CN1115687A - Reactor and use thereof - Google Patents
Reactor and use thereof Download PDFInfo
- Publication number
- CN1115687A CN1115687A CN 95104244 CN95104244A CN1115687A CN 1115687 A CN1115687 A CN 1115687A CN 95104244 CN95104244 CN 95104244 CN 95104244 A CN95104244 A CN 95104244A CN 1115687 A CN1115687 A CN 1115687A
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- China
- Prior art keywords
- reactor
- bed
- support layer
- solid material
- hydrotreating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000011343 solid material Substances 0.000 claims abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 239000003921 oil Substances 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 10
- 239000012634 fragment Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims 2
- 239000002245 particle Substances 0.000 claims 1
- 238000005520 cutting process Methods 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 description 12
- 238000005187 foaming Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 230000008676 import Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 238000005553 drilling Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HHUIAYDQMNHELC-UHFFFAOYSA-N [O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O HHUIAYDQMNHELC-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00743—Feeding or discharging of solids
- B01J2208/00761—Discharging
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
一种反应器它包括一个正垂直延伸的容器，该容器包括(a)至少一个气体和/或液体进口，(b)至少一个反应器流出物的出口，和(c)至少一个固体物料床，其中每个固体物料床位于水平固定在该容器中的支承层上，所述支承层上有至少一个在正常操作期间被破碎板密封的孔口，因而可避免气体和液体旁通到后续床。反应器通过将结块后的催化剂切成小碎片并破裂破碎板而卸料。催化剂碎片经这样形成的孔口除去。该反应器特别适合用于烃油加氢处理中。
A reactor comprising a vertically extending vessel comprising (a) at least one gas and/or liquid inlet, (b) at least one reactor effluent outlet, and (c) at least one bed of solid material, wherein each bed of solid material rests on a support layer fixed horizontally in the vessel, said support layer having at least one orifice sealed by a breaker plate during normal operation, thereby avoiding gas and liquid bypass to subsequent beds. The reactor was discharged by cutting the agglomerated catalyst into small pieces and breaking the breaker plates. Catalyst debris is removed through the orifices thus formed. The reactor is particularly suitable for use in hydroprocessing of hydrocarbon oils.
Description
The present invention relates to reactor and uses thereof.More particularly, the present invention relates to reactor that (hydrogenation) that is particularly suitable for hydrocarbon ils handles and uses thereof.
Being used for the reactor that hydrocarbon oil hydrogenation handles has one or more horizontal direction fixed supporting courses usually, beds can the position thereon.When catalyst activity was no longer satisfactory, catalyzer need be replaced with the catalyzer after fresh or the regeneration.Because the hydrotreatment of hydrocarbon ils can form coke usually, it makes the granules of catalyst caking form a solid, removes used catalyst and quite requires great effort.There is variety of way to remove the catalyzer of agllutination at present.A kind of method is perforate on supporting course, removes after small shreds is cut into catalyzer in these holes.Reset fresh subsequently or the regenerated catalyst bed can carry out through identical hole.
At US-A-5, in 028,314, a kind of hydrodesulfurizationprocess process is disclosed, wherein use stationary catalyst bed in hydrogen, to carry out the desulfurization of the heavy-hydrocarbon oil of metallic pollution.These catalyst beds are placed on reaction vessel with two or more successive bed along row, and these are supported by the supporting course of basic horizontal in the reactor.These catalyzer can regularly pass through to bore a centre hole at catalyst bed upper edge reactor axis hydraulic pressure from reactor, and the catalyst bed of hydraulic pressure cutting caking becomes small shreds and removes these fragments through the hole of reactor bottom.Reinstall live catalyst subsequently.For removing the used catalyst small shreds, the supporting course of arrangement catalyst bed has the hole of a certain diameter, is preferably placed at the center.
US-A-5, the shortcoming of reactor described in 028,314 be during normal running inevitably liquids and gases enter downstream and bed from a bed bypass.Liquid is not wish from such bypass that a bed enters into another bed during operation, because this makes that the control of process is quite difficult, thereby the quality of the product of final acquisition is had detrimentally affect.In addition, the sedimentation of the hole contraposition catalyzer thereon on the supporting course will have detrimentally affect, thereby the homogeneity that granules of catalyst distributes on beds is had detrimentally affect, and particularly near the porose area, sedimentation is with inhomogeneous.
At EP-A-0, in 562,913, a reactor is disclosed, it comprises the solid materials bed of an import and outlet and between sequentially connect, like this each to bed of order by one also supporting position bed thereon supporting course separately.Each supporting course is equipped with two ends and is linked to tubular barrel on the bed.Each tubular barrel has can remotely-controlled closing device.This class teletype control comprises uses mechanical means as being linked to chain or the stay cord on the close plate of removable envelope in the tubular barrel, must spur described chain or stay cord for moving described plate; Thereby the perforate of realization tubular barrel.Sealing plate is positioned at certain distance below the inherent described tube of the tubular barrel top.This reactor it is said the hydrotreatment that is suitable for petroleum fractions, be particularly suitable in a reactor, using under the situation of different catalysts bed, can make (bed-by-bed) discharging of reactor " by bed " on the structure principle of disclosed reactor, thereby avoid the granules of catalyst of different beds when the reactor discharging to mix.
Be disclosed in EP-A-0,562, the shortcoming of the reactor in 913 is that certain distance causes that in other words, the position of described plate makes in the tubular barrel at sealing plate top and has granules of catalyst below the tubular barrel tops that are linked on two order beds because sealing plate is positioned at.If total caking that granules of catalyst takes place during the heavy-hydrocarbon oil hydrotreatment, clearly in tubular barrel this class caking will block described tube and general also will hinder sealing plate control.In addition, the sealing plate that uses mechanical means to be open in the tubular barrel also is undesirable from work angle, because the coke that forms during the heavy-hydrocarbon oil hydrotreatment will be adhered in the tubular barrel on the sealing equipment, even be not impossible open described sealing equipment like this, also be difficult to open it.
The present invention is intended to overcome the defective of above-mentioned prior art system.In addition, the purpose of this invention is to provide a reactor, it is at an easy rate with low cost operation and discharging and be suitable for during hydrocarbon oil hydrogenation handles.
Therefore the present invention relates to a reactor, it comprises a just vertically extending container, and this container comprises:
(a) import of at least one gas and/or liquid,
(b) outlet of at least one reactor effluent and
(c) at least one solid materials bed, wherein each solid materials berth is on horizontal direction is fixed on supporting course in this container, and described supporting course comprises the aperture of at least one plate sealing that is broken when normal running.
" normal running " is meant that raw material enters reactor from import, and the known partial hydrogenation that is fit to occur in the solid materials bed handle and/or the condition of conversion reaction under, thereby raw material contacted with solid materials it is carried out desirable processing and conversion, then, after the processing and/or transform after raw material leave reactor from outlet.
In an embodiment preferred, reactor contains the solid materials bed of at least two sequentially connects.
The advantage of this reactor is that during normal running not conforming to has gas and liquid to enter follow-up bed through the bypass of the aperture of supporting course, because seal fully in the aperture on supporting course during the normal running.On the other hand, if shut-down operation when catalyzer need replace, the catalyzer of caking is easy to remove with known method such as hydrojet or hydraulic pressure drilling, and the catalyzer of caking can be cut into small shreds, as above-mentioned US-A-5, described in 028,314.Subsequently by on these crushing shells, applying enough big pressure reduction, for example by the water spray that also is used for the caking catalyzer is cut into pieces or water drilling with the crushing shell pressure break.Therefore, on supporting course, form through hole, through these apertures catalyst debris is removed from reactor like this.
Another advantage of reactor of the present invention is its less expensive working method, thereby can avoid using the mechanical means that is used for controlling the sealing equipment in aperture on the supporting course.In addition, can not produce catalyst agglomeration in the aperture on supporting course, because crushing shell is positioned at the top in aperture and covers it fully yet.
Breaking of crushing shell can be finished with any method well known in the art in principle, wherein can impose enough big pressure reduction so that crushing shell breaks on crushing shell.Clearly, cause the pressure reduction during crushing shell disruptive pressure reduction must be higher than normal running,, cling to preferred 0.1 to 20 crust, most preferably 0.1 to 10 crust 0.1 to 50 for the hydrotreatment process at the pressure reduction of executing during the normal running on crushing shell.The absolute pressure that is used for the hydrotreatment process is usually at 5 to 300 crust, and preferred 50-200 clings to.
Can improve on the crushing shell pressure reduction in various manners to being enough to cause described plate disruptive value, for example, by executing mechanical force to crushing shell as push away or clash into this plate.Machinery drilling and water spray also are the technology that suits, and also can consider to use CO
2Booster or explosive.
Reaction vessel of the present invention has at least one, the solid materials bed that preferred at least two orders link to each other, and each berth is on supporting course.(structure that is also referred to as " internals " usually is well known in the art to suitable supporting course.For example Chang Yong supporting course or internals comprise the infiltration plate of one or more supported beam supports, and catalyzer is positioned on the described infiltration plate.Gaseous state that reaction forms in beds or liquid product enter subsequent catalyst bed or reactor outlet through the infiltration plate.Internals can comprise auxiliary facility such as nozzle, cooling or heating installation and gas turbulator.Air pressure that forms and/or liquid product can be removed and be incorporated into the postorder beds on reactor top or reclaim as product from a beds.
Say that in principle the bed number that order links to each other not is that bed number crucial, maximum is determined by practicality and economy to using the present invention.
The tube that aperture extend perpendicular on supporting course is crossed supporting course forms.Described tube can be any geometrical shape, the suitably sealing of plate as long as they can be broken.Its example comprises cylindrical, rectangle or conically shaped.
The aperture number is crucial especially on supporting course, can be 1 to 40 according to the diameter in reactor inside diameter and each aperture.Preferably, the aperture number is 1 to 10, more preferably 1 to 6.The diameter in each aperture should be enough to allow and passes through with the hydrojet cutting or with the catalyst debris that formation is cut in common drilling.Suitable diameter can from little to 5cm to greatly to 11m.From the size and the weight of used crushing shell, preferably use the aperture of diameter from 15 to 75cm.
The position of aperture on supporting course is not crucial especially.But the position in preferred aperture should be as far as possible through the Reactor inlet crushing shell that breaks, as by using hydrojet or hydraulic pressure to bore.Therefore, when two or more beds was particularly arranged, preferably at least one Reactor inlet was positioned on the same vertical axis with aperture on the supporting course that links to each other in order.Be that this helps discharging from reactor, particularly use hydrojet or hydraulic pressure to bore.Reactor outlet also preferably with supporting course that Reactor inlet and order link to each other on the aperture be positioned on the same vertical axis, but this is unimportant, clearly, reactor can have the equipment of the crushing shell so that use is broken more than an import and/or outlet.Therefore, if reactor has more than an import, preferably the aperture number on each supporting course equals the Reactor inlet number but the present invention is not limited to such structure.
Crushing shell must be made with the material of normal operating condition in the ability hydrocarbon oil hydrogenation process, so that it is not broken during normal running.Therefore, suitable material comprises stupalith, as silicon-dioxide, aluminum oxide or silicon-dioxide-aluminum oxide because these materials relatively more cheap, be easy to get, have desired properties simultaneously.Other suitable material comprises metal particularly copper and metal alloy, flint clay, cement class material or brick class material.In stupalith, the aluminum oxide after the foaming is most preferred.Aluminum oxide after the foaming is to make by rousing in the aluminum oxide after rare gas element such as air or nitrogen extremely heat.
In another embodiment preferred of the present invention, above-mentioned reactor is a trickle reactor.For reactor of the present invention, this means the equipment that distributing gas and/or liquid are arranged on the bed of top.This kind equipment is being known in the art.Have the equipment of this class distributing gas and/or liquid to suit at least one upper support layer, being preferably on all follow-up supporting courses also has this kind equipment.
The solid materials principle that forms the solid materials bed can be to occurring in reaction in the reactor any material of catalytic activity to be arranged.Because reactor of the present invention is particularly suitable for the hydrotreatment of (residual) hydrocarbon ils, solid materials is preferably formed by the granules of catalyst that is used for hydrogenation treatment of hydrocarbon oil.
Fig. 1 illustrates the embodiment of a reactor of the present invention.The left side of figure illustrates the reactor after empty or the discharging, and right-hand part shows the reactor that is suitable for operating after the charging.Reactor (1) comprises Reactor inlet (2), reactor outlet (9) and be bearing in the pipe (4) of layer on (3), and this layer (3) is useful on the equipment of liquid distribution on the subsequent catalyst bed that will enter.Pipe (4) can be used to add fresh catalyzer.Reactor (1) further includes the supporting course (7) of aperture (5), aperture (5) be broken during operation plate (6) sealing.Beds (8) is positioned on the supporting course (7) during operation, and these supporting courses also are useful on the equipment of distributing gas and/or liquid.
The present invention also relates to use above-mentioned reactor, comprise
(a) during normal running, be broken plate sealing of all apertures on supporting course,
(b) in normal running with remove between the solid, the catalyzer behind the caking is cut or fragment and pressure reduction are executed on each crushing shell subsequently, be enough to make they break and
(c) fragment of solid materials is removed from reactor through the aperture of the formation in step (b).
As mentioned above, drilling or hydrojet are well suited for the crushing shell that breaks.But with hydrojet crushing shell being executed a pressure reduction through Reactor inlet, it is broken is most preferred selection.Be described in US-A-5, the method in 028,314 is of great use in this respect.
Reactor of the present invention is preferred for the particularly residual hydrocarbon ils of hydrotreatment of hydrocarbon ils, and reactor of the present invention is suitable for the hydrogenating desulfurization of this class oil most, hydrodemetallation (HDM) or hydrocracking.
After reactor is unstowed, be easy to the live catalyst of resetting through Reactor inlet.By through import dress live catalyst, begin to be fills up to the top bed from minimum bed and finish by bed.At every turn, after a bed was full of, new crushing shell first-selection was placed on the supporting course aperture, and the solid particulate bed will be positioned on the supporting course, fill this bed with live catalyst subsequently.In case this bed is filled, cover the aperture of next supporting course with crushing shell, fill this bed then, continue this program and be filled until all beds.
The following example is used for illustrating the aluminum oxide effect after the foaming that is used for preparing crushing shell.
Enforcement is executed
Apply pressure on the foaming rear oxidation aluminium block by hydrojet, hole thereon by the hydraulic pressure that on the aluminum oxide after the foaming, applies 600 crust.Foaming rear oxidation aluminium block breaks when hydraulic pressure reaches 800 crust.
The purpose of present embodiment is the influence of explanation reactor operating condition to the crushing shell mechanical property of materials.
Be of a size of 13 * 13 * 113mm (wide * height * length) with one, quality is that 25g and density are 1.4g/cm
3Foaming after alumina rod place one week of mini-reactor, reactor operating condition be 150 the crust hydrogen pressures, H is arranged in the charging
2S." dirty " lath is removed from reactor subsequently.
Measure the Young's modulus and the breaking tenacity of dirty lath and cleaning lath.The results are given in the table 1.
Can find out that from table 1 reactor operating condition does not make the mechanical property variation of the aluminum oxide after the foaming.
Can find out that from executing 1 and 2 the aluminum oxide after the foaming is to be used for the present invention's reaction
The influence of table 1 reactor operating condition
| Young's modulus (N) | Rupture strength (MPa) | |
| Dirty lath | ????64 | ????5.2 |
| The cleaning lath | ????56 | ????4.5 |
Claims (15)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP94201201.4 | 1994-04-29 | ||
| EP94201201 | 1994-04-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1115687A true CN1115687A (en) | 1996-01-31 |
Family
ID=8216834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95104244 Pending CN1115687A (en) | 1994-04-29 | 1995-04-26 | Reactor and use thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3774249B2 (en) |
| CN (1) | CN1115687A (en) |
| CA (1) | CA2148069C (en) |
| DE (1) | DE69503173T2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443411A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Process method for prolonging operation period of hydrogenation device |
| CN102443410A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for prolonging operation period of hydrogenation device |
-
1995
- 1995-04-26 CN CN 95104244 patent/CN1115687A/en active Pending
- 1995-04-27 JP JP12564095A patent/JP3774249B2/en not_active Expired - Fee Related
- 1995-04-27 DE DE1995603173 patent/DE69503173T2/en not_active Expired - Fee Related
- 1995-04-27 CA CA 2148069 patent/CA2148069C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443411A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Process method for prolonging operation period of hydrogenation device |
| CN102443410A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for prolonging operation period of hydrogenation device |
| CN102443411B (en) * | 2010-10-13 | 2013-12-04 | 中国石油化工股份有限公司 | Process method for prolonging operation period of hydrogenation device |
| CN102443410B (en) * | 2010-10-13 | 2013-12-04 | 中国石油化工股份有限公司 | Method for prolonging operation period of hydrogenation device |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2148069C (en) | 2004-08-31 |
| CA2148069A1 (en) | 1995-10-30 |
| JP3774249B2 (en) | 2006-05-10 |
| JPH08323186A (en) | 1996-12-10 |
| DE69503173T2 (en) | 1998-12-03 |
| DE69503173D1 (en) | 1998-08-06 |
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