CN1990834B - Residual oil hydroprocessing method - Google Patents
Residual oil hydroprocessing method Download PDFInfo
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- CN1990834B CN1990834B CN2005101355613A CN200510135561A CN1990834B CN 1990834 B CN1990834 B CN 1990834B CN 2005101355613 A CN2005101355613 A CN 2005101355613A CN 200510135561 A CN200510135561 A CN 200510135561A CN 1990834 B CN1990834 B CN 1990834B
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Abstract
The invention relates to a method for petroleum residue hydrogenation. It comprises mixing raw oil and hydrogen gas, feeding them into hydrogenation protection reactor, carrying out hydrogenation and foreign matter removal reaction through catalyst bed from down to up, the outlet flowout in hydrogenation protection reactor is fed directly into fixed bed refining reactor without separation for hydrogenation and refiness. The hydrogenation protection reactor is packed with two or more than two kinds of catalyst section by section, the catalysts possess the same carrier, and the active metal loading amount on lower part is lower than that on the upper part. The method can process petroleum residue containing high concentration of metal, and is characterized by high metal removal rate, proper temperature, controllable process and long operation period.
Description
Technical field
The invention belongs to a kind ofly in the method that has under the situation of hydrogen refining hydrocarbon ils, more particularly, is a kind of hydroprocessing process of residual oil.
Background technology
That world's crude oil becomes just gradually is heavy, become bad, but the demand of heavy fuel oil (HFO) progressively reduces, and the lightweight oil demand is increasing, therefore the residual oil lighting is seemed more and more important.Along with the increasingly stringent of environmental regulation, oil refining enterprise production is cleaned oil product and accomplished that the requirement of cleaner production is more and more higher in addition, also more and more stricter.Residual hydrogenation equipment makes it become the important technology of refinery's cleaning processing high-sulfur, high-metal residual oil because have plurality of advantages such as liquid product yield height, environmental friendliness.Can be used as the catalytic cracking unit raw material through the hydrogenated residue that removes impurity such as sulphur, metal, nitrogen after the residual hydrocracking, not only can produce low-sulfur, the low high-quality light-end products of nitrogen, and reduce the pollution of production process greatly environment.
Residue Hydrotreating Technology mainly contains four types in the world at present, i.e. fixed bed, ebullated bed, moving-bed and suspension bed.Wherein fixed-bed process is because of the desulfuration efficiency height, and processing safety is good than other hydrogenation technique, technology maturation, thereby be a kind of technology most widely used in the residual hydrogenation.But for the fixed bed Residue Hydrotreating Technology, because of the metallic impurity in the residual oil raw material (as vanadium, nickel, calcium, iron etc.), unsaturated component and dirty thing be easy to be deposited in the surface and the space between the granules of catalyst of catalyzer, the blocking catalyst aperture causes catalyst deactivation, and cause bed layer pressure to fall quick rising, make device frequent shutdowns and catalyst changeout more.Therefore need solve this type of problem effectively.
WO0061706 discloses a kind of upflowing reactive system of hydrotreating heavy feedstocks.Stock oil and hydrogen enter reactor from the bottom, sequence of flow is by the beds in the reactor from bottom to top, obtain the generation oil that metal, sulphur and carbon residue have reduced.This up-flow reactor comprises plural at least beds, and bed is a vertical mode.Distributing disc is arranged at reactor bottom and bed bottom, plays quenching oil between the bed.At least comprise two kinds of catalyzer in up-flow reactor, wherein the hydrogenation activity of the catalyzer of bottom bed is lower than top.The catalyzer that is adopted in this patent requires to be of a size of the spherical catalyst of narrow distribution, and wherein its diameter of the hole of lower catalytic agent at least 20% is about 130～170 dusts, and its diameter of the hole of top catalyzer at least 30% is about 95～135 dusts.Detailed description about catalyzer is seen US5,071,805, US5,215,955 and US5,472,928.But these catalyzer mainly are the catalyzer that is adapted to the online metathetical moving-bed of catalyzer system, though so these catalyzer intensity height, catalyst life is low, the anti-coking poor performance.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of hydroprocessing process of residual oil.
Method provided by the invention is: stock oil and hydrogen enter the hydrogenation protecting reactor after mixing; carry out hydrogenation by beds from bottom to up and take off the impurity reaction; the logistics of hydrogenation protecting reactor outlet directly enters fixed bed refining reaction device without separating, and carries out hydrofining reaction.Segmentation is filled with two or more catalyzer in the hydrogenation protecting reactor, and catalyzer has identical carrier, and the activity of such catalysts content of metal of bottom filling is lower than the activity of such catalysts content of metal of adjacent upper.
Method provided by the invention can be processed the residual oil of high metal content; by in the hydrogenation protecting reactor, using preferred grading method of catalyst; not only the demetallization per height, temperature rise is suitable, easy to control but also the operational cycle is long, can realize the requirement to fixed bed high-activity hydrofining catalyst better protection.
Embodiment
Stock oil of the present invention is one or more mixing oils and the formed mixture of heavy distillate arbitrarily in long residuum, vacuum residuum, the topped crude, and the viscosity of its mixture (100 ℃) is not more than 400 square millimeters/second.But the heavy oil that the present invention's processing metal content is high, for example metallic nickel and vanadium are greater than the heavy oil feedstock of 100ppm.
Method provided by the invention comprises:
Stock oil and hydrogen enter the hydrogenation protecting reactor after mixing, from bottom to up by beds, and at hydrogen dividing potential drop 10.0～20.0Mpa, preferred 11.0～16.0Mpa, 340～440 ℃ of average reaction temperature, preferred 360～420 ℃, hydrogen to oil volume ratio 200～1200Nm
3/ m
3, preferred 200～600Nm
3/ m
3, volume space velocity is 0.1～3.0h during liquid
-1, preferred 0.25～0.8h
-1Reaction conditions under, carry out hydrodemetallation (HDM), hydrodesulfurization reaction, the logistics of hydrogenation protecting reactor outlet directly enters fixed bed hydrogenation refining reaction device without separating, and carries out hydrofining reaction.The major function of hydrogenation protecting reactor is a part of metal and the easy coking material that removes in the stock oil, reduces the foreign matter content in the fixed-bed reactor charging of downstream.Highly active Hydrobon catalyst can be protected on the one hand, the whole needs of stock oil demetalization, desulfurization can be satisfied on the other hand.In the hydrogenation protecting reactor; because feed stream is mobile from bottom to top, so catalyzer can omit microdilatancy in the bed, can avoid because of coking and metal particularly the bed that causes of the deposition of metal such as iron, calcium stop up; reduce bed layer pressure and fall, help prolonging running period.According to raw materials used kind, different in kind, and the requirement of the character of purpose product is different, can adjust flexibly the reaction conditions of hydrogenation protecting reactor, to satisfy the requirement of fixed bed refining reaction device charging.
Segmentation is filled with two or more catalyzer in the hydrogenation protecting reactor of the present invention, and different types of catalyzer is the catalyzer of the resulting different hydrogenation activities of active metal component of load different content on the identical carrier.Two kinds of adjacent catalyzer are compared arbitrarily, and the activity of such catalysts content of metal of bottom filling is lower than the activity of such catalysts content of metal of top filling.Because hydrogenation protecting reactor main task is demetalization, therefore use grading method of the present invention, can give full play to the metal removal activity of catalyzer and hold the metal ability, improved the metal removal rate of integer catalyzer, prolonged catalyst operation.In addition, because that catalyzer of the present invention has is suitable desulphurizing activated, after having adopted suitable grading method, make the temperature rise of hydrogenation protecting reactor be easier to control.
Catalyzer of the present invention contains a kind of alumina supporter and the molybdenum and/or the tungsten that load on this carrier with double-hole, and cobalt and/or nickel, the carrier of catalyzer has following pore distribution: bore dia is the 45-70% that the pore volume of 10-20 nanometer accounts for total pore volume, bore dia is the 20-40% that the pore volume of 500-1200 nanometer accounts for total pore volume, and bore dia is less than 10 nanometers, between the 20-500 nanometer and the 10-30% that accounts for total pore volume greater than the pore volume sum of 1200 nanometers.The carrier of described catalyzer contains halogen, is benchmark with the carrier total amount, and the content of aluminum oxide is 95-99.9 weight %, and in element, the content of halogen is 0.1-5 weight %, and its acid amount is less than 0.2 mmole/gram.For hydrogenation protecting reactor of the present invention, because catalyzer can not onlinely be replaced, must keep high reactivity in whole running period, therefore very high to the life of catalyst requirement, catalyzer must have good anti-coking performance.Because carrier acid amount is low in the catalyzer provided by the invention, make it keep the higher active while of hydrodemetallation (HDM), carbon deposition quantity is low, so catalyzer anti-coking performance is strong, long service life.
Preparation of catalysts method provided by the invention is as follows: a kind of hydrated aluminum oxide is mixed with an amount of extrusion aid of fluorine-containing expanding agent, water carry out moulding after mixing; In 650-800 ℃, roasting time 2-8 hour; With the aqueous solution dipping of the reactive metal that contains different amounts, drying and roasting are promptly at last.The shape of this catalyzer is sphere or elliposoidal.
Segmentation is filled with two kinds of catalyzer in the described hydrogenation protecting reactor, and the activity of such catalysts content of metal of bottom filling is: molybdenum and/or tungsten 0.5～7 weight %, cobalt and/or nickel 0.3～2 weight %; The activity of such catalysts content of metal of top filling is: molybdenum and/or tungsten 5～15 weight %, cobalt and/or nickel 1～8 weight %.The admission space scope of the catalyzer of bottom: 20～99%; The admission space scope of the catalyzer on top: 1～80%.
Segmentation is filled with three kinds of catalyzer in the described hydrogenation protecting reactor, and the activity of such catalysts content of metal of bottom filling is: molybdenum and/or tungsten 0.5～7 weight %, cobalt and/or nickel 0.3～1.8 weight %; The activity of such catalysts content of metal of middle part filling is: molybdenum and/or tungsten 4.5～10 weight %, cobalt and/or nickel 1.3～2.5 weight %; The activity of such catalysts content of metal of top filling is: molybdenum and/or tungsten 7～15 weight %, cobalt and/or nickel 1.8～8 weight %.The admission space scope of the catalyzer of bottom: 20～60%; The admission space scope of the catalyzer at middle part: 10～60%; The admission space scope of the catalyzer on top: 10～60%.Different types of catalyzer in the hydrogenation protecting reactor can be packed in single beds or a plurality of beds in segmentation, and each bed temperature can adopt and inject cold oil or the control of cold hydrogen between bed, preferably injects cold oil.
If unsaturates, solid particle polluter, bituminous matter or metallic iron in the stock oil, calcium, sodium content are higher; for falling, the pressure that prevents beds reaches limit value too quickly; can be below SA catalyzer (being the front by the logistics direction) adds that a certain amount of activity is lower herein, particle and bed porosity are bigger protective material with the running of assurance device long period ground; protectant add-on is generally 1～20% of whole hydrogenation protecting reactor catalyst volume, and concrete data can be decided according to feedstock property.
Advantage of the present invention:
1, because the present invention has adopted the grading method of catalyst of optimizing, and can adjust accordingly, can give full play to the metal removal activity of catalyzer and hold the metal ability according to the character of different material, so metal removal rate height of the present invention, catalyzer long service life.
2, because the present invention is desulphurizing activated moderate, adopt the appropriate catalyst grading method again, made the temperature rise of hydrogenation protecting reactor be easy to control, so smooth operation, the production cycle is long.
3, because the present invention is by using the reactive metal with a kind of support of the catalyst load different content, prepare different hydrogenation activity catalyzer, therefore simplified Catalyst Production technology, reduced the Catalyst Production cost.
Following example will give further instruction to the present invention, but not thereby limiting the invention.Employed hydrogenation catalyst is to make with following method among the embodiment:
Take by weighing pseudo-boehmite powder 300 grams that the Chang Ling catalyst plant is produced, adding 12 gram polyvinyl alcohol, 140 gram ammonium citrates mix, the aqueous solution that adds 300 milliliters of hydrofluoric acid containing, 8 grams, mix under the room temperature and pinched 10 minutes, be extruded into the cylindrical bar of 2.5 millimeters of φ on banded extruder, rolling is the spheroidal particle of 2.5 millimeters of φ in spheronizator then, and spheroidal particle was 120 ℃ of dryings 2 hours, in 750 ℃ of roastings 2 hours, get carrier afterwards; The acid content of carrier, fluorine content, specific surface, pore distribution and pore volume are listed in the table 1.The result who is provided by table 1 can show, the alumina supporter with double-hole provided by the invention have a very low acid content.
Get above-mentioned carrier 200 grams, contain molybdenum oxide 40 grams per liters with 500 milliliters, the ammonium molybdate of nickel oxide 8 grams per liters and nickelous nitrate mixing solutions dipping 1 hour filter the back and dried 2 hours in 120 ℃, and 500 ℃ of roastings 4 hours obtain catalyzer U1.Active metal component content is as shown in table 2 among the catalyzer U1.
Get above-mentioned carrier 200 grams, contain molybdenum oxide 60 grams per liters with 500 milliliters, the ammonium molybdate of nickel oxide 12 grams per liters and nickelous nitrate mixing solutions dipping 1 hour filter the back and dried 2 hours in 120 ℃, and 500 ℃ of roastings 4 hours obtain catalyzer U2.Active metal component content is as shown in table 2 among the catalyzer U2.
Get above-mentioned carrier 200 grams, contain molybdenum oxide 80 grams per liters with 500 milliliters, the ammonium molybdate of nickel oxide 16 grams per liters and nickelous nitrate mixing solutions dipping 1 hour filter the back and dried 2 hours in 120 ℃, and 500 ℃ of roastings 4 hours obtain catalyzer U3.Active metal component content is as shown in table 2 among the catalyzer U3.
Used raw material A is the mixture of vacuum residuum and vacuum gas oil among the embodiment, and raw material B is a long residuum, and the two character is as shown in table 3.This two kinds of feed sulphur content height as seen from Table 3, wherein raw material B metal content is also higher.
In following examples, impurity removal percentage is defined as:
Embodiment 1
Stock oil A with enter the hydrogenation protecting reactor after hydrogen mixes, from bottom to up successively by catalyzer U1 and catalyzer U3, carry out hydrogenation and take off the impurity reaction, the logistics of hydrogenation protecting reactor outlet is that metal content is low, the hydrogenated oil that carbon residue content is low.The filling ratio of catalyzer U1 is 25% of a total catalyst volume, and the filling ratio of catalyzer U3 is 75% of a total catalyst volume.The reaction conditions of hydrogenation protecting reactor and hydrogenated oil character are as shown in table 4, and the hydrogenated oil impurity removal percentage is as shown in table 5, up to 75.4%, good metal removal effect are arranged by the visible demetallization per of table 5.
Embodiment 2
Stock oil B with enter the hydrogenation protecting reactor after hydrogen mixes, from bottom to up successively by catalyzer U1 and catalyzer U3, carry out hydrogenation and take off the impurity reaction, the logistics of hydrogenation protecting reactor outlet is that metal content is low, the hydrogenated oil that carbon residue content is low.The filling ratio of catalyzer U1 is 33% of a total catalyst volume, and the filling ratio of catalyzer U3 is 67% of a total catalyst volume.The reaction conditions of hydrogenation protecting reactor and hydrogenated oil character are as shown in table 4, and the hydrogenated oil impurity removal percentage is as shown in table 5, up to 75.9%, good metal removal effect are arranged by the visible demetallization per of table 5.
Embodiment 3
Stock oil B with enter the hydrogenation protecting reactor after hydrogen mixes; from bottom to up successively by catalyzer U1, catalyzer U2 and catalyzer U3; carry out hydrogenation and take off the impurity reaction, the logistics of hydrogenation protecting reactor outlet is that metal content is low, the hydrogenated oil that carbon residue content is low.The filling ratio of catalyzer U1 is 33.3% of a total catalyst volume, and the filling ratio of catalyzer U2 is 33.3% of a total catalyst volume, and the filling ratio of catalyzer U3 is 33.3% of a total catalyst volume.The reaction conditions of hydrogenation protecting reactor and hydrogenated oil character are as shown in table 4, and the hydrogenated oil impurity removal percentage is as shown in table 5, by table 5 visible under higher air speed demetallization per still up to 73.8% good metal removal effect is arranged.
Table 1
Table 2
| The catalyzer numbering | U1 | U2 | U3 |
| Active metallic content, weight % | |||
| Molybdenum | 3.9 | 5.9 | 7.8 |
| Nickel | 0.75 | 1.13 | 1.5 |
Table 3
| Raw material | A | B |
| Density (20 ℃), g/cm 3 | 0.9930 | 0.9625 |
| Viscosity (100 ℃), mm 2/s | 186.1 | 37.06 |
| Carbon residue, weight % | 15.7 | 10.6 |
| Constituent content, weight % | ||
| Sulphur | 3.9 | 3.1 |
| Nitrogen | 0.30 | 0.43 |
| Carbon | 85.70 | 84.88 |
| Hydrogen | 10.66 | 11.16 |
| Metal content, μ g/g | ||
| Nickel | 18.9 | 50.5 |
| Vanadium | 58.6 | 151 |
| Iron | 9.9 | 10.6 |
| Calcium | 4.3 | 14.8 |
| Sodium | 3.9 | 10.5 |
Table 4
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| The catalyst loading ratio | U1:U3＝1:3 | U1:U3＝1:2 | U1:U2:U3＝1：1：1 |
| Stock oil | A | B | B |
| Reaction conditions |
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| The hydrogen dividing potential drop, MPa | 15.0 | 14.0 | 14.5 |
| Average reaction temperature, ℃ | 380 | 380 | 390 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 300 | 300 | 300 |
| Volume space velocity during liquid, h -1 | 0.50 | 0.50 | 0.70 |
| Hydrogenated oil character | |||
| Carbon residue, weight % | 9.69 | 6.37 | 6.70 |
| Sulphur, weight % | 1.7 | 1.2 | 1.3 |
| Nitrogen, weight % | 0.24 | 0.33 | 0.35 |
| Metal content, μ g/g | |||
| Nickel | 7.8 | 17.1 | 18.5 |
| Vanadium | 11.3 | 31.5 | 34.2 |
| Iron | 3.7 | 7.8 | 8.0 |
| Calcium | 1.9 | 5.6 | 5.9 |
| Sodium | 2.0 | 3.4 | 3.2 |
Table 5
| Stock oil | Demetallization per, % | The nickel removal rate, % | Vanadium removal rate, % | Desulfurization degree, % | Take off carbon yield, % |
| Embodiment 1 | 75.4 | 58.7 | 80.7 | 56.4 | 38.3 |
| Embodiment 2 | 75.9 | 66.1 | 79.1 | 61.3 | 39.9 |
| Embodiment 3 | 73.8 | 63.4 | 77.4 | 58.1 | 36.8 |
Claims (9)
1. the hydroprocessing process of a residual oil; stock oil and hydrogen enter the hydrogenation protecting reactor after mixing; carry out hydrogenation by beds from bottom to up and take off the impurity reaction; the logistics of hydrogenation protecting reactor outlet directly enters fixed bed refining reaction device without separating; carry out hydrofining reaction; it is characterized in that segmentation is filled with two or more catalyzer in the hydrogenation protecting reactor; catalyzer has identical carrier; the activity of such catalysts content of metal of bottom filling is lower than adjacent top activity of such catalysts content of metal; described hydrogenation protecting reactor reaction condition is: hydrogen dividing potential drop 10.0～20.0MPa; 340～440 ℃ of average reaction temperature, hydrogen to oil volume ratio 200～1200Nm
3/ m
3; Volume space velocity is 0.1～3.0h during liquid
-1
2. method according to claim 1, it is characterized in that catalyzer contains a kind of alumina supporter and the molybdenum and/or the tungsten that load on this carrier with double-hole, and cobalt and/or nickel, the carrier of catalyzer has following pore distribution: bore dia is the 45-70% that the pore volume of 10-20 nanometer accounts for total pore volume, bore dia is the 20-40% that the pore volume of 500-1200 nanometer accounts for total pore volume, and bore dia is less than 10 nanometers, between the 20-500 nanometer and the 10-30% that accounts for total pore volume greater than the pore volume sum of 1200 nanometers.
3. method according to claim 1 is characterized in that the carrier of described catalyzer contains halogen, is benchmark with the carrier total amount, the content of aluminum oxide is 95-99.9 weight %, in element, the content of halogen is 0.1-5 weight %, and its acid amount is less than 0.2 mmole/gram.
4. method according to claim 1 is characterized in that being filled with in the described hydrogenation protecting reactor two kinds of catalyzer, and the activity of such catalysts content of metal of bottom filling is: molybdenum and/or tungsten 0.5～7 weight %, cobalt and/or nickel 0.3～2 weight %; The activity of such catalysts content of metal of top filling is: molybdenum and/or tungsten 5～15 weight %, cobalt and/or nickel 1～8 weight %.
5. according to claim 1 or 4 described methods, it is characterized in that being filled with in the described hydrogenation protecting reactor two kinds of catalyzer, the admission space scope of the catalyzer of bottom: 20～99%; The admission space scope of the catalyzer on top: 1～80%.
6. method according to claim 1 is characterized in that being filled with in the described hydrogenation protecting reactor three kinds of catalyzer, and the activity of such catalysts content of metal of bottom filling is: molybdenum and/or tungsten 0.5～7 weight %, cobalt and/or nickel 0.3～1.8 weight %; The activity of such catalysts content of metal of middle part filling is: molybdenum and/or tungsten 4.5～10 weight %, cobalt and/or nickel 1.3～2.5 weight %; The activity of such catalysts content of metal of top filling is: molybdenum and/or tungsten 7～15 weight %, cobalt and/or nickel 1.8～8 weight %.
7. according to claim 1 or 6 described methods, it is characterized in that being filled with in the described hydrogenation protecting reactor three kinds of catalyzer, the admission space scope of the catalyzer of bottom: 20～60%; The admission space scope of the catalyzer at middle part: 10～60%; The admission space scope of the catalyzer on top: 10～60%.
8. method according to claim 1, described stock oil are one or more mixing oils and the formed mixtures of heavy distillate arbitrarily in long residuum, vacuum residuum, the topped crude.
9. method according to claim 1, described hydrogenation protecting reactor reaction condition is: hydrogen dividing potential drop 11.0～16.0MPa, 360～420 ℃ of average reaction temperature, hydrogen to oil volume ratio 200～600Nm
3/ m
3; Volume space velocity is 0.25～0.8h during liquid
-1
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| CN102453530B (en) * | 2010-10-26 | 2015-05-20 | 中国石油化工股份有限公司 | Hydrogenation method for processing heavy oil |
| CN102453529A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Method for processing heavy material by using up-flow reactor system |
| CN102465034B (en) * | 2010-11-04 | 2014-08-20 | 中国石油化工股份有限公司 | Processing method of inferior residuum |
| US8894838B2 (en) | 2011-04-29 | 2014-11-25 | E I Du Pont De Nemours And Company | Hydroprocessing process using uneven catalyst volume distribution among catalyst beds in liquid-full reactors |
| CN102899081B (en) * | 2011-07-28 | 2015-03-18 | 中国石油化工股份有限公司 | Wax oil hydrotreating method |
| CN103059936B (en) * | 2011-10-20 | 2014-10-29 | 中国石油化工股份有限公司 | Hydrotreating method of heavy oil |
| CN103059928B (en) * | 2011-10-24 | 2014-12-31 | 中国石油化工股份有限公司 | Hydrotreating device and application thereof as well as residual oil hydrotreating method |
| CN103131469B (en) * | 2011-11-25 | 2015-05-13 | 中国石油天然气股份有限公司 | Fixed bed residue oil hydrotreating method |
| CN103374392B (en) * | 2012-04-13 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of hydrogenation modification method of catalytically cracked stock |
| CN103374389B (en) * | 2012-04-13 | 2015-07-29 | 中国石油化工股份有限公司 | The hydroprocessing process of a kind of iron and the high mink cell focus of calcium contents |
| CN103374388B (en) * | 2012-04-13 | 2015-07-29 | 中国石油化工股份有限公司 | The hydroprocessing process of a kind of iron and the high mink cell focus of calcium contents |
| CN104927913B (en) * | 2014-03-21 | 2017-01-18 | 中国石油化工股份有限公司 | Inferior hydrocarbon oil material hydrotreating method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5472928A (en) * | 1989-07-19 | 1995-12-05 | Scheuerman; Georgieanna L. | Catalyst, method and apparatus for an on-stream particle replacement system for countercurrent contact of a gas and liquid feed stream with a packed bed |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5472928A (en) * | 1989-07-19 | 1995-12-05 | Scheuerman; Georgieanna L. | Catalyst, method and apparatus for an on-stream particle replacement system for countercurrent contact of a gas and liquid feed stream with a packed bed |
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