CN110396425A - Micro-interface strengthens the device and method that liquid phase circulation adds hydrogen - Google Patents
Micro-interface strengthens the device and method that liquid phase circulation adds hydrogen Download PDFInfo
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- CN110396425A CN110396425A CN201910768245.1A CN201910768245A CN110396425A CN 110396425 A CN110396425 A CN 110396425A CN 201910768245 A CN201910768245 A CN 201910768245A CN 110396425 A CN110396425 A CN 110396425A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to petroleum refinings and technical field of petrochemical industry, strengthen the device and method that liquid phase circulation adds hydrogen more particularly, to a kind of micro-interface.Described device includes: head tank, heating furnace, microbubble generator, hydrogenation unit, hydrogenator and separator；The heated furnace of the discharge end of the head tank is connected to the microbubble generator, and the hydrogenation unit is connected to the microbubble generator；The discharge end of the microbubble generator is connected to the hydrogenator, and the discharge end of the hydrogenator is connected to the separator.The described method includes: microbubble stream carries out hydrogenation reaction in hydrogenator, through separator collection hydrogenation products；Mainly by preheating feedstock oil and hydrogen, gas-liquid mixed obtains the microbubble stream in microbubble generator.The present invention can increase substantially the space utilization rate of reactor, and nearly 10-20% can be improved；It can reduce the pressure in device system simultaneously, installation cost be greatly reduced.
Description
Technical field
The present invention relates to petroleum refinings and technical field of petrochemical industry, strengthen liquid phase circulation more particularly, to a kind of micro-interface
Add the device and method of hydrogen.
Background technique
Currently, boat coal, diesel oil deepness hydrogenation purification are mainly recycled using hydrogen and the technology of liquid phase circulation, while
There is tubular type liquid-phase hydrogenatin technique.
When the trickle bed reactor operation of conventional hydrogen circulation, excessive circulating hydrogen is 10 of amounts of hydrogen needed for chemical depletion
Times.Gas and liquid mixing cocurrent pass through downwards inner member and catalyst bed, and vapor liquid equilibrium shape is in catalyst bed
State.In catalyst surface, dissolves in hydrogen and charging and chemically reacted between reactive material, the hydrogen in liquid phase gradually subtracts
It is few, so vapor phase hydrogen is gradually dissolved in liquid phase and is supplemented.It can be seen that: the reaction speed in traditional trickle bed reactor is main
It is influenced by mass transfer velocity, under normal circumstances, mass transfer velocity is more many slowly than kinetic reaction speed.
It, being capable of deep hydrogenation using liquid phase circulation hydrogen addition technology, it is ensured that the sulfur content in oil product is lower.Entirely add hydrogen
Hydrogen flowing quantity in treatment process reduces and saves hydrogen gas circulating system and circulating hydrogen compressor, can save device for enterprise and build
If investment, and reduce Clean Fuel Production cost.
Liquid phase circulation adds the status of hydrogen to be: (1) liquid-phase hydrogenatin pressure is higher than gas phase hydrogenation, higher particularly with hydrogen-consuming volume
Oil product (diesel oil or wax oil) causes the pressure rating of the affiliated facilities such as process pipe to improve, without too big excellent in investment cost
Gesture；(2) hydrogen make-up between more beds needs that multiple air and liquid mixers are arranged in inside reactor, leads to complicated for operation, reaction
Device space utilization rate is lower.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of micro-interface and strengthens the device that liquid phase circulation adds hydrogen, to solve existing skill
The low technical problem of reactor fluctuation of service, space utilization rate present in art.
The second object of the present invention is to provide a kind of micro-interface and strengthens the method that liquid phase circulation adds hydrogen, this method stability
It is good, high reliablity.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
Micro-interface strengthens the device that liquid phase circulation adds hydrogen, comprising: head tank, heating furnace, microbubble generator plus hydrogen list
Member, hydrogenator and separator；
The heated furnace of the discharge end of the head tank is connected to the microbubble generator, and the hydrogenation unit is connected to institute
State microbubble generator；The discharge end of the microbubble generator is connected to the hydrogenator, the hydrogenator
Discharge end is connected to the separator.
The present invention is provided with microbubble generator in the device that liquid phase circulation adds hydrogen, in microbubble generator, hydrogen
It is rapidly dissolved in oil product, and a certain amount of the exess of H2 gas forms uniform microbubble with a large amount of microbubble state and oil product
Stream, the quasi- hydrogenator that is homogeneously directly brought into of this gas-liquid carry out hydrogenation reaction.By the microbubble of a large amount of stable suspersions come
The hydrogen make-up constantly into oil product does not improve merely the solubility of hydrogen by high pressure, can suitably reduce device system
Interior pressure, is greatly reduced installation cost, can especially make diesel oil and wax oil liquid phase circulation that the economic benefit of hydrogen be added significantly to mention
It rises.
Meanwhile the present invention can be not necessarily to additional benefit hydrogen and exhaust system, keep entire reaction process simpler, and run steady
Qualitative more preferable, reaction effect is more preferable.Midway benefit hydrogen system is even cancelled in reduction in hydrogenator, is greatly improved and adds
The space utilization rate of hydrogen reactor improves production efficiency.
The present invention is formed by metastable homogeneous microbubble stream, meets basic hydrogen supply demand into hydrogenator,
It can cancel or reduce air and liquid mixer and exhaust system in existing liquid phase circulation hydrogenation technique, hydrogenator is run more
Steadily, operation difficulty reduces, and space utilization rate improves.Hydrogen storage equipment etc. is mixed compared to hypergravity, improves equipment safety reliability,
Energy consumption is reduced simultaneously, improves capacity usage ratio, and can be improved gas liquid ratio.
Also, in the microbubble stream formed by microbubble generator, bubble substantially exists with micron-sized scale,
It can simplify operating process, reduce system pressure, save equipment investment, and can improve under lower operating pressure making for hydrogen
With efficiency, good plus hydrogen environment is provided.
In a preferred embodiment of the invention, the discharge end of the head tank is connected to the heating by feed pump
Furnace.Conventional pump or booster pump can be used in the feed pump, suitably to adjust the pressure of feedstock oil.
Optionally, flow control valve is provided between the feed pump and the heating furnace.Heating furnace is sent into for adjusting
In feedstock oil amount and conveying speed etc..
In a preferred embodiment of the invention, including at least two head tanks, the first head tank and the second head tank, institute
It states the first head tank and the second head tank is connected to by pump, the discharge end of second head tank is connected to described by feed pump
Heating furnace.
Wherein, the pump between the first head tank and the second head tank is preferably booster pump, and feedstock oil is pressurized to properly
Pressure.
Optionally, flow control valve is provided between the booster pump and second head tank.The is sent into for adjusting
Amount and conveying speed of feedstock oil in two head tanks etc..
Heating furnace of the invention can be heated to 320-400 DEG C such as heating to feedstock oil to be reacted.
Further include circulating pump in an of the invention preferred embodiment, the hydrogenator by the circulating pump with
The microbubble generator is connected.
Reactant after the outflow of hydrogenator discharge end, be according to condition divided into two strands (according to the sulfur content of reaction product and
Temperature is divided into two strands, requires to be separated according to concrete technology condition), one carries out subsequent separator, one passes through circulation
Pump carries out circulation plus hydrogen back to microbubble generator.
Optionally, flow control valve is provided between the circulating pump and the microbubble generator.It is sent into for adjusting
Amount and conveying speed of the oil product of microbubble generator etc..
In the embodiment of the invention, the hydrogenation unit is hydrogen gas lines.The hydrogen gas lines are used for micro-
Fresh hydrogen is conveyed in bubble generator.
Optionally, flow control valve is provided in the hydrogen gas lines.For adjusting the hydrogen for being sent into microbubble generator
Amount and conveying speed etc..
In the embodiment of the invention, the hydrogenator includes downflow reactor and up-flow reactor
Any one of.It can be selected in conventional hydro reactor according to actual needs, and can no setting is required in hydrogenator
Hydrogen unit is mended, the space utilization rate of reactor is increased substantially.
The quasi- equal phase gas-liquid mixture stream of microbubble generator output immerses hydrogenator and contacts with catalyst, is formed
Gas, solid, liquid three-phase, liquid phase are continuous phase, and gas phase is micron-sized evenly dispersed phase, carry out efficient hydrogenation reaction；Once liquid
Amounts of hydrogen in phase is gradually reduced with reaction, and micron-sized bubble is quickly dissolved in liquid phase, the hydrogen one in liquid phase
Directly it is in dynamic saturation state.
In a specific embodiment of the invention, it may be provided with microbubble flow distributor in the hydrogenator, it is described
Microbubble flow distributor is connected to the microbubble generator.As the microbubble flow distributor may be disposed at the hydrogenation reaction
The catalyst bed interlayer of device is preferably provided at first catalyst bed interlayer.
In actual operation, hydrogen is mended if necessary to midway, it can be by the microbubble flow distributor in hydrogenator to adding
The microbubble stream for meeting temperature condition is directly injected into hydrogen reactor.
The structure of the microbubble flow distributor is identical as gas distributor structure, and difference is the microbubble flow distributor
For injecting microbubble stream into hydrogenator.
In the embodiment of the invention, the microbubble generator can be cyclone-type microbubble generator.It is former
High speed rotation, the formation low pressure at hollow shaft aspirate hydrogen to material oil wherein, under the effect of microbubble generator inner eddy flow,
Hydrogen is torn by high speed liquid phase material and is divided into a large amount of bubbles.One side hydrogen is quickly dissolved into feedstock oil, another aspect mistake
Surplus hydrogen is formed with micron-sized bubble shape and oil product and intends equal phase gas-liquid mixture stream.
In a preferred embodiment of the invention, including more than two microbubble generators, each microbubble hair
It is connected in series or in parallel between raw device.Each microbubble generator can be all connected to hydrogenator, heating furnace and circulation
Pump.
In actual operation, as included multiple microbubble generators, then the gas-liquid amount and gas in each microbubble generator
Liquor ratio can be identical, can also be different.
In the embodiment of the invention, the separator is thermal low-pressure separators.
Preferably, counterbalance valve is provided between the hydrogenator and the separator.For adjusting the flowing of oil product
Deng.
The present invention also provides a kind of micro-interfaces to strengthen the method that liquid phase circulation adds hydrogen, includes the following steps:
Microbubble stream carries out hydrogenation reaction in hydrogenator, through separator collection hydrogenation products；
Mainly by preheating feedstock oil and hydrogen, gas-liquid mixed obtains the microbubble stream in microbubble generator.
Optionally, the temperature after the feedstock oil preheating is 320-400 DEG C.
Optionally, in the microbubble generator gas-liquid mixed condition are as follows: temperature be 100-380 DEG C, pressure 2-
10MPa.Wherein, temperature is preferably 120-320 DEG C, pressure 2-9MPa.
Optionally, under standard state, the gas liquid ratio in the microbubble generator is 1 ﹕, 1~80 ﹕ 1.
Optionally, what reacted device obtained obtain, and recycle oil is sent into microbubble generator carries out circulation hydrogenation reaction.
Optionally, the volume ratio of the recycle oil and feedstock oil is 1 ﹕, 1~10 ﹕ 1.
In actual operation, the feedstock oil includes boat coal, diesel oil and any one or more of mixing of wax oil.
Compared with prior art, the invention has the benefit that
(1) in the device of the invention, it can reduce even to cancel and mend hydrogen unit, increase substantially the space utilization of reactor
Nearly 10-20% can be improved in rate；Whole device operation simultaneously is more steady, and there is no the gearings between more beds, and reaction effect is more
It is good；
(2) in microbubble generator of the invention, hydrogen is rapidly dissolved in oil product, and a certain amount of the exess of H2 gas with
A large amount of microbubble state and oil product form uniform microbubble stream, by the microbubble of a large amount of stable suspersions come constantly to oil product
Middle hydrogen make-up does not improve merely the solubility of hydrogen by high pressure, can suitably reduce the pressure in device system, greatly
Width reduces installation cost, can especially make diesel oil and wax oil liquid phase circulation that the economic benefit of hydrogen be added significantly to be promoted；
(3) in circulation method of hydrotreating of the invention, system pressure is relatively low, and system stability and safety are more preferable.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is that the micro-interface that one embodiment of the invention provides strengthens the apparatus structure schematic diagram that liquid phase circulation adds hydrogen；
Fig. 2 be another embodiment of the present invention provides micro-interface strengthen liquid phase circulation and add the apparatus structure schematic diagram of hydrogen.
Appended drawing reference:
The first head tank of 1-；2- booster pump；The second head tank of 3-；
4- feed pump；5- heating furnace；6- circulating pump；
7- hydrogen gas lines；8- microbubble generator；9- hydrogenator；
10- separator；11- microbubble flow distributor.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that it is following described embodiments are some of the embodiments of the present invention, rather than it is whole
Embodiment is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same
Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
In the description of the present invention, it should be noted that term " center ", "upper", "lower", "left", "right", "vertical",
The orientation or positional relationship of the instructions such as "horizontal", "inner", "outside" be based on the orientation or positional relationship shown in the drawings, merely to
Convenient for description the present invention and simplify description, rather than the device or element of indication or suggestion meaning must have a particular orientation,
It is constructed and operated in a specific orientation, therefore is not considered as limiting the invention.In addition, term " first ", " second ",
" third " is used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance.
In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term " installation ", " phase
Even ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or be integrally connected；It can
To be mechanical connection, it is also possible to be electrically connected；It can be directly connected, can also can be indirectly connected through an intermediary
Connection inside two elements.For the ordinary skill in the art, above-mentioned term can be understood at this with concrete condition
Concrete meaning in invention.
Fig. 1 is the structural schematic diagram that the micro-interface that one embodiment of the invention provides strengthens liquid phase circulation hydrogenation plant.This reality
The micro-interface for applying example offer strengthens liquid phase circulation hydrogenation plant, including head tank, heating furnace 5, microbubble generator 8 plus hydrogen list
Member, hydrogenator 9 and separator 10.The heated furnace 5 of the discharge end of the head tank is connected to the microbubble generator 8,
The hydrogenation unit is connected to the microbubble generator 8；It is anti-that the discharge end of the microbubble generator 8 is connected to described plus hydrogen
Device 9 is answered, the discharge end of the hydrogenator 9 is connected to the separator 10.
Specifically, the hydrogenation unit can be hydrogen gas lines 7.The hydrogen gas lines 7 are used for into microbubble generator 8
Convey fresh hydrogen.Further, it is provided with flow control valve in the hydrogen gas lines 7, is sent into microbubble hair for adjusting
Amount and conveying speed of hydrogen in raw device 8 etc..The pressure of hydrogen in the hydrogen gas lines 7 can be adjusted according to actual needs
Section.
It is understood that the hydrogenator 9 can be times in downflow reactor or up-flow reactor
One kind, and it is not limited to this, it can be selected in conventional hydro reactor according to actual needs, and can nothing in hydrogenator
It need to be arranged and mend hydrogen unit, increase substantially the space utilization rate of reactor.
Optionally, described device includes more than one head tank, such as may include two head tanks, the first head tank 1
With the second head tank 3.
Specifically, first head tank 1 is connected to the second head tank 3, the discharge end of second head tank 3 by pump
The heating furnace 5 is connected to by feed pump 4.
Optionally, first head tank 1 is connected to second head tank 3 by booster pump 2.Fresh feed oil is
In one head tank 1 after mixing, feedstock oil convenient pressure is increased to by booster pump 2 to be sent into the second head tank 3.
Further, it is provided with flow control valve between the booster pump 2 and second head tank 3, is sent into adjusting
Amount and conveying speed of feedstock oil in second head tank 3 etc..
It is understood that the feed pump 4 can be conventional pump either booster pump, suitably to adjust the pressure of feedstock oil
Power.
Optionally, it is provided with flow control valve between the feed pump 4 and the heating furnace 5, is sent into heating for adjusting
The amount and delivery pipe speed of feedstock oil in furnace 5.
Optionally, described device further includes circulating pump 6, and the discharge end of the hydrogenator 9 is connected by the circulating pump 6
It is connected to the microbubble generator 8.Further, flow tune is provided between the circulating pump 6 and the microbubble generator 8
Valve is saved, for adjusting amount and the conveying speed etc. of being sent into the oil product of microbubble generator 8.
Optionally, the microbubble generator 8 is cyclone-type microbubble generator.Feedstock oil high speed rotation wherein, In
Low pressure is formed at hollow shaft, aspirates hydrogen, and under the effect of microbubble generator inner eddy flow, hydrogen is torn by high speed liquid phase material
It is divided into a large amount of bubbles.One side hydrogen is quickly dissolved into feedstock oil, and on the other hand superfluous hydrogen is with micron-sized bubble
Form and oil product, which are formed, intends equal phase gas-liquid mixture stream.It is understood that the microbubble generator 8 is also possible to other kinds
The microbubble generator of class can be realized for hydrogen and feedstock oil to be mixed to form and intend equal phase gas-liquid mixture stream.
Optionally, described device includes more than two microbubble generators, the company of series connection between each microbubble generator
It connects.
In actual operation, as included multiple microbubble generators, then the gas-liquid amount and gas in each microbubble generator
Liquor ratio can be identical, can also be different.
Optionally, the separator 10 is thermal low-pressure separators.Further, the hydrogenator 9 is separated with described
It is provided with counterbalance valve between device 10, for adjusting the flowing etc. of oil product.
Referring to FIG. 2, its be another embodiment of the present invention provides micro-interface strengthen liquid phase circulation and add the apparatus structure of hydrogen
Schematic diagram.Specifically, being provided with microbubble flow distributor 11 in the hydrogenator 9, the microbubble flow distributor 11 connects
It is connected to the microbubble generator 8.As the microbubble flow distributor may be disposed at the catalyst bed of the hydrogenator 9
Between, it is preferably provided at first catalyst bed interlayer.
In actual operation, hydrogen is mended if necessary to midway, it can be by the microbubble flow distributor in hydrogenator to adding
The microbubble stream of combined temp condition is directly injected into hydrogen reactor.
The structure of the microbubble flow distributor is identical as gas distributor structure, and difference is the microbubble flow distributor
For injecting microbubble stream into hydrogenator.
The present invention also provides a kind of micro-interfaces to strengthen the method that liquid phase circulation adds hydrogen, includes the following steps:
Microbubble stream carries out hydrogenation reaction in hydrogenator, through separator collection hydrogenation products；
Mainly by preheating feedstock oil and hydrogen, gas-liquid mixed obtains the microbubble stream in microbubble generator.
Specifically, the feedstock oil includes boat coal, diesel oil and any one or more of mixing of wax oil.
After being sent into heating furnace, the temperature of feedstock oil is heated to 320-400 DEG C.Under standard state, according to micro- gas
The gas liquid ratio steeped in generator is 1 ﹕, 1~80 ﹕ 1, and the feedstock oil after heating is mixed with hydrogen, makes to carry out in microbubble generator
The temperature of gas-liquid mixed is 100-380 DEG C, pressure 2-10MPa, and preferable temperature is 120-320 DEG C, pressure 2-9MPa.
Microbubble stream obtained in microbubble generator is sent into hydrogenator by reactor top, in hydrogenator
Preceding 30% bed, react the most violent, hydrogen-consuming volume is larger, generally more than 70%, still there is a small amount of microbubble to suspend, microbubble energy
Enough meet the hydrogen consumption of entire hydrogenator.After hydrogenation reaction, is flowed out from hydrogenator bottom, be divided into two strands, one
Into subsequent separator, one returns to microbubble generator by circulating pump, carries out circulation plus hydrogen.Optionally, described to follow
The volume ratio of ring oil and fresh feed oil is 1 ﹕, 1~10 ﹕ 1.
With reference to the device of Fig. 2, midway hydrogen make-up is such as needed, microbubble stream can be supplemented by microbubble flow distributor 11,
Guarantee the hydrogen for having sufficient in subsequent bed.
Embodiment 1
The present embodiment is the specific method that circulation plus hydrogen are carried out using above-mentioned apparatus, is included the following steps:
It (1) is by volume to be incited somebody to action by booster pump after 2 ﹕ 1 are mixed in the first head tank with straight-run diesel oil by coker gas oil
Mixed fresh feed oil is pressurized to 5.0MPa and is delivered in the second head tank；
(2) feedstock oil in the second head tank is delivered in heating furnace by feed pump, is sent into after being heated to 350 DEG C micro-
Bubble generator, while hydrogen being sent into microbubble generator by hydrogen gas lines, hydrogen and raw material in microbubble generator
The gas liquid ratio of oil is 40 ﹕ 1 (volume ratio)；
(3) hydrogen is mixed in microbubble generator under the conditions of 350 DEG C, 5MPa with feedstock oil, is obtained quasi- homogeneous
Microbubble stream；
(4) homogeneous microbubble will be intended to stream in downflow reactor, is carried out under the conditions of 350 DEG C, 5MPa plus hydrogen is anti-
It answers, after hydrogenation reaction, the material of outflow reactor is divided into two strands, one enters separator, and another stock is returned by circulating pump
It returns to microbubble generator and is recycled hydrogenation reaction again.
Diesel oil liquid-phase circulating hydrodesulfurizationsystem is carried out using this technique, sulphur can be produced under 350 DEG C, the process conditions of 6MPa and contained
50ppm refined diesel oil below is measured, sulfur removal rate reaches 98%.
Using apparatus and method of the present invention, the space utilization rate for greatly improving reactor (reduces midway to supplement
Hydrogen link saves this segment space), while operation stability is more preferable.Also, reactor internal pressure is low (to be followed by original liquid phase
Ring adds the operating pressure 9MPa of hydrogen to be down to 6MPa), plant investment amplitude is reduced, the market competitiveness that liquid phase circulation adds hydrogen is improved.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. micro-interface strengthens the device that liquid phase circulation adds hydrogen characterized by comprising head tank, heating furnace, microbubble occur
Device, hydrogenation unit, hydrogenator and separator；
The heated furnace of the discharge end of the head tank is connected to the microbubble generator, and the hydrogenation unit is connected to described micro-
Bubble generator；The discharge end of the microbubble generator is connected to the hydrogenator, the discharging of the hydrogenator
End is connected to the separator.
2. micro-interface according to claim 1 strengthens the device that liquid phase circulation adds hydrogen, which is characterized in that further include circulation
Pump, the hydrogenator are connected by the circulating pump with the microbubble generator；
Preferably, flow control valve is provided between the circulating pump and the microbubble generator.
3. micro-interface according to claim 1 or 2 strengthens the device that liquid phase circulation adds hydrogen, which is characterized in that described plus hydrogen
Unit is hydrogen gas lines；
Preferably, flow control valve is provided in the hydrogen gas lines.
4. micro-interface according to claim 1 or 2 strengthens the device that liquid phase circulation adds hydrogen, which is characterized in that described plus hydrogen
Reactor includes any one of downflow reactor and up-flow reactor；
Optionally, microbubble flow distributor is provided in the hydrogenator, the microbubble flow distributor is connected to described
Microbubble generator；
Optionally, the bubble flow distributor is set to the catalyst bed interlayer of the hydrogenator.
5. micro-interface according to claim 1 or 2 strengthens the device that liquid phase circulation adds hydrogen, which is characterized in that described device
Including more than two microbubble generators, it is connected in series or in parallel between each microbubble generator.
6. micro-interface according to claim 1 or 2 strengthens the device that liquid phase circulation adds hydrogen, which is characterized in that the separation
Device is thermal low-pressure separators；
Preferably, counterbalance valve is provided between the hydrogenator and the separator.
7. a kind of micro-interface strengthens the method that liquid phase circulation adds hydrogen, which comprises the steps of:
Microbubble stream carries out hydrogenation reaction in hydrogenator, through separator collection hydrogenation products；
Mainly by preheating feedstock oil and hydrogen, gas-liquid mixed obtains the microbubble stream in microbubble generator.
8. micro-interface according to claim 7 strengthens the method that liquid phase circulation adds hydrogen, which is characterized in that the microbubble hair
The condition of gas-liquid mixed in raw device are as follows: temperature is 100-380 DEG C, pressure 2-10MPa；
Preferably, in the microbubble generator gas-liquid mixed condition are as follows: temperature be 120-320 DEG C, pressure 2-9MPa.
9. micro-interface according to claim 7 or 8 strengthens the method that liquid phase circulation adds hydrogen, which is characterized in that the raw material
Temperature after oil preheating is 320-400 DEG C；
Optionally, under standard state, the gas liquid ratio in the microbubble generator is 1 ﹕, 1~80 ﹕ 1.
10. micro-interface according to claim 7 or 8 strengthens the method that liquid phase circulation adds hydrogen, which is characterized in that reacted device
Obtained recycle oil is sent into microbubble generator and carries out circulation hydrogenation reaction；
Preferably, the volume ratio of the recycle oil and feedstock oil is 1 ﹕, 1~10 ﹕ 1；
Preferably, the feedstock oil includes boat coal, diesel oil and any one or more of mixing of wax oil.
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