CN112175667A - Mixed oil hydrogenation micro-interface enhanced reaction system and method - Google Patents
Mixed oil hydrogenation micro-interface enhanced reaction system and method Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 125
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 169
- 239000001257 hydrogen Substances 0.000 claims abstract description 138
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 138
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 136
- 239000007789 gas Substances 0.000 claims abstract description 113
- 239000000839 emulsion Substances 0.000 claims abstract description 93
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- 238000012546 transfer Methods 0.000 claims abstract description 8
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- 229910052717 sulfur Inorganic materials 0.000 claims description 21
- 239000011593 sulfur Substances 0.000 claims description 21
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 8
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- 229910052742 iron Inorganic materials 0.000 description 1
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical group [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical group [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical group [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
Classifications
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0278—Feeding reactive fluids
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- 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
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a mixed oil hydrogenation micro-interface enhanced reaction system and a method, comprising the following steps: the device comprises a liquid phase feeding unit, a gas phase feeding unit, a micro-interface generator, a fixed bed reactor and a separation tank. Compared with the traditional fixed bed reactor, the micro-interface generator is arranged on the fixed bed reactor, pressure energy of gas and/or kinetic energy of liquid in the reaction process are converted into surface energy of hydrogen bubbles before reaction raw materials enter the reactor for reaction, the hydrogen bubbles are crushed into micro bubbles with the diameter of more than or equal to 1 mu m and less than 1mm, the interphase area between mixed oil and hydrogen in the hydrogenation reaction process is effectively increased, the mass transfer efficiency between the mixed oil and the hydrogen is improved, the mixed oil and the hydrogen micro bubbles are mixed to form gas-liquid emulsion after crushing, and further the reaction efficiency between the mixed oil and the hydrogen is enhanced in a lower preset pressure range.
Description
Technical Field
The invention relates to the technical field of mixed oil processing, in particular to a mixed oil hydrogenation micro-interface strengthening reaction system and a method.
Background
In recent years, with increasing shortage of petroleum resources, the trend of crude oil upgrading and degradation is getting worse, and with the development of economy, the demand for light oil products is increasing, so that maximum upgrading and benefit maximization of heavy oil become the pursuit targets of oil refining enterprises.
The main means for processing heavy oil are hydrocracking, catalytic cracking and delayed coking. Hydrocracking is difficult to process coking mixed oil and residual oil due to large investment and high operation cost, and application of delayed coking is limited due to low liquid yield, poor product quality and other factors. The catalytic cracking has low operation cost, high yield of light oil products and good quality of mixed oil products, and can process heavy inferior raw materials such as mixed oil, residual oil and the like, thereby obtaining wide process application.
With the increasingly stricter quality standards of gasoline and diesel oil products in China, how to solve the problems of high sulfur content of catalytic cracking mixed oil, high sulfur and aromatic hydrocarbon content of catalytic cracking diesel oil and low cetane number becomes a hotspot of research in recent years. At present, a plurality of catalytic cracking catalysts, auxiliary agents and process technologies are developed, wherein the catalytic cracking raw material pre-hydrogenation technology becomes an effective means for solving the problem of high sulfur content of the catalytic mixed oil. The pre-hydrogenation of the catalytic cracking raw material not only reduces the contents of sulfur, nitrogen and aromatic hydrocarbon, but also is beneficial to improving the catalytic cracking conversion rate, increasing the catalytic cracking light yield, reducing the sulfur content of the mixed oil, and improving the cetane numbers of the mixed oil olefin and the diesel oil.
Among various methods for converting straight-run mixed oil into light straight-run mixed oil, the process of using mixed oil hydrogenation as a catalytic cracking raw material is a good process route. Most of sulfur and nitrogen impurities are removed from the mixed oil after hydrotreating, part of aromatic hydrocarbon is saturated, the hydrogen content is increased, the conversion rate of catalytic cracking raw materials can be increased, the coke yield is reduced, the yield of catalytic cracking light oil is increased, a product with improved quality is obtained, the sulfur content of the obtained mixed oil is low, and the cetane numbers of the olefin and diesel oil of the mixed oil are improved; meanwhile, the mixed oil can be hydrotreated to produce 15% low-sulfur diesel oil as a byproduct, so that the diesel-gasoline ratio of a refinery is improved. Therefore, the process of using the oil generated by hydrotreating the mixed oil as the catalytic cracking raw material is also widely applied.
The coking mixed oil has high sulfur and nitrogen contents, particularly high basic nitrogen contents, high carbon residue and high aromatic hydrocarbon contents, and is easy to lose catalytic activity when directly entering a catalytic cracking device for processing, so that the catalyst is seriously inactivated, the yield of the mixed oil of the catalytic cracking device is low, and the yield of coke is increased, so that the hydrogenation pretreatment of the coking mixed oil is more necessary compared with other mixed oil components.
Disclosure of Invention
Therefore, the invention provides a mixed oil hydrogenation micro-interface enhanced reaction system and a method thereof, which are used for solving the problem of overhigh energy consumption caused by the fact that hydrogen cannot be fully contacted with mixed oil in the prior art.
In one aspect, the invention provides a mixed oil hydrogenation micro-interface enhanced reaction system, comprising:
the liquid-phase feeding unit is used for storing and conveying the mixed oil in the hydrogenation reaction process;
the gas-phase feeding unit is used for storing and conveying hydrogen in the hydrogenation reaction process;
at least one Micro Interfacial Generator (MIG) connected to the liquid-phase feeding unit and/or the gas-phase feeding unit, respectively, for converting pressure energy of gas and/or kinetic energy of liquid into surface energy of hydrogen bubbles, so as to break the hydrogen bubbles into microbubbles with a diameter of 1 μm or more and less than 1mm, thereby increasing the mass transfer area between the mixed oil and hydrogen during hydrogenation reaction, and thinning the liquid film, and mixing the mixed oil and the microbubbles after breaking to form a gas-liquid emulsion, thereby enhancing the reaction efficiency between the mixed oil and hydrogen within a preset pressure range;
the fixed bed reactor is connected with the micro-interface generator and is used for loading the gas-liquid emulsion and providing a reaction space for mixed oil and micro-bubbles in the gas-liquid emulsion;
and the separation tank is connected with the fixed bed reactor and is used for carrying out gas-liquid separation on the mixture of the treated mixed oil and the mixed gas after the hydrogenation reaction in the fixed bed reactor is finished.
Further, in the above mixed oil hydrogenation micro-interface enhanced reaction system, the micro-interface generator is selected from one or more of a pneumatic micro-interface generator, a hydraulic micro-interface generator and a gas-liquid linkage micro-interface generator.
Further, in the mixed oil hydrogenation micro-interface strengthening reaction system, when the number of the micro-interface generators is greater than or equal to two, the micro-interface generators are arranged in series and/or in parallel. Further, in the above mixed oil hydrogenation micro-interface strengthening reaction system, the liquid-phase feeding unit includes:
the liquid raw material tank is used for storing the mixed oil in the hydrogenation reaction process;
the feeding pump is connected with the liquid raw material tank and is used for providing power for conveying the mixed oil;
the liquid feeding preheater is connected with the feeding pump and is used for preheating the mixed oil conveyed by the feeding pump so as to enable the mixed oil to reach a preset temperature and conveying the mixed oil to the corresponding micro-interface generator;
when the liquid-phase feeding unit is used for conveying the mixed oil, the feeding pump starts to operate, the mixed oil is pumped out of the liquid raw material tank and conveyed to the liquid feeding preheater, and the mixed oil is heated to a preset temperature by the liquid feeding preheater and then conveyed to the micro-interface generator.
Further, in the above mixed oil hydrogenation micro-interface strengthening reaction system, the gas-phase feeding unit includes:
the gas raw material buffer tank is used for storing the hydrogen in the hydrogenation reaction process;
the compressor is connected with the gas raw material buffer tank and used for providing power for conveying the hydrogen;
the gas feeding preheater is connected with the compressor and used for preheating the hydrogen conveyed by the compressor so as to enable the hydrogen to reach a preset temperature and conveying the hydrogen to the corresponding micro-interface generator;
when the gas-phase feeding unit is used for conveying hydrogen, the compressor starts to operate, the hydrogen is pumped out of the gas raw material buffer tank and conveyed to the gas feeding preheater for preheating, and after preheating is completed, the gas feeding preheater conveys the hydrogen to the micro-interface generator so that the micro-interface generator can break hydrogen bubbles into the micro-bubbles.
Further, in the above mixed oil hydrogenation micro-interface enhanced reaction system, the fixed bed reactor comprises:
the reaction tank is a tank body and is used for providing a reaction space for the gas-liquid emulsion, and a discharge hole for outputting the reacted mixed oil and the mixed gas is formed in the reaction tank;
and when the gas-liquid emulsion flows through the catalyst bed, the catalyst in the catalyst bed layer can contact with the gas-liquid emulsion to improve the reaction efficiency of each substance in the gas-liquid emulsion.
Further, in the above-mentioned mixed oil hydrogenation micro-interface intensification reaction system, the knockout drum top is equipped with the gaseous phase export for carry gas mixture, and the knockout drum bottom is equipped with the liquid phase export for carry the mixed oil after the processing, and after the gas-liquid emulsion reaction in the fixed bed reactor was accomplished, the knockout drum carried the mixture after the reaction to the knockout drum, and the mixed oil after handling in the mixture subsides to the knockout drum bottom and export from in the system via the liquid phase export by the action of gravity, and the mixed gas in the mixture exports from in the system via the gaseous phase export.
Compared with the prior art, the invention has the advantages that the micro-interface generator is arranged on the fixed bed reactor, the pressure energy and/or the kinetic energy of the liquid in the reaction process are converted into the surface energy of the hydrogen bubbles before the reaction raw materials enter the reactor for reaction, the hydrogen bubbles are crushed into micro bubbles with the diameter of more than or equal to 1 mu m and less than 1mm, the interphase area between the mixed oil and the hydrogen in the hydrogenation reaction process is effectively increased, the mass transfer efficiency between the mixed oil and the hydrogen is improved, the mixed oil and the hydrogen micro bubbles are mixed to form gas-liquid emulsion after crushing, the reaction efficiency between the mixed oil and the hydrogen is further enhanced in a lower preset pressure range, the gas-liquid ratio in the reaction process is effectively reduced, and the material consumption of the gas is greatly reduced, meanwhile, the energy consumption of the subsequent gas cyclic compression is also obviously reduced. In addition, the method has the advantages of low process severity, high production safety, low ton product cost and strong market competitiveness.
Particularly, in the mixed oil hydrogenation micro-interface enhanced reaction system provided by the invention, the micro-interface generator can crush hydrogen bubbles into micron-sized micro-bubbles, the micro-bubbles are not easy to generate bubble coalescence in the motion collision with catalyst particles, the original form can be maintained, the contact area of gas and liquid in the fixed bed reactor is increased by geometric multiple, and the emulsification and mixing are more sufficient and stable, so that the effects of mass transfer enhancement and macro-reaction are achieved.
Furthermore, in the mixed oil hydrogenation micro-interface enhanced reaction system provided by the invention, the micro-interface generator can be selected from one or more of a pneumatic micro-interface generator, a hydraulic micro-interface generator and a gas-liquid linkage micro-interface generator, the type, the number and the arrangement mode of the micro-interface generator are selected according to specific use requirements, hydrogen bubbles can be fully and effectively crushed into micro-bubbles before the mixed oil and hydrogen enter the fixed bed reactor, so that the hydrogen bubbles can be fully contacted with the mixed oil, and finally, a gas-liquid emulsion is formed, and the gas-liquid emulsion can be fully reacted under the catalytic action of a catalyst after entering the fixed bed reactor.
Further, a feeding pump and a compressor are respectively arranged in the liquid-phase feeding unit and the gas-phase feeding unit, so that when the system operates, the feeding pump and the compressor can respectively provide power for the transportation of the mixed oil and the hydrogen, the mixed oil and the hydrogen can be conveyed to a specified device at a specified speed, and the operating efficiency of the system is improved.
Further, still be equipped with liquid feeding preheater and gaseous feeding preheater respectively in liquid phase feed unit and the gaseous phase feed unit, when carrying miscella and hydrogen, liquid feeding preheater and gaseous feeding preheater can preheat miscella and hydrogen respectively, and like this, fixed bed reactor just need not to carry out high power heating to miscella and hydrogen again when moving, has practiced thrift the resource consumption of fixed bed has reduced the energy consumption of system.
Further, at least one layer of catalyst bed plate is arranged in the fixed bed reactor, and the reaction rate of the gas-liquid emulsion can be further improved by fully contacting multiple layers of catalysts with the gas-liquid emulsion, so that the operation efficiency of the system is further improved.
Furthermore, the separating tank can separate the gas and the liquid of the mixture after reaction by using the gravity action, and no redundant separating device is needed to be used for the separating tank, so that the energy consumption of the system is further reduced.
On the other hand, the invention provides a micro-interface reinforced mixed oil hydrogenation reaction method, which comprises the following steps:
step 1: adding a specified amount of the mixed oil to the liquid feedstock tank and a specified amount of hydrogen to the gaseous feedstock buffer tank prior to operating the system;
step 2: starting the system after the addition is finished, extracting the mixed oil from the liquid raw material tank through a feed pump, and extracting hydrogen from the gas raw material buffer tank through a compressor;
and step 3: the mixed oil flows through a liquid feeding preheater, the liquid feeding preheater heats the mixed oil to a preset temperature, hydrogen flows through a gas feeding preheater, and the gas feeding preheater heats the hydrogen to the preset temperature;
and 4, step 4: the mixed oil is preheated and then shunted, the shunted mixed oil can be respectively conveyed to the corresponding micro-interface generators, the hydrogen is preheated and then shunted, and the shunted hydrogen can be respectively conveyed to the corresponding micro-interface generators;
and 5: each micro-interface generator can control the proportion of the micro-interface generator to receive the mixed oil and the hydrogen, break the hydrogen into micro-bubbles with the size of micron, and mix the micro-bubble mixed oil and the micro-bubbles to form a gas-liquid emulsion after breaking;
step 6: after the micro-interface generators are mixed, outputting the gas-liquid emulsion to a fixed bed reactor, controlling the pressure and the temperature in the fixed bed reactor, and enabling the gas-liquid emulsion to flow in a specified direction;
and 7: allowing the gas-liquid emulsion to flow through the catalyst bed layer, controlling the airspeed of the gas-liquid emulsion, and enabling a catalyst arranged in the catalyst bed layer to promote the reaction of sulfur elements in the mixed oil in the gas-liquid emulsion and the microbubbles to generate treated mixed oil and hydrogen sulfide gas so as to treat the mixed oil, wherein the hydrogen sulfide gas and the hydrogen gas form mixed gas;
and 8: after the reaction is finished, the mixture formed by the processed mixed oil and the mixed gas is conveyed to the separation tank by the fixed bed reactor, the mixture is settled in the separation tank, the processed mixed oil is settled on the lower layer of the separation tank and is output from the system through the liquid phase outlet for subsequent processing, and the mixed gas stays on the upper layer of the separation tank after the processed mixed oil is settled and is output from the system through the gas phase outlet for subsequent processing.
Further, the reaction pressure in the fixed bed reactor in the step 6 is 0.8-1.2MPa, and the reaction temperature is 300-.
Further, the space velocity of the gas-liquid emulsion in the step 7 is 1-6.5h-1。
Compared with the prior art, the method has the beneficial effects that compared with the traditional mixed oil hydrogenation reaction process, the micro-interface reinforced mixed oil hydrogenation reaction method provided by the invention has the advantages of low process severity, high production safety, low ton product cost and strong market competitiveness. In particular, when different catalysts are used in the method of the present invention, the operation temperature can be properly adjusted according to the activity temperature of the catalyst, so the system of the present invention also has the advantages of greatly or doubly reducing the operation pressure and increasing the space velocity (handling capacity) under different catalyst systems.
Furthermore, in the hydrogenation reaction method of the micro-interface reinforced mixed oil, the temperature and the pressure in the reaction tank are limited, so that the energy consumption of the system is controlled to be the lowest while the high-efficiency reaction of the gas-liquid emulsion in the reaction tank is ensured, and the energy consumption of the system can be further reduced.
Furthermore, in the hydrogenation reaction method of the micro-interface reinforced mixed oil provided by the invention, the space velocity of the catalyst is also controlled, so that all substances in the gas-liquid emulsion can be reacted at the highest efficiency, and the operation efficiency of the system is further improved.
Drawings
FIG. 1 is a schematic structural diagram of a bottom-mounted mixed oil hydrogenation micro-interface enhanced reaction system provided by the present invention;
FIG. 2 is a schematic structural diagram of a bottom-mounted multi-stage mixed oil hydrogenation micro-interface enhanced reaction system according to the present invention;
FIG. 3 is a schematic structural diagram of a top-mounted mixed oil hydrogenation micro-interface enhanced reaction system provided by the present invention;
FIG. 4 is a schematic structural diagram of an overhead multi-stage mixed oil hydrogenation micro-interface enhanced reaction system according to the present invention;
FIG. 5 is a schematic structural diagram of a side-mounted mixed oil hydrogenation micro-interface enhanced reaction system provided by the invention.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the invention is further described below with reference to examples; it should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only for explaining the technical principle of the present invention, and do not limit the scope of the present invention.
It should be noted that in the description of the present invention, the terms of direction or positional relationship indicated by the terms "upper", "lower", "left", "right", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, which are only for convenience of description, and do not indicate or imply that the device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
Furthermore, it should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
Referring to fig. 1-2, a bottom-mounted mixed oil hydrogenation micro-interface enhanced reaction system according to an embodiment of the present invention includes a liquid feeding unit 1, a gas feeding unit 2, a micro-interface generator (MIG) 3, a fixed bed reactor 4, and a separation tank 5; the micro-interface generator 3 is respectively connected with the liquid feeding unit 1 and the gas feeding unit 2 and is used for receiving the mixed oil conveyed by the liquid feeding unit 1 and the hydrogen conveyed by the gas feeding unit 2; the fixed bed reactor 4 is connected with the micro-interface generator 3, and the output end of the micro-interface generator 3 is arranged in the fixed bed reactor 4 and used for outputting the gas-liquid emulsion in the micro-interface generator 3 to the fixed bed reactor; the separation tank 5 is connected with the fixed bed reactor 4 and used for receiving the mixture output by the fixed bed reactor 4 and carrying out gas-liquid separation on the mixture.
When the system is in operation, the liquid feeding unit 1 is started, the mixed oil stored in the liquid feeding unit is conveyed to the micro-interface generator 3, meanwhile, the gas feeding unit 2 is started, the hydrogen stored in the liquid feeding unit is conveyed to the micro-interface generator 3, the micro-interface generator 3 can smash the hydrogen, the hydrogen is smashed to the micro-scale, micro-bubbles with the diameter larger than or equal to 1 micron and smaller than 1mm are formed, after the smashing is completed, the micro-interface generator 3 mixes the micro-bubbles with the mixed oil to form a gas-liquid emulsion, the micro-interface generator 3 outputs the gas-liquid emulsion to the fixed bed reactor 4 after the mixing of the gas-liquid emulsion is completed, the gas-liquid emulsion is subjected to efficient reaction in the fixed bed reactor by controlling the temperature and the air pressure in the fixed bed reactor 4 and the airspeed of the gas-liquid emulsion, and the generated mixture is output to the separation tank 5 by the fixed bed reactor 4 after the, the separation tank 5 separates the treated mixed oil in the mixture from the mixed gas of hydrogen and hydrogen sulfide and performs subsequent treatment respectively.
It can be understood that the system of the present invention can be used for not only the hydrotreatment of the mixed oil, but also the hydrogenation of diesel oil, gasoline, lubricating oil or other types of oil products with small molecular weights, as long as the system can hydrogenate the oil products to enable the oil products to perform high-efficiency reaction and achieve the specified standard after the reaction. Of course, the system of the present invention can also be used in other multiphase reactions, such as multiphase fluid formed by micron-scale particles, such as by micro-interface, micro-nano interface, ultramicro interface, micro-bubble biochemical reactor or micro-bubble biological reactor, using micro-mixing, micro-fluidization, micro-bubble fermentation, micro-bubble bubbling, micro-bubble mass transfer, micro-bubble reaction, micro-bubble absorption, micro-bubble oxygenation, micro-bubble contact, etc. to form multiphase micro-mixed flow, multi-phase micro-nano flow, multi-phase emulsified flow, multi-phase micro-structured flow, gas-liquid-solid micro-mixed flow, gas-liquid-solid micro-nano flow, gas-liquid-solid emulsified flow, gas-liquid-solid micro-structured flow, micro-bubble flow, micro-foam flow, micro-gas-nano emulsified flow, micro-dispersed flow, two micro-mixed flow, micro-turbulence, micro-bubble, Or multiphase fluid (micro interface fluid for short) formed by micro-nano-scale particles, thereby effectively increasing the phase boundary mass transfer area between the gas phase and/or the liquid phase and/or the solid phase in the reaction process.
With continued reference to fig. 1, the liquid feed unit 1 includes: a liquid feedstock tank 11, a feed pump 12 and a liquid feed preheater 13; wherein the feed pump 12 is connected to the liquid feedstock tank 11 for pumping out the mixed oil in the liquid feedstock tank 11; the liquid feeding preheater 13 is arranged at the output end of the feeding pump 12, and the liquid feeding preheater 13 is connected with the micro-interface generator 3, so as to preheat the mixed oil output by the feeding pump 12 and convey the mixed oil to the micro-interface generator 3 after preheating. When the liquid feed unit 1 is in operation, the feed pump 12 pumps the mixed oil stored in the liquid feedstock tank 11 and delivers the mixed oil to the liquid feed preheater 13, and the liquid feed preheater 13 delivers the mixed oil to the micro-interfacial surface generator 3 after preheating the mixed oil to a predetermined temperature.
Specifically, the liquid material tank 11 is a tank body for storing the mixed oil, and the liquid material tank 11 is connected to the feed pump 12 for delivering the mixed oil to a designated position through the feed pump 12 when the system is in operation. It is to be understood that the liquid material tank 11 may be a metal oil tank or a nonmetal oil tank as long as the liquid material tank 11 can be loaded with a predetermined amount of the mixed oil.
Specifically, the feed pump 12 is a centrifugal pump, which is disposed at the outlet of the liquid material tank 11 to provide power for the delivery of the mixed oil. When the liquid feed unit 1 is in operation, the feed pump 12 starts to operate, and the mixed oil in the liquid raw material tank 1 is pumped out and conveyed to the liquid feed preheating unit 13. It is understood that the type and power of the feed pump 12 are not particularly limited in this embodiment, as long as the feed pump 12 is capable of delivering the mixed oil at a given flow rate.
Specifically, the liquid feed preheater 13 is a preheater for preheating the mixed oil, and a flow dividing pipe is disposed at an outlet of the liquid feed preheater 13 for respectively conveying the preheated mixed oil to the interior of each of the micro-interface generators. When charge pump 12 carries the miscella, the miscella can flow through liquid feeding preheater 13, and liquid feeding preheater 13 can preheat the miscella and carry out the reposition of redundant personnel after the miscella reaches preset temperature, carries the miscella respectively to the inside of each micro interface generator. It is understood that the kind of the preheater and the heating method of the liquid feed preheater 13 are not specifically limited in this embodiment, as long as the liquid feed preheater 13 can preheat the mixed oil to a predetermined temperature.
With continued reference to fig. 1, the gas feed unit 2 includes: a gas raw material buffer tank 21, a compressor 22, and a gas feed preheater 23; wherein, the compressor 22 is connected with the gas raw material buffer tank 21 and is used for pumping out the hydrogen in the gas raw material buffer tank 21; the gas feed preheater 23 is disposed at an output end of the compressor 22, and the gas feed preheater 23 is connected to the micro-interface generator 3, so as to preheat the hydrogen output by the compressor 22, and deliver the hydrogen to the micro-interface generator 3 after preheating. When the gas feed unit 2 is in operation, the compressor 22 extracts the hydrogen stored in the gas raw material buffer tank 21 and delivers the hydrogen to the gas feed preheater 23, and the gas feed preheater 23 delivers the hydrogen to the micro-interface generator 3 after preheating the hydrogen to a predetermined temperature.
Specifically, the gas material buffer tank 21 is a tank for storing hydrogen, and the gas material buffer tank 21 is connected to the compressor 22 for delivering hydrogen to a designated location through the compressor 22 when the system is in operation. It is to be understood that the present embodiment is not particularly limited as long as the gas raw material buffer tank 21 can load a prescribed amount of hydrogen gas.
Specifically, the compressor 22 is disposed at the outlet of the gas raw material buffer tank 21 to power the delivery of hydrogen gas. When the gas feed unit 2 is operated, the compressor 22 is operated to extract hydrogen gas from the gas raw material tank 2 and deliver the hydrogen gas to the gas feed preheating unit 23. It is to be understood that the power of the compressor 22 is not particularly limited in this embodiment, provided that the compressor 22 is capable of delivering hydrogen at a specified flow rate.
Specifically, the gas feed preheater 23 is a preheater for preheating hydrogen, and a flow dividing pipe is disposed at an outlet of the gas feed preheater 23 for respectively conveying the preheated hydrogen to the interior of each of the micro-interface generators. When the compressor 22 delivers hydrogen, the hydrogen flows through the gas feed preheater 23, and the gas feed preheater 23 preheats the hydrogen and splits the hydrogen after the hydrogen reaches a predetermined temperature, so as to deliver the hydrogen to the interior of each micro-interface generator. It is understood that the type of preheater and the heating method of the gas feed preheater 23 are not particularly limited in this embodiment, as long as the gas feed preheater 23 can preheat the hydrogen to a predetermined temperature.
With continued reference to fig. 1, the micro-interface generator 3 includes: first micro-interface generator 31 and second micro-interface generator 32, first micro-interface generator 31 and the vertical setting of second micro-interface generator 32 are in 4 bottoms of fixed bed reactor, and first micro-interface generator 31 and second micro-interface generator 32 are parallel to each other, and each micro-interface generator delivery outlet sets up inside fixed bed reactor 4 for export the gas-liquid emulsion to fixed bed reactor 4. When micro-interface generator 3 operates, appointed volume of miscella and hydrogen can be received respectively to first micro-interface generator 31 and second micro-interface generator 32, and first micro-interface generator 31 and second micro-interface generator 32 can smash the hydrogen of receiving and make hydrogen breakage to the micron scale in order to form the microbubble after the receipt is accomplished, mix microbubble and miscella with the miscella after the breakage is accomplished, export the gas-liquid emulsion to after the completion of mixing fixed bed reactor 4. It can be understood that the connection mode of the micro-interface generator 3 and the fixed bed reactor 4 can be a pipeline connection, and the output end of the micro-interface generator 3 is arranged inside the fixed bed reactor 4 or in other connection modes, so long as the micro-interface generator 3 can output the gas-liquid emulsion to the inside of the fixed bed reactor 4.
Specifically, the first micro-interface generator 31 is an air-liquid linkage micro-interface generator, and is disposed at the bottom of the fixed bed reactor 4 and connected to the liquid feed preheater 13 and the gas feed preheater 23, respectively, so as to crush hydrogen and output an air-liquid emulsion formed by mixing micro-bubbles with mixed oil to the inside of the fixed bed reactor 4. When the micro-interface generator 3 operates, the first micro-interface generator 31 receives the specified amount of the mixed oil and the hydrogen gas, and crushes the hydrogen gas bubbles to a micron scale by using the pressure energy of the gas and the kinetic energy of the liquid, after the crushing is completed, the microbubbles and the mixed oil are violently mixed to form a gas-liquid emulsion, and after the mixing is completed, the gas-liquid emulsion is output to the fixed bed reactor 4.
Specifically, second micro-interface generator 32 is a pneumatic micro-interface generator, and it sets up fixed bed reactor 4 bottom and respectively with liquid feeding preheater 13 and gaseous feeding preheater 23 link to each other for broken hydrogen and export the gas-liquid emulsion that microbubble and oil mixture formed to inside fixed bed reactor 4. When the micro-interface generator 3 operates, the first micro-interface generator 31 receives the specified amount of the mixed oil and the hydrogen respectively, and uses the pressure of the gas to crush the hydrogen bubbles to a micron scale, after the crushing, the micro-bubbles and the mixed oil are mixed vigorously to form a gas-liquid emulsion, and after the mixing, the gas-liquid emulsion is output to the fixed bed reactor 4.
With continued reference to FIG. 1, the fixed bed reactor 4 comprises: a reaction tank 41 and a catalyst bed 42; wherein the catalyst bed 42 is disposed inside the reaction tank 41 to load the catalyst. When fixed bed reactor 4 operates, micro-interface generator 3 can export the gas-liquid emulsion to retort 41 bottom, and the gas-liquid emulsion can upwards flow gradually after getting into retort 41 bottom, the gas-liquid emulsion in the flow in-process with catalyst contact and the beginning reaction of catalyst bed 42 built-in, the sulphur element that makes the miscella contain in the gas-liquid emulsion reacts with the microbubble and generates hydrogen sulfide to this desulfurization of accomplishing the miscella. It is to be understood that the catalyst may be one or a mixture of more of a molybdenum-based catalyst, a cobalt-based catalyst, a tungsten-based catalyst, a nickel-based catalyst, and an iron-based catalyst, as long as the catalyst can improve the reaction efficiency of each substance in the gas-liquid emulsion. Of course, the system of the present invention is suitable for the above mentioned catalyst system and also for other hydrogenation catalyst systems not mentioned, as long as the system of the present invention can be satisfied that when different catalysts are used, the operation temperature can be properly adjusted according to the activity temperature of the used catalyst, and the system can still greatly or doubly reduce the operation pressure and increase the space velocity (throughput) under different catalyst systems.
Specifically, the reaction tank 41 is a cylindrical metal tank, and has a feed inlet at the bottom thereof for receiving the gas-liquid emulsion output from the micro-interface generator 3, and a discharge outlet at the top thereof, the discharge outlet being connected to the separation tank 5 for outputting the mixture after the reaction to the separation tank 5 for gas-liquid separation. Fixed bed reactor 4 is when the operation, 41 feed inlets of retort can be received the gas-liquid emulsion of 3 outputs at the micro-interface to for the gas-liquid emulsion provides reaction space, form the mixture of handling back miscella and mist after the gas-liquid emulsion reaction is accomplished, retort 41 can be through the discharge gate with the mixture output extremely knockout drum 5. It is understood that the size and material of the reaction tank 41 are not particularly limited in this embodiment, as long as the reaction tank 41 can be loaded with a specified amount of gas-liquid emulsion and has a specified strength to withstand a preset reaction temperature and reaction pressure.
Specifically, the catalyst bed 42 is at least one bed plate, and a catalyst is fixedly disposed in the bed plate to increase the reaction speed of the gas-liquid emulsion. When the fixed bed reactor 4 operates, the gas-liquid emulsion in the reaction tank 41 flows upwards from the bottom of the reaction tank 41 and passes through the catalyst bed layer 42 in the flowing process, at this time, the catalyst in the catalyst bed layer 42 contacts with the gas-liquid emulsion, and the catalyst promotes the sulfur element in the mixed oil in the gas-liquid emulsion to react with the micro-bubbles to generate hydrogen sulfide so as to treat the mixed oil. It is understood that the catalyst bed 42 may be a grid, mesh, ceramic ball or other type of structure, so long as the catalyst bed 42 is capable of securely holding the catalyst. Of course, the number of layers of the catalyst bed 42 may be one, two or other number of layers, as long as the catalyst bed 42 can achieve the specified reaction efficiency of each substance in the gas-liquid emulsion.
As shown in fig. 1, the separation tank 5 is a metal tank body, and is connected to the discharge port of the reaction tank 41, so as to perform gas-liquid separation on the mixture output from the reaction tank 41. And a gas phase outlet is formed in the top end of the separation tank 5 and used for outputting hydrogen and hydrogen sulfide gas, and a liquid phase outlet is formed in the bottom end of the separation tank and used for outputting the processed mixed oil. After the fixed bed reactor 4 outputs the reacted mixture to the separation tank 5, the separation tank 5 performs gas-liquid separation on the mixed gas in the mixture and the treated mixed oil by using the action of gravity, outputs the mixed gas containing hydrogen and hydrogen sulfide gas through a gas phase outlet, and outputs the treated mixed oil through a liquid phase outlet. It is understood that the size and material of the separation tank 5 are not particularly limited in this embodiment, as long as the separation tank 5 has a predetermined strength and can hold a predetermined volume of the mixture.
With continued reference to fig. 2, a bottom-mounted multi-stage mixed oil hydrogenation micro-interface enhanced reaction system according to an embodiment of the present invention is provided, and the components of the system are the same as those of the system shown in fig. 1.
Different from the system shown in fig. 1, in the present embodiment, a plurality of catalyst beds 42 are disposed inside the reaction tank 41, and a gas inlet connected with a micro interface generator is disposed between each catalyst bed 42 except for the lowermost catalyst bed 42, so as to crush and convey the hydrogen output by the gas feeding unit 2 into the reaction tank; a plurality of shunt tubes are arranged at the outlet of the gas feed preheating unit 23, and are used for conveying the preheated hydrogen to the gas inlet at the bottom of each catalyst bed layer 42, so as to ensure the hydrogen content in the reaction tank 41.
After the gas feeding preheating unit 23 finishes preheating the hydrogen, the hydrogen is output, a flow dividing pipe is arranged at an outlet of the gas feeding preheating unit, the hydrogen starts to be divided after being output and is respectively conveyed to corresponding parts, and a part of the hydrogen is conveyed into the micro-interface generator 3 and is smashed into micro-bubbles and forms a gas-liquid emulsion with the mixed oil; and the other part of hydrogen is sent to the bottom of each catalyst bed 42 in a segmented manner through the air inlet provided with the micro-interface generator between each catalyst bed 42 in the reaction tank 41, so that the reaction efficiency of each substance in the gas-liquid emulsion in the reaction tank 41 is ensured by maintaining the content of the hydrogen in the reaction tank 41 in a specified range.
Referring to fig. 3, the top-mounted mixed oil hydrogenation micro-interface strengthening reaction system according to an embodiment of the present invention has the same components as those of the system shown in fig. 1.
Different from the system shown in fig. 1, the micro interface generator 3 is disposed at the top of the reaction tank 41 in this embodiment, and the discharge port of the reaction tank 41 is disposed at the bottom of the tank body, so that the gas-liquid emulsion output by the micro interface generator 3 flows from top to bottom in the reaction tank 41 by gravity, thereby reducing the energy consumption of the system.
When the first micro-interface generator 31 and the second micro-interface generator 32 output the gas-liquid emulsion to the reaction tank 41, the gas-liquid emulsion is located above the inside of the reaction tank 41 and moves downward under the action of gravity, contacts with the catalyst in the catalyst bed 42 during the movement of the gas-liquid emulsion and starts to react, and is output to the separation tank 5 through the discharge port at the bottom of the reaction tank 41 after the reaction is completed. Since the gas-liquid emulsion is moved downward by using the gravity, the system of the present embodiment does not need to provide power for the movement of the gas-liquid emulsion in the reaction tank 41, thereby further reducing the energy consumption required for the system.
Referring to fig. 4, the bottom-mounted multi-stage mixed oil hydrogenation micro-interface strengthening reaction system according to an embodiment of the present invention has the same components as those of the system shown in fig. 3.
Different from the system shown in fig. 1, in the embodiment, a plurality of catalyst beds 42 are arranged inside the reaction tank 41, and a gas inlet connected with a micro-interface generator is arranged between each catalyst bed 42 except the lowermost catalyst bed 42, so as to crush the hydrogen output by the gas feeding unit 2 and convey the hydrogen to the inside of the reaction tank; a plurality of shunt tubes are arranged at the outlet of the gas feed preheating unit 23, and are used for conveying the preheated hydrogen to the gas inlet at the bottom of each catalyst bed layer 42, so as to ensure the hydrogen content in the reaction tank 41.
After the gas feeding preheating unit 23 finishes preheating the hydrogen, the hydrogen is output, a flow dividing pipe is arranged at an outlet of the gas feeding preheating unit, the hydrogen starts to be divided after being output and is respectively conveyed to corresponding parts, and a part of the hydrogen is conveyed into the micro-interface generator 3 and is smashed into micro-bubbles and forms a gas-liquid emulsion with the mixed oil; and the other part of hydrogen is sent to the bottom of each catalyst bed 42 in a segmented manner through the air inlet provided with the micro-interface generator between each catalyst bed 42 in the reaction tank 41, so that the reaction efficiency of each substance in the gas-liquid emulsion in the reaction tank 41 is ensured by maintaining the content of the hydrogen in the reaction tank 41 in a specified range.
Referring to fig. 5, a side-mounted mixed oil hydrogenation micro-interface enhanced reaction system according to an embodiment of the present invention is provided, and the components of the system are the same as those of the system shown in fig. 1.
Different from the system shown in fig. 1, in the embodiment, a third micro-interface generator 33 is further disposed in the micro-interface generator 3, the third micro-interface generator 33 is disposed at the outlet of the gas feed preheater 23, and the third micro-interface generator 33 is connected in parallel with the second micro-interface generator 32 for respectively breaking up the specified amount of hydrogen; the third micro-interface generator 33 is also connected in series with the first micro-interface generator 31 for performing multi-stage fragmentation of the hydrogen gas, thereby further reducing the diameter of the micro-bubbles.
Particularly, the first micro-interface generator 31 and the second micro-interface generator 32 are respectively disposed on the sidewall of the bottom of the reaction tank 4, and the first micro-interface generator 31 and the second micro-interface generator 32 are oppositely disposed, so that the first micro-interface generator 31 and the second micro-interface generator 32 impact each other when outputting the gas-liquid emulsion, and the gas-liquid emulsion is more uniformly mixed.
When the liquid feeding unit 1 and the gas feeding unit 2 respectively convey the mixed oil and the hydrogen to the micro-interface generator, the third micro-interface generator 33 and the second micro-interface generator 32 respectively receive the mixed oil and the hydrogen with specified amounts, the hydrogen is crushed to micro-scale to form micro-bubbles and the mixed oil and the micro-bubbles are mixed to form a gas-liquid emulsion, after the crushing, the third micro-interface generator 33 can convey the gas-liquid emulsion to the first micro-interface generator 31 to be further crushed, after the crushing is completed, the first micro-interface generator 31 and the second micro-interface generator 32 can respectively output the gas-liquid emulsion inside to the bottom of the reaction tank 4 and move from bottom to top, because of the opposite arrangement of the two micro-interface generators, when the second micro-interface generator 32 and the third micro-interface generator 33 output the gas-liquid emulsion, the two gas-liquid emulsion streams can be collided at the bottom of the reaction tank 41, thereby achieving the secondary mixing of the gas-liquid emulsion and further improving the mass transfer area of the mixed oil and the micro bubbles between the gas-liquid emulsion.
The following will further explain the using method and effect of the mixed oil hydrogenation micro-interface enhanced reaction system in the present invention by referring to the specific examples.
A hydrogenation reaction method of micro-interface reinforced mixed oil comprises the following steps:
step 1: adding a specified amount of mixed oil to the liquid raw material tank 11 and a specified amount of hydrogen gas to the gas raw material buffer tank 21 before operating the system;
step 2: starting the system after the addition is completed, pumping the mixed oil from the liquid raw material tank 11 through the feed pump 12, and pumping the hydrogen from the gas raw material buffer tank 21 through the compressor 22;
and step 3: the mixed oil flows through a liquid feed preheater 13, the liquid feed preheater 13 heats the mixed oil to a preset temperature, the hydrogen flows through a gas feed preheater 23, and the gas feed preheater 23 heats the hydrogen to a preset temperature;
and 4, step 4: the mixed oil is preheated and then shunted, the shunted mixed oil can be respectively conveyed to the corresponding micro-interface generators 3, the hydrogen is preheated and then shunted, and the shunted hydrogen can be respectively conveyed to the corresponding micro-interface generators 3;
and 5: each micro-interface generator 3 controls the proportion of the received mixed oil and the hydrogen, the hydrogen is smashed into micro-bubbles with the average diameter of more than or equal to 1 mu m and less than 1mm, and after the smashing is finished, each micro-interface generator 3 mixes the micro-bubbles and the mixed oil to form a gas-liquid emulsion;
step 6: after the micro-interface generators 3 are mixed, outputting the gas-liquid emulsion to a fixed bed reactor 4, controlling the pressure in the fixed bed reactor to be 0.8-1.2MPa and the temperature to be 350 ℃, and enabling the gas-liquid emulsion to flow in a specified direction;
and 7: the gas-liquid emulsion flows through the catalyst bed layer 42, and the space velocity of the gas-liquid emulsion is controlled to be 1-6.5h-1In the range, the catalyst arranged in the layer promotes the sulfur element in the mixed oil in the gas-liquid emulsion to react with the micro bubbles to generate the treated mixed oil and hydrogen sulfide gas so as to treat the mixed oil, and the hydrogen sulfide gas and the hydrogen gas form mixed gas;
and 8: after the reaction is finished, the mixture formed by the mixed oil and the mixed gas after the treatment of the fixed bed reactor 4 is conveyed to the separation tank 5, the mixture is settled in the separation tank 5, the treated mixed oil is settled on the lower layer of the separation tank 5 and is output from the system through a liquid phase outlet for subsequent treatment, and the mixed gas stays on the upper layer of the separation tank 5 after the treated mixed oil is settled and is output from the system through a gas phase outlet for subsequent treatment.
Example 1
In this example, the standard volume ratio of hydrogen to the mixed oil in the first micro-interfacial generator was 0.45: 1; the standard volume ratio of hydrogen to mixed oil in the micro-interface generator is 600: 1; the average diameter of the microbubbles is more than or equal to 1 μm and less than 1 mm; the air pressure in the fixed reactor 4 is controlled to be 0.8 MPa; the reaction temperature is controlled at 300 ℃; the catalyst is iron-molybdenum catalyst; the airspeed is controlled to be 1h-1. And (3) detection results: the sulfur content in the raw material gasoline before treatment is 110ppm, and the sulfur content in the treated mixed oil is reduced to 35 ppm.
Example 2
In this example, the standard volume ratio of hydrogen to the mixed oil in the first micro-interfacial generator is 0.20: 1; the standard volume ratio of hydrogen to oil mixture in the second micro-interfacial generator was 655: 1; the average diameter of the microbubbles is more than or equal to 1 μm and less than 1 mm; the air pressure in the fixed reactor 4 is controlled to be 1 MPa; the reaction temperature is controlled at 330 ℃; the catalyst is iron-cobalt catalyst; the airspeed is controlled to be 3h-1. And (3) detection results: the sulfur content in the raw material gasoline before treatment is 110ppm, and the sulfur content in the treated mixed oil after treatment is reduced to 43 ppm.
Example 3
In this example, the standard volume ratio of hydrogen to the mixed oil in the first micro-interfacial generator is 0.35: 1; the standard volume ratio of hydrogen to the mixed oil in the second micro-interface generator is 720: 1; the average diameter of the microbubbles is more than or equal to 1 μm and less than 1 mm; the air pressure in the fixed reactor 4 is controlled to be 1.2 MPa; the reaction temperature is controlled at 350 ℃; the catalyst is a molybdenum-nickel catalyst; the airspeed is controlled to be 6.5h-1. And (3) detection results: the sulfur content in the raw material gasoline before treatment is 110ppm, and the sulfur content in the treated mixed oil is reduced to 38 ppm.
Example 4
In this example, the standard volumes of hydrogen and oil mixture in the first micro-interfacial generatorThe ratio is 0.20: 1; the standard volume ratio of the hydrogen to the mixed oil in the second micro-interface generator is 680: 1; the average diameter of the microbubbles is more than or equal to 1 μm and less than 1 mm; the air pressure in the fixed reactor 4 is controlled to be 1.1 MPa; the reaction temperature is controlled at 340 ℃; the catalyst is tungsten-nickel catalyst; the airspeed is controlled to be 4h-1. And (3) detection results: the sulfur content in the raw material gasoline before treatment is 110ppm, and the sulfur content in the treated mixed oil is reduced to 35 ppm.
So far, the technical solutions of the present invention have been described in connection with the preferred embodiments shown in the drawings, but it is easily understood by those skilled in the art that the scope of the present invention is obviously not limited to these specific embodiments. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention; various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A mixed oil hydrogenation micro-interface strengthening reaction system is characterized by comprising:
the liquid-phase feeding unit is used for storing and conveying the mixed oil in the hydrogenation reaction process;
the gas-phase feeding unit is used for storing and conveying hydrogen in the hydrogenation reaction process;
at least one micro interface generator, which is respectively connected with the liquid phase feeding unit and/or the gas phase feeding unit, and is used for converting the pressure energy of the gas and/or the kinetic energy of the liquid into the surface energy of the hydrogen bubbles, so that the hydrogen bubbles are crushed into micro bubbles with the diameter of more than or equal to 1 μm and less than 1mm, the mass transfer area between the mixed oil and the hydrogen in the hydrogenation reaction process is increased, the liquid film is thinned, and the mixed oil and the micro bubbles are mixed to form a gas-liquid emulsion after being crushed, so that the reaction efficiency between the mixed oil and the hydrogen is enhanced within a preset pressure range;
the fixed bed reactor is connected with the micro-interface generator and is used for loading the gas-liquid emulsion and providing a reaction space for mixed oil and micro-bubbles in the gas-liquid emulsion;
and the separation tank is connected with the fixed bed reactor and is used for carrying out gas-liquid separation on the mixture of the treated mixed oil and the mixed gas after the hydrogenation reaction in the fixed bed reactor is finished.
2. The micro-interface enhanced reaction system for hydrogenation of mixed oil according to claim 1, wherein the micro-interface generator is selected from one or more of a pneumatic micro-interface generator, a hydraulic micro-interface generator and a gas-liquid linkage micro-interface generator.
3. The micro-interface enhanced reaction system for mixed oil hydrogenation according to claim 2, wherein when the number of the micro-interface generators is greater than or equal to two, the micro-interface generators are arranged in series and/or in parallel.
4. The mixed oil hydrogenation micro-interface enhancement reaction system of claim 1, wherein the liquid-phase feeding unit comprises:
the liquid raw material tank is used for storing the mixed oil in the hydrogenation reaction process;
the feeding pump is connected with the liquid raw material tank and is used for providing power for conveying the mixed oil;
the liquid feeding preheater is connected with the feeding pump and is used for preheating the mixed oil conveyed by the feeding pump so as to enable the mixed oil to reach a preset temperature and conveying the mixed oil to the corresponding micro-interface generator;
when the liquid-phase feeding unit is used for conveying the mixed oil, the feeding pump starts to operate, the mixed oil is pumped out of the liquid raw material tank and conveyed to the liquid feeding preheater, and the mixed oil is heated to a preset temperature by the liquid feeding preheater and then conveyed to the micro-interface generator.
5. The mixed oil hydrogenation micro-interface enhancement reaction system of claim 1, wherein the gas phase feeding unit comprises:
the gas raw material buffer tank is used for storing the hydrogen in the hydrogenation reaction process;
the compressor is connected with the gas raw material buffer tank and used for providing power for conveying the hydrogen;
the gas feeding preheater is connected with the compressor and used for preheating the hydrogen conveyed by the compressor so as to enable the hydrogen to reach a preset temperature and conveying the hydrogen to the corresponding micro-interface generator;
when the gas-phase feeding unit is used for conveying hydrogen, the compressor starts to operate, the hydrogen is pumped out of the gas raw material buffer tank and conveyed to the gas feeding preheater for preheating, and after preheating is completed, the gas feeding preheater conveys the hydrogen to the micro-interface generator so that the micro-interface generator can break hydrogen bubbles into the micro-bubbles.
6. The micro-interface enhanced reaction system for mixed oil hydrogenation according to claim 1, wherein the fixed bed reactor comprises:
the reaction tank is a tank body and is used for providing a reaction space for the gas-liquid emulsion, and a discharge hole for outputting the reacted mixed oil and the mixed gas is formed in the reaction tank;
and when the gas-liquid emulsion flows through the catalyst bed, the catalyst in the catalyst bed layer can contact with the gas-liquid emulsion to improve the reaction efficiency of each substance in the gas-liquid emulsion.
7. The micro-interface reinforced reaction system for mixed oil hydrogenation according to claim 1, wherein the top end of the separation tank is provided with a gas phase outlet for delivering the mixed gas, the bottom end of the separation tank is provided with a liquid phase outlet for delivering the treated mixed oil, when the reaction of the gas-liquid emulsion in the fixed bed reactor is completed, the separation tank delivers the reacted mixture to the separation tank, the treated mixed oil in the mixture settles to the bottom end of the separation tank under the action of gravity and is output from the system through the liquid phase outlet, and the mixed gas in the mixture is output from the system through the gas phase outlet.
8. A hydrogenation reaction method for micro-interface reinforced mixed oil is characterized by comprising the following steps:
step 1: adding a specified amount of the mixed oil to the liquid feedstock tank and a specified amount of hydrogen to the gaseous feedstock buffer tank prior to operating the system;
step 2: starting the system after the addition is finished, extracting the mixed oil from the liquid raw material tank through a feed pump, and extracting hydrogen from the gas raw material buffer tank through a compressor;
and step 3: the mixed oil flows through a liquid feeding preheater, the liquid feeding preheater heats the mixed oil to a preset temperature, hydrogen flows through a gas feeding preheater, and the gas feeding preheater heats the hydrogen to the preset temperature;
and 4, step 4: the mixed oil is preheated and then shunted, the shunted mixed oil can be respectively conveyed to the corresponding micro-interface generators, the hydrogen is preheated and then shunted, and the shunted hydrogen can be respectively conveyed to the corresponding micro-interface generators;
and 5: each micro-interface generator can control the proportion of the micro-interface generator to receive the mixed oil and the hydrogen, break the hydrogen into micro-bubbles with the size of micron, and mix the micro-bubble mixed oil and the micro-bubbles to form a gas-liquid emulsion after breaking;
step 6: after the micro-interface generators are mixed, outputting the gas-liquid emulsion to a fixed bed reactor, controlling the pressure and the temperature in the fixed bed reactor, and enabling the gas-liquid emulsion to flow in a specified direction;
and 7: allowing the gas-liquid emulsion to flow through the catalyst bed layer, controlling the airspeed of the gas-liquid emulsion, and enabling a catalyst arranged in the catalyst bed layer to promote the reaction of sulfur elements in the mixed oil in the gas-liquid emulsion and the microbubbles to generate treated mixed oil and hydrogen sulfide gas so as to treat the mixed oil, wherein the hydrogen sulfide gas and the hydrogen gas form mixed gas;
and 8: after the reaction is finished, the mixture formed by the processed mixed oil and the mixed gas is conveyed to the separation tank by the fixed bed reactor, the mixture is settled in the separation tank, the processed mixed oil is settled on the lower layer of the separation tank and is output from the system through the liquid phase outlet for subsequent processing, and the mixed gas stays on the upper layer of the separation tank after the processed mixed oil is settled and is output from the system through the gas phase outlet for subsequent processing.
9. The method as claimed in claim 8, wherein the reaction pressure in the fixed bed reactor in the step 6 is 0.8-1.2MPa, and the reaction temperature is 300-350 ℃.
10. The method of claim 8, wherein the space velocity of the gas-liquid emulsion in step 7 is 1-6.5h-1。
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| CN114849592A (en) * | 2022-05-11 | 2022-08-05 | 湖南长科诚享石化科技有限公司 | Method and system for pre-atomizing catalytic feed oil |
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| CN114849592A (en) * | 2022-05-11 | 2022-08-05 | 湖南长科诚享石化科技有限公司 | Method and system for pre-atomizing catalytic feed oil |
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