CN102311761B - Low hydrogen-oil ratio hydrotreating method and reactor - Google Patents
Low hydrogen-oil ratio hydrotreating method and reactor Download PDFInfo
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- CN102311761B CN102311761B CN201010222023.9A CN201010222023A CN102311761B CN 102311761 B CN102311761 B CN 102311761B CN 201010222023 A CN201010222023 A CN 201010222023A CN 102311761 B CN102311761 B CN 102311761B
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Abstract
The invention discloses a low hydrogen-oil ratio hydrotreating method and a reactor. Hydrogen is directly transported to the top space of the reactor, a liquid distributor is arranged at the inner top of the reactor, the liquid distributor consists of an upper hollow disc structure and at least one Venturi ejector communicated with the hollow disc, and raw oil is directly transported into the hollow disc of the liquid distributor through a pipeline, enters the Venturi ejector through the hollow disc, is sprayed as vaporous fluid at an outlet of the Venturi ejector to be dispersed in gas, then flows downwards and is hydrotreated through a catalyst bed layer. With the hydrotreating method and the reactor disclosed by the invention, the reaction hydrogen-oil ratio can be reduced, the use efficiency of the hydrogen is improved, a good hydrogenation environment is provided, and simultaneously the utilization ratio of catalysts and reactor volume is improved.
Description
Technical field
The present invention relates to a kind of low hydrogen/gasoline ratio fixed bed hydrogenation treatment method and reactor, particularly in fixed bed hydrogenation technique, improve processing method and the reactor of hydrogen utilization efficiency and then reduction hydrogen-oil ratio.
Background technology
Conventional fixed bed hydrogenation technique is to remove the most economical effective means of the impurity such as sulphur, nitrogen in stock oil.In the operation of fixed bed hydrogenation device, often adopt higher hydrogen-oil ratio and hydrogen dividing potential drop, to guarantee catalyst activity, promote the carrying out of the reactions such as hydrogenating desulfurization, denitrogenation, aromatic saturation and cracking.Yet the hydrogen gas circulating system that pressure is higher needs high investment cost and running cost, has indirectly increased the oil manufacture cost.If the hydrogen flowing quantity in the hydrotreatment process can be reduced, can be for enterprise saves facility investment and process cost, and then reduce the production cost of clean fuel.
The state of fixed-bed reactor mass transfer is generally: stock oil is evenly distributed on the granules of catalyst surface, and hydrogen passes in the beds space.So hydrogen need to be dissolved in stock oil, could contact with catalyzer, participate in hydrogenation reaction.That is to say, when the higher hydrogen dividing potential drop of fixed bed hydrogenation process using and hydrogen-oil ratio operation, the actual amounts of hydrogen the provided amounts of hydrogen required considerably beyond chemical reaction, this operator scheme is only in order to strengthen the mass transfer power of hydrogen, guarantees the hydrogen solubility in stock oil.Therefore, can, by optimizing and improve the service efficiency of the equipment such as the gas-liquid allotter raising hydrogen of reactor, reduce the process cost of hydrogenation unit.
In existing fixed bed hydrogenation technique, hydrogen injects simply stock oil in pipeline, not through mixing fully.According to processing condition measuring and calculating, under reaction conditions, in pipeline, hydrogen volume is about more than 10 times of stock oil volume, so its flow state belongs to, to take gas phase be that main gas-liquid two-phase flows.Under this situation, gas-liquid two-phase flows and generally is rendered as stratified flow, annular-flow or plug flow form.Stratified flow shows as gas-liquid two-phase and separately flows, and has a level and smooth separation surface between two-phase; Annular-flow shows as liquid phase and is membranaceous mobile along tube wall, and gas phase is in the pipeline intermediate flow; Plug flow shows as liquid and gas and forms the cylindric alternate mobile in pipeline of different lengths.As can be seen here, the flow state of gas-liquid two-phase causes its contact area less, can not make hydrogen fully be dissolved in stock oil before entering reactor.
At fixed-bed reactor top operated by rotary motion gas-liquid distributor, but gas-liquid distributor is for gas-liquid is evenly distributed on whole beds diametrically, to the meltage that increases hydrogen in liquid phase without obvious effect.Existing fixed bed hydrogenation reactor gas-liquid allotter is mainly overflow type divider and suction type bubble cap type divider, and the overflow type divider does not have molten hydrogen function substantially.Suction type bubble cap type divider principle of work is: at gas-liquid two-phase from top to bottom in co-current process, liquid phase falls into catch tray, the mechanism that on catch tray, the many pipe cores of distribution and bubble cap form, when in catch tray, liquid level approaches the bubble cap lower rim, the circulation of gas phase cuts and dwindles suddenly, makes the gas phase flow velocity increase suddenly, in bubble cap and between the annular space between the bubble cap inner central tube, produces negative pressure, cause gas phase to bring liquid phase into pipe core, flow into next bed.This kind of mode must have a large amount of recycle hydrogens to drive, and liquid phase also is inhaled into next bed, can't be atomized into small liquid pearl, promotes that the function of molten hydrogen is poor.Therefore, dissolve the less stock oil of hydrogen when contact reactor upper catalyst bed layer, show as the hydrogen deficient that participates in hydrogenation reaction, cause reactor top catalyst activity lower, utilization ratio is not high, the problems such as coking that simultaneously also exist the dissolved hydrogen deficiency to cause.
CN200420115970.8 discloses a kind of suction type bubble cap type divider, because the liquid phase crushing effect is bad, so increased a simple fixedly swirler on pipe core top.Although can liquid phase is further broken, can't realize the atomization of liquid phase, molten hydrogen effect need further be advanced to improve.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of low hydrogen/gasoline ratio fixed bed hydrogenation treatment method and reactor, the inventive method is under the prerequisite that guarantees the gas-liquid distributed uniform, further improved the hydrogen solute effect, and then improved the utilization ratio of catalyzer, reduced facility investment and process cost simultaneously.
In the hydroprocessing process of low hydrogen/gasoline ratio of the present invention, hydrogen directly is delivered to reactor head space, at the reactor inner top, the liquid phase divider is set, the liquid phase divider consists of top hollow disc structure and at least one venturi-type eductors of being communicated with hollow disc, stock oil directly is delivered in the hollow disc of liquid phase divider by pipeline, enter venturi-type eductors through hollow disc, in the venturi-type eductors outlet, spraying is, during vaporific fluid is dispersed in gas phase, then flows downward and carry out the hydrotreatment reaction through beds.
In the inventive method, stock oil and hydrogen enter respectively reactor, and stock oil forms vaporific material through the liquid phase divider and is dispersed in hydrogen.The hollow disc diameter of liquid phase divider is reactor inside diameter 50%～90%, according to the scale of reactor, the venturi-type eductors of suitable number evenly is set at the hollow disc downside.
In the inventive method, also can tube-in-tube structure be set in the venturi-type eductors outlet position, beds below the annular slot of hydrogen between venturi-type eductors and sleeve enters, tube-in-tube structure has reduced the gas communication sectional area, improve gas flow rate, further increased dispersion effect.
In the inventive method, the hydrotreatment reaction conditions requires specifically to determine according to feedstock property and quality product, is generally: 100～450 ℃ of temperature of reaction, and reaction pressure 0.5～18.0MPa, be preferably 2.5～15.0MPa; Hydrogen-oil ratio (volume) is 50: 1～600: 1, is preferably 200: 1～400: 1; Volume space velocity 0.6～5.0h during liquid
-1, be preferably 2.0～4.0h
-1.Wherein hydrogen-oil ratio, when reaching identical hydrotreatment reaction effect, can reduce greatly than existing method.
A kind of hydrotreating reactor of the present invention, reactor head arranges hydrogen inlet, at the reactor inner top, the liquid phase divider is set, the liquid phase divider consists of top hollow disc structure and at least one venturi-type eductors of being communicated with hollow disc, and stock oil directly is delivered in the hollow disc of liquid phase divider by pipeline.The hollow disc diameter of liquid phase divider is reactor inside diameter 50%～90%.In the venturi-type eductors outlet position, tube-in-tube structure is set, between venturi-type eductors and sleeve, there is annular slot.
Advantage of the present invention is:
1, adopt venturi-type eductors, stock oil can form the saturated solution of hydrogen very soon, and the part microbubble can be evenly distributed in stock oil with emulsified state, be brought into beds, can participate in hydrogenation reaction directly, improve the utilization ratio of reactor upper catalyst bed layer, be conducive to improve beds W-response performance.
2, because hydrogen fully is dissolved in stock oil, make the utilising efficiency of hydrogen greatly improve, so can adopt lower reactive hydrogen oil ratio, reduce the load of circulating hydrogen compressor, reduce the regular job expense of device.
3,, with respect to conventional gas-liquid allotter, the gas-liquid allotter adopted in the present invention has that cost is low, the efficiency advantages of higher.
The accompanying drawing explanation
Fig. 1 is processing method schematic flow sheet of the present invention.
In figure: 1-stock oil, 2-hydrogen, 3-liquid phase divider hollow disc, 4-reactor, 5-venturi-type eductors, 6-distribution plate, 7-phase chamber, 8-beds.
Embodiment
In the inventive method, before stock oil enters reactor, with hydrogen, do not mix, directly enter the liquid phase divider in reactor, from a plurality of venturi-type eductors of liquid phase divider with vaporific ejection.Hydrogen directly enters the phase chamber on reactor top, and stock oil obtains higher linear velocity under the throttling action of Venturi jet, the hydrogen of phase chamber can be sucked and strongly tears, and makes it fully to be dissolved in stock oil.The supersaturated solution that now stock oil is hydrogen, and a large amount of microbubbles is scattered in stock oil, during the contact reactor beds, can carry out hydrogenation reaction downwards fully.The present invention can reduce the reactive hydrogen oil ratio, improves the service efficiency of hydrogen, and good hydrogenation environment is provided, and improves the utilization ratio of catalyzer and reactor volume simultaneously.
The fixed bed hydrogenation that the catalyzer that hydroprocessing process of the present invention is used is this area routine is processed catalyzer, wherein the reactive metal of catalyzer can for nickel, cobalt, molybdenum or tungsten etc. one or more, can use as required the commercial goods hydrotreating catalyst, also can prepare by this area ordinary method.As catalyzer forms, can comprise by weight percentage: nickel or cobalt are 0.5%～10% (calculating by its oxide compound), molybdenum or tungsten are 1%～30% (calculating by its oxide compound), carrier can be aluminum oxide, silicon oxide, aluminium oxide-silicon oxide, titanium oxide, one or more in various molecular sieves etc.Catalyzer is extrudate or spherical.The bulk density of catalyzer is 0.5～1.1g/cm
3, granules of catalyst diameter (spherical diameter or bar shaped diameter) is 0.04～1.0mm, specific surface area is 80～400m
2/ g.
The raw material that the present invention processes is any hydrocarbon raw material.Generally include one or more mixing of spray vapour fuel fraction, diesel oil distillate, catalytic cracking light cycle oil (LCO), wax tailings (CGO), light vacuum gas oil (LVGO), heavy vacuum gas oil (HVGO) etc.
As shown in Figure 1, a kind of technological process of the present invention is: after stock oil 1 enters reactor 4, through liquid phase divider hollow disc 3, be evenly distributed in each venturi-type eductors, eject high velocity liquid stream.Hydrogen directly enters phase chamber 7 after preheating, by high velocity liquid stream, is carried and is entered beds.
For further illustrating the solution of the present invention and effect, enumerate following examples and comparative example:
Embodiment
The present embodiment is a kind of embodiment that hydrocarbon oil hydrogenation is processed, and the operating process schematic diagram is with reference to accompanying drawing 1.
Adopt stock oil character in Table 1, catalyzer is selected the FH-UDS Hydrobon catalyst of Fushun Petrochemical Research Institute's development and production.The composition of FH-UDS catalyzer and quality index are in Table 2, and processing condition are in Table 3, and refined diesel oil character is in Table 4.
Comparative example
With embodiment, compare, comparative example adopts conventional gas-liquid partition tray, and stock oil character is in Table the composition of 1, FH-UDS catalyzer and quality index in Table 2, and processing condition are in Table 3, and refined diesel oil character is in Table 4.
Table 1 stock oil character
The composition of table 2 catalyzer and quality index
Table 3 processing condition
| Processing condition | Embodiment | Comparative example |
| Temperature of reaction, ℃ | 360 | 360 |
| Reaction pressure, MPa | 5.0 | 5.0 |
| Hydrogen to oil volume ratio | 250∶1 | 800∶1 |
| Volume space velocity, h -1 | 2.0 | 2.0 |
Table 4 treated oil character
Above result can be found out, adopt hydrogen of the present invention fully to be dissolved in liquid phase material with oversaturated state, in the situation that hydrogen to oil volume ratio significantly reduces, still obtain hydrogenation effect preferably, illustrate that hydrogen utilization ratio and reactor upper catalyst bed layer efficiency obviously improve.
Claims (8)
1. the hydroprocessing process of a low hydrogen/gasoline ratio, it is characterized in that: hydrogen directly is delivered to reactor head space, at the reactor inner top, the liquid phase divider is set, the liquid phase divider consists of top hollow disc structure and at least one venturi-type eductors of being communicated with hollow disc, stock oil directly is delivered in the hollow disc of liquid phase divider by pipeline, enter venturi-type eductors through hollow disc, in the venturi-type eductors outlet, spraying is, during vaporific fluid is dispersed in gas phase, then flows downward and carry out the hydrotreatment reaction through beds; In the venturi-type eductors outlet position, tube-in-tube structure is set, beds below the annular slot of hydrogen between venturi-type eductors and sleeve enters; Stock oil is one or more mixing of spray vapour fuel fraction, diesel oil distillate, catalytic cracking light cycle oil, wax tailings, light vacuum gas oil and heavy vacuum gas oil; The reactive metal that beds is used catalyzer is one or more in nickel, cobalt, molybdenum or tungsten; The hydrogen to oil volume ratio of described low hydrogen/gasoline ratio hydroprocessing process is 50:1～600:1.
2. it is characterized in that in accordance with the method for claim 1: the hollow disc diameter of liquid phase divider is reactor inside diameter 50%～90%.
3. in accordance with the method for claim 1, it is characterized in that: catalyzer forms and can comprise by weight percentage: nickel or cobalt are calculated as 0.5%～10% by its oxide compound, molybdenum or tungsten are calculated as 1%～30% by its oxide compound, and carrier is one or more in aluminum oxide, silicon oxide, aluminium oxide-silicon oxide, titanium oxide, molecular sieve.
4. in accordance with the method for claim 1, it is characterized in that: the hydrotreatment reaction conditions is 100～450 ℃ of temperature of reaction, reaction pressure 0.5～18.0MPa, and during liquid, volume space velocity is 0.6～5.0h
-1.
5. in accordance with the method for claim 1, it is characterized in that: the hydrotreatment reaction pressure is 2.5～15.0MPa, and hydrogen to oil volume ratio is 200:1～400:1, and during liquid, volume space velocity is 2.0～4.0h
-1.
6. in accordance with the method for claim 1, it is characterized in that: the hydrotreating reactor structure that hydroprocessing process is used is as follows: reactor head arranges hydrogen inlet, at the reactor inner top, the liquid phase divider is set, the liquid phase divider consists of top hollow disc structure and at least one venturi-type eductors of being communicated with hollow disc, and stock oil directly is delivered in the hollow disc of liquid phase divider by pipeline.
7. it is characterized in that in accordance with the method for claim 6: the hollow disc diameter of liquid phase divider is reactor inside diameter 50%～90%.
8. in accordance with the method for claim 6, it is characterized in that: in the venturi-type eductors outlet position, tube-in-tube structure is set, between venturi-type eductors and sleeve, there is annular slot.
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| CN103789006B (en) * | 2012-11-03 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of two-phase hydrogenation reactor and two-phase hydrogenation method |
| CN103789005B (en) * | 2012-11-03 | 2016-03-02 | 中国石油化工股份有限公司 | Molten hydrogen methods in a kind of two-phase hydrogenation reactor |
| CN106520186B (en) * | 2015-09-09 | 2018-08-17 | 中国石化工程建设有限公司 | A kind of heavy oil faces hydrogen method for thermal cracking |
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