces are usually oriented at an angle of 20 - 60 degrees with the horizontal, and the diameter of the downwardly-facing base of the cone can be about 2 to 10 times the inside diameter of the withdrawal conduit. Although the flat inclined baffle 30 conEiguration is suitable for use in reactors having inside diameter up to about 1.5 feet, a conical-shaped or a convex-shaped baffle is preferred for use in larger diameter reactors.
_ g _ A further embodiment of this invention i5 shown in Figure 3, which is an extension of the Figure 1 reactor configuration. From ebullated catalytic bed reactor 24, an effluent stream 41 containing liquid and vapor fractlons is withdrawn from the upper part of the reactor through conduit 40 above catalyst bed level 25a and liquid level 31. As shown, the lower end of the vertical withdrawal conduit 40 is bent by at least about 90, so that the lower surface 40a of the conduit or an extension thereof acts as a solids deflecting surface similarly to baffles 30 and 38. This effluent stream 41 contains a lesser concentration of uncon-verted coal and ash solids compared to the reactor liquid, and is withdrawn through removable conduit 40 loca~ed near the top of the reactor.
The effluent stream 41 is passed to hot phase separator 42, from which vapor portion 43 and liquid portion 44 are removed separately. The resulting vapor portion 43 is passed to hydrogen purification step 50, from which the recovered hydrogen gas is repressured and recycled at 51 for use as the hydrogen-rich gas at 20, along with any high purity make-up hydrogen gas needed at 20a.
The liquid condensate stream at 44 is pressure-reduc~d at 45 and passed to low pressure phase separator 46, from which resulting vapor stream 47 is passed to fractionation system 54. Also from separator 46, liquid portion 48 is withdrawn and passed to liquid-solids separation step 52 t which can comprise multiple hydroclones or a solvent preci-pitation system. Overflow stream 53 containing a reduced concentration of particulate solids is also passed to rac~
tionation system S4,where ~he material is usually separated by fractional distillation into a gaseous and light ends stream normally boiling up to about 450F removed at 55, a distiLlate liquid fraction normally boiling bet~een about 450 and 650F removed at 56, and a bottom fraction removed at 57 having a normal boiling range in excess o~ 6504F and usually about 80~ to 975F. A,portion 56a of the relatively solids-free oil at 56 is usually recycled as coal slurr~,finy oil 15 to the system. The underflow liquid stream at 59~
containing an increased concentration of fine unconverted coal and ash solids, is passed to a vacuum distillation step 60. Overhead liquid stream 61 is preferably added to distillate stream 57 to provide heavy fuel oil product 58.
Vacuum bottoms stream 62 is withdrawn as a heavy product material.
If desired, a portion of the liquid recycle stream 29 usually recycled directly to the reactor for maintaining the desired ebullation of catalyst bed in the reactor 24, is withdrawn at 63 as a solids-enriched liquid stream for eparate processing. This liquid stream containing coal increased concentration of~solids, such as 20-40 W ~ solids, is pressure-reduced at 65 and passed with underflow stream 59 to vacuum distillation at 60. Vacuum overhead stream 61 may be combined with liquid product 58, while bot-toms stream 62 may be passed to a coking step or serve as feedstock for producing the hydrogen needed in the system.
It is an advantage of this invention that the solids deflection means provided in the reactor upper end provides sufficient solids separation that an external conventional solids separation step such as by hydroclones centrifuge filtration or solvent precipitation, is minimized or mav even be eliminated depending upon the acceptable solids con-centration level in the product oil streams. Thus~ elimina-tion of such an external solids separation step reduces the process cost and complexity.
8~
This invention will be further described by reference to the following example of operations.
EX~LE
Illinois No. 6 bituminous coal having 50-300 mesh size (U.S. Sieve Series) was fed as a coal/oil slurry with hydrogen into a 6-inch diameter reactor containing an ebullated catalyst bed, maintained at elevated temperatures and pressure conditions to produce hydrocarbon liquid and gas products. The reactor was provided with a flat metal baffle about 4-inch average diameter, positioned at a 45~ angle with the horizontal plane and having its center located about 1.3 inches upstream of a 1.125 inch inside diameter withdrawal conduit, similarly as shown in Figure 1. The operating conditions and results for the catalytic reaction step with and without the baffle and for otherwise quite similar operating conditions are provided in Table 1 below.
EBULLATED BED REACTOR OPERATIONS WTTH AND WITHOVT
RETENTION OF COAL SOLID~S
Run No. 130-66 Run No. 30-67 Without Baffle With Baffle In Reactor In Reactor Coal Feed, W % Water 2.82 1.87 Coal Feed, W % Ash 11.07 10.93 Coal Feed Rate, Lbs/Hr 164 177 Hydrogen Makeup, SCFH 1890 1890 Catalyst Bed Expansion, %50 50 7 Recycle Gas SCFH 1075 1676 Recycle Oil, SCFH 410 451 Reactor Temperature, F 826 831 Reactor H? Pressure, psig2700 2700 Internal Slurry Recycle Rate, Gpm/Ft2 Reactor (Average) 48 34 Start of Run 43 46 After 8 Hours 52 36 t~ 7 It is noted that a si~niicantly lower internal s]urr~
recycle rate was required for producing the desired 50~
catalyst bed expansion in Run No. 130-67, using the internal deflection baffle, actually reflecting a reduction of about 30% in the rate during the period of operationO ~he general relationship between the reactor liquid recycle rate for 50~
catalyst bed expansion and the percent total solids in the reactor liquid, i.e. unconverted coal and ash or mineral matter, is shown in Figure 4, and is based on data sub-sequently obtained for catalytic hydrogenation of coal.
Thus, this reduced liquid recycle rate required for Run No.
130-67 to achieve the same catalyst bed expansion indicates increased density and viscosity of the reactor liquid. The differences ln the operating conditions are not sufficient to have any substantial effect on the internal recycle liquid requirements. Thus, it is seen that the internal deflection baffle means provides for increased viscosi.ty and=
coal solids concentration in the reactor liquid. This indi-cates that increased conversion of the coal solids can be achieved by use of such deflecting means critically located upstream of the reactor effluent withdrawal conduit~ and also that separation of unconverted coal and ash solids can be achieved in the ebullated bed reactor system by such solids deflection means.
It i~ recogni.zed that modifications and variations of this invention can be made without departing from the spirit and scope thereof, and which is defined solely by the following claims.
~OAI. HYD~OG~NATION PROCESS HAV~NG IMCREASED SOLIDS
RE~ENTION IN EBULLATED BED REACTOR
BACKGROUND OF INVENTI0~l This invention pertains to improved catalytic hydrogena-tlon of coal to produce increased percentages of lo~-boiling hydrocarbon liquid products. It pertains particularly to coal hydrogenation processes using an upflow ebullated cata-lyst bed type reactor in which an increased percentage of unconverted coal solids is retained in the reactor for further conversion reaction therein, thereby producing increased percentages of light hydrocarbon liquid and gas products.
In conventional ebullated catalyst bed reaction pro-cesses for the hydroconversion of hydrocarbon feedstocks, as described in U. S. Patent No. 3,519,555 to Keith, et al, a reactor liquid concentration of a desired equilibrium pro-duct distribution is maintained as determined by the reac-tants and process conditions. A continuous reaction process exists with both internal and external recycled streams. In a conventional ebullated bed hydrogenation reaction process for coal, the reactor liquid solids concentration which usually comprises about equal amounts oE unconverted coal and ash may range from 10-25 W % fine particulate solids.
Such solids concentration in the reactor is usually main-tained by ~rovidinga liquid-solid separation step downstream of the reactor and recycling a liquid stream containing a reduced concentration of solids to the reactor, as generally taught by U. S. Patent 3,540,995 to Wolk, et al. However, it is desirable to increase the percent hydroconversion of coal solids and semi-solid materials in the reactor so as to , ~
~1'3t~ 7 provide for increased yields of light hydrocarbon liquid products by using basically simpler solids separation proce-dures within the reaction zone, and thereby minimize or possibly avoid the need for providing an e~ternal liquid-solids separation step in the process.
U. S. 3,188,286 to Van Driesen discloses a hydrocracking process for heavy hydrocarbon oils, whlch uses inclined wall mounted baffles or a cylindrical screen within an ebullated bed catalytic reactor to help retain particulate catalyst material within the reactor. Also, U.S, 3 677,71~ to Weber et al discloses use of a phase separation device located in the upper~portion of the ebullated bed catalyst reactor to help retain catalyst in the reactor. However, a procedure or means for desirably retaining ~ine unconverted coal solids within an ebullated bed catalytic reactor for achieving increased conversion of such coal solids to 'nydro-carbon liquid products has apparently not been previously disclosed or used.
SUMMARY OF INVENTION
The present invention provides an improved reaction pro-cess and apparatus for catalytic hydrogenation of coal to produce hydrocarbon liquld and gas products, wherein coal solids are selectively retained in the reactor liquid for prolonged hydrogenation reactions and improved conversion therein. Such increased retention of coal solids in the reactor is accomplished by deflecting solid coal particles larger than about 30 microns which rise with the upflowing liquid away from the opening jnto the effluent stream with-7'7 drawal conduit and back into the reactor liquid. Suchdeflecting of fine coal solids is accomplished by suitable deflection means critically positioned in the upper portion of the reactor vessel near and associated with the withdraw-al conduit. This solids deflection means, such as a baf~le, provides -for increased retention in the reactor of the larger particle size least reacted coal solids and semi-solids material for prolonged hydrogenation reaction at the reaction conditions. The retention of such solids having particle size usually larger than about 30 microns and pre-ferably within the range of 40~200 microns prolongs the residence -time and thus increases the hydrogena-tion reaction and percentage conversion of these heavy hydrocarbon materials to lower boiling components, such as light and medium hydrocarbon liquid and gas products.
By using this reactor system having solids deflection and retention means incorporated therein ~ the solids con-centration in the reactor slurry llquid is increased to exceed about 15 W % and may be increased up to about 30 W %
concentration or more in the liquid. Such higher solids concentration in the reactor results in 10 - 2~ W % more unconverted coal being retained in the reactor for ~urther reaction therein, and provides improved yields of light and medium liquid fraction products from the coal. A minor por-tion of the reactor recycled liquid containing larger size coal and ash particles is withdrawn from the reactor as needed to maintain the solids concentration in the reactor below an allowable level, such as about 30 W %.
Accordingly, this invention provides a significant increase in coal conversion reaction efficiency and increased throughput per unit reactor volume, D~SCXIPTION OF INVEMTIO~
____ In accordance with the invention, an ebullated bed catalyst reactor for coal hydrogenation is provided with a solids deflection baffle or retention device used within the reactor, and such baffle is critically located within the reactor upper portion to effect the increased solids con-centrations desired in the reactor liquid. The baffle is located so as to partially shield the inlet to the effluent withdrawal conduit from upflowing coal solids and thereby reduce the amount of particulate coal solids (unconverted coal and ash) entering the conduit with the combined efflu-ent liquid, and gas stream and selectively retain such solids in the slurry liquid being recycled through the ebullated catalyst bed.
The reactor deflection baf1e may be varied in position and shape. The reactor baffle can be made any shape, such as flat, curved downwardly, or conical-shaped, and is pre-ferably attached to and supported by the withdrawal conduit.
The baffle can be oriented within the reactor either hori-zontally or inclined with the horizontal plane at an angle between 0 to about 45. The deflection baffle angle should usualy not exceed about 45 with the horizontal, so that the larger upflowing particles will be deflected back downwardly into the reactor liquid. The center line distance between the withdrawal conduit lower end and the upper surface of the baffle should be at least equal to the conduit inside diameter and is preferably 1.2-10 times the conduit dia-meter. Also the baffle is sized relative to the inside diameter of the reactor withdrawal conduit so that the hor-izontal projection of the baffle area should exceed the in-7~7 side cross sectional area of the condui-t '~y about 2 to 2~
times the conduit area. These dimensional and area rela-tionships provide for selectively retaining in the reactor the desired increased concentration of unconverted coal solids for further reaction. If desiredJ the position of the solids deflection baffle in the reactor may be made variable for process control purposes.
This invention is particularly applicable to catalytic reaction systems having internal recycle of reactor liquid to provide the desired amount of expansion and ebulla-tion of the catalyst bed such as for H-Coal~ coal liquefaction pro-cesses. Reaction conditions maintained in the reactor should be within the broad range of 750-950F temperature and 1000-4000 psi hydrogen partial pressure. Coal feed rate or space velocity should be between about 5-60 pound/hr/ft3 reactor volume. The catalyst particle size used should be sufficiently large for it to be reliably retained in the ebullated bed and not be ~c-ar-~i~d--out--with the recycled liquid. The catalyst particles are usually larger than about 0.016 inch (400 microns) effective diameter~ and preferably are in the range of 0.020 to 0.0~5 inch diameter (500-1600 microns). Such increased upflow velocity of reactor liquid permits greater feedstream throughput to be achieved for a particular size reactor.
For such ebullated catalyst bed reactors using internal liquid recycle, the deflection baffle is also located suf-ficiently removed from the top of the liquid-gas separation device (recycle cup) so as to avoid any catalyst carryover from the ebullated bed into the recycle cup. Such catalyst carryover causes undesired recirculation of catalyst par-ticles through the liquid recycle pump, which not only causes increased attrition of the catalyst but can also cause serious erosion damage to the pump, The reactor hav-7~
ing deflectlon baffle means in its upper portion is usuallyand preferahly used for coal hydrogenation processes liti-lizing upflow or ebullated type catalyst beds. However~ the invention can also be advantageously used for coal hydroge-nation processes without an externally added catalyst, in which it is desired to maintain a high percentage of ash solids in the reaction zone for their catalytic effect on the hydroconversion reaction~
It is an additional feature of the invention that use of this deflection baffle arrangement for providing increased solids retention in the reactor permits selectively withdrawing a low solids concentration liquid effluent stream from the upper portion of the reactor, and also withdrawing a high solids concentration minor stream from the internal liquid recycle loop separately from the reactor upper effluent stream Because a portion of the liquid-solids separation for -the coal hydrogenation process occurs within the reactor, this arrangement thereby reduces the downstream liquid-solids separation requirements of the process. The high solids concentrations stream-can usually be successfully processed in a vacuum distillation step, and the heavy vacuum bottoms portion containing high con-centration of solids can be used either as fuel, or as feed for producing the hydrogen needed in the process.
If the reactor is operated at high feed rates or space velocities which results in more unconverted coal in the product streams, it may be necessary to remove some o~ the coal solids from the recycle liquid stream. Such solids removal may be accomplished in a solvent precipitation step instead of using expensive hydroclones for liquid-solids separation.
DESCRIP5'ION _ ~R~WIMGS
E'igure 1 is a schematlc diacJram showing the principal elements of a liquid phase catalytic reaction process for hydrogenating coal, using a reactor containing a solids deflection means.
Figure 2 shows a typical reactor containing a coni~cal-shaped solids deflection means.
Figure 3 shows a typical coal liquefaction process utilizing a reactor containing solids deflection means, and from which s-treams having varying solids concentration are withdrawn from the reactor for further processing.
Figure 4 is a graph showing the typical relationship between reactor liquid recycle flow rate and weight percent coal solids in the reactor liquid.
DESCRIPTION OF PREFERRED EMBODIMENTS
As shown in Figure 1, coal at 10, such as bituminous or sub-bituminous coal having an ash content of 5-12 W %, is usually ground, dried, and screened at 12, and is sized to substantial]y all pass 30 mesh screen (0.023 inch) and preferably is 40-32S mesh screen size (0.0165-0017 inch) U.S. Sieve Series. The particulate coal from conduit 13 is then slurried at 14 with a slurrying oil 15 to provide an oil/coal weight ratio ranging from about 1 to about 5. The resulting coal-oil slurry at 16 is pressurized at 18 to elevated pressure and is combined with a hydrogen-rich gas at 20. The coal-liquid-gas mixture is then heated at heater 21 and introduced through flow distributor 22 into the bottom of the upflow hydrogenation reactor 24 containing ebullated catalyst bed 25, usually having catalyst particle size of 0.020 to 0.065 inch (500-1600 microns).
The reactor 24 is adapted for providing a liquid-phase reaction of the coal gas and a particulate hydrogenation catalyst placed in random motion therein by the upflowing liquid. Reaction conditions are preferably maintained within the ranges of 780-900F temperature and 1500~3500 psi hydrogen partial pressure. Coal feed rate should preferably be about 10-40 pound/hr/ft3 reactor volume. The reactor liquid is preferably recycled internally downward through recycle cup 26 and downcomer conduit 27 to recycle pump 28 so as to maintain the desired extent of catalyst bed expan-sion in the reactor, such as about 10 to 100 percent over the bed settled height. Such reactor liquid recycle rate usually ranges between about 20-50 gallons per minute per ft2 reactor cross-sectional area. Fresh catalyst is added at connection 23a and used catalyst is withdrawn at 23b as needed to maintain the desired catalytic activity in the reactor.
As also shown in Figure 1, a deflection means such as baffle 30 is provided in -the vapor disengagement zone 26a located above liquid recycle cup 26. The baffle 30 is solid and oriented in such positlon so as to deflect upflowing coal solids downwardly/and thus partially shield the opening 32a to effluent withdrawal condult 32. Baffle 30 thereby provides for a partial separation of fine unconverted coal and ash solids from larger sized solids in the reactor, and thus selectively reduces the percentage of larger coal solids entering the withdrawal conduit 32 along with com-bined liquid and vapor portions. An increased concentration of fine unconverted coal and ash solids having particle size preferably within the range of about 40-300 microns is retained in the reactor liquid for further reaction therein.
~t~
~ne suitable deflec~or or baffle ~oni~Juration for thi.s invention includes a flat plate oriented at an angle with the horizontal of about 0 to 45 degrees, and usually haviny a horizontally projected area equal to about 2 to 20 times the cross-sectional area of the withdrawal conduit, as generally shown in Figure 1. ~affle 30 is preferably supported from conduit 32 by at least three structural rods 33, as is better shown in Figure 2. The conduit 32 and connçcted baffle 30 are preferably made removable from the upper end of reactor 24 through removable bolted flange 3~.
A catalytically reacted effluent stream containing combined hydrocarbon liquid and gas components is withdrawn through conduit 32, and passed to phase separator 36. A gaseous stream is removed at 37, and liquid -containing a minor concentration of fine solids is removed at 39. Also, if desired, a portion 29a of recycle liquid stream 29 containing increased concentration of coal and ash solids can be withdrawn from the reactor for separate processing.
Another suitable deflection baffle configuration is conical-shaped baffle 3~ as shown in Fiqure 2, with the cone apex oriented upwardly and centrally aligned with the effluent conduit 32. The baffle conical surfaces are usually oriented at an angle of 20 - 60 degrees with the horizontal, and the diameter of the downwardly-facing base of the cone can be about 2 to 10 times the inside diameter of the withdrawal conduit. Although the flat inclined baffle 30 conEiguration is suitable for use in reactors having inside diameter up to about 1.5 feet, a conical-shaped or a convex-shaped baffle is preferred for use in larger diameter reactors.
_ g _ A further embodiment of this invention i5 shown in Figure 3, which is an extension of the Figure 1 reactor configuration. From ebullated catalytic bed reactor 24, an effluent stream 41 containing liquid and vapor fractlons is withdrawn from the upper part of the reactor through conduit 40 above catalyst bed level 25a and liquid level 31. As shown, the lower end of the vertical withdrawal conduit 40 is bent by at least about 90, so that the lower surface 40a of the conduit or an extension thereof acts as a solids deflecting surface similarly to baffles 30 and 38. This effluent stream 41 contains a lesser concentration of uncon-verted coal and ash solids compared to the reactor liquid, and is withdrawn through removable conduit 40 loca~ed near the top of the reactor.
The effluent stream 41 is passed to hot phase separator 42, from which vapor portion 43 and liquid portion 44 are removed separately. The resulting vapor portion 43 is passed to hydrogen purification step 50, from which the recovered hydrogen gas is repressured and recycled at 51 for use as the hydrogen-rich gas at 20, along with any high purity make-up hydrogen gas needed at 20a.
The liquid condensate stream at 44 is pressure-reduc~d at 45 and passed to low pressure phase separator 46, from which resulting vapor stream 47 is passed to fractionation system 54. Also from separator 46, liquid portion 48 is withdrawn and passed to liquid-solids separation step 52 t which can comprise multiple hydroclones or a solvent preci-pitation system. Overflow stream 53 containing a reduced concentration of particulate solids is also passed to rac~
tionation system S4,where ~he material is usually separated by fractional distillation into a gaseous and light ends stream normally boiling up to about 450F removed at 55, a distiLlate liquid fraction normally boiling bet~een about 450 and 650F removed at 56, and a bottom fraction removed at 57 having a normal boiling range in excess o~ 6504F and usually about 80~ to 975F. A,portion 56a of the relatively solids-free oil at 56 is usually recycled as coal slurr~,finy oil 15 to the system. The underflow liquid stream at 59~
containing an increased concentration of fine unconverted coal and ash solids, is passed to a vacuum distillation step 60. Overhead liquid stream 61 is preferably added to distillate stream 57 to provide heavy fuel oil product 58.
Vacuum bottoms stream 62 is withdrawn as a heavy product material.
If desired, a portion of the liquid recycle stream 29 usually recycled directly to the reactor for maintaining the desired ebullation of catalyst bed in the reactor 24, is withdrawn at 63 as a solids-enriched liquid stream for eparate processing. This liquid stream containing coal increased concentration of~solids, such as 20-40 W ~ solids, is pressure-reduced at 65 and passed with underflow stream 59 to vacuum distillation at 60. Vacuum overhead stream 61 may be combined with liquid product 58, while bot-toms stream 62 may be passed to a coking step or serve as feedstock for producing the hydrogen needed in the system.
It is an advantage of this invention that the solids deflection means provided in the reactor upper end provides sufficient solids separation that an external conventional solids separation step such as by hydroclones centrifuge filtration or solvent precipitation, is minimized or mav even be eliminated depending upon the acceptable solids con-centration level in the product oil streams. Thus~ elimina-tion of such an external solids separation step reduces the process cost and complexity.
8~
This invention will be further described by reference to the following example of operations.
EX~LE
Illinois No. 6 bituminous coal having 50-300 mesh size (U.S. Sieve Series) was fed as a coal/oil slurry with hydrogen into a 6-inch diameter reactor containing an ebullated catalyst bed, maintained at elevated temperatures and pressure conditions to produce hydrocarbon liquid and gas products. The reactor was provided with a flat metal baffle about 4-inch average diameter, positioned at a 45~ angle with the horizontal plane and having its center located about 1.3 inches upstream of a 1.125 inch inside diameter withdrawal conduit, similarly as shown in Figure 1. The operating conditions and results for the catalytic reaction step with and without the baffle and for otherwise quite similar operating conditions are provided in Table 1 below.
EBULLATED BED REACTOR OPERATIONS WTTH AND WITHOVT
RETENTION OF COAL SOLID~S
Run No. 130-66 Run No. 30-67 Without Baffle With Baffle In Reactor In Reactor Coal Feed, W % Water 2.82 1.87 Coal Feed, W % Ash 11.07 10.93 Coal Feed Rate, Lbs/Hr 164 177 Hydrogen Makeup, SCFH 1890 1890 Catalyst Bed Expansion, %50 50 7 Recycle Gas SCFH 1075 1676 Recycle Oil, SCFH 410 451 Reactor Temperature, F 826 831 Reactor H? Pressure, psig2700 2700 Internal Slurry Recycle Rate, Gpm/Ft2 Reactor (Average) 48 34 Start of Run 43 46 After 8 Hours 52 36 t~ 7 It is noted that a si~niicantly lower internal s]urr~
recycle rate was required for producing the desired 50~
catalyst bed expansion in Run No. 130-67, using the internal deflection baffle, actually reflecting a reduction of about 30% in the rate during the period of operationO ~he general relationship between the reactor liquid recycle rate for 50~
catalyst bed expansion and the percent total solids in the reactor liquid, i.e. unconverted coal and ash or mineral matter, is shown in Figure 4, and is based on data sub-sequently obtained for catalytic hydrogenation of coal.
Thus, this reduced liquid recycle rate required for Run No.
130-67 to achieve the same catalyst bed expansion indicates increased density and viscosity of the reactor liquid. The differences ln the operating conditions are not sufficient to have any substantial effect on the internal recycle liquid requirements. Thus, it is seen that the internal deflection baffle means provides for increased viscosi.ty and=
coal solids concentration in the reactor liquid. This indi-cates that increased conversion of the coal solids can be achieved by use of such deflecting means critically located upstream of the reactor effluent withdrawal conduit~ and also that separation of unconverted coal and ash solids can be achieved in the ebullated bed reactor system by such solids deflection means.
It i~ recogni.zed that modifications and variations of this invention can be made without departing from the spirit and scope thereof, and which is defined solely by the following claims.
Claims (21)
1. A process for hydrogenation of coal to produce hydrocarbon liquid and gas products comprising:
(a) slurrying the coal with a hydrocarbon liquid and feeding the coal-oil slurry and hydrogen gas into a reactor containing particulate contact solids;
(b) passing said coal slurry and gas upwardly through the reactor under liquid phase conditions in which the solids are placed in random motion in the upflowing liquid, and at temperature between about 750 and about 950°F and hydrogen partial pressure between about 1000 and 4000 psig to produce hydro-genation reaction of the coal;
(c) withdrawing a reacted combined effluent stream con-taining gaseous and liquid fractions from the reac-tor while simultaneously deflecting particulate unconverted coal solids in the upflowing slurry liquid away from the effluent withdrawal stream, thereby increasing the concentration and residence time of larger unconverted coal solids in the reac-tor liquid for improved conversion therein so that the remaining effluent stream withdrawn from the reactor contains fine sized solids; and (d) separating said effluent stream into gaseous and liquid fractions and recovering hydrocarbon liquid product.
(a) slurrying the coal with a hydrocarbon liquid and feeding the coal-oil slurry and hydrogen gas into a reactor containing particulate contact solids;
(b) passing said coal slurry and gas upwardly through the reactor under liquid phase conditions in which the solids are placed in random motion in the upflowing liquid, and at temperature between about 750 and about 950°F and hydrogen partial pressure between about 1000 and 4000 psig to produce hydro-genation reaction of the coal;
(c) withdrawing a reacted combined effluent stream con-taining gaseous and liquid fractions from the reac-tor while simultaneously deflecting particulate unconverted coal solids in the upflowing slurry liquid away from the effluent withdrawal stream, thereby increasing the concentration and residence time of larger unconverted coal solids in the reac-tor liquid for improved conversion therein so that the remaining effluent stream withdrawn from the reactor contains fine sized solids; and (d) separating said effluent stream into gaseous and liquid fractions and recovering hydrocarbon liquid product.
2. The process of claim 1, wherein the effluent stream withdrawn from the reactor has solids concentration less than the solids concentration maintained in the reactor liquid.
3. The process of claim 1, wherein the reactor contains an ebullated bed of particulate catalyst having particle size larger than about 0.016 inch effective diameter.
4. The process of claim 1, wherein the coal feed has particle size range of 30 to 325 mesh (U.S. Sieve Series) and the coal-oil slurry contains a coal/oil weight ratio of from about 1 to about 5.
5. The process of claim 1, wherein the fine sized coal solids in the effluent stream withdrawn from the reactor are smaller than about 50 microns.
6. The process of claim 1, wherein a minor portion of the reactor slurry liquid is withdrawn from the bottom of the reactor for further processing.
7. The process of claim 6, wherein the liquid stream having coal and ash solids concentration exceeding about 15 weight percent withdrawn from the reactor liquid is sub-jected to a low pressure distillation step.
8. The process of claim 1, wherein the deflection of particulate coal solids away from the reactor effluent withdrawal stream is varied so as to control the percent unconverted coal solids in the effluent liquid stream.
9. A process for the catalytic hydrogenation of coal to produce hydrocarbon liquid and gas products, which comprises:
(a) passing the coal in particulate form with a slurrying oil and hydrogen gas upwardly through an expanded bed of catalytic solids in a reactor while maintaining the reactor at hydrogenation con-ditions of temperature in the range of 780-900°F
and hydrogen partial pressure between about 1500-3500 psig and hydrogenating the coal;
(b) withdrawing a hydrogenated effluent stream con-taining hydrocarbon gaseous and liquid fractions from the reactor upper end, while simultaneously deflecting unconverted coal solids larger than about 30 microns into the reactor liquid away from said effluent stream, so that the effluent stream contains coal solids concentration less than the solids concentration in the reactor liquid;
(c) phase separating the reactor effluent stream into gas and liquid portions;
(d) passing the liquid portion to a liquid-solids separation step for partial removal of particulate solids from the liquid;
(e) fractionating the remaining liquid containing reduced solids concentration to provide at least three fractions comprising a light ends fraction, a middle distillate liquid fraction, and a bottom liquid fraction;
(f) recycling a portion of said middle liquid fraction to the reactor for slurrying the coal; and (g) withdrawing from the fractionation step said liquid product streams
(a) passing the coal in particulate form with a slurrying oil and hydrogen gas upwardly through an expanded bed of catalytic solids in a reactor while maintaining the reactor at hydrogenation con-ditions of temperature in the range of 780-900°F
and hydrogen partial pressure between about 1500-3500 psig and hydrogenating the coal;
(b) withdrawing a hydrogenated effluent stream con-taining hydrocarbon gaseous and liquid fractions from the reactor upper end, while simultaneously deflecting unconverted coal solids larger than about 30 microns into the reactor liquid away from said effluent stream, so that the effluent stream contains coal solids concentration less than the solids concentration in the reactor liquid;
(c) phase separating the reactor effluent stream into gas and liquid portions;
(d) passing the liquid portion to a liquid-solids separation step for partial removal of particulate solids from the liquid;
(e) fractionating the remaining liquid containing reduced solids concentration to provide at least three fractions comprising a light ends fraction, a middle distillate liquid fraction, and a bottom liquid fraction;
(f) recycling a portion of said middle liquid fraction to the reactor for slurrying the coal; and (g) withdrawing from the fractionation step said liquid product streams
10. A process for hydrogenating coal to produce hydro-carbon liquid and gas products, wherein a coal-oil slurry is provided and introduced with hydrogen into a reactor con-taining an ebullated bed of particulate catalyst, said reac-tor being maintained within a temperature range of 750-950°F
and hydrogen partial pressure of 1500-4000 psig and a liquid slurry is recycled in the reactor to hydrogenate the coal and produce hydrocarbon liquid and gaseous material, wherein the improvement comprises:
(a) retaining unconverted coal solids larger than about 30 microns in the reactor liquid by deflecting such solid particles into the upflowing liquid slurry by a solids deflecting means located upstream of the withdrawal conduit, said coal solids being deflected downwardly into the reactor liquid; and (b) withdrawing an effluent stream from said reactor upper end, said stream containing gaseous and liquid fractions and containing coal solids par-ticles smaller than about 50 microns.
and hydrogen partial pressure of 1500-4000 psig and a liquid slurry is recycled in the reactor to hydrogenate the coal and produce hydrocarbon liquid and gaseous material, wherein the improvement comprises:
(a) retaining unconverted coal solids larger than about 30 microns in the reactor liquid by deflecting such solid particles into the upflowing liquid slurry by a solids deflecting means located upstream of the withdrawal conduit, said coal solids being deflected downwardly into the reactor liquid; and (b) withdrawing an effluent stream from said reactor upper end, said stream containing gaseous and liquid fractions and containing coal solids par-ticles smaller than about 50 microns.
11. The process of claim 10, wherein the solids con-centration in the reactor liquid is at least about 5 W %
greater than the coal solids concentration in the reactor effluent stream.
greater than the coal solids concentration in the reactor effluent stream.
12. A reactor apparatus for treating a liquid with a gas while containing a bed of finely divided solids, which comprises (a) a pressurizable vessel having means for introducing liquid, gas and finely divided solids into the vessel;
(b) a withdrawal conduit extending within the upper portion of said vessel; and (c) deflection means positioned within the upper portion of the vessel so as to shield the inlet end of said withdrawal conduit to selectively reduce the entry of larger particulate solids into the conduit.
(b) a withdrawal conduit extending within the upper portion of said vessel; and (c) deflection means positioned within the upper portion of the vessel so as to shield the inlet end of said withdrawal conduit to selectively reduce the entry of larger particulate solids into the conduit.
13. The apparatus of claim 12, wherein the deflection means is a baffle having an area which exceeds the withdrawal conduit opening area.
14. The apparatus of claim 13, wherein the baffle is solid and is attached to and supported by the withdrawal conduit.
15. The apparatus of claim 13, wherein the withdrawal conduit is positioned substantially vertically and the baffle is inclined to the horizontal at an angle of 0-45 degrees.
16. The apparatus of claim 13, wherein the horizontally projected area of the baffle exceed the cross-sectional area of the withdrawal conduit.
17. The apparatus of claim 13, wherein the vertical spacing between the withdrawal conduit lower end and the baffle exceeds the inside diameter of the withdrawal conduit.
18. The apparatus of claim 13, wherein the baffle is conical-shaped with the large diameter facing downwardly.
19. The apparatus of claim 13, wherein the withdrawal conduit and baffle are removable through a flanged opening in the upper end of the reactor.
The apparatus of claim 13, wherein the deflection means is made moveable relative to the withdrawal conduit lower end.
21. A reactor apparatus for treating a liquid with a gas while containing a bed of finely divided solids, which comprises;
(a) a pressurizable vessel having means for introducing liquid, gas and finely divided solids into the vessel;
(b) a withdrawal conduit extending within the upper portion of said vessel; and (c) solid deflection baffle means attached to said withdrawal conduit so as to partially shield the inlet end of said conduit to selectively reduce the entry of larger particulate solids into the conduit.
(a) a pressurizable vessel having means for introducing liquid, gas and finely divided solids into the vessel;
(b) a withdrawal conduit extending within the upper portion of said vessel; and (c) solid deflection baffle means attached to said withdrawal conduit so as to partially shield the inlet end of said conduit to selectively reduce the entry of larger particulate solids into the conduit.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US33243381A | 1981-12-21 | 1981-12-21 | |
| US332,433 | 1981-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1196877A true CA1196877A (en) | 1985-11-19 |
Family
ID=23298216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000418157A Expired CA1196877A (en) | 1981-12-21 | 1982-12-20 | Coal hydrogenation process having increased solids retention in ebullated bed reactor |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS58111892A (en) |
| AU (1) | AU9137582A (en) |
| CA (1) | CA1196877A (en) |
| DE (1) | DE3245494A1 (en) |
| GB (1) | GB2111848A (en) |
| ZA (1) | ZA829012B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818050A (en) * | 2015-05-07 | 2015-08-05 | 北京中科诚毅科技发展有限公司 | Multi-optimized slurry bed hydrogenation reactor, application and design method thereof |
| CN107694483A (en) * | 2017-09-22 | 2018-02-16 | 北京中科诚毅科技发展有限公司 | A kind of new structure hydrogenation reactor and its design method and purposes |
| CN108970544A (en) * | 2017-06-02 | 2018-12-11 | 何巨堂 | A kind of liquid product reflux power of gas-liquid material upstream hydrogenator increases method |
| CN111804245A (en) * | 2019-04-12 | 2020-10-23 | Ifp 新能源公司 | Three-phase reactor comprising a recirculation cup with a gradually decreasing cross-section and a varying inclination angle |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4495055A (en) * | 1982-04-05 | 1985-01-22 | Hri, Inc. | Coal catalytic hydrogenation process using direct coal slurry feed to reactor with controlled mixing conditions |
| US4557904A (en) * | 1984-03-26 | 1985-12-10 | Union Carbide Corporation | Integral reactor apparatus |
| US6846405B2 (en) * | 2001-08-31 | 2005-01-25 | Exxonmobil Chemical Patents Inc. | Circulating fluid bed reactor system |
| DE102005021056A1 (en) * | 2005-05-06 | 2006-11-09 | Basf Ag | Process for the isolation of methylglycinnitrile-N, N-diacetonitriles from an aqueous crude mixture |
| CN107790073A (en) * | 2017-09-28 | 2018-03-13 | 北京中科诚毅科技发展有限公司 | A kind of reactor novel internal structure and its design method and purposes |
| CN108148739B (en) * | 2018-02-08 | 2023-05-16 | 沈阳农业大学 | Circulation degassing type fluidized bed bioreactor |
| WO2021050010A1 (en) * | 2019-09-09 | 2021-03-18 | Ptt Exploration And Production Public Company Limited | A condensate decontamination device |
| CN113566470B (en) * | 2021-08-20 | 2023-01-31 | 楼建军 | Hydrogen slurry generator, system and method for continuously preparing hydrogen slurry in batches |
-
1982
- 1982-12-03 GB GB08234509A patent/GB2111848A/en not_active Withdrawn
- 1982-12-08 ZA ZA829012A patent/ZA829012B/en unknown
- 1982-12-09 DE DE19823245494 patent/DE3245494A1/en not_active Withdrawn
- 1982-12-09 AU AU91375/82A patent/AU9137582A/en not_active Abandoned
- 1982-12-20 CA CA000418157A patent/CA1196877A/en not_active Expired
- 1982-12-20 JP JP57222242A patent/JPS58111892A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818050A (en) * | 2015-05-07 | 2015-08-05 | 北京中科诚毅科技发展有限公司 | Multi-optimized slurry bed hydrogenation reactor, application and design method thereof |
| CN108970544A (en) * | 2017-06-02 | 2018-12-11 | 何巨堂 | A kind of liquid product reflux power of gas-liquid material upstream hydrogenator increases method |
| CN107694483A (en) * | 2017-09-22 | 2018-02-16 | 北京中科诚毅科技发展有限公司 | A kind of new structure hydrogenation reactor and its design method and purposes |
| CN107694483B (en) * | 2017-09-22 | 2018-12-21 | 北京中科诚毅科技发展有限公司 | A kind of hydrogenator and its design method and purposes |
| CN111804245A (en) * | 2019-04-12 | 2020-10-23 | Ifp 新能源公司 | Three-phase reactor comprising a recirculation cup with a gradually decreasing cross-section and a varying inclination angle |
| CN111804245B (en) * | 2019-04-12 | 2024-01-09 | Ifp 新能源公司 | Three-phase reactor comprising a recirculation cup with a gradually decreasing cross section and varying inclination angle |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2111848A (en) | 1983-07-13 |
| DE3245494A1 (en) | 1983-06-30 |
| AU9137582A (en) | 1983-06-30 |
| JPS58111892A (en) | 1983-07-04 |
| ZA829012B (en) | 1984-09-26 |
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