CN102039105B - Gas-liquid reverse flow reactor and gas-liquid reverse flow hydrogenation process method - Google Patents
Gas-liquid reverse flow reactor and gas-liquid reverse flow hydrogenation process method Download PDFInfo
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- CN102039105B CN102039105B CN2009102042722A CN200910204272A CN102039105B CN 102039105 B CN102039105 B CN 102039105B CN 2009102042722 A CN2009102042722 A CN 2009102042722A CN 200910204272 A CN200910204272 A CN 200910204272A CN 102039105 B CN102039105 B CN 102039105B
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Abstract
The invention discloses a gas-liquid reverse flow reactor and a gas-liquid reverse flow hydrogenation process method. The reactor comprises at least two catalyst beds, wherein an inner member for supplying gas and discharging the gas is arranged between at least two adjacent catalyst beds; the inner member comprises a gas-liquid contact member and a gas collection member; the gas-liquid contact member is arranged at the upper part of the gas collection member; the gas collection member comprises a separation plate, a liquid degrading pipeline and a gas discharging pipeline; the separation plate is provided with a through hole; the through hole is connected with the liquid degrading pipeline and the gas discharging pipeline; the liquid degrading pipeline is in a short pipe structure and is arranged below the separation plate; the gas discharging pipeline is arranged above the separation plate; and the gas discharging pipeline passes through the former catalyst bed or is communicated with the exterior of the reactor. The reactor is used in the reverse flow hydrogenation process method provided by the invention. The reactor and gas-liquid reverse flow hydrogenation process provided by the invention can effectively control the hydrogen-oil ratio of different catalyst beds, thereby ensuring the stable operation of a reverse flow reaction.
Description
Technical field
The present invention relates to a kind of gas-liquid counter current reactor and gas-liquid counter current hydrogenation method, relate in particular to the reactor of a kind of gas-liquid counter current reactor, particularly hydrocarbon raw material and hydrogen countercurrent hydrogenation and use the hydrogenation method of this reactor.
Background technology
At present, in petroleum refining and field of chemical technology, for the efficient that increases reaction and the energy consumption of saveall, each petrochemical industry major company of the world more and more payes attention to researching and developing gas-liquid counter current operant response device.Reason is the reaction efficiency that gas-liquid counter current operant response device not only can increase gas-liquid two-phase; Reduce the use amount of effective catalyst; Save production cost, increase benefit, but also can make inhale, the reactor of exothermic reaction carries out chemical reaction under accurate isothermal reaction condition; Reduce the running cost of device, increased factory's benefit.
Along with the day by day strictness of the world to the oil quality regulation, hydrocarbons hydrogenation technology also tends to adopt gas-liquid counter current operant response device gradually.Because more employing hydrogen of existing hydrocarbons hydrogenation technology and hydrocarbon raw material also flow to current downflow; Contact and carry out the fixed bed hydrogenation technology of catalytic reaction with beds; But the little molecule of the hydrogen sulfide that generates in the course of reaction, ammonia and hydro carbons can further react this technology; Like desulfurization, denitrogenation, aromatic hydrocarbons is saturated and hydrocracking etc. has bigger inhibitory action, and reaction rate is descended.Especially take off arylation reaction, reason is that to take off arylation reaction be reversible reaction, and reaction depth and reaction temperature are inversely proportional to; And be divided into direct ratio with hydrogen, and industrial hydrogenation plant is an adiabatic reactor, inevitably causes reaction temperature increasingly high; The aromatic hydrocarbons saturation rate is reduced; So segmentation hydrogenation and/or gas-liquid counter current hydrogenation technique just become the better means of the problems referred to above, the hydrogen dividing potential drop that this technology not only can augmenting response is in time removed the H that reaction produces
2S, NH
3, can also make the reaction temperature of reactor be tending towards the isothermal or the less temperature difference.
USP 5,985, and 135 propose the two-stage hydrogenation method of a kind of up-flow reactor and downflow reactor, wherein connect a stripper plant at the back at first stage reactor.But this technology does not still fundamentally solve the problem that removes of pernicious gas, and investment is bigger.
In order fundamentally to solve the problem that removes of pernicious gas, more oil refinery company is at research gas-liquid counter current hydrogenation technique.But the hydrocarbons hydrogenation treatment reactor all is the function catalyst that the simple function beds adopts single type at present, it is seated in forms a beds together.Be reflected under the liquid phase state and carry out,, can only adopt catalyst particle for guaranteeing the catalyst efficiency factor.In addition,, be in again in the soaked with liquid, can only adopt solid construction could guarantee catalyst strength because beds is very high.Therefore, the catalyst of commercial Application all is sphere or the bar shaped catalyst below the particle diameter 3mm, and this type of beds voidage is 0.35-0.45, and is much littler than the voidage (＞0.95) of the counter-current operation of routine.Reactor at so big or small bed voidage carries out counter-current operation, is prone to produce liquid flooding, causes the device running unstable.
USP5,985,131, propose have the catalyst packing method of gas bypassing to avoid liquid flooding among the USP 6,007,787.Though this invention can reduce the liquid holdup of reactor; Suitably increased the scope of reactor gas-liquid operation; But it does not have to associate with the gas-liquid distribution of whole reactor, still is easy to generate liquid flooding, and the utilization rate of reactor is not high yet in addition; Hydrocarbons hydrogenation is handled so large-scale reactor, and operability is lower.At chemical industry and environmental technology field, also there is similar problem in some process.
USP 5,183, proposed the countercurrent hydrogenation purification techniques in 556, but identical with other existing counter-current operation device, the countercurrent reaction section all adopts single catalyst, or non-noble metal sulfide catalyst or noble metal catalyst.There is the problem that is prone to take place liquid flooding on the one hand in this scheme, also is not suitable for the deep desulfuration of feedstock oil, the processed of taking off virtue on the other hand.Reason is: the bigger speed that it further reacts of feedstock oil reaction depth is more little; Certainly will need highly active catalyst in order to reach product requirement; Like the saturated noble metal catalyst that preferably uses of aromatic hydrocarbons; If but in the whole beds of counter-current operation, used high activated catalyst such as noble metal catalyst, the catalyst on countercurrent reaction section top could be prone to make catalysqt deactivation because of the high hydrogen sulfide dividing potential drop.Otherwise, can reduce because of the low in hydrogen sulphide dividing potential drop is prone to make catalyst to lose the sulphur activity in the bottom of countercurrent reaction section, until there not being activity if whole adverse current beds uses conventional base metal sulfide catalyst.
CN02133121.9 discloses a kind of diesel oil hydrotreating method; Employing is along the liquid flow direction catalyst activity improves gradually, the beds voidage increases gradually two or more beds; The voidage of reactor head beds is 0.25～0.55, and the voidage of reactor bottom beds is 0.35～0.90.This method is different to the liquid-gas ratio of reactor diverse location in the diesel oil countercurrent hydrogenation process, has used the catalyst of different voidages, has solved the liquid flooding problem to a certain extent.But the loadings of the catalyst that voidage is high significantly reduces than typical catalyst, and when reaching the same reaction degree of depth, the reactor volume that needs obviously strengthens.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of gas-liquid counter current reactor and gas-liquid counter current hydrogenation method, and reactor adopts suitable version, controls the gas-liquid ratio of differential responses section effectively, has improved the operational stability of countercurrent hydrogenation technology.
Gas-liquid counter current reactor of the present invention comprises at least two beds; The inner member of gas make-up and gas discharging is set between at least one adjacent catalyst bed layer, and this inner member comprises gas-liquid contact member and gas collection member, and the gas-liquid contact member is arranged on gas and collects member top; Gas is collected member and is comprised division board, downspout road and discharge duct; Division board has through hole, and through hole is connected with discharge duct with the downspout road of setting, and the downspout road is arranged on below the division board for the short tube structure; Discharge duct is arranged on above the division board, discharge duct pass a beds or with the reactor exterior.
Counter-current reactor of the present invention is a hydrocarbon raw material gas-liquid counter current hydrogenation reactor; Beds uses the hydrocarbons hydrogenation catalyst; The different catalyst bed can use identical hydrogenation catalyst; Also can use different hydrogenation catalysts, generally can use commercially available Hydrobon catalyst, hydrotreating catalyst, catalyst for hydro-upgrading etc. according to the needs of reaction.Can use the catalyst of common shape and granularity, also can use the higher catalyst of voidage.
In the counter-current reactor of the present invention; Gas-liquid contanct equipment can be various equipment with gas-liquid contact, mixed effect; Like the air and liquid mixer in this area, gas-liquid allotter etc.; Concrete like coiled gas distributor, tower disc type air and liquid mixer etc., gas-liquid contanct equipment communicates with additional feed channel.
In the counter-current reactor of the present invention; Gas is collected in the member; Downspout road and discharge duct can be provided with one or several, and preferably a plurality of downspouts road evenly is arranged on the division board, impels liquid distribution even; Discharge duct is a center that is arranged on division board, and discharge duct also can be provided with several being evenly distributed on the division board.The lower port in downspout road can be provided with the bubble-cap with fluid-tight effect.
In the counter-current reactor of the present invention, by conventional design liquid inlet opening, gas feed mouth, liquid discharge outlet, gas discharge outlet etc. can also be set, reactor bottom is provided with gas gas cloth device.
The key of counter-current reactor of the present invention is to adopt the suitable gas of structure to collect member (other structure of reactor can adopt this area conventional structure), adjusts the gas-liquid volume ratio of different catalysts bed flexibly, guarantees the stable operation of counter-current reactor.
Gas-liquid counter current hydrogenation method of the present invention uses reactor of the present invention; Process comprises: the liquid phase hydrocarbon raw material gets into reactor from reactor head; Hydrogen gets into reactor from each beds bottom; At first the hydrogenation catalyst bed on reactor top carries out hydrogenation reaction, and reaction back liquid phase effluent gets into next hydrogenation catalyst bed through the downspout road, and the discharge duct that the gas phase that flows on next hydrogenation catalyst bed course is collected member through gas is discharged.
Process of the present invention is applicable to the gas-liquid counter current hydro-conversion of all kinds of weight distillates and residual oil; Be particularly useful for reaction temperature and be positioned at the weight distillate hydrogenation processing within the feedstock oil boiling range, like the hydrotreatment processes such as raw material of diesel oil (180～390 ℃) hydrodesulfurization, the hydrocracking, ethene steam cracking tail oil (200～465 ℃) hydrogenation (decolouring) or the production industrial chemicals that take off virtue, bright stock or cuts such as hydrogenation production lube base oil, VGO, production spinning asphalt, needle coke.
The countercurrent reaction process conditions can specifically be confirmed according to feedstock property, product quality requirement and the catalyst performance that uses; Be generally: 240～427 ℃ of reaction temperatures; Reaction pressure is 1.0～20.0MPa, and hydrogen to oil volume ratio is more than 50, to be generally 100～800; Be preferably 150～500, volume space velocity is 0.1～7.5h during liquid
-1The hydrogen to oil volume ratio of different catalysts bed can be identical, also can be different.Hydrogenation catalyst can use the conventional hydrogenation catalyst in this area as required, and the different catalysts bed can use identical or different hydrogenation catalyst.Generally can use 2～8 beds, be preferably 2～4.
In the counter-current reactor of the present invention; Through the inner member of suitable structure is set; Between adjacent two beds, the gas phase that next beds is upwards flowed is collected and is directly discharged without an adjacent last beds, can realize that the different catalysts bed operates under different gas liquid ratio conditions; In the gas phase of discharging; Comprise the small-molecule substance that generates in the course of reaction and at the raw material of reaction condition gasified, liquid-gas ratio increases greatly when having reduced the beds normal running of reactor middle and upper part effectively, and the problem of the liquid flooding that causes.Also solved simultaneously the problem that forms interior circulating effect normal running because of the partial material " gasification-liquefaction " that axial temperature difference in the reactor causes more greatly.
Description of drawings
Fig. 1 is a kind of concrete structure sketch map of counter-current reactor of the present invention.
Fig. 2 is that gas is collected the element structure sketch map among Fig. 1.
Fig. 3 is the another kind of concrete structure sketch map of counter-current reactor of the present invention.
Among the figure: 1-first beds, 2-second beds, 3-gas is collected member, 4-gas-liquid contact member, 5-division board, 6-discharge duct, 7-downspout road, 8-reactor evacuated pipeline.
The specific embodiment
Further specify the structure of reactor of the present invention and the method for operating of hydrogenation technique below in conjunction with accompanying drawing.
According to illustrated in figures 1 and 2, a kind of specific reactor structure of the present invention adopts two beds: first beds 1 and second beds 2.The inner member of gas make-up and the impure excess air of discharging is set between two beds, and this inner member comprises gas-liquid contact member 4 and gas collection member 3, and gas-liquid contact member 4 is arranged on the top that gas is collected member 3.Gas is collected member 3 and is comprised division board 5; Division board 5 has through hole; Through hole is connected with discharge duct 6 with the downspout road 7 of setting, and downspout road 7 is arranged on for the short tube structure below the division board 3, discharge duct 6 be arranged on division board 3 above; Discharge duct 6 passes first beds 1 (or with reactor exterior, as shown in Figure 3).
Further set forth technical scheme of the present invention below in conjunction with instance.
Embodiment
Adopt the present invention, raw materials used character is seen table 1-1, and catalyst is selected the FH-UDS Hydrobon catalyst of Fushun Petrochemical Research Institute's development and production for use.The composition of FH-UDS catalyst and quality index are seen table 1-2, and process conditions are seen table 1-3, and refined diesel oil character is seen table 1-4.Reactor is provided with two beds, and two beds use identical Hydrobon catalyst, and consumption is identical.Can the long period stable operation under said process conditions.
Table 1-1 feedstock oil character
The composition and the quality index of table 1-2 catalyst
Table 1-3 process conditions
| | Condition | 1 | |
| Average reaction temperature, ℃ | 360 | 365 | |
| Reaction pressure, MPa | 6.0 | 6.0 | |
| The cumulative volume air speed, h -1 | 1.5 | 2.0 | |
| The first and second beds hydrogen to oil volume ratio | 300∶1 300∶1 | 150∶1 200∶1 |
Table 1-4 refined oil character
Comparative example
Compare with embodiment, do not have inner member between two beds of reactor, liquid flooding than taking place at 300 o'clock in the hydrogen oil body, and hydrogenation process can't stable operation.
Claims (8)
1. gas-liquid counter current reactor; This gas-liquid counter current reactor comprises at least two beds, it is characterized in that: the inner member of gas make-up and gas discharging is set between at least one adjacent catalyst bed layer, and this inner member comprises gas-liquid contact member and gas collection member; The gas-liquid contact member is arranged on gas and collects member top; Gas is collected member and is comprised division board, downspout road and discharge duct, and division board has through hole, and through hole is connected with discharge duct with the downspout road of setting; The downspout road is the short tube structure; Be arranged on below the division board, discharge duct is arranged on above the division board, discharge duct pass a beds or with the reactor exterior; The gas-liquid counter current reactor is a hydrocarbon raw material gas-liquid counter current hydrogenation reactor, and beds uses the hydrocarbons hydrogenation catalyst; Gas-liquid contanct equipment in the gas-liquid counter current reactor is coiled gas distributor or tower disc type air and liquid mixer.
2. according to the described reactor of claim 1, it is characterized in that: gas-liquid contanct equipment communicates with additional feed channel.
3. according to the described reactor of claim 1; It is characterized in that: gas is collected in the member; Downspout road and discharge duct are provided with one or several, and discharge duct is a center that is arranged on division board, and discharge duct perhaps is provided with several being evenly distributed on the division board.
4. according to claim 1 or 3 described reactors, it is characterized in that: the lower port setting in downspout road has the bubble-cap of fluid-tight effect.
5. according to the described reactor of claim 1, it is characterized in that: counter-current reactor is provided with liquid inlet opening, gas feed mouth, liquid discharge outlet, gas discharge outlet, and reactor bottom is provided with gas gas cloth device.
6. gas-liquid counter current hydrogenation method; It is characterized in that: use the described reactor of the arbitrary claim of claim 1 to 5; Process comprises: the liquid phase hydrocarbon raw material gets into reactor from reactor head; Hydrogen gets into reactor from each beds bottom; At first the hydrogenation catalyst bed on reactor top carries out hydrogenation reaction, and reaction back liquid phase effluent gets into next hydrogenation catalyst bed through the downspout road, and the discharge duct that the gas phase that flows on next hydrogenation catalyst bed course is collected member through gas is discharged.
7. according to the described method of claim 6, it is characterized in that: the countercurrent reaction process conditions are: reaction temperature 240-427 ℃, reaction pressure is 1.0-20.0MPa, and hydrogen to oil volume ratio is 50～800, and volume space velocity is 0.1-7.5h during liquid
-12～8 beds are set in the reactor.
8. according to the described method of claim 7, it is characterized in that: hydrogen to oil volume ratio is 100～800.
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| CN103965953B (en) * | 2013-01-30 | 2015-07-22 | 中国石油天然气股份有限公司 | Distillate oil two-phase hydrogenation reactor and hydrogenation process method |
| CN108114669B (en) * | 2016-11-25 | 2019-12-13 | 中国石油化工股份有限公司 | Baffle type impact-reducing flow-equalizing disc |
| CN109821495B (en) * | 2019-03-01 | 2021-02-09 | 清华大学 | Multistage reaction device for preparing ethylene and/or acetylene from hydrocarbon and preparation method |
| CN109908843B (en) * | 2019-04-23 | 2019-12-31 | 宁波巨化新材料有限公司 | Propionaldehyde hydrogenation reactor |
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| CN2369747Y (en) * | 1999-04-08 | 2000-03-22 | 中国石油化工集团公司 | Gas and liquid distributor in filling bed |
| CN1488431A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Gas-liquid counter current processing and treating method |
| CN101275083A (en) * | 2008-05-20 | 2008-10-01 | 中国石油化工集团公司 | Hydrogenation method for hydrocarbon oils |
| CN101381623A (en) * | 2008-09-12 | 2009-03-11 | 中国石油化工集团公司 | Liquid-solid two-phase hydrogenation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2369747Y (en) * | 1999-04-08 | 2000-03-22 | 中国石油化工集团公司 | Gas and liquid distributor in filling bed |
| CN1488431A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Gas-liquid counter current processing and treating method |
| CN101275083A (en) * | 2008-05-20 | 2008-10-01 | 中国石油化工集团公司 | Hydrogenation method for hydrocarbon oils |
| CN101381623A (en) * | 2008-09-12 | 2009-03-11 | 中国石油化工集团公司 | Liquid-solid two-phase hydrogenation method |
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