CN102441349B - Hydrogenation technological method for reducing skimming of catalyst - Google Patents
Hydrogenation technological method for reducing skimming of catalyst Download PDFInfo
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- CN102441349B CN102441349B CN2010105090449A CN201010509044A CN102441349B CN 102441349 B CN102441349 B CN 102441349B CN 2010105090449 A CN2010105090449 A CN 2010105090449A CN 201010509044 A CN201010509044 A CN 201010509044A CN 102441349 B CN102441349 B CN 102441349B
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Abstract
The invention provides a hydrogenation technological method for reducing the skimming of a catalyst, which is characterized in that: a standby gas-liquid distributor is arranged on a catalyst bed layer at the top of a hydrogenation reactor; the standby gas-liquid distributor consists of a long center pipe and a bubble cap; the upper end of the long center pipe is above the catalyst bed layer; the bubble cap is arranged at an upper part of the long center pipe, and a gap for materials to flow exists between the bubble cap and the long center pipe; the opening at the upper end of the long center pipe is closed by a pressure rupture film; the lower part of the long center pipe extends into the catalyst bed layer; and the rupture differential pressure of the pressure rupture films is lower than 0.45 MPa and higher than 0.1 MPa. According to the method provided by the invention, no big change is required to be carried out on the existing device, the long-term operation for the device can be realized with smaller investment, the catalyst of the whole bed layer is sufficiently utilized, and meanwhile, the pressure drop of the reactor is reduced, so that the production safety is ensured, and the economic benefit is increased.
Description
Technical field
The present invention relates to a kind of hydrogenation method that catalyst is skimmed head that reduces, belong to the petrochemical technology field.
Background technology
In recent years, because petroleum resources in world wide scarcity and various countries constantly increase the demand of the energy day by day, people more and more pay attention to the utilization of residual oil.A kind of as decarburization technique, slag oil coking process has the advantages such as small investment, operating cost are low, has therefore obtained development widely.
Coking distillate (coking naphtha, coker gas oil, wax tailings) olefin(e) centent is high, and the content of heteroatoms such as sulphur, nitrogen, silicon are high, and stability is poor, can not be directly as product, uses, even can not be directly as the charging of downstream unit.For making coking distillate meet the end product standard or meeting the charging requirement of downstream unit, must carry out hydrofinishing or hydrotreatment.
In the process of coking distillate hydrogenation and removing sulphur, nitrogen, owing in raw material, containing alkadienes, silicon and the tiny impurity such as coke powder, so often affect the operational stability of device.As Daqing petrochemical company 300kt/a Hydrogenation of Coker Gasoline device, within the half a year that goes into operation, occur that twice system pressure difference is too high, cause being forced to stop work (the rising analysis of causes of coking gasoline hydrogenation refining system pressure difference and countermeasure, " refining and chemical industry ", the 19th volume: 20).The too fast problem of reactor catalyst bed pressure drop rising also appears in Guangzhou Branch 300kt/a hydrogenation plant when processing coker gasoline.This device once, within the time of a year and a half, caused stopping work defect elimination 5 times (analysis of causes and countermeasure that the hydrofining reaction system pressure drop raises, " China and foreign countries' energy ", 2007, the 12 volumes) because the reaction system bed pressure drop raises.Two I Hydrogenation of Coker Gasoline devices of Anqing branch company oil refining will be stopped work in 1 year and be skimmed for 2～3 times, have a strong impact on normal operation (Coke Inhibitor for Coker Gasoline Hydrofining Unit, " petrochemical technology ", 2006,13 (4): 5) of device.All there is Similar Problems in various degree in domestic and international device of the same type, the increase of pressure differential between bed, make the inner members such as the support bar of catalyst and gripper shoe when bearing catalyst weight, again must the outer pressure of commitment, bring hidden trouble for the safety operation of device.Therefore, the bed pressure drop rising is too fast is the outstanding problem that affects coking distillate hydrogenation plant long-term operation always.
The rising of coking distillate hydrogenation reactor pressure drop mainly comes from the bed coking of catalyst top.Through large quantity research, show, the coking factor is very complicated, mainly due to the polymerization of the unsaturated hydro carbons such as alkadienes in raw material and mechanical admixture that upstream device is brought into, is deposited on beds top and causes.Polymerization just can occur in the alkadienes in raw material under cryogenic conditions, first generate oligomer, to high polymer, transforms until coking rapidly subsequently.The content of iron is generally higher in the sample of coking, with organic hydrocarbon, to have formed aphthenic acids after the feedstock oil dissolved oxygen, the iron of naphthenic acid corrosion device generates iron naphthenate, stably be dissolved in feedstock oil, iron naphthenate is easy to occur hydrogenolysis after mixed hydrogen, and be deposited on reactor top bed with hydrogen sulfide reaction generation ferrous sulfide, and promote the coking reaction of coking parent, accelerated the obstruction of beds.In addition, in raw material, contain a small amount of tiny coke powder and have very strong adsorptivity, easily and the organic macromolecule compound that forms in polymerisation be bonded together, make burnt dirty particle grow up gradually, when it grows up to a certain size, will be deposited in reactor, result in blockage.
For the reaction coking, cause the too high problem of pressure drop, present solution has following several:
1, carry out the management work of raw material, adopt the modes such as nitrogen protection, avoid raw material to contact with air, at utmost reduce the chance of unsaturated hydro carbons formation colloid in raw material.This is a kind of passive raw material guard method, if the raw material mechanical admixture of upstream input is more, diene content is very high, or carries a lot of coke powders secretly, and the party's rule is helpless.
2, mix refining virgin kerosene or straight-run diesel oil, diluted the unsaturated hydro carbons such as alkadienes in the raw material, reduced the severity of hydrogenation plant, make the device operation more stable.But the method has been sacrificed the processing capacity of hydrogenation device for treatment coking distillate, has in fact reduced the air speed to coking distillate, and economy is poor.
3, between the entrance and exit of pretreatment reaction device, by-pass is set, during normal production, reaction mass enters heating furnace after by the pretreatment reaction device, when pretreatment reaction device beds Pressure Drop raises, reaction mass enters heating furnace through by-pass, partly or entirely more after catalyst changeout, reaction mass switches to the pretreatment reaction device again and enters heating furnace until the pretreatment reaction device.Although the method can assurance device operation downtime not, in the not pretreated situation of raw material, can cause larger impact to the main reactor temperature rise, make the more difficult control of operation.
4,, in preposition/rearmounted reactor process, adopt the mode of two reactor series connection to operate.After preposition reactor is saturated by silicon, by the handover operation of pipeline, makes the raw material rearmounted reactor of first flowing through, and then pass through lead reactor.Due to the impact that can reduce the main reactor temperature rise, so can be than the more coking distillate of above-mentioned bypass reactor processing.But the method need to increase a reactor, and complicated operation.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of hydrogenation method that catalyst is skimmed head that reduces.Without existing apparatus is carried out to large change, can be under less investment, the long-term operation of implement device, and take full advantage of the catalyst of whole bed, and reduce simultaneously reactor pressure and fall, guarantee production safety, increase economic benefit.
The hydrogenation method that the present invention reduces catalyst slash head comprises following content: on the beds of hydrogenation reactor top, standby gas-liquid allotter is set, standby gas-liquid allotter consists of long central tube and bubble cap, long central tube upper end is on beds, bubble cap is arranged on long central tube top and has the gap for Flow of Goods and Materials with long central tube, long central tube upper end open is sealed by the pressure burst rupture of membranes, long central tube bottom extends in beds, and the burst pressure of pressure burst rupture of membranes is poor less than 0.45MPa and greater than 0.1MPa.
In the inventive method, at the reactor catalyst bed pressure drop hour, standby gas-liquid allotter is not enabled, unit normal run, with normal fixed bed reactors operation without any difference.On gas-liquid partition tray, under feedstock oil and hydrogen are backward by the bubble cap gas-liquid allotter mixing of routine, enter beds and carry out hydrogenation reaction.When the pressure drop of beds top larger, or substantially can't be when the gas-liquid logistics, the pressure burst rupture of membranes at long central tube top breaks under the effect of pressure differential, the gas-liquid logistics can enter the beds bottom by long central tube and proceed hydrogenation reaction.
In the inventive method, the pressure burst rupture of membranes at the long central tube of standby gas-liquid allotter top is the existing common equipment in pressure vessel safety field, be generally the pressure burst rupture of membranes, the pressure burst rupture of membranes is general selects resistant to elevated temperatures alloy material to make, the general heat resistance of wanting should surpass 300 ℃, as the stainless steel pressure rupture disk etc., and can be definite according to concrete reaction feed temperature, its pressure differential of bearing, less than 0.45MPa, is preferably 0.2～0.35MPa.Concrete operations can be carried out type selecting or adjusting according to the maximum differential pressure that actual production and reactor can bear.The diameter of the long central tube of standby gas-liquid allotter is generally 2～20cm, and quantity evenly arranges according to the scale of hydrogenation reactor, in general the sectional area sum should be not less than reactor cross section long-pending 5%, be not more than reactor cross section long-pending 30%.The length of the long central tube of standby gas-liquid allotter is 10%～90% of hydrogenation reactor top catalyst bed layer height, is preferably 20%～50%.
In the inventive method, the activity of different catalysts bed hydrogenation catalyst can be identical, also can be different, preferably the activity by reagent flow direction catalyst increases successively, the activity of catalyst is general relevant to active metallic content in catalyst, the catalyst activity that active metallic content is high is generally higher, the activity of catalyst is also relevant to support, auxiliary agent kind, preparation method etc., concrete catalyst can be selected commercial goods, this area catalyst as required, also can be by the existing method preparation in this area.Reactor can arrange 2～5 beds.The concrete kind of catalyst and consumption can be according to feedstock properties, and required reaction effect is specifically determined.
The hydrogenation catalyst that the inventive method is used can be the product of this area routine, reactive metal wherein can for nickel, cobalt, molybdenum or tungsten etc. one or more.As comprised by weight percentage: nickel or cobalt are 0.2%～15.0% (calculating by its oxide), molybdenum or tungsten are 1%～30% (calculating by its oxide), carrier can be aluminium oxide, silica, aluminium oxide-silica etc. one or more.Catalyst is extrudate or spherical.The bulk density of catalyst is 0.5～0.8g/cm
3, catalyst granules diameter (spherical diameter, bar shaped diameter or clover diameter etc.) is 0.8～10mm, and length is 1.0～50.0mm, and specific area is greater than 150m
2/ g, pore volume is greater than 0.30cm
3/ g.
Fixed bed hydrogenation operation condition of the present invention is generally: reaction mass enters from reactor top, from reactor bottom, discharges, and reaction pressure is 1.0～18.0MPa, is preferably 2.0～15.0MPa; During liquid, volume space velocity is 0.5～5.0h
-1, be preferably 1.0～3.0h
-1Reaction temperature is controlled at 160～420 ℃, is preferably 200～390 ℃; Hydrogen to oil volume ratio is 100: 1～1800: 1, is preferably 300: 1～1000: 1.
The inventive method can be used in the fixed bed hydrogenation technical process of coking distillate, also can be used in the raw material fixed bed hydrogenation aspect that other alkene, alkadienes and content of impurities are higher, as the fixed bed hydrogenation technical process of coal tar or residual oil etc.
The inventive method, after rupture disk is opened, although the actual catalytic amount that works reduces, can be carried out the conditioned reaction effect by operating conditions such as suitable raising reaction temperatures, can meet the needs of the hydrogenation reaction degree of depth.
Advantage of the present invention is:
1, rupture disk is responded to the pressure differential of beds automatically, and when pressure differential reached the condition of setting, it can open the overflow pipe passage automatically, without human intervention, did not increase the Operating Complexity of device.
2, the inventive method is simple, easy-to-use, without existing apparatus is carried out to large change, can be under essentially identical operating condition the long-term operation of implement device, do not need to stop work catalyst skimmed to head, increase the service cycle of device, increase economic efficiency.
3, the inventive method can make the gas-liquid logistics walk around beds top in the situation that coking or obstruction occur on beds top, can utilize to greatest extent the catalyst of beds bottom, cuts the waste.
The accompanying drawing explanation
Fig. 1 is process hydrogenation reactor top structure schematic diagram of the present invention.
In figure: 1-gas-liquid partition tray, 2-beds, the long central tube of 3-, 4-bubble cap distributor, 5-pressure burst rupture of membranes, the standby gas-liquid allotter of 6-.Wherein bubble cap distributor 4 and standby gas-liquid allotter 6 evenly arrange as required a plurality of, in figure only take 1 as the signal describe.
The specific embodiment
For further setting forth specific features of the present invention, in connection with accompanying drawing, be illustrated.
By reference to the accompanying drawings 1, the present invention is a kind of to be reduced catalyst and skims the hydrogenation method of head and be:
When the Pressure Drop of beds 2 was in normal range (NR), feedstock oil and hydrogen mixture material entered the bubble cap distributor 4 on conventional gas-liquid partition tray 1, and the contact catalyst bed, carry out hydrogenation reaction downwards, and this moment, standby gas-liquid allotter 6 did not start.Pressure Drop when beds 2 tops increases, while causing the gas-liquid logistics substantially can't pass through, the pressure burst rupture of membranes 5 at long central tube 3 tops of standby gas-liquid allotter 6 breaks under the effect of pressure differential, the gas-liquid logistics can enter the beds bottom by long central tube 3 and proceed hydrogenation reaction.
For explanation the solution of the present invention and effect, by following examples, further illustrate the solution of the present invention and effect.While for other raw material, maybe needing to produce other index product, can corresponding adjustment catalyst or the technology contents such as operating condition.
Embodiment 1
Adopt FHRS-1 (hydrogenation is caught silicea), FZC-102B (hydrogenation protecting agent), the FH-40C (main Hydrobon catalyst) of Fushun Petrochemical Research Institute's Development and Production.According to schematic diagram structure shown in Figure 1, reactor arranges two beds, the first beds filling FHRS-1, and the long central tube on gas-liquid partition tray extends downward the centre of bed.The second beds filling FZC-102B, FH-40C.Feedstock oil character is in Table 1, and the process conditions after 100 days of turning round and product property are in Table 2.
Comparative example 1
This comparative example adopts traditional Hydrogenation of Coker Gasoline device.Beds all loads identical with embodiment.Feedstock oil character is in Table 1, and the process conditions after 100 days of turning round and product property are in Table 2.
Table 1 feedstock oil character
Table 2 operating condition and product property
| Embodiment 1 | Comparative example 1 | |
| Reaction hydrogen pressure/MPa | 3.0 | 3.0 |
| Hydrogen to oil volume ratio | 650∶1 | 650∶1 |
| Volume space velocity/h -1 | 2.0 | 2.0 |
| Average reaction temperature/℃ | 288 | 293 |
| Pressure burst rupture of membranes burst pressure is poor/MPa | 0.23 | |
| Product property | ||
| Density (20 ℃)/gcm -3 | 0.7238 | 0.7233 |
| The boiling range scope/℃ | 46～193 | 44～191 |
| Sulphur/μ gg -1 | 23.0 | 21.0 |
| Nitrogen/μ gg -1 | 4.8 | 3.6 |
| Bromine valency/gBr (100mL) -1 | 1.8 | 1.6 |
| Reactor pressure decrease/MPa (30 days) | 0.11 | 0.10 |
| Reactor pressure decrease/MPa (60 days) | 0.21 | 0.19 |
| Reactor pressure decrease/MPa (90 days) | 0.09 | 0.26 |
| Reactor pressure decrease/MPa (100 days) | 0.12 | Stop work |
Above result can find out, reaches while setting reactor catalyst bed upper pressure is poor, and technique of the present invention can realize automatically hydrogenation reaction being proceeded in gas-liquid mass transport to the bottom of reactor catalyst bed.The present invention can extension fixture service cycle, and take full advantage of the catalyst of whole bed, reduce simultaneously reactor pressure and fall, guarantee production safety.
Claims (8)
1. one kind is reduced the hydrogenation method that catalyst is skimmed head, it is characterized in that: on the beds of hydrogenation reactor top, standby gas-liquid allotter is set, standby gas-liquid allotter consists of long central tube and bubble cap, long central tube upper end is on beds, bubble cap is arranged on long central tube top and has the gap for Flow of Goods and Materials with long central tube, long central tube upper end open is sealed by the pressure burst rupture of membranes, long central tube bottom extends in beds, and the burst pressure of pressure burst rupture of membranes is poor less than 0.45MPa and greater than 0.1MPa; The hydrogenation operation condition is: reaction mass enters from reactor top, from reactor bottom, discharges, and reaction pressure is 1.0～18.0MPa, and during liquid, volume space velocity is 0.5～5.0h
-1, reaction temperature is controlled at 160～420 ℃, and hydrogen to oil volume ratio is 100: 1～1800: 1; Hydrogenation technique is for the fixed bed hydrogenation technical process of coking distillate, or for the fixed bed hydrogenation technical process of coal tar or residual oil.
2. in accordance with the method for claim 1, it is characterized in that: the pressure burst rupture of membranes at the long central tube of standby gas-liquid allotter top is that resistant to elevated temperatures alloy material is made, and heat resistance is over 300 ℃.
3. according to the described method of claim 1 or 2, it is characterized in that: the pressure burst rupture of membranes is the stainless steel pressure rupture disk.
4. according to the described method of claim 1 or 2, it is characterized in that: the pressure differential that the pressure burst rupture of membranes bears is 0.2～0.35MPa.
5. according to the described method of claim 1 or 2, it is characterized in that: the diameter of the long central tube of standby gas-liquid allotter is 2～20cm, and the length of the long central tube of standby gas-liquid allotter is 10%～90% of hydrogenation reactor top catalyst bed layer height.
6. it is characterized in that in accordance with the method for claim 1: hydrogenation reactor arranges 2～5 beds.
7. in accordance with the method for claim 1, it is characterized in that: the reactive metal of hydrogenation catalyst is one or more in nickel, cobalt, molybdenum or tungsten, comprise by weight percentage: take the nickel of oxide or cobalt as 0.2%～15.0%, take the molybdenum of oxide or tungsten as 1%～30%.
8. in accordance with the method for claim 1, it is characterized in that the hydrogenation operation condition is: reaction pressure is 2.0～15.0MPa, and during liquid, volume space velocity is 1.0～3.0h
-1, reaction temperature is controlled to be 200～390 ℃, and hydrogen to oil volume ratio is 300: 1～1000: 1.
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| CN114570290B (en) * | 2022-03-17 | 2023-10-17 | 上海科瑞德能源科技有限公司 | Method for prolonging operation period of hydrogenation device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1464034A (en) * | 2002-06-17 | 2003-12-31 | 中国石油化工股份有限公司安庆分公司 | Process for catalyzed gasoline hydrogenation desulfurization |
| CN2757911Y (en) * | 2004-11-30 | 2006-02-15 | 中国石油化工股份有限公司 | Suction split flow type gas liquid distributor |
| CN1765479A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Gas liquid distributor with incrustation sediment function |
| CN200963585Y (en) * | 2006-10-20 | 2007-10-24 | 中国石油化工集团公司 | Gas-liquid distributor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2933877B1 (en) * | 2008-07-15 | 2011-04-15 | Inst Francais Du Petrole | REACTOR FOR TREATMENT OR HYDROTREATMENT WITH A GRANULAR BED AND AN ESSENTIALLY LIQUID PHASE AND AN ESSENTIALLY GAS PHASE THROUGH THE BED |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1464034A (en) * | 2002-06-17 | 2003-12-31 | 中国石油化工股份有限公司安庆分公司 | Process for catalyzed gasoline hydrogenation desulfurization |
| CN1765479A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Gas liquid distributor with incrustation sediment function |
| CN2757911Y (en) * | 2004-11-30 | 2006-02-15 | 中国石油化工股份有限公司 | Suction split flow type gas liquid distributor |
| CN200963585Y (en) * | 2006-10-20 | 2007-10-24 | 中国石油化工集团公司 | Gas-liquid distributor |
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