CN103657463B - A kind of gas-liquid mixing processes and application thereof and gas-liquid reaction method - Google Patents
A kind of gas-liquid mixing processes and application thereof and gas-liquid reaction method Download PDFInfo
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Abstract
The invention provides a kind of gas-liquid mixing processes and application thereof, the method comprises injects liquid by gas by the through hole that average pore size is nano-scale, thus is mixed with described liquid by described gas.Present invention also offers a kind of gas liquid reaction method, the method comprises employing gas-liquid mixing processes provided by the invention and is mixed with liquid by gas, and reacts.Gas high degree of dispersion can also be dissolved in a liquid by gas-liquid mixing processes of the present invention at faster speed.
Description
Technical field
The present invention relates to a kind of gas-liquid mixing processes and application thereof, the invention still further relates to a kind of gas liquid reaction method.
Background technology
In recent years, along with the scarcity day by day of petroleum resources, crude oil heaviness, in poor quality trend are on the rise, by S, N, O and the tenor also corresponding increase of the intermediate oil of crude distillation gained.But the laws and regulations of countries in the world require but more and more harsher to S, N, the O in various fuel oil and tenor.Hydrotreatment removes S, N, O and metal impurities in hydrocarbon ils, improves the conventional means of midbarrel oil quality.
In traditional trickle bed hydroprocessing technique, in order to take away a large amount of reaction heat, suppress catalyst carbon deposit green coke, need a large amount of recycle hydrogens and the corresponding circulatory system thereof, make the volume of hydrogenation reaction device comparatively huge on the one hand, also improve cost of investment and the operation energy consumption of hydrogenation reaction device on the other hand.
When carrying out hydrotreatment in trickle bed reactor, hydrogen needs to enter liquid phase from gas phase, is then jointly adsorbed on the surface of catalyst with reactant, thus reacts under the effect of catalyst active center.This mass transport process of hydrogen can have a negative impact to the reaction rate of hydroprocessing technique undoubtedly.
For the deficiency of traditional trickle bed hydroprocessing technique, researcher develops liquid-phase hydrogenatin technique.
US6428686 discloses a kind of hydrotreating method, the method comprises: by fresh feed oil and diluent and in a large number hydrogen mix, the mixture obtained to enter in reactor with catalyst exposure and carries out hydrogenation reaction after gas-liquid separation device isolates excessive gas.Wherein, described diluent is the material (such as: the isocrackate of circulation or isomerization product) hydrogen to relatively high solubility, improves the hydrogen carrying amount of hydrocarbon ils whereby, thus eliminates the demand for recycle hydrogen.
Disclosed in CN101280217A and CN101787305A, the technical process of liquid-solid two-phase hydrogenation method for hydrocarbon oil is: by fresh feed oil, recycle oil and the mixing of supersaturation hydrogen, send in hydrogenation reactor after the mixture obtained is carried out gas-liquid separation in gas-liquid separation device, with catalyst exposure to react.
Although above-mentioned liquid phase hydrogenating method all eliminates the demand for recycle hydrogen, but still have the following disadvantages: need to use diluent or recycle oil to improve the carrying amount of hydrogen in feedstock oil, it reduce the fresh feed oil processing amount of hydrotreater, production efficiency is had a negative impact.
Therefore, need a kind of hydrocarbon ils liquid-phase hydrogenatin treatment process without the need to diluent or recycle oil badly, with simplification of flowsheet route, reduce cost of investment and operating cost, realize efficient industrial production.
Summary of the invention
One object of the present invention is to provide a kind of gas-liquid mixing processes, and gas high degree of dispersion can also be dissolved in a liquid by the method at faster speed.
The present inventor finds: hydrogen is injected hydrocarbon ils by the through hole that average pore size is nano-scale, even if do not use diluent or recycle oil, also can be highly dispersed in hydrocarbon ils by hydrogen with speed faster.This completes the present invention.
A first aspect of the present invention provides a kind of gas-liquid mixing processes, and the method comprises injects liquid by gas by the through hole that average pore size is nano-scale, thus is mixed with described liquid by described gas.
A second aspect of the present invention provides the application of gas-liquid mixing processes according to the present invention in gas and liquid comes into contact react.
A third aspect of the present invention provides a kind of gas liquid reaction method, and the method comprises reacts gas and liquid comes into contact, wherein, adopts gas-liquid mixing processes provided by the invention, by gas inject liquid, thus by described liquid and gas and vapor permeation, to react.
According to gas-liquid mixing processes of the present invention, gas is injected liquid by the through hole that average pore size is nano-scale, gas high degree of dispersion also can be dissolved in a liquid at faster speed.
Accompanying drawing explanation
Fig. 1 is the structural representation of a kind of embodiment of the mixing arrangement that gas-liquid mixing processes according to the present invention uses;
Fig. 2 is the structural representation of the another kind of embodiment of the mixing arrangement that gas-liquid mixing processes according to the present invention uses;
Fig. 3 is the structural representation of another embodiment of the mixing arrangement that gas-liquid mixing processes according to the present invention uses;
Fig. 4 is the cross sectional representation of a kind of embodiment of the film pipe that gas-liquid mixing processes according to the present invention uses;
Fig. 5 is a kind of preferred embodiment according to gas liquid reaction method of the present invention;
The embodiment that Fig. 6 is connected in series for illustration of multiple reactor in gas liquid reaction method according to the present invention;
The embodiment that Fig. 7 is connected in parallel for illustration of multiple reactor in gas liquid reaction method according to the present invention; And
Fig. 8 is for illustration of the part I in Fig. 5.
Detailed description of the invention
A first aspect of the present invention provides a kind of gas-liquid mixing processes, and the method comprises injects liquid by gas by the through hole that average pore size is nano-scale, thus is mixed with described liquid by described gas.
In the present invention, described average pore size is the average pore size of the through hole of nano-scale can be generally 1 nanometer to 1000 nanometer.From improving gas dispersion mixing in a liquid further, and then make gas more uniformly to disperse angle in a liquid to set out sooner, described average pore size is that the average pore size of the through hole of nano-scale is preferably 30 nanometer to 1000 nanometers, be more preferably 30 nanometer to 800 nanometers, more preferably 50 nanometer to 500 nanometers.Described average pore size adopts ESEM method to measure.
Gas can carry out in various mixing arrangement according to gas-liquid mixing processes of the present invention, as long as can be injected liquid, to be mixed with liquid by described gas by the through hole that average pore size is nano-scale by this mixing arrangement.Preferably, described mixing arrangement comprises at least one fluid passage for receiving fluids and at least one is for holding the gas passage of gas, between described fluid passage and gas passage by have described average pore size be the through hole of nano-scale component adjoin, described gas is injected in described liquid by described through hole.
In the present invention, term " fluid passage " refers to can the space of receiving fluids; Term " gas passage " refers to the space that can hold gas.
According to gas-liquid mixing processes of the present invention, position relationship between described fluid passage and described gas passage is not particularly limited, if between described fluid passage and described gas passage by have average pore size be the through hole of nano-scale component adjoin.
In a kind of embodiment of the mixing arrangement used at gas-liquid mixing processes according to the present invention, as shown in Figure 1, gas passage 2 is positioned within fluid passage 1, and having average pore size is that the inwall of the component 3 of the through hole of nano-scale forms described gas passage 2.
In the another kind of embodiment of the mixing arrangement used at gas-liquid mixing processes according to the present invention, as shown in Figure 2, gas passage 2 is positioned at the side of fluid passage 1, and described fluid passage 1 and described gas passage 2 are that the component 3 of the through hole of nano-scale separates by having average pore size.
The one of the mixing arrangement used at gas-liquid mixing processes according to the present invention preferred embodiment in, as shown in Figure 3, gas passage 2 is centered around the outside of fluid passage 1, is that the component 3 of the through hole of nano-scale separates by having average pore size between described gas passage 2 and described fluid passage 1.
According to gas-liquid mixing processes of the present invention, having average pore size is that the component of the through hole of nano-scale can make the gas be contained in described gas passage be the through hole of nano-scale by described average pore size for various and enter in the liquid be contained in described fluid passage, is formed as the component of the bubble of nano-scale.Preferably, to have average pore size described in be the component of the through hole of nano-scale is pipeline.
In one embodiment of the invention, described component is formed by porous material, the average pore size of the through hole in described component is nano-scale (can be 1 nanometer to 1000 nanometer, be preferably 30 nanometer to 1000 nanometers, be more preferably 30 nanometer to 800 nanometers, more preferably 50 nanometer to 500 nanometers).
In another embodiment of the invention, described component comprises matrix and attachment perforated membrane on the matrix, described matrix has through hole, described perforated membrane can be positioned at described matrix be contained on the surface of liquid comes into contact of described fluid passage, also can be positioned on the surface contacted with the gas being contained in described gas passage of described matrix.Preferably, described perforated membrane be positioned at described matrix be contained on the surface of liquid comes into contact of described fluid passage.The average pore size of the through hole in described perforated membrane is nano-scale (can be 1 nanometer to 1000 nanometer, be preferably 30 nanometer to 1000 nanometers, be more preferably 30 nanometer to 800 nanometers, more preferably 50 nanometer to 500 nanometers).The average pore size of the through hole on described matrix is not particularly limited, as long as can by gas.Preferably, the average pore size of the through hole on described matrix is micron-scale (that is, being greater than 1 micron to 1000 microns) or nano-scale (that is, 1 nanometer to 1000 nanometer), and the average pore size of the through hole namely on described matrix can be 1 nanometer to 1000 micron.According to method of the present invention, described porous material and perforated membrane can adopt the conventional method of this area to prepare, and also can be commercially available, repeat no more herein.
In this embodiment, described component is preferably film pipe (that is, will have the void channels of through hole as matrix, the inwall of described void channels and/or outer wall have described perforated membrane).Described film pipe can be common various inorganic film tubes (such as: inorganic ceramic membrane pipe) or organic film pipe, if formed described film pipe material can not with described liquid and described gas and the product generation chemical interaction formed by described liquid and described gas reaction.Described film pipe can adopt conventional method to prepare, and also can be commercially available, repeat no more herein.
According to gas-liquid mixing processes of the present invention, when described component is pipeline, described pipeline can with a housing with the use of.That is, described pipeline is placed in a housing, and Existential Space between the inwall making the outer wall of described pipeline and described housing.
When described component is pipeline, the space of the inwall formation of described pipeline is the described fluid passage for receiving fluids, and the space that the outer wall of described pipeline and the inwall of described housing are formed is the described gas passage for holding gas; Or the space of the inwall formation of described pipeline is the described gas passage for holding gas, and the space that the outer wall of described pipeline and the inwall of described housing are formed is the described fluid passage for receiving fluids.Preferably, the space of the inwall formation of described pipeline is the described fluid passage for receiving fluids, and the space that the outer wall of described pipeline and the inwall of described housing are formed is the described gas passage for holding gas.
When described component is film pipe, preferably using the space that contacts with the perforated membrane on described film pipe as fluid passage.Such as: time on the inner surface that described perforated membrane is positioned at described film pipe, the space of the inwall formation of described film pipe is as the described fluid passage for receiving fluids, and the space that the outer wall of described film pipe and the inwall of described housing are formed is as the described gas passage for holding gas.
According to the present invention, described in have average pore size be the component of the through hole of nano-scale when being pipeline, described pipeline can have a described fluid passage, also can have multiple described fluid passage.From further raising according to the efficiency of method of the present invention (namely, in the identical time by more substantial gas dissolution in liquid) angle, as Fig. 4 (for as described in the schematic diagram of cross section of pipeline) shown in, described pipeline 4 has the fluid passage 1 that multiple (such as 4-20) is parallel to each other.When described fluid passage is multiple, the plurality of fluid passage is preferably uniformly distributed.
According to the present invention, described housing can be the various component with hollow structure and at least one opening, described opening is communicated with source of the gas or wet tank, so that gas or liquid are imported in the space (that is, described gas passage or described fluid passage) formed by the inwall of described housing and the outer wall of described pipeline.
According to gas-liquid mixing processes of the present invention, it is in the through hole of nano-scale that gas is sent into average pore size by the various methods that this area can be adopted to commonly use, and then by this gas inject liquid.Such as, can by pressure differential between gas and liquid (such as: the difference between the pressure in the pressure in described gas passage and described fluid passage) by gas inject liquid.The present invention is not particularly limited for described pressure extent, as long as it is in the through hole of nano-scale that this pressure differential is enough to gas be sent into average pore size, and makes gas enter the bubble being formed as nano-scale in described liquid.
Gas-liquid mixing processes according to the present invention may be used for various gas to mix with liquid.Preferably, according to gas-liquid mixing processes of the present invention, described gas is hydrogen-containing gas, and described liquid is hydrocarbon ils.More preferably, described gas is hydrogen, and described liquid is hydrocarbon ils.
The occasion of reacting is carried out after gas-liquid mixing processes according to the present invention is specially adapted to gas to mix with liquid.
Thus, a second aspect of the present invention provides the application of gas-liquid mixing processes according to the present invention in gas and liquid comes into contact being reacted.
According to a second aspect of the invention, after gas-liquid mixing processes provided by the invention can be adopted to be mixed with liquid by gas, send in reactor and react; Also can adopt gas-liquid mixing processes provided by the invention by gas and liquid in the reactor original position react after mixing.
A third aspect of the present invention provides a kind of gas liquid reaction method, and the method comprises reacts gas and liquid comes into contact, wherein, adopts gas-liquid mixing processes provided by the invention, by gas inject liquid, thus by described liquid and gas and vapor permeation, to react.
According to gas liquid reaction method of the present invention by adopting gas-liquid mixing processes provided by the invention, can by gas high degree of dispersion and rapid solution in a liquid, being applicable to various needs mixes gas with liquid, to carry out the occasion of gas liquid reaction.The instantiation of described gas liquid reaction can include but not limited to: ethene is at PdCl
2-CuCl
2acetum in carry out being oxidized to produce acetaldehyde reaction, with air oxidation isopropylbenzene with produce hydrogen phosphide cumene reaction, with hydrogen peroxide, alkene epoxidation is prepared the reaction of epoxides and the hydrogenation process of all kinds of hydrocarbon ils.According to concrete reaction type, described gas liquid reaction can be carried out in the presence of a catalyst, also can carry out in the absence of a catalyst.
Gas liquid reaction method according to the present invention is particularly suitable for the hydrogenation process of the common various hydrocarbon ils in oil refining field.That is, according to method of the present invention, described gas is preferably hydrogen, and described liquid is preferably hydrocarbon ils.
Gas liquid reaction method according to the present invention is when the hydroprocessing processes for hydrocarbon ils, described hydrocarbon ils can be the common various hydrocarbon ils carrying out hydrotreatment that need in this area, and described hydrotreatment can be the common various hydroprocessing processes (such as: hydrocracking and hydrofinishing) in this area.When the hydroprocessing processes for hydrocarbon ils, the reaction of hydrocarbon ils and hydrogen can this area commonly use there is the existence of the catalyst of catalytic hydrogenation under carry out, the described catalyst with catalytic hydrogenation can carry out suitable selection according to the type of the kind of hydrocarbon ils and hydrotreatment, is not particularly limited.
When the hydroprocessing processes for hydrocarbon ils, described hydrotreatment can for conventional various hydroprocessing techniques.Preferably, described hydrotreatment is liquid-phase hydrogenatin process.When method of the present invention being applied to the liquid-phase hydrogenatin process of hydrocarbon ils, hydrogen is injected hydrocarbon ils by the through hole that average pore size is nano-scale by gas liquid reaction method according to the present invention, can be dissolved in hydrocarbon ils by hydrogen high degree of dispersion and at faster speed; Even if do not use such as diluent and recycle oil that hydrocarbon ils also can be made to carry more hydrogen, thus eliminate the demand for diluent and recycle oil; And before hydrocarbon oil-hydrogen mixture is sent in hydrogenation reactor carrying out hydrotreatment, without the need to carrying out gas-liquid separation.In the present invention, described liquid-phase hydrogenatin process can be carried out under the hydrocarbon ils liquid-phase hydrogenatin treatment conditions of routine, is not particularly limited, repeats no more herein.
In existing hydrocarbon ils liquid-phase hydrogenatin processing method, even if by means of diluent or recycle oil, still need a large amount of hydrogen to inject hydrocarbon ils, that just can guarantee hydrocarbon ils takes the demand that hydrogen amount meets hydrotreatment.Gas liquid reaction method according to the present invention is when the hydroprocessing processes for hydrocarbon ils, can be dissolved in hydrocarbon ils by hydrogen high degree of dispersion and at faster speed, thus method according to the present invention is when mixing hydrogen with hydrocarbon ils, and the amount of the hydrogen of injection can lower than the note hydrogen amount of existing liquid-phase hydrogenatin treatment process.Usually, according to method of the present invention, according to the hydrogen consumption of hydrocarbon ils and the hydrogenation reaction degree of expection, the amount of the hydrogen of injection can be hydrogen the saturated meltage of hydrocarbon ils 0.1-4 doubly, be preferably 0.5-3 doubly.Described saturated meltage refers under hydrocarbon ils liquid-phase hydrogenatin treatment conditions, is dissolved in the grams of the hydrogen in 100g hydrocarbon ils.The various methods that this area can be adopted to commonly use, to determine the saturated meltage of hydrogen in hydrocarbon ils, repeat no more herein.
According to gas liquid reaction method of the present invention, can carry out in a reactor, also can carry out in a plurality of reactors.When carrying out in a plurality of reactors, can for being connected in parallel between described multiple reactor, also can for being connected in series.Time between multiple reactor for being connected in series, along the flow direction of liquid, only gas access can be set at the arrival end of first reactor, also gas access can be set at the arrival end of each reactor.When multiple reactor is for being connected in parallel, a gas access only can be set, gas is mixed with liquid, then the liquid carrying gas be sent in each reactor respectively; Also gas access can be set at the arrival end of each reactor.
Fig. 5 describes the one of gas liquid reaction method of the present invention preferred embodiment for the hydroprocessing processes of hydrocarbon ils.In this embodiment, in mixing arrangement 5, hydrogen 7 is injected hydrocarbon ils 8, take the catalyst exposure that hydrogen hydrocarbon ils enters in hydrogenation reactor 6 and has catalytic hydrogenation, thus carry out hydrogenation reaction.According to this embodiment, multiple hydrogenation reactor can be set, can for being connected in series between multiple hydrogenation reactor, also can for being connected in parallel.When multiple hydrogenation reactor is connected in series, along the flow direction of hydrocarbon ils, mixing arrangement can be arranged on the arrival end of first hydrogenation reactor; Also as shown in Figure 6, a mixing arrangement 5 can be set at the arrival end of each hydrogenation reactor 6.When multiple hydrogenation reactor is connected in parallel, a mixing arrangement only can be set, hydrocarbon ils is mixed with hydrogen, then the mixture obtained be sent into respectively in the multiple hydrogenation reactors be connected in parallel; Also as shown in Figure 7 a mixing arrangement 5 can be set at the arrival end of each hydrogenation reactor 6.
Fig. 8, for illustration of the part I in Fig. 5, shows the annexation between mixing arrangement 5 and hydrogenation reactor 6.As shown in Figure 8, described mixing arrangement 5 comprises gas passage 2 and fluid passage 1, be that the component 3 of the through hole of nano-scale adjoins by having average pore size between gas passage 2 and fluid passage 1, wherein, the inwall of component 3 forms fluid passage 1, the outer wall of component 3 and the inwall of housing 9 form gas passage 2, the closed at both ends of gas passage 2, housing 9 have the opening (not shown) be communicated with hydrogen source gas.On the entrance pipe that this mixing arrangement 5 is connected to hydrogenation reactor 6 on 10.During practical operation, hydrocarbon ils enters in hydrogenation reactor 6 by fluid passage 1, when hydrocarbon ils is by fluid passage 1, the hydrogen in gas passage 2 is injected hydrocarbon ils by component 3, and then disperses and be dissolved in hydrocarbon ils; Taking hydrogen hydrocarbon ils enters in hydrogenation reactor 6 subsequently, under the existence of catalyst with catalytic hydrogenation, carry out hydrogenation reaction.
Can adopt and in various manners mixing arrangement 5 is connected on entrance pipe 10, such as: a ring flange (Fig. 8 shows one of them ring flange 11) respectively can be set at the two ends of mixing arrangement 5, be connected with the flangeseal on corresponding entrance pipe separately (as shown in Figure 8, the ring flange 11 of mixing arrangement one end is tightly connected with the ring flange 12 on entrance pipe 10); The other end of entrance pipe 10 is connected with the ring flange 14 at entrance 15 place of hydrogenation reactor 6 by ring flange 13.
The present invention is described in detail below in conjunction with embodiment and comparative example.
In following examples and comparative example, ESEM method is adopted to measure average pore size.
In following examples and comparative example, adopt the method specified in GB1792-1988 to measure mercaptan sulfur content in aviation kerosine, adopt the method specified in GB/T380-1997 to measure total sulfur content in aviation kerosine.
In following examples and comparative example, pressure is all in gauge pressure.
Embodiment 1-6 is for illustration of gas-liquid mixing processes according to the present invention.
In embodiment 1-6 and comparative example 1-4, with reference to the disclosed (experimental study of gas holdup in fining air bubbles process such as Liu Yan, process engineering journal, 9th volume supplementary issue 1: the 97-101 page, in June, 2009) volumetric expansion method mensuration Average Air Content, namely calculate Average Air Content according to the liquid level difference before and after ventilation.Concrete method of testing is: test in the arrangement as shown in fig. 5, wherein, the hydrogenation reactor 6 in Fig. 5 with internal diameter be 34mm, length be 1500mm glass tube replace; During test, in mixing arrangement 5, gas is mixed with liquid, then send in glass tube, and the height measuring the liquid level in glass tube (counts H
2); The equivalent same liquid not carrying gas is sent in glass tube, and the height measuring the liquid level in glass tube (counts H
1), by following formulae discovery Average Air Content:
Embodiment 1
In this embodiment, mixing arrangement 5 comprises the pipeline formed by porous material and (is purchased Tianyuan Genie et Environnement in Beijing, external diameter is 25.4mm, cross-section of pipeline as shown in Figure 4, pipeline is evenly distributed with 19 fluid passages, the internal diameter of each fluid passage is 3.3mm, and the average pore size of the through hole on tube wall is 50nm) and the housing (internal diameter is 34mm) that uses with this tube fit, the space that the outer wall of pipeline and the inwall of housing are formed is gas passage.
Hydrogen is injected water by the condition listed according to table 1, and measure Average Air Content, result is listed in Table 1, and wherein, the height of the hydrostatic column that the water not carrying hydrogen is formed in glass tube is 200mm.
Comparative example 1
Adopt the method identical with embodiment 1 that hydrogen is injected water, unlike, in mixing arrangement, the average pore size of the through hole on the tube wall of the pipeline formed by porous material is 5 μm.The Average Air Content obtained is listed in Table 1.
Comparative example 2
Adopt the method identical with embodiment 1 that hydrogen is injected water, unlike, the O type porcelain ring of the pipeline formed by porous material in mixing arrangement by Φ 3mm loads the interlayer replacement that the thickness formed is 250mm.The Average Air Content obtained is listed in Table 1.
Embodiment 2
Adopt the method identical with embodiment 1, under the condition that table 1 is listed, hydrogen is injected water, unlike, mixing arrangement 5 comprises film pipe and (is purchased Tianyuan Genie et Environnement in Beijing, external diameter is 25.4mm, the average pore size of the through hole on matrix is 100 μm, the average pore size of the through hole on perforated membrane is 250nm, perforated membrane is positioned on the outer wall of film pipe) and the housing (internal diameter is 40mm) that uses with this tube fit, the space of the inwall formation of film pipe is as fluid passage, the space that the outer wall of film pipe and the inwall of housing are formed is as gas passage, the cross section of film pipe as shown in Figure 4, be evenly distributed with 7 fluid passages, the internal diameter of each fluid passage is 6mm, hydrogen is injected water.The Average Air Content obtained is listed in Table 1.
Embodiment 3
Adopt the method identical with embodiment 1, under the condition that table 1 is listed, hydrogen is injected aviation kerosine, unlike, mixing arrangement 5 comprises film pipe, and (be purchased from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, external diameter is 25.4mm, and the average pore size of the through hole on matrix is 100 μm; The average pore size of the through hole on perforated membrane is 500nm, perforated membrane is positioned on the inwall of film pipe) and the housing (internal diameter is 40mm) that uses with this tube fit, the space of the inwall formation of film pipe is as fluid passage, the space that the outer wall of film pipe and the inwall of housing are formed is as gas passage, the cross section of pipeline as shown in Figure 4, be evenly distributed with 19 fluid passages, the internal diameter of each fluid passage is 3.3mm.The Average Air Content obtained is listed in Table 1.
Table 1
Embodiment 4
Adopt the device identical with embodiment 1, under the condition that table 2 is listed, oxygen is injected water.The Average Air Content obtained is listed in table 2.
Comparative example 3
Adopt the device identical with comparative example 1, under the condition that table 2 is listed, oxygen is injected water.The Average Air Content obtained is listed in table 2.
Comparative example 4
Adopt the device identical with comparative example 2, under the condition that table 2 is listed, oxygen is injected water.The Average Air Content obtained is listed in table 2.
Embodiment 5
Adopt the device identical with embodiment 2, under the condition that table 2 is listed, oxygen is injected water.The Average Air Content obtained is listed in table 2.
Embodiment 6
Adopt the device identical with embodiment 3, under the condition that table 2 is listed, oxygen is injected aviation kerosine.The Average Air Content obtained is listed in table 2.
Table 2
The result display of table 1 and table 2, according to gas-liquid mixing processes of the present invention can by gas high degree of dispersion and rapid solution in a liquid, thus make liquid have higher gas carrying amount.
Embodiment 7-10 is used for illustrating according to gas-liquid mixing processes of the present invention and applies and gas-liquid reaction method.
Embodiment 7
The method shown in Fig. 5 of employing, in aviation kerosine, hydrogen is injected by mixing arrangement, (internal diameter is 65mm will to take hydrogen boat coal feedstock oil feeding tubular fixed-bed reactor, 1 beds is provided with in tubular reactor, Catalyst packing ratio of height to diameter is 25, the catalyst used is the hydrogenation catalyst that to be purchased from the trade mark of Fushun Petrochemical Research Institute of China Petrochemical Industry be RSS-2) in, carry out hydrofinishing under the conditions shown in Table 3.Feedstock oil illustrates in table 3 with the character of the hydrogenation products obtained.
Wherein, in the fluid passage of mixing arrangement, temperature is 260 DEG C, and pressure is 2.0MPa; Relative to the feedstock oil of 100 weight portions, the amount of the hydrogen of injection is that (wherein, the chemical hydrogen consumption amount of 100 raw material oil is 0.02 weight portion to 0.025 weight portion; Under Hydrofinishing conditions shown in table 3, the saturated meltage of hydrogen in feedstock oil is 0.05 % by weight).
Mixing arrangement comprises the pipeline formed by porous material and (is purchased from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, external diameter is 25.4mm, cross-section of pipeline as shown in Figure 4, pipeline is evenly distributed with 19 fluid passages, the internal diameter of each fluid passage is 3.3mm, the average pore size of the through hole on tube wall is 50nm) and the housing (internal diameter is 40mm) that uses with this tube fit, the space that the outer wall of pipeline and the inwall of housing are formed is gas passage.
Comparative example 5
The method identical with embodiment 7 is adopted to carry out hydrofinishing to aviation kerosine, unlike, do not use mixing arrangement 5, but be that hydrogen passes in the mixture of fresh aviation kerosine and circulation aviation kerosine (relative to the fresh aviation kerosine of 100 weight portion by the mixing arrangement of 250mm by being loaded the thickness formed by the O type porcelain ring of Φ 3mm, the amount of circulation aviation kerosine is 200 weight portions, the amount of the hydrogen injected is 0.075 weight portion) then take hydrogen mixture after gas-liquid separation device isolates excessive gas by what obtain, inject hydrogenation reactor and carry out hydrofining reaction, wherein, the character of the hydrogenation products obtained illustrates in table 3.
Comparative example 6
The method identical with embodiment 7 is adopted to carry out hydrofinishing to aviation kerosine, unlike, the average pore size of the through hole on the tube wall of the pipeline formed by porous material in mixing arrangement is 5 μm (being purchased from BeiJing ZhongTianYuan Environment Engineering Co., Ltd).The character of the hydrogenation products obtained illustrates in table 3.
Table 3
Embodiment 8
The method identical with embodiment 7 is adopted to carry out hydrofinishing to aviation kerosine, unlike:
Mixing arrangement comprises film pipe and (is purchased Tianyuan Genie et Environnement in Beijing, external diameter is 25.4mm, the average pore size of the through hole on matrix is 100 μm, the average pore size of the through hole on perforated membrane is 250nm, and perforated membrane is positioned on the outer wall of film pipe) and the housing (internal diameter is 40mm) that uses with this tube fit; The cross section of film pipe as shown in Figure 4, is evenly distributed with 7 fluid passages, and the internal diameter of each fluid passage is 6mm; The space that the outer wall of film pipe and the inwall of housing are formed is gas passage;
In the fluid passage of mixing arrangement, temperature is 260 DEG C, and pressure is 2.0MPa; Relative to the feedstock oil of 100 weight portions, the amount of the hydrogen of injection is that (wherein, the chemical hydrogen consumption amount of 100 raw material oil is 0.02 weight portion to 0.04 weight portion; Under Hydrofinishing conditions shown in table 4, the saturated meltage of hydrogen in feedstock oil is 0.05 % by weight), under the condition shown in table 4, carry out hydrotreatment;
Feedstock oil illustrates in table 4 with the character of the hydrogenation products obtained.
Table 4
Embodiment 9
The method identical with embodiment 7 is adopted to carry out hydrofinishing to aviation kerosine, unlike:
Mixing arrangement comprises film pipe and (is purchased from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, external diameter is 25.4mm, the average pore size of the through hole on matrix is 100 μm, the average pore size of the through hole on perforated membrane is 500nm, and perforated membrane is positioned on the inwall of film pipe) and the housing (internal diameter is 40mm) that uses with this tube fit; As shown in Figure 4, be evenly distributed with 19 internal diameters is the fluid passage of 3.3mm to the cross section of pipeline; The space that the outer wall of film pipe and the inwall of housing are formed is gas passage;
In the fluid passage of mixing arrangement, temperature is 280 DEG C, and pressure is 4.0MPa; Relative to the feedstock oil of 100 weight portions, the amount of the hydrogen of injection is that (wherein, the chemical hydrogen consumption amount of 100 raw material oil is 0.05 weight portion to 0.05 weight portion; Under Hydrofinishing conditions shown in table 5, the saturated meltage of hydrogen in feedstock oil is 0.05 % by weight); Under condition shown in table 5, carry out hydrofinishing;
The character of the hydrogenation products obtained illustrates in table 5;
The catalyst used is the hydrogenation catalyst that to be purchased from the trade mark of Fushun Petrochemical Research Institute of China Petrochemical Industry be FH-UDS.
Embodiment 10
The method identical with embodiment 9 is adopted to carry out hydrofinishing to aviation kerosine, unlike, fixed bed reactors are autoclave fixed bed reactors ((internal diameter is 1600mm, is provided with 1 beds in reactor, and the ratio of height to diameter of Catalyst packing is 6.0).The character of the hydrogenation products obtained illustrates in table 5.
Table 5
The result of embodiment 7-10 shows, adopts method of the present invention to be mixed with hydrocarbon ils by hydrogen, even if not by means of diluent or recycle oil, also can by hydrogen high degree of dispersion and rapid solution in various hydrocarbon ils; Further, adopt method of the present invention to carry out hydrofinishing to hydrocarbon ils and can obtain better hydrofinishing effect.
Claims (6)
1. a gas liquid reaction method, the method comprises reacts gas and liquid comes into contact, described gas is hydrogen, and described liquid is hydrocarbon ils, and described reaction is carried out under the catalyst with catalytic hydrogenation exists, it is characterized in that, the method comprises: in mixing arrangement, hydrogen is injected hydrocarbon ils, obtains taking hydrogen hydrocarbon ils, described in take hydrogen hydrocarbon ils enter from bottom hydrogenation reactor with there is the catalyst exposure of catalytic hydrogenation, to react, export hydrogenation products from the top of hydrogenation reactor;
Described mixing arrangement comprises at least one for holding the fluid passage of described liquid and at least one is for holding the gas passage of described gas, between described fluid passage and described gas passage by have average pore size be the through hole of nano-scale component adjoin, described gas is injected in described liquid by described through hole;
Described reaction is carried out under liquid-phase hydrogenatin treatment conditions;
The amount of hydrogen injecting hydrocarbon ils be under described liquid-phase hydrogenatin treatment conditions, the 0.1-4 of the saturated meltage of hydrogen in described hydrocarbon ils doubly, described in take hydrogen hydrocarbon ils and the catalyst with catalytic hydrogenation contact carry out under the condition that there is not recycle oil.
2. method according to claim 1, wherein, described component is formed by porous material, and the average pore size of the through hole in described component is nano-scale; Or
Described component comprises matrix and attachment perforated membrane on the matrix, and described matrix has through hole, and the average pore size of the through hole in described perforated membrane is nano-scale.
3. method according to claim 2, wherein, described perforated membrane be positioned at described matrix be contained on the surface of described liquid comes into contact of described fluid passage.
4. method according to claim 2, wherein, described component is pipeline.
5. method according to claim 4, wherein, the inwall of described pipeline forms described fluid passage, and outer wall and a housing of described pipeline form described gas passage.
6. according to the method in claim 1-5 described in any one, wherein, the average pore size of described through hole is 30-1000nm.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210360982.6A CN103657463B (en) | 2012-09-21 | 2012-09-21 | A kind of gas-liquid mixing processes and application thereof and gas-liquid reaction method |
| SG11201502233XA SG11201502233XA (en) | 2012-09-21 | 2013-09-18 | Hydrocarbon oil hydrotreating method |
| KR1020157010329A KR101838579B1 (en) | 2012-09-21 | 2013-09-18 | Hydrocarbon oil hydrotreating method |
| SG10201702254UA SG10201702254UA (en) | 2012-09-21 | 2013-09-18 | Hydrocarbon oil hydrotreating method |
| PCT/CN2013/083791 WO2014044196A1 (en) | 2012-09-21 | 2013-09-18 | Hydrocarbon oil hydrotreating method |
| EP13838513.3A EP2899252B1 (en) | 2012-09-21 | 2013-09-18 | Hydrocarbon oil hydrotreating method and apparatus |
| US14/430,499 US9862896B2 (en) | 2012-09-21 | 2013-09-18 | Hydrocarbon oil hydrotreating method |
| BR112015006344-6A BR112015006344B1 (en) | 2012-09-21 | 2013-09-18 | hydrocarbon oil hydrotreatment method |
| JP2015532291A JP6395709B2 (en) | 2012-09-21 | 2013-09-18 | Hydrocarbon oil hydrotreating method |
| RU2015114768/04A RU2596828C1 (en) | 2012-09-21 | 2013-09-18 | Hydrocarbon oil hydrotreating method and device |
| DK13838513.3T DK2899252T3 (en) | 2012-09-21 | 2013-09-18 | Hydrocarbon Oil Hydrocarbon Process and Device |
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| CN201210360982.6A CN103657463B (en) | 2012-09-21 | 2012-09-21 | A kind of gas-liquid mixing processes and application thereof and gas-liquid reaction method |
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| CN105084318B (en) * | 2014-05-20 | 2018-05-11 | 湖南长岭石化科技开发有限公司 | A kind of preparation method of hydrogen peroxide |
| CN105713656B (en) * | 2014-12-01 | 2017-09-01 | 中国石油天然气股份有限公司 | Micro-bubble intra-reactor hydrogen dissolving reactor and application method thereof |
| CN109679684B (en) * | 2017-10-19 | 2020-09-11 | 中国石油化工股份有限公司 | Liquid phase hydrogenation reaction system and method |
| CN109679682B (en) * | 2017-10-19 | 2020-09-11 | 中国石油化工股份有限公司 | Hydrogen dissolving equipment and hydrogen dissolving method |
| CN109679690B (en) * | 2017-10-19 | 2020-09-11 | 中国石油化工股份有限公司 | Liquid-phase hydrogenation system and liquid-phase hydrogenation method |
| CN108485701B (en) * | 2018-03-30 | 2020-05-29 | 中海油天津化工研究设计院有限公司 | Method for hydrorefining membrane dispersion liquid phase circulation |
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