US2749290A - Method and apparatus for continuous percolation of liquid hydrocarbons - Google Patents

Method and apparatus for continuous percolation of liquid hydrocarbons Download PDF

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US2749290A
US2749290A US237268A US23726851A US2749290A US 2749290 A US2749290 A US 2749290A US 237268 A US237268 A US 237268A US 23726851 A US23726851 A US 23726851A US 2749290 A US2749290 A US 2749290A
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adsorbent
column
liquid
oil
particles
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Joe E Penick
Ernest A Bodkin
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ExxonMobil Oil Corp
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Socony Mobil Oil Co Inc
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Priority to GB16449/52A priority patent/GB770392A/en
Priority to FR1074553D priority patent/FR1074553A/fr
Priority to DES29337A priority patent/DE966390C/de
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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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil
    • C10G25/08—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil according to the "moving bed" method
    • 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
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/12—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by gravity in a downward flow

Definitions

  • This invention relates to a process for treating liquid hydrocarbons, particularly lubricating oils and lower boiling petroleum fractions which are of low asphalt contentwith solid adsorbents for thepurpose of removing small amounts of impurities or undesirable contaminants therefrom. It is also applicable to processes for Washing and treating adsorbents to recover liquid materials therefrom, to processes for separation of liquid materials by adsorption, and to solvent extraction processes and the like involving contacting of liquid hydrocarbons with a solid adsorbent material.
  • Typical of the oil treating processes with which this invention is particularly concerned are decolorizatiom neutralization, removal of suspended colloidal or dissolved impurities such as carbon, coke or oxygen and nitrogen-containing impurities and other gum-forming compounds and improvement of demulsibility properties of the oil.
  • a major object of this invention is the provision of an improved method and apparatus for effecting continuous uniform countercurrent contacting between an upwardly flowing liquid hydrocarbon and acolumnar mass of gravitating adsorbent of palpable particulate form, which method and apparatus overcomes the above mentioned difliculties;
  • a further object is the provision in a process for countercurrent contacting of a liquid oilwith a downwardly moving column of adsorbent particles of an improved method and apparatus for eifecting uniform and continuous engagement and disengagement of the liquid and absorbent materials.
  • Another object is the provision in a system for countercurrently contacting a liquid hydrocarbon with a column of downwardly moving adsorbent of palpable particle form of an improved method and apparatus for supplying fresh adsorbent to the column and for removing contacted liquid therefrom Without substantial entrainment of adsorbent particles.
  • Another object is the provision in a continuous percolation process for decolorizing and purifying lubricating oils of low asphalt content of an eflicient method for continuously effecting uniform countercurrent contact of the oil with a column of downwardly; moving ad sorbent particles.
  • a column of adsorbent of palpable particle form is maintained along an intermediate portion of a confined treating zone, a body of treated liquid hydrocarbon is maintained above the colum and open to its surface. Also, a body of liquid hydrocarbon feed is maintained below the column and in communication therewith only through restricted passages through which the oil is permitted to How from the body into the column but through which the. ad-
  • sorbent is prevented from flowing, so that the adsorbent.
  • Liquid hydrocarbon feed is supplied to the body of liquid feed so as to force the liquid up into and through the.
  • Treated liquid is withdrawn from the body thereof above the column at a level well above the level of" adsorbent discharge from the confined feed. stream.
  • the rateof adsorbent supply to theconiined feed stream is controlled below the maximum possible rate of adsorbent settling in the liquid existing in the lower portion of said stream and the wetted adsorbent particles are discharged from the. confined feed stream at a level under the surface of the treated liquid body and spaced substantially above.
  • the adsorbent employed should be made up of palpableparticlescf size within the range about 4-100 mesh and preferably about l0 -6O and Further difficulties arise in eiiecting still more preferably 15-30 mesh by Tyler Standard Screen Analysis.
  • the particles may take the form of pellets, capsules, pills, spheres or the like or granules of irregular shape such as are obtained from grinding and screening.
  • adsorbent in palpable particulate form and palpable particle form adsorbents as employed herein in describing and in claiming this invention are intended to generically cover partiles of any or all of these shapesployed but preferably the preparation thereof should be controlled to provide a pore structure similar to that of the clay type adsorbents wherein substantially more than 30 percent of the total pore volume is occupied by macropores. Gels of this type are described in United States Patent 2,188,007, issued January 23, 1940.
  • adsorbents of the synthetic gel type or otherwise having mostly micropores and less than 30 percent macropores may be employed in the process of this invention although with somewhat inferior results when used for lubricating oil purification.
  • gels of this latter type have been found to give superior results in the treatment of distillate fuel oils by the method of this invention.
  • adsorbents of this latter type are disclosed in United States Patents 2,3 84,946 and 2,106,744.
  • the invention in its broadest form is intended to be applicable to adsorbents of this type as well as the preferred adsorbents of larger pore structure.
  • Figure l is an elevational view, partially in section, of a preferred form of the invention
  • Figure 2 is a horizontal cross-sectional view along line 2-2 of Figure 1
  • Figure 3 is a horizontal cross-sectional view along line 3-3 of Figure 1
  • Figure 4 is a detailed view of one of the elements of the apparatus of Figure 1
  • Figure 5 is a horizontal cross-sectional view taken at a level corresponding at 22 of Figure 1 of a modified form of the apparatus of Figure 1
  • Figure 6 is an elevational view, partially in section, of a less preferred form of the invention. All of these drawings are highly diagrammatic in form.
  • Figure 7 is an elevational view, partially in section, of a modified form of the upper portion of the apparatus of Figure l
  • Figure 8 is a cross-sectional view taken along line 8-8 of Figure 7.
  • FIG. 1 there is shown a vertical treater 10 closed on its ends but vented to the atmosphere at its upper end by means of vent 11.
  • the treater may be of any desirable cross-sectional shape, the vessel shown being of circular shape.
  • Above the treater there is provided a single adsorbent feed conduit 12 which extends down from a surge or supply hopper (not shown).
  • the conduit 12 terminates on its lower end on the bottom of the cylindrical receptacle 13 which is of substantially larger diameter than the conduit so as to provide an annular space 14 for receiving adsorbent particles issuing from vertical slots 15 provided along a lower portion of conduit 12.
  • a slidable sleeve 16, operated by cable and crank 17 is provided to permit adjustment of the amount of slot area open for adsorbent escape from conduit 12.
  • a plurality of pipes 18 connect through the bottom of receptacle 13 at spaced points arranged in a ring symmetrical with respect the conduit 12. These pipes extend downwardly through the top of treater 10 and terminates at their lower ends at a level in the upper section of the treater below its upper end and adjacent the open upper ends of vertical tubes 20.
  • the adsorbent flow control and divider arrangement above described is the subject of claims in application Serial Number 237,264, filed in the United States Patent Ofiice on July 17, 1951.
  • One tube 20 is sus pended by means of straps 21 below the lower end of each pipe 18, the tubes being of substantialy larger crosssectional area than the pipes 18.
  • the tubes 20 terminate on their lower ends at .a common level in the upper scction of the vessel 10 which is substantially below the oil collector channel 22 and outlet pipe 23 and substantially above the surface level of the adsorbent column 24.
  • the oil collector channel or trough 22 may be open on its top and is provided with horizontal rows of spaced orifices 25 located at two vertically spaced levels along its opposite sides.
  • the trough 22 is supported by bracket 26 on one end which is closed and by the members forming the collecting basin 27 on its opposite end.
  • the general arrangement of the trough across the treater may be best understood by reference to Figure 2 in conjunction with Figure 1.
  • An oil outlet pipe 23 connects through the vessel wall into the basin 27.
  • the liquid collecting channel and its arrangement in the treater is the subject of claims in application Serial Number 265,832, filed in the United States Patent Oilice on January 10, 1952.
  • a horizontal partition 30 extends across the lower section of treater 10 above the bottom thereof so as to provide a plenum or liquid distribution space 31.
  • a plurality of uniformly spaced nozzles 33 are distributed uniformly over the entire cross-sectional area of the partition 30 to provide a passage for liquid flow from the plenum space into the portion of the vessel above the partition.
  • a plurality of adsorbent drain conduits 37 fit tightly through the partition at spaced points uniformly distributed across its cross-section and terminate on their open upper ends just above or even with the upper face of partition 30. These conduits extend downwardly through the plenum space 31 and the bottom of the treater.
  • the lateral arrangement of the nozzles and adsorbent drain conduits on the partition 30 is shown in Figure 3.
  • An inlet header conduit 35 closed on its inner end is positioned across the space 31. Oil is supplied into the conduit 35 from pipe 36 which connects through the bottom of the treater and onto one end of the conduit 35. A plurality of oil dirtributor holes 50 are arranged at spaced intervals along either side of the header 35.
  • the adsorbent drain conduits 37 connect in a ring through the top of the funnel shaped collector vessel 38. A single outlet 51 depends from the lower end of vessel 38 and extends down to a motor driven, liquid tight measuring and flow control valve 39.
  • each nozzle is made up of several parts, one being a body portion 4?) which screws through the partition 30 and has a central passageway for liquid flow.
  • a circular orifice plate 41 rests on a shoulder (not shown) at the top of the body portion 40.
  • a flanged upwardly extending support member rests on the orifice and the support member has a passage through its center and openings along its side for escape of liquid laterally from the central passage.
  • a screw 43 screws into the upper end of the central passage of the support member so as to close oi? the same.
  • the head of the screw also serves to hold inplace the screen 42.
  • the support member and orifice plate are held in place by the nut 44.
  • a columnar mass 55 of adsorbent of palpable particle form As an example, the adsorbent may comprise l30 mesh size (Tyler) granular fuller's earth.
  • a body of treated liquid oil 56 is maintained above the column and open to its surface entirely thereacross.
  • a body of feed liquid 57 is maintained immediately below the column 56 in the plenum space 31 and in liquid flow communication therewith through the restricted passages formed by the nozzles 33. The particles are excluded from the restricted passages and from the liquid body in plenum space 31 by means of the screens 42 on the nozzles 33.
  • Liquid feed oil is supplied to the body 57 via inlet 36 and distributor 35 so that the liquid is forced up through the restricted passages formed by nozzles 33 into the lower end of column 55.
  • a pressure drop is incurred due to flow through the orifices 41 which are of equal size and uniformly distributed with respect the bed cross section, so as a result the oil enters the bed at a uniform rate over its entire horizontal cross-sectional area.
  • the liquid oil passes upwardly through the bed at a rate controlled at the oil inlet which is below the column disrupting velocity.
  • uniform countercurrent contacting of the oil and adsorbent is effected and the oil purification and decolorization is accomplished with high eliiciency.
  • the treated oil product passes upwardly from the surface of the column 55 through the body of liquid 56.
  • very effective settling of any entrained adsorbent is effected and the treated oil leaves the treater via pipe 23 substantially free of entrained particles.
  • the soaking tubes extend down under the surface of the body of treated oil 56 and the oil rises up into the lower portion of the tubes to seek its normal level.
  • Fresh adsorbent is dropped from pipes 18, at rates controlled by the slot opening 15 so that the particles fall freely through the upper portions of the soaking tubes 20 which are free of liquid and then settle freely through the liquid oil in the lower portion of the tubes.
  • the adsorbent is wetted with oil and entrained air or gas is displaced and caused to escape upwardly through the tubes 20 and out through the vent 11.
  • the wetted and degasified adsorbent discharges from the tubes 23 well above the surface of column 55 and settles through the lower portion of the treated liquid body onto the column surface.
  • Spent adsorbent bearing carbonaceous deposits is withdrawn from the bottom of the column downwardly through but out of contact with the body of liquid feed oil and then out from the bottom of the treater via conduits 37.
  • Some liquid oil having properties similar to the feed oil is withdrawn along with the adsorbent particles in the void spaces between the particles.
  • the rate of adsorbent throughput is controlled to provide the desired decolorization of the oil being tneated. Once the required adsorbent to oil throughput ratio has been decided upon for a given operation and the oil throughput rate set, the required adsorbent throughput rate can be calculated. T he sleeve 16 is adjusted to permit the required amount of adsorbent to pass to the tubes 29. Once the proper rate is set in this manner, the controller 14 serves only as a fixed constant throttle on the rate of adsorbent introduction. The rate of adsorbent movement through the column 55 and the surface level of the column is thereafter during that operation controlled by means of the valve 39 on the drain conduit 51.
  • the valve 39 which is of the positive displacement type is motor driven and the motor speed and hence the rate of displacement through valve 39 is controlled automatically in response to variations in the column surface level "within the treater.
  • the rate of adsorbent withdrawal is regulated to maintainthe column surface level within a narrow range of levels all more than three and preferably more than six inches below the lower ends of tubes 26.
  • the particular mechanism for automatically measuring the column surface level and adjusting the valve 39 which is shown in Figure 1, involves the measurement of the pressure drop due to oil flow through a vertical section of the treater between taps 47 and 48 arranged at vertically spaced points shortly above and below the desired column surface level.
  • the adsorbent in the preferred operation the adsorbent is caused to freely fall through the tubes 20 and a lower portion of liquid body $6 onto the adsorbent column 55.
  • the adsorbent then flows through the adsorbent column and the discharge streams 37 under conditions controlled to maintain the adsorbent in the continuous phase, i. e. the adsorbent particles touch and rest upon each other and the liquid oil fills the void spaces between the adsorbent particles.
  • any suitable means known to the art may be employed for supplying fresh adsorbent to the upper ends of tubes 2%) at a controlled or fixed rate.
  • any suitable means known to the art may be employed for supplying fresh adsorbent to the upper ends of tubes 2%) at a controlled or fixed rate.
  • vessels of relatively small cross-sectional area only one soaking tube 24 may be required.
  • Means other than that shown may be substituted for effecting withdrawal of the liquid oil from the upper portion of the liquid body 56.
  • the outlet device may simply comprise one or more pipes connected to the vessel shell at the proper level.
  • the adsorbent column may be divided into sectors by vertical partitions and to supply one or more soaking tubes 20 for each sector of the column in the treater.
  • Such an arrangement is shown in Figure 5, in which the vertical partitions are shown at '70 and 71.
  • the partitions 71 may extend the entire length of the column or may extend through only an upper or lower portion thereof.
  • the method for introduction of liquid into the lower section of the column and for maintaining the body of feed liquid below the column may be modified from that shown.
  • simple orifices or nipples of restricted internal diameters may be substituted in partition 30 for nozzles 33 and a screen may be arranged across the vessel above the partition to prevent adsorbent particles from entering the orifices and the body of liquid therebelow.
  • Baffle plates may be provided over the orifices to disperse the flow.
  • restricted passages and restricted passageways are employed herein in describing and claiming this invention in a broad sense as covering orifices, nozzles, nipples, of small internal diameter and other suit able passageways of restricted cross section adopted to accomplish the function of oil distribution in the manner described.
  • this invention is broad to the particular method for adsorbent supply and treated liquid disengagement from the adsorbent and withdrawal disclosed herein, without regard to the particular method for liquid feed introduction to the column or spent adsorbent withdrawal therefrom.
  • the novel method of treater operation wherein the moving adsorbent column is maintained between two bodies of liquid from which the particles are excluded and wherein fresh adsorbent is supplied to said column by passing downward through at least an upper portion of the liquid body above said column as a confined stream of relatively small cross section and discharging the particles from said stream a substantial distance below the surface of the body of treated oil while treated oil product is withdrawn from the liquid body at a level well above the discharge level of the confined adsorbent feed stream.
  • FIG. 6 An example of a modified form of the invention is shown in Figure 6.
  • the fresh adsr bent from inlet conduit 12 is measured at a controlled rate by valve 80 into the vertical soaking tube which in this case extends through the top of treater 10.
  • a vent 84 is provided on the tube 20 just below the valve 80.
  • Adsorbent is withdrawn from the bottom of the treater through conduits 85 in which there are provided orifices 86 to control the withdrawal at a fixed rate.
  • the column level is controlled by increasing or decreasing the rate of adsorbent feed in response to fall or rise in the column surface as indicated by float 87 which actuates the motor control instruments 82 and 83.
  • the liquid feed enters from inlet 36 to a laterally extending manifold 88 which in turn feeds the spider arrangement conduits 89.
  • the conduits 89 of which only one may be seen are spaced horizontally apart at equal intervals across the housing cross-section and extend lengthwise nearly entirely across the housing to their closed ends.
  • Orifices 91 are provided at spaced intervals along the conduits 89 so as to provide a uniform orifice area distribution over the entire cross section of the treater.
  • a screen 99 which is of smaller mesh size than the particles of adsorbent but which permits free passage of liquid is wrapped around the conduits to prevent entry of adsorbent into the conduits.
  • the valve 80 may be a suitable gate or needle valve and preferably one which provides a symmetrical opening within the feed conduit 20.
  • a suitable adjustable valve for use at this point may be one having an adjustable iris diaphragm such as the valve disclosed in United States Patent 2,458,- 162.
  • adsorbent withdrawal arrangement may be similar to that shown in Figure l with a fixed orifice substituted for the valve 39.
  • FIG. 7 and 8 A modified arrangement for delivering fresh dry adsorbent to the soaking tubes is shown in Figures 7 and 8 which should be read together.
  • the main adsorbent feed conduit 12 extends into the upper section of the treater.
  • the soaking tube 20 is of annular cross-sectional shape and is supported within the housing by bars 106.
  • Adsorbent issuing from the slots 15 is spread by means of frusto-conical bat'fie which terminates on its lower end over the open upper end of the soaking tube.
  • the outer wall of the tube 20 may extend upwardly a short distance above the base of battle 105 to prevent escape of any stray particles over the outer rim of the soaking tube.
  • Tubes extend through the annular tube 20 at several points spaced around its upper section at the surface level of the liquid body 56 for by pass of liquid passing up through the space inside the annular tube 20 to the outlet 23.
  • the purpose of the soaking tubes 20 is to permit continuous uninterrupted supply of adsorbent to the column in the treating zone without entrainment in the etlluent liquid hydrocarbon stream.
  • the adsorbent in the dry state contains gas and is relatively light, and in that condition it is readily suspended and entrained in tip-flowing liquid oil streams.
  • the liquid oil seeks its level within the lower portion of tubes 20 but in contrast to the remainder of the body 56, the liquid columns within the tubes 20 has no upward velocity component.
  • the dry adsorbent readily settles into the column of liquid within the tubes and occluded gas is replaced by liquid.
  • the tubes 28 discharge at least 6 inches and preferably 18 to 36 inches below the surface of the liquid body 56. It has been found that if adsorbent is supplied to the tubes at a sulficient rate to provide a compact column thereof in the tubes. there is a tendency for the liquid hydrocarbon to seep up through the column of adsorbent above tle ordinary liquid level in the tube and to cause plugging of the tube by the wetted adsorbent.
  • the rate of adsorbent supply to tubes 20 should be restricted so that the adsorbent falls freely through the upper portion of the tubes above the liquid level therein and settles freely through the liquid column in the lower portions of the tubes.
  • the rate of adsorbent supply to the tubes 20, and the superficial volumetric velocity in the upper portions of the tubes 20 is limited below the maximum settling rates of the dry particles in the liquid in the lower portions of the tubes and in the portion of the liquid body therebelow.
  • the rate of adsorbent supply to the upper end of any soaking tube must be below that defined by the equation I 71O,000D- 1M1 ST
  • U is the rate of adsorbent supply in cubic feet per hour per square foot of soaking tube horizontal crosssectional area (the adsorbent volume here referred to is on the apparent volume basis, that is, the volume of an equal amount of the dry adsorbent when fiowing as a substantially compact throttled stream or as poured into a graduate without agitation of the graduate)
  • Z is the viscosity in centipoises of the liquid hydrocarbon under the condition in the treater and specifically within the ar' raaee lower portion of the tube 20 and is below about 560 centipoises
  • D is the average adsorbent particle diameter in inches (calculated by averaging the reciprocal of the particle diameters), and above about 0.01 inch
  • 8a is the dry adsorbent apparent density in grams per cubic centimeter (conveniently determined
  • the rate of ad sorbent supply to each soaking tube should be approximately that defined by the equation 11 U 443,00OD2 Sa s L) Z 1-1 ST Since the upper portions of the tube 20 are not filled with a compact mass of adsorbent, ample flow area is provided in the tube for escape of gas displaced from the adsorbent. However, it has been found desirable to limit the vertical distance from the liquid body surface to the upper end of the tube or to a vent on the tube below about 3 feet and preferably below about 1 /2 feet.
  • the lower ends of the tubes should be l8-36 inches above the surface of the adsorbent column. Also, the lower ends of the tubes 20 should be more than three and preferably more than six inches and for best operation 18-36 inches below the surface of the body of liquid oil 56. In order to maintain minimum liquid velocities in the body 56 it is desirable that Within the limits above discussed the tubes 20 occupy as little of the housing cross section as possible.
  • the lateral dimensions of each tube amounts to only a small fraction of the corresponding lateral dimensions of the treater but each tube should have lateral dimensions in any direction greater than 3 and preferably greater than 6 inches. In any case, the total of the cross-sectional areas of all the soaking tubes amounts to only a minor fraction of that of the liquid oil body 56, usually less than about 5 percent.
  • H is the vertical distance in feet between the column surface and the surface of liquid body 56, and within the the range 6 inches to 8 feet;
  • R is the superficial oil rate through the liquid body 56 in 42 gallon barrels per day per square foot of liquid body horizontal cross-sectional area;
  • Z is the liquid oil viscosity under the conditions in .10 the liquid body 56 and within the range 02-500 centipoises;
  • the operating conditions within the treater may involve temperatures within the range atmospheric to 700 F. and pressures near or moderately below or in excess of atmospheric pressure.
  • the relative amounts of adsorbent and liquid oil feed passed through the treater depend upon the degree of decolorization or other treatment desired. In general, the volumetric ratio of liquid oil measured at 60 F. to adsorbent (packed density) falls within the range 0.3 to 30.
  • the superficial velocity of liquid oil through the treater should be within the range /;:-20 feet per hour and preferably Within the range 1-10 feet per hour. (Based on oil at treating temperature and free cross-sectional area of treater when empty.) In all cases, the oil velocity should be controlled below that which would interfere with the downward direction of flow of the adsorbent particles. While some expansion in the columnar mass due to oil flow may be tolerated, oil velocities should be avoided which are so high as to cause the adsorbent particles to move upwardly through the treating zone since such high velocities would prevent true countercurrent contacting of the oil and adsorbent with resultant decrease in the efficiency of the treating process.
  • the adsorbent particles touch each other as they move downwardly within the column so that it may be said that in this portion of the treating zone the adsorbent is the continuous phase whereas in the portion of the treater occupied by the body of treated oil above the surface of the column, the liquid oil is the continuous phase.
  • the superficial velocity of the liquid hydrocarbon in the portion of the treater occupied by the adsorbent column should be maintained below the maximum defined by the equation,
  • V is the superficial velocity of the oil in feet per hour (calculated on the basis of the total zone cross sectional area when empty of adsorbent) and the remaining variables are as defined in connection with Equation 1.
  • the superficial velocity should be below that defined by the equation,
  • the oil viscosity should be below 500 centipoises and usually a viscosity in the range of about 5 centipoises is preferred.
  • the vertical length of the adsorbent column in the treating zone should be greater than about 5 feet and preferably from l050 feet.
  • the invention may be applied to the adsorbent washing step of the continuous percolation process wherein occluded oil is washed from a down-flowing column of adsorbent by means of an upwardly percolating solvent such as petroleum naphtha, carbon tetrachloride, carbon disulfide or normal heptane.
  • an upwardly percolating solvent such as petroleum naphtha, carbon tetrachloride, carbon disulfide or normal heptane.
  • the same limits discussed hereinabove apply to the washing step except that the operating temperature may be somewhat lower.
  • the pressure drop due to flow through the orifices at the desired total throughput rate amounts at least to the sum of four times the flow head in the plenum space plus one-fourth of the pressure drop due to flow through the column exclusive of the hydrostatic head, or pressure drop due to flow across the plenum chamber to the restricted passageway plus one-fourth of the pressure drop due to oil flow through the vertical length of adsorbent column above the restricted passageway exclusive of hydrostatic head.
  • the pressure drop through the passageways at the required flow rate should be at least one-fourth of and preferably equal to the pressure drop due to oil flow through the column of adsorbent.
  • the restricted passages thus required have a total cross section amounting usually to less than one percent of the treater cross section. In general, for proper distribution of the oil into the column, the minimum number of spaced restricted liquid flow passages is defined by the equation,
  • A is the horizontal cross-sectional area in square feet of the adsorbent column and L is its vertical length in feet above the restricted oil inlet passages.
  • adsorbent withdrawal pipe should be provided for each 12 square feet of column cross section in order to insure uniform withdrawal of adsorbent all across the column. In any case, less than l7 square feet of column area should be allotted to each withdrawal conduit. Further, the minimum diameter of the withdrawal conduits should be at least 20 times the diameter of the particles, otherwise frequent stoppage of the flow will be encountered.
  • the preferred method for adsorbent withdrawal shown in Figure 1 is disclosed in detail and claimed in application Serial Number 237,267, filed in the United States Patent Ofiice on July 17, 1951.
  • an apparatus was constructed in the manner disclosed in Figure l.
  • the treater measured 8 feet in diameter and the column height above partition 30 was about 17 feet.
  • the depth of the feed liquid body below the column was about 1.2 feet and of the treated liquid body above the column about 3 feet.
  • the adsorbent was supplied through six soaking tubes 1% feet in length and 9 inches in internal diameter.
  • the feed pipes 18 were one inch standard pipe size.
  • the channel 22 was omitted and the oil outlet pipe 23 was located 6 inches below the top of the tubes 20.
  • the adsorbent column surface was maintained about 18 inches below the lower ends of tubes 20.
  • the adsorbent employed was 15-30 mesh size (Tyler) fullers earth which was passed through the treater at a rate of 550 pounds per hour which was about 0.072 pound of adsorbent per pound of treated oil product. About 3.3 barrels of oil per hour were withdrawn from the treater with the spent adsorbent. This oil was separated from the adsorbent and recycled to the treater. The adsorbent was washed, dried and regenerated and returned at its original activity to the treater for reuse therein.
  • a method for countercurrently contacting a liquid hydrocarbon feed which remains in the liquid phase during the contacting with a downwardly moving column of adsorbent which comprises, maintaining a column of adsorbent of palpable particle form along an intermediate portion of a confined, elongated contacting zone, maintaining a body of liquid hydrocarbon feed in a lower portion of said treating zone immediately below said column of adsorbent and in liquid fiow communication with the bottom of said column, substantially excluding the particles of adsorbent from said body of liquid, maintaining a body of contacted liquid in an upper portion of said treating zone immediately above and open to the surface of said column, withdrawing used adsorbent from the lower section of said column while maintaining said body of feed liquid free of said particles, replenishing said column at its upper end with feed adsorbent while substantially excluding the feed adsorbent from at least the upper portion of said body of contacted liquid hydrocarbon, introducing liquid hydrocarbon feed into the body of feed liquid so as to force the liquid to flow upwardly into and through said
  • a method for treating a liquid hydrocarbon feed which remains in the liquid phase during the treating by countercurrent contact with a downwardly moving column of adsorbent which comprises, maintaining a column of adsorbent of palpable particle form along an intermediate portion of a confined, elongated treating zone, maintaining a body of liquid hydrocarbon feed in a lower portion of said treating zone immediately below said column of absorbent and in liquid flow communication with the bottom of said column, substantially excluding the particles of adsorbent from said body of liquid, maintaining a body of treated liquid in an upper portion of said treating zone immediately above and open to the surface of said column, withdrawing used adsorbent from the lower section of said treating zone by passing a m-gage the adsorbent downwardly along with some liquid hydrocarbon as a plurality of confined horizontally spaced streams through said body of iiquid feed but out of contact therewith and then out from the lower section of said treating zone, supplying fresh adsorbent to the upper end of said column by passing it downwardly through at
  • a method for treating oils of low asphalt content to purify the same which comprises, introducing an adsorbent of palpable particulate form into the upper section of a confined treating zone in a plurality of horizontally spaced confined feed streams discharging a substantial distance below the surface of a body of the treated oil maintained in the upper section of said zone, at a plurality of points uniformly distributed across the horizontal cross-sectional area of said treating zone, causing the adsorbent particles to fall freely through a vertical section of said body of oil onto a column of said adsorbent and passing the adsorbent in said column downwardly within said treating zone countercurrently tothe liquid oil undergoing treatment, while controlling the velocity of oil flow below the column disrupting velocity, withdrawing spent adsorbent from a plurality of points uniformly distributed across the bottom of said column as a plurality of confined streams which extend downwardly through a lower portion of said treating zone in which there is maintained a body of liquid feed oil, while excluding entry of free adsorbent particles
  • a method for treating oils of low asphalt content to purify the same which comprises, maintaining a column of adsorbent of palpable particle form along an intermediate portion of a confined treating zone; maintaining a body of treated liquid oil above said column and open to the column surface and maintaining an adsorbent free body of liquid oil feed below said column and in liquid flow communication with the column above through a plurality of restricted passages from which the adscrbent particles are substantially excluded, said passages being uniformly distributed over the horizontal crosssectional area of said treating zone; passing fresh adsorbent downwardly through an upper portion of said body of treated oil from which adsorbent is otherwise substantially excluded as a plurality of spaced confined streams of freely falling particles, the adsorbent contacting liquid oil within said confined streams, whereby gas is removed from the adsorbent; discharging said streams into a lower portion of said body of treated oil at a plurality of points spaced substantially above the column surface and uniformly distributed over the horizontal cross-sectional area of said treating zone; permitting the a
  • the method for continuously supplyingadsorbent to said column without entrainment in the efiiuent contacted hydrocarbons which comprises, maintaining a body of contacted liquid hydrocarbons above said column and passing the contacted hydrocarbons upwardly from the surface of said column as said body to efiect settling of any entrained adsorbent particles and withdrawing the contacted liquid hydrocarbons from the upper portion of said body, passing feed adsorbent downwardly through an upper portion of said body as at least one confined stream of freely falling particles, said stream being restricted in cross section to only a minor fraction of that of said body and the adsorbent in the lower portion of said stream being brought into contact with liquid hydrocarbons isolated in said stream from the main portion of said body, whereby the adsorbent particles are degasified and wet in said stream, discharging said
  • a method for treating oils of low asphalt content to purify the same which comprises, maintaining a column of adsorbent of palpable particle form along an intermediate portion of a confined treating zone, maintaining a body of treated liquid oil above said column and open to the column surface, passing fresh adsorbent downwardly through an upper portion of said body of treated oil from which adsorbent is otherwise substantially excluded as a plurality of spaced confined streams of freely falling particles, the adsorbent contacting liquid oil withing said confined streams, whereby gas is removed from the adsorbent, discharging said streams into a lower portion of said body of treated oil at a plurality of points spaced substantially above the column surface and uniformly distributed over the horizontal cross-sectional area of said treating zone, permitting the adsorbent particles from said stream to descend freely through the oil onto the surface of said column, withdrawing spent adsorbent from the lower section of said column so as to promote downward movement of the adsorbent particles in said column, introducing the liquid oil feed into the lower section of
  • the method for supplying adsorbent to said column and withdrawing contacted liquid from said contacting zone without substantial entrainment of the adsorbent particles which comprises: maintaining a column of contacted liquid hydrocarbon material above the surface of said adsorbent column in said contacting zone; passing the dry adsorbent downwardly through a confined passage discharging it at a location more than six inches below the surface of said body of liquid and more than six inches above the surface of said column, said passage i being limited in cross-sectional area to only a minor fraction of that of said body of liquid and being open on its lower end to said body whereby the liquid rises into said passage to wet the particles of adsorbent falling therethrough; causing the adsorbent to drop from the lower end of said passage and to
  • a method for treating oils of low asphalt content to purify the same which comprises: maintaining a column of adsorbent of palpable particle form along an intermediate portion of a confined treating zone; maintaining a body of treated liquid oil above said column and across its entire surface; passing fresh adsorbent downwardly from a location above said body of treated oil through an upper portion of said body from which adsorbent is otherwise excluded as a plurality of spaced confined streams of adsorbent particles which fall freely through an upper portion of said streams and settle freely through liquid oil within a lower portion thereof, said streams having a total horizontal cross-sectional area amounting to only a minor fraction of that of said body of liquid; discharging the particles from the lower ends of said streams into the open body of treated oil at a evel more than six inches below its surface and more than six inches above the surface of said column of adsorbent and permitting the particles to settle freely down through the intervening portion of said body of liquid onto said column; continuously supplying fresh adsorbent to said confined streams at
  • a method for treating oils of low asphalt content to purify the same which comprises, maintaining a column of adsorbent of palpable particle form along an intermediate portion of a confined treating zone; maintaining a body of treated liquid oil above said column and open to the column and across its entire surface; passing fresh adsorbent downwardly through at least one vertical confined passage from a level above said body of oil to a discharge level more than six inches below the sur' face of said body of treated oil and more than six inches above the surface of said column, said passage having maximum lateral dimensions amounting to only a small fraction of the corresponding lateral dimensions of said liquid body and minimum lateral dimensions greater than about 3 inches, and said passage being open on its lower end so that liquid oil rises into the lower portion thereof to seek its level and thereby to wet the particles of adsorbent dropping through said passage; causing free fall of the particles through the upper portion of said passage not occupied by liquid by supplying adsorbent to said passage at a rate below that defined by the equation r si) where U is the rate
  • a liquid hydrocarbon. material is. treated by passing it upwardly through a column or downwardly moving adsorbent of palpable particle form in a confined treating zone and the treated liquid is withdrawn from the upper section of said zone
  • the method for supplying. adsorbent to said column and withdrawing treated liquid from said treating zone without substantial entrainment of the adsorbent particles which comprises, maintaining a body of treated liquid hydrocarbon material above said column: and entirely across its surface, maintaining a continuously supplied single. feed stream of adsorbent above said treating zone, splitting said feed. stream into a plurality of confined secondary streams. and discharging. said secondary streams into a plurality of horizontally spaced vertical passages uniformly distributed over the entire cross-section of.
  • each. of said passages being greater than 3 inches in minimum lateral dimension but all of said passages occupying only a small fraction of the horizontal cross-sectional area of said liquid. body, said passages opening on their lower ends to said liquid body so that the liquid seeks its level therein, controlling the rate of adsorbent supply from said single stream to said secondary streams so: that the adsorbent.
  • U is the rate of adsorbent supply to saidpassages .1 in cubic feet per hour per square foot of. passage crosssectional area
  • Z' is the. viscosity in centipoises of the treated liquid hydrocarbon under the conditions in said passages
  • D isthe. average particle diameter ininches of adsorbent
  • Sa the apparent density in grams per cubic centimeter of the dry adsorbent
  • ST is the true density in grams. per cubic centimeter of the dry adsorbent
  • Sn is the. density in grams per cubic centimeter of. the treated liquid under the conditions in said passage
  • F isthe fractionof.
  • passages occupying only a minor fraction of the horizontal cross-sectional area of said body of liquid but having 7 1 8 minimum lateraldimensions greater than about 3 inches and said passages being open ontheir lower ends so that the liquid oil rises into lower portions thereof to seek its level and to wet the particles of adsorbent falling through the passages; causing free fall of the particles through the upper portion of said passages not occupied by liquid by supplying adsorbent to said passages at a rate approximately equal to that defined by the equation where U is the rate of adsorbent supply to each passage in cubic feet per hour per square foot of passage cross section, Z is the viscosity in centipoises of the oil inthe treating zone and is below about 560 centipoises, D is the average adsorbent particle diameter in inches and is above about 0.01 inch, Sa and Sr are the apparent and true densities respectively in grams per cubic centimeter of the dry adsorbent, Sr.
  • Amethod for countercurrently contacting a liquid hydrocarbon feed which remains as a liquid during the contacting and a downwardly moving column of adsorbent which comprises, introducing an adsorbent of palpable particle form into a body of contacted liquid hydrocarbons maintained in the upper section of a confined" contacting zone as a confined stream discharging well. below the surface of said body of liquid and causing the adsorbent to fall freely as dispersed particles downwardly through a vertical section of said body onto a column of said adsorbent maintained below said body of contacted hydrocarbon liquid, passing the adsorbent downwardly within said column countercurrently to the liquid hydrocarbon material, withdrawing spent adsorbenf along with some liquid hydrocarbon feed from.
  • the lower section of said column as at least one confined stream, controlling the linear rate of flow in said confined stream sufficiently low to maintain the adsorbent as the continuous phase in said stream by regulating the flow in said stream at a level substantially below where it leaves said column, introducing liquid hydrocarbon feed into the lower section of said column and passing it upwardly therethrough while controlling the velocity of oil flow below a column disrupting. velocity, whereby countercurrent contacting of the hydrocarbon liquid and adsorbent is effected and withdrawing contacted liquid hydrocarbon from said body thereof at a level above that of the adsorbent discharge from said confined adsorbent feed stream.
  • a method for treating oils of low asphalt content to purify the same which comprises, introducing an adsorbent of palpable particulate form into the upper section of a confined treating zone in a plurality of horizontally spaced confined feed streams discharging substantially under the surface of a body of the treated oil maintained in the upper section of said zone, at a plurality of points uniformly distributed across the horizontal cross-sectional area of said treating zone, causing the adsorbent particles to fall freely through a vertical section of said body of oil onto a column of said adsorbent and passing the adsorbent in said column downwardly within said treating zone countercurrently to the liquid oil undergoing treatment, while controlling the velocity of oil flow suificiently low to maintain the solid material as the continuous phase in said column, withdrawing spent adsorbent along with some oil from the lower section of said column as at least one confined stream while maintaining the solid material as the continuous phase in said stream by controlling the flow below that at which the oil would exist as the continuous phase, said control being imposed on said stream
  • a method for countercurrently contacting a liquid hydrocarbon feed which remains as a liquid during the contacting and with a downwardly moving column of adsorbent which comprises, introducing an adsorbent of palpable particulate form into the upper section of a confined treating zone as at least one confined feed stream discharging into a body of contacted oil maintained in the upper section of said zone at a point well below the surface of said body and causing the adsorbent to fall freely as dispersed particles downwardly through a vertical section of said body onto a column of said adsorbent maintained below said body of contacted oil, passing the adsorbent in said column downwardly within said treating zone countercurrently to the liquid oil undergoing contacting, while controlling the velocity of oil flow below the column disrupting velocity, withdrawing spent adsorbent along with some liquid oil from the lower section of said column as at least one confined stream, while maintaining the velocity of flow in said stream sufficiently high to maintain the liquid as the continuous phase in said stream, introducing liquid oil feed into the lower
  • a method for countercurrently contacting a liquid hydrocarbon feed which is maintained as a liquid during the contacting and a downwardly moving column of adsorbent which comprises, maintaining a column of adsorbent of palpable particle-form throughout a substantial portion of the length of a confined contacting zone, maintaining a body of contacted liquid hydrocar-.
  • a method for treating oils of low asphalt content to decolorize the same which comprises, maintaining a column of adsorbent of palpable particle-form throughout a substantial portion of the length of a confined, treating zone, maintaining a body of treated oil above said column and across its entire surface, introducing liquid oil feed into the lower section of said column and passing it upwardly therethrough at a rate controlled below that which would interfere with uniform downward flow of adsorbent particles in said column, flowing the treated oil upwardly within said treating zone from the surface of said column as said body to effect settling of any entrained adsorbent particles, withdrawing the treated oil from the upper portion of said liquid body, withdrawing spent adsorbent along with some liquid oil downwardly from the lower section of said column as at least one confined stream of gravitating material so as to promote downward movement of the particles in said column, imposing a fixed restriction on said stream to limit the flow therein to a constant rate which is suitable for effecting the desired decolorization of said oil feed, passing fresh adsorbent downwardly from
  • the method for supplying adsorbent to said column and withdrawing treated liquid from said treating zone without substantial entrainment of the adsorbent particles which comprises, maintaining a body of treated liquid hydrocarbon material above said column and entirely across its surface, maintaining a continuously supplied confined column of adsorbent extending downwardly from. a location above said treating zone to a location within the: upper section thereof above. said liquid body,
  • a method for countercurrently contacting a liquid hydrocarbon feed which is maintained as a liquid during the contacting and a downwardly moving column of adsorbent which comprises, maintaining a column of adsorbent of palpable particle-form throughout a substantial portion of the length of a confined contacting zone, maintaining a body of contacted liquid hydrocarbon above said column and open to the column surface, introducing liquid hydrocarbon feed material into the lower section of said column and passing it upwardly therethrough at a rate controlled below that which would interfere with uniform downward flow of adsorbent particles in said column, flowing the contacted liquid hydrocarbon material upwardly within the contacting zone from the surface of said column as said liquid body to efiect settling of any entrained adsorbent particles, withdrawing the contacted liquid hydrocarbon material from the upper section of said liquid body, withdrawing wet contacted adsorbent from the lower section of said column through a confined passage as a confined, downwardly extending stream of gravitating adsorbent, supplying adsorb
  • the method for supplying adsorbent to replenish said column and for withdrawing contacted liquid from said zone without substantial entrainment of the adsorbent particles which comprises, passing the contacted liquid hydrocarbon material upwardly from the surface of said column and through a portion of the confined zone thereabove and withdrawing the liquid from said confined zone at a level spaced substantially above the column surface so that a liquid body of the contacted hydrocarbon material is maintained above the column, introducing feed adsorbent of palpable particle form into said liquid body as at least one confined stream of substantially smaller cross-section than said liquid body, which stream discharges into said body a substantial distance below its surface but above the column surface, whereby a settling space is provided in the liquid body 22 above the; level of adsorbent discharge thereint'o and causing the adsorbent particlesto fall freely through
  • An apparatus for effecting countercurrent contact of a liquid oil'with a downwardly moving column of adsorbent particles which comprises, an upright contacting vessel, a partition across the lower section of said vessel spaced above the bottom thereof so as to define a plenum chamber, a plurality of uniformly distributed, spaced nozzles in said partition for liquid flow from said plenum chamber to the. portion of the vessel thereabove, aplural-ity of uniformly distributed laterally spaced conduits of adsorbentwithdrawal extending through. said partition and downwardly through said plenum chamber andiIthe bottom of said vessel, means to introduce liquid oil.
  • a device at a locationalong the upper section of said vessel spaced a substantial distance 'above said partition to measure the surface.
  • column of adsorbent within theupper section of said vessel a plurality of laterally spaced uniformly distributed, vertical tubes positioned within the upper section of said vessel, said tubes terminating on their open upper ends short of the upper end of said vessel and on their open lower ends at a common level more than six inches above the level of said level measuring device, said tubes having lateral dimensions amounting to only a small fraction of the corresponding dimensions of said vessel so that only a small fraction of the horizontal cross-sectional area of said vessel is occupied by said tubes but the minimum lateral dimension in every direction at any location along each of said tubes being greater than about 3 inches, means to supply adsorbent to the upper ends of said tubes and an outlet for treated liquid oil arranged for withdrawal of oil from the space in said vessel between said tubes at a level below the upper ends of said tubes and more than 6 inches above the lower ends thereof.
  • An apparatus for effecting countercurrent contact of a liquid oil with a downwardly moving column of adsorbent particles which comprises, an upright contacting vessel, a member defining a plenum chamber within the lower section of said vessel, said plenum chamber communicating with the portion of the vessel thereabove only through a plurality of laterally spaced restricted passageways which are uniformly distributed across the horizontal cross-sectional area of said vessel, means to supply liquid oil to said plenum chamber, means to withdraw adsorbent from the lower section of said vessel, a device at a location along the upper section of said vessel to measure the surface level of the column of adsorbent within the upper section of said vessel, a plurality of laterally spaced uniformly distributed, vertical tubes positioned within the upper section of said vessel, said tubes terminating on their open upper ends short of-the upper end of said vessel and on their open lower ends at a common level more than six inches above the level of said level measuring device, said tubes having lateral dimensions amounting to only a small fraction of the corresponding dimensions of said
  • the improved means for supplying adsorbent to said vessel and withdrawing contacted liquid therefrom which comprises, at least one annular tube, open on its ends, positioned vertically within the upper section of said vessel and below its upper end, at least one adsorbent supply conduit extending downwardly from a supply location above said vessel to a location within the said vessel spaced above the upper end of said annular tube, said conduit having a plurality of apertures distributed around its sidewall near its lower end, a closure member across the lower end of said conduit, a sleeve mounted slidably on the lower section of said conduit and adapted to cover said apertures to any desired extent, means associated with said sleeve for ad- ,justing the same from outside of said vessel, an upwardly and having sides which slope upwardly and inwardly towards and at least as far as

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
US237268A 1951-07-17 1951-07-17 Method and apparatus for continuous percolation of liquid hydrocarbons Expired - Lifetime US2749290A (en)

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US237268A US2749290A (en) 1951-07-17 1951-07-17 Method and apparatus for continuous percolation of liquid hydrocarbons
GB14861/52A GB770391A (en) 1951-07-17 1952-06-12 Method and apparatus for treating liquid hydrocarbons with moving absorbents
GB16449/52A GB770392A (en) 1951-07-17 1952-06-30 Method and apparatus for continuous percolation of liquid hydrocarbons
FR1074553D FR1074553A (fr) 1951-07-17 1952-07-16 Procédé et appareil de percolation continue d'hydrocarbures liquides
DES29337A DE966390C (de) 1951-07-17 1952-07-17 Verfahren und Vorrichtung zur Behandlung fluessiger Kohlenwasserstoffe mit Adsorbiermitteln in gegenlaeufiger Bewegung

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US3867197A (en) * 1972-03-27 1975-02-18 Degussa Process for the releasing of materials from voluminous precipitates or suspensions
US3968038A (en) * 1974-07-10 1976-07-06 Uddeholms Aktiebolag Apparatus for treating liquids
CN112473182A (zh) * 2020-11-10 2021-03-12 湖南创源生物科技有限公司 一种便于清洗的糖液脱色罐

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CN109622192B (zh) * 2018-12-25 2020-12-29 宁波越茂活性炭有限公司 一种活性炭处理装置

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US2132151A (en) * 1935-03-13 1938-10-04 Pennsylvania Petroleum Res Cor Apparatus for treating mineral oils
US2412135A (en) * 1943-01-28 1946-12-03 Socony Vacuum Oil Co Inc Method and apparatus for hydrocarbon conversion
US2459056A (en) * 1945-12-31 1949-01-11 Sinclair Refining Co Gas-solid contacting apparatus
US2477281A (en) * 1947-03-10 1949-07-26 Soncony Vacuum Oil Company Inc Method for hydrocarbon conversion
US2490336A (en) * 1945-11-17 1949-12-06 Socony Vacuum Oil Co Inc Method for conversion of petroleum hydrocarbons
US2552436A (en) * 1947-12-06 1951-05-08 Standard Oil Dev Co Process for treating lubricating oil with solid adsorbents
US2552435A (en) * 1947-12-06 1951-05-08 Standard Oil Dev Co Lubricating oil treating process
US2564717A (en) * 1949-04-28 1951-08-21 Sun Oil Co Continuous adsorption process
US2618586A (en) * 1950-11-03 1952-11-18 Wigton Abbott Corp Process for desulfurizing petroleum products in the liquid phase

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US2132151A (en) * 1935-03-13 1938-10-04 Pennsylvania Petroleum Res Cor Apparatus for treating mineral oils
US2412135A (en) * 1943-01-28 1946-12-03 Socony Vacuum Oil Co Inc Method and apparatus for hydrocarbon conversion
US2490336A (en) * 1945-11-17 1949-12-06 Socony Vacuum Oil Co Inc Method for conversion of petroleum hydrocarbons
US2459056A (en) * 1945-12-31 1949-01-11 Sinclair Refining Co Gas-solid contacting apparatus
US2477281A (en) * 1947-03-10 1949-07-26 Soncony Vacuum Oil Company Inc Method for hydrocarbon conversion
US2552436A (en) * 1947-12-06 1951-05-08 Standard Oil Dev Co Process for treating lubricating oil with solid adsorbents
US2552435A (en) * 1947-12-06 1951-05-08 Standard Oil Dev Co Lubricating oil treating process
US2564717A (en) * 1949-04-28 1951-08-21 Sun Oil Co Continuous adsorption process
US2618586A (en) * 1950-11-03 1952-11-18 Wigton Abbott Corp Process for desulfurizing petroleum products in the liquid phase

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US3867197A (en) * 1972-03-27 1975-02-18 Degussa Process for the releasing of materials from voluminous precipitates or suspensions
US3968038A (en) * 1974-07-10 1976-07-06 Uddeholms Aktiebolag Apparatus for treating liquids
CN112473182A (zh) * 2020-11-10 2021-03-12 湖南创源生物科技有限公司 一种便于清洗的糖液脱色罐

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DE966390C (de) 1957-08-01
FR1074553A (fr) 1954-10-06
GB770392A (en) 1957-03-20

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