CN111495287A - Side-mounted micro-interface enhanced reaction device and method for residual oil hydrogenation reaction - Google Patents
Side-mounted micro-interface enhanced reaction device and method for residual oil hydrogenation reaction Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 41
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 105
- 230000005587 bubbling Effects 0.000 claims abstract description 54
- 239000007789 gas Substances 0.000 claims abstract description 39
- 239000007791 liquid phase Substances 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000012071 phase Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 5
- 238000005728 strengthening Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 49
- 239000000047 product Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 238000007142 ring opening reaction Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000005501 phase interface Effects 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- YSIITVVESCNIPR-UHFFFAOYSA-N Troxipide Chemical compound COC1=C(OC)C(OC)=CC(C(=O)NC2CNCCC2)=C1 YSIITVVESCNIPR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
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- B01J8/224—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement
- B01J8/228—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement externally, i.e. the particles leaving the vessel and subsequently re-entering it
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- B01J8/1845—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/14—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
- C10G45/16—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles suspended in the oil, e.g. slurries
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/22—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen dissolved or suspended in the oil
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
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- 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
- C10G47/36—Controlling or regulating
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- B01J2208/00548—Flow
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00743—Feeding or discharging of solids
- B01J2208/00769—Details of feeding or discharging
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
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- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention discloses a side-mounted micro-interface enhanced reaction device and a side-mounted micro-interface enhanced reaction method for residual oil hydrogenation reaction. Preheating hydrogen and residual oil raw materials with catalysts, then feeding the preheated hydrogen and residual oil raw materials into a bubble crusher to form a micron-sized bubble system, then feeding the micron-sized bubble system into a bubbling reactor, flowing from bottom to top, and carrying out hydrogenation reaction under the action of the catalysts; and the reacted product enters a gas-liquid separator for separation, gas is discharged from a gas-phase outlet, liquid with the catalyst enters a circulating pump from a liquid-phase outlet for subsequent conveying, part of the liquid is extracted as the hydrogenated oil product, and the rest of the liquid circularly enters a bubble breaker for bubble breaking according to process requirements. The reaction device and the method have the advantages of ultralow hydrogenation reaction pressure, small gas-liquid ratio, large gas-liquid mass transfer area, high reaction rate, low energy consumption, flexible process, high production safety and the like.
Description
Technical Field
The invention relates to a side-mounted micro-interface enhanced reaction device and method for residual oil hydrogenation reaction.
Background
Since the seventies of the last century, the quality of crude oil produced from petroleum has begun to deteriorate, and the heavy oil content in crude oil, particularly the yield of residual oil, has tended to increase. The residual oil can be divided into various types according to the differences of crude oil producing areas, oil refining processes and the like, and the physical and chemical properties of different types are different. It can be generally divided into two main categories of atmospheric residuum and vacuum residuum. The main components of the residual oil comprise saturated hydrocarbon, aromatic hydrocarbon, colloid and asphaltene, and the residual oil can be deeply hydrogenated under the action of a catalyst at high temperature and high pressure, and a light fuel oil product is obtained through a series of complex physicochemical changes such as ring-opening cracking and the like.
With the increasing demand of various countries in the world on light oil products and the continuous stricter requirement on environmental protection, people pay more attention to the hydrogenation reaction technology of residual oil. The traditional residual oil hydrogenation reaction generally adopts a suspension bed hydrogenation reactor, and although the reactor has strong adaptability to raw materials and simple operation, the hydrogenation reaction efficiency is lower because the reactor is controlled by mass transfer. The fundamental reason is that the bubble size in the reactor is large (generally 3-10 mm), so the gas-liquid phase boundary mass transfer area is small (generally 100-2/m3) Thus limiting mass transfer efficiency. Therefore, engineering has to employ high temperature (470 ℃ or higher) and high pressure (20 MPa or higher) operations to enhance the reaction process by increasing the solubility of hydrogen to increase the mass transfer rate. However, high temperature and high pressure cause a series of side effects: high energy consumption and production cost, high investment intensity, short equipment operation period, more faults, poor intrinsic safety and the like, thereby bringing challenges to industrialized mass production. Diameter of bubble (Sauter diameter) d32Is a key parameter for determining the size of the interfacial area and is a core factor for determining the gas-liquid reaction rate. d32When the volume mass transfer coefficient is gradually increased, the volume mass transfer coefficient is gradually increased; especially when d is32When the diameter is less than 1mm, the volume mass transfer coefficient is dependent on d32The decrease in (c) increases rapidly in an exponential-like fashion. Thus, d is32The bubbles with the diameter between 1 mu m and 1mm can be called micro-bubbles, the phase interface formed by the micro-bubbles is called micro-interface, the phase interface system formed by micro-bubble groups is called micro-interface system, according to Yang-L aplace equation, the internal pressure of the bubbles is inversely proportional to the radius of the bubbles, so the micro-bubbles are also beneficial to improving the gas-liquid reaction in the bubblesAnd the solubility of the gas is improved. Therefore, in the gas-liquid reaction process, the micro-interface system can strengthen gas-liquid mass transfer, and further accelerate the gas-liquid reaction. The microbubbles have the characteristics of rigidity and good independence and are not easy to coalesce, so that gas and liquid of the microbubble system are fully mixed, a system containing a large number of microbubbles can be obtained, and a higher interfacial area (more than or equal to 1000 m) is formed in the reactor-1) Thereby accelerating the reaction rate.
Disclosure of Invention
The invention aims to provide a side-mounted micro-interface enhanced reaction device and a side-mounted micro-interface enhanced reaction method for residual oil hydrogenation reaction. It comprises a reactor main body, a bubble breaker, a gas-liquid separator and other components. The bubble breaker can reduce the bubble size of a gas-liquid system from 3-10mm to 1 μm-1mm, thereby greatly increasing the gas content and the gas-liquid mass transfer area of the system, accelerating the heterogeneous reaction process, improving the gas utilization rate, improving the environmental problem caused by excessive discharge, and improving the mass transfer rate and the hydrogenation reaction efficiency, so as to solve the problems of high temperature, high pressure, high material consumption, high investment, high safety risk and the like in the residual oil hydrogenation process, thereby reducing the investment cost and the operating cost of equipment.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a side-mounted micro-interface strengthening reaction device for residual oil hydrogenation reaction comprises:
the top of the bubbling reactor is provided with a second discharge hole;
the gas inlet device comprises a hydrogen buffer tank, a compressor and a first preheater which are connected in sequence and is used for conveying raw material gas;
the liquid inlet device comprises a residual oil raw material tank, a feeding pump and a second preheater which are connected in sequence and is used for conveying raw material liquid;
the bubble crusher is arranged laterally at the lower part of the bubbling reactor, and is provided with a gas phase inlet, a liquid phase inlet and a first discharge port, and the first discharge port is connected with the bubbling reactor; the gas phase inlet is connected with a first preheater of the gas inlet device, and the liquid phase inlet is connected with a second preheater of the liquid inlet device;
the gas-liquid separator is provided with a second feed inlet, a gas-phase outlet and a liquid-phase outlet; the second feed port is connected with a second discharge port at the top of the bubbling reactor;
and the circulating pump is connected with the liquid phase outlet of the gas-liquid separator.
In the micro-interface enhanced reaction device, because bubbles are small, gas-liquid separation is slow, and a special gas-liquid separator is required to be arranged behind a reactor to realize the separation of micro-bubbles and liquid containing a catalyst.
As a further improvement of the invention, the bubble breaker is a pneumatic bubble breaker or a gas-liquid linkage type bubble breaker. The bubble breaker can be a pneumatic type, a hydraulic type and a gas-liquid linkage type according to an energy input mode, wherein the pneumatic type breaker is driven by gas, and the input gas quantity is far larger than the liquid quantity; the hydraulic breaker is driven by liquid, and the input gas amount is generally smaller than the liquid amount; the gas-liquid linkage type bubble breaker is driven by gas and liquid together. Micro-bubbles with the average diameter of 1 μm-1mm can be formed in the bubble breaker. The micro-bubble size is micron-sized, is similar to a rigid ball, is not easy to coalesce in the main body of the micro-interface strengthening reaction device, and only changes along with the consumption of components in the gas bubble or the change of external pressure in the reaction process, so the micro-interface strengthening reaction device can improve the gas-liquid phase interface area to 1000m2/m3Therefore, the multi-phase reaction time is obviously reduced, and the energy consumption and material consumption are greatly reduced.
As a further improvement of the present invention, the bubble breaker is provided in plurality; the bubble breakers are connected in series to form a bubble breaker group and then connected with the bubbling reactor, or connected with the bubbling reactor in parallel, or connected with the bubbling reactor in a series-parallel mixed mode.
Furthermore, a plurality of bubble breakers or bubble breaker groups connected in parallel with the bubbling reactor are vertically connected with the bubbling reactor and are arranged in a hedging manner, so that micro-bubble systems are relatively collided and mixed; a plurality of bubble breakers or bubble breaker groups connected in parallel with the bubbling reactor are tangentially arranged with the bubbling reactor and are tangentially arranged; when the opposite-cutting type arrangement is adopted, the micro-bubble system enters the rotating mixing in a tangential direction.
As a further improvement of the invention, part of the liquid output by the circulating pump is taken as a finished oil product to be produced, and the rest part of the liquid circularly enters the bubble breaker for bubble breaking according to the process requirement. Extracting the separated liquid containing the catalyst, further separating the extracted liquid in a suspension separator, re-feeding the catalyst into a feed liquid pump or a reactor main body, and extracting the liquid serving as finished oil; the other part of the liquid material containing the catalyst can be used as driving liquid and is pumped to the hydraulic crusher by the feed liquid pump.
The invention also provides a method for residual oil hydrogenation reaction by using the device, which comprises the following steps:
preheating hydrogen and residual oil raw materials with catalysts, then respectively entering a bubble breaker from a gas phase inlet and a liquid phase inlet to form a micron-sized bubble system, then entering a bubbling reactor from a first discharge port of the bubble breaker, flowing from bottom to top, and carrying out hydrogenation reaction under the action of the catalysts;
and the reacted product enters a gas-liquid separator for separation, gas is discharged from a gas-phase outlet, liquid with the catalyst enters a circulating pump from a liquid-phase outlet for subsequent conveying, part of the liquid is extracted as the hydrogenated oil product, and the rest of the liquid circularly enters a bubble breaker for bubble breaking according to process requirements.
As a further improvement of the present invention, the standard volume ratio of the gas feedstock to the liquid feedstock entering the bubble breaker is 300-2000: 1. For example, for the residual oil hydrogenation ring-opening reaction system, the reaction ratio is generally 300-1500: 1; preferably 400-; for residual oil hydrodesulfurization systems, it is generally 500-.
As a further improvement of the invention, the operating pressure in the bubble breaker and in the bubbling reactor is 1-16 MPa. For example, for a residual oil hydrogenation ring-opening reaction system, the pressure is generally 1-10 MPa; preferably 2-5 MPa; for residue hydrodesulphurisation systems, typically 8-16 MPa.
As a further improvement of the invention, the catalyst is a powder catalyst with the particle size of 100nm-1000 μm; preferably 100nm to 100 μm.
As a further improvement of the invention, the bubbling reactionThe space velocity in the device is controlled to be 0.2-1.5h-1(ii) a Preferably 0.5-1.2h-1。
As a further improvement of the invention, the operation temperature in the bubble breaker is 400-480 ℃. For example, for a residual oil hydrogenation ring-opening reaction system, the temperature is generally 440-480 ℃; for residual oil hydrodesulfurization systems, the temperature is generally 400-450 ℃.
The reaction system of the invention ensures that the internal system of the bubble breaker enters the reactor, the operation temperature and the pressure of the bubble breaker are slightly higher than those of the reactor, when the size of bubbles in the bubble breaker is smaller, the reaction is more favorable, and the operation temperature and the pressure in the reactor can be further reduced.
Compared with the traditional bubbling reactor, the invention has the advantages that:
1. the energy consumption is low. Conventional bubble reactors increase the solubility of hydrogen in the residuum by high pressure (18-25MPa) to enhance mass transfer. The invention achieves the effect of strengthening mass transfer by increasing the interfacial area of gas-liquid two phases. The pressure can be suitably reduced, thereby reducing energy consumption.
2. The hydrogen-oil ratio is low. In order to ensure that the residual oil can be fully reacted in the conventional bubbling reactor, the gas-oil ratio is generally controlled to be 2000-3000: 1. The mass transfer and further reaction of the method are enhanced, so that the hydrogen-oil ratio can be greatly reduced, the material consumption of hydrogen is reduced, and the energy consumption of cyclic compression is reduced.
3. Low process severity, high production safety, low ton product cost and strong market competitiveness.
Drawings
FIG. 1 is a schematic diagram of a side-mounted micro-interface enhanced reaction system for residue hydrogenation;
FIG. 2 is a schematic diagram of the hedging arrangement of a micro-interface reactor disruptor;
FIG. 3 is a schematic view of the rotational arrangement of a micro-interface reactor disruptor;
wherein: 1-a liquid phase inlet of the gas-liquid linkage type bubble breaker; 2-gas phase inlet of gas-liquid linkage bubble breaker; 3-gas-liquid linkage type bubble breaker; 4-a bubbling reactor; 5-a gas-liquid separator; 6-gas phase outlet of gas-liquid separator; 7-the liquid phase outlet of the gas-liquid separator; 8-a circulating pump; 9-residuum feed tank; 10-a feed pump; 11-a second preheater; 12-a hydrogen buffer tank; 13-a compressor; 14-a first preheater; 15-a pneumatic bubble breaker; 16-liquid phase inlet of pneumatic bubble breaker; 17-gas phase inlet of the pneumatic bubble breaker; 18-oil recovery.
Detailed Description
The technical scheme of the invention is further explained by the following description and the specific implementation mode in combination with the attached drawings.
Example 1
This example illustrates the structure of the apparatus of the present invention, and the side-mounted micro-interface enhanced reactor for residue hydrogenation shown in fig. 1 comprises:
the top of the bubbling reactor 4 is provided with a second discharge hole;
the gas inlet device comprises a hydrogen buffer tank 12, a compressor 13 and a first preheater 14 which are connected in sequence and is used for conveying raw material gas;
the liquid inlet device comprises a residual oil raw material tank 9, a feeding pump 10 and a second preheater 11 which are connected in sequence and used for conveying raw material liquid;
the bubble crusher is arranged laterally at the lower part of the bubbling reactor 4, and is provided with a gas phase inlet, a liquid phase inlet and a first discharge port, and the first discharge port is connected with the bubbling reactor; the gas phase inlet is connected with a first preheater 14 of the gas inlet device, and the liquid phase inlet is connected with a second preheater 11 of the liquid inlet device;
in this embodiment, a gas-liquid linkage type bubble breaker 3 and a pneumatic bubble breaker 15 are adopted to form a group of bubble breakers, a liquid-phase inlet 1 of the gas-liquid linkage type bubble breaker and a liquid-phase inlet 16 of the pneumatic bubble breaker are connected with a second preheater 11 and a circulating pump 8, and a gas-phase inlet 2 of the gas-liquid linkage type bubble breaker and a gas-phase inlet of the pneumatic bubble breaker are connected with a first preheater 14.
The bubble breaker can also be a pneumatic bubble breaker/gas-liquid linkage type bubble breaker, or more than three bubble breakers, the bubble breakers are connected in series to form a bubble breaker group and then are connected with the bubbling reactor, or are connected with the bubbling reactor in parallel (fig. 1 shows that the two bubble breakers and the bubbling reactor are connected in parallel), or are connected with the bubbling reactor in a series-parallel mixing mode. Two bubble breakers compare a bubble breaker, can form the vortex flow in bubbling type reactor, mix more fully, and cost and gas-liquid input all can increase during a plurality of bubble breakers, can set up according to specific reaction demand.
The gas-liquid separator 5 is provided with a second feeding hole, a gas-phase outlet 6 and a liquid-phase outlet 7; the second feed port is connected with a second discharge port at the top of the bubbling reactor 4;
and the circulating pump 8 is connected with the liquid phase outlet of the gas-liquid separator. And part of liquid output by the circulating pump is taken as a finished oil product to be extracted, and the rest part of the liquid circularly enters the bubble crusher for bubble crushing according to the process requirement.
The two bubble breakers of this embodiment may be vertically disposed at both ends of one diameter of the sectional circle of the bubbling reactor in an opposed arrangement, as shown in fig. 2. When the bubble breakers are multiple, the bubble breakers directly connected with the bubbling reactor can be uniformly arranged in a radial shape;
the two bubble breakers may also be arranged tangentially to the bubble reactor, with the points of tangency located at each end of a diameter of the cross-sectional circle of the bubble reactor, in a tangential arrangement, as shown in fig. 3. When the bubble breakers are a plurality of, the tangent points between the bubble breakers which are directly connected with the bubbling reactor and the bubbling reactor can be uniformly arranged in a radial shape.
Example 2
This example illustrates one embodiment of the process of the present invention, using a residuum hydrocracking ring opening reaction as an example.
The residual oil raw material is extracted from a residual oil raw material tank 9, mixed with a catalyst through a feeding pump 10, and then passes through a second preheater 11, one path of the residual oil raw material enters a gas-liquid linkage type bubble crusher 3 arranged on the side surface of the shell of the bubbling type reactor 4 through a liquid phase inlet 1 of the gas-liquid linkage type bubble crusher, and the other path of the residual oil raw material enters a pneumatic type bubble crusher 15 arranged on the side surface of the shell of the bubbling type reactor 4 through a liquid phase inlet 16 of the pneumatic type bubble crusher. Meanwhile, hydrogen raw materials are extracted from a hydrogen buffer tank 12, pass through a compressor 13 and then pass through a first preheater 14, and then enter a gas-liquid linkage type bubble crusher 3 arranged on the side surface of the shell of the bubbling type reactor 4 through a gas phase inlet 2 of the gas-liquid linkage type bubble crusher on one path, and enter a pneumatic type bubble crusher 15 arranged on the side surface of the shell of the bubbling type reactor 4 through a gas phase inlet 17 of the pneumatic type bubble crusher on the other path. The arrangement of the gas-liquid linkage type bubble breaker 3 and the pneumatic breaker 15 is an opposite impact type arrangement, as shown in fig. 2. Under the action of the gas-liquid linkage type bubble crusher 3 and the pneumatic bubble crusher 15, hydrogen is crushed into micro bubbles with the average diameter of 300-400 microns, gas and liquid are mixed vigorously to form a gas-liquid micro interface reaction system, the gas-liquid micro interface reaction system enters the side face of the bubbling reactor 4 and flows from bottom to top, and hydrogenation ring-opening reaction is carried out.
The reaction product is led out from a second discharge hole at the top end of the bubbling reactor 4 and enters a gas-liquid separator 5, unreacted hydrogen and a gas product generated by the reaction are extracted from a gas-phase outlet 6 of the gas-liquid separator, liquid with a catalyst is extracted from a liquid-phase outlet 7 of the gas-liquid separator and is conveyed by a circulating pump 8, part of the liquid is extracted as an oil product 18 after ring opening by hydrogenation, and the rest part of the liquid can circularly enter a gas-liquid linkage type bubble crusher 3 and a pneumatic type bubble crusher 15 which are arranged on the side surface of the shell of the bubbling reactor 4 through a liquid-phase inlet 1 of the gas-liquid linkage type bubble crusher according to the process requirements and is continuously used for bubble crushing.
In this embodiment, the standard volume ratio of the fresh hydrogen and the residual oil entering the gas-liquid linkage type bubble crusher 3 is 0.3: 1; the standard volume ratio of fresh hydrogen and residual oil entering the pneumatic bubble crusher is 800: 1.
the reaction pressure in the bubble breaker is 10MPa, and the reaction temperature is 450 ℃. The bubbling reactor 4 adopts a carbon-supported iron catalyst with the grain diameter of 100nm-1000 μm. The airspeed is controlled to be 0.2h-1. The yield of light oil was 80%, which was substantially the same as that of the conventional suspended bed reactor at 20MPa and 470 ℃.
Example 3
The difference between this embodiment and embodiment 2 is that the gas-liquid linkage type bubble breaker 3 and the pneumatic bubble breaker 15 are arranged in a tangential manner as shown in fig. 3.
The standard volume ratio of the fresh hydrogen and the residual oil entering the gas-liquid linkage type bubble crusher 3 is 300: 1; the standard volume ratio of fresh hydrogen and residual oil entering the pneumatic bubble crusher is 1000: 1. the hydrogen is broken into microbubbles with an average diameter of 400-1 mm.
The reaction pressure in the bubble breaker is 1MPa, and the reaction temperature is 480 ℃. The bubbling reactor 4 adopts a carbon-supported iron catalyst with the grain diameter of 100nm-1000 μm. The space velocity is controlled to be 1.5h-1. The yield of light oil was 79%.
Example 4
This example illustrates one embodiment of the process of the present invention, using a residue hydrodesulfurization reaction as an example.
The standard volume ratio of the fresh hydrogen and the residual oil entering the gas-liquid linkage type bubble crusher 3 is 1500: 1; the standard volume ratio of fresh hydrogen and residual oil entering the pneumatic bubble crusher is 800: 1. the hydrogen gas is broken into microbubbles having an average diameter of 1 to 300 μm.
Reaction products enter a gas-liquid separation tank 5 from a second discharge port at the top end of the bubbling reactor 4, unreacted hydrogen, gas such as hydrogen sulfide generated by reaction and the like are extracted from a gas-phase outlet 6 of the gas-liquid separation tank, liquid with a catalyst is extracted from a liquid-phase outlet 7 of the gas-liquid separation tank and is conveyed by a circulating pump 8, part of the liquid is extracted as oil 18 after hydrodesulfurization, and the rest of the liquid can circularly enter a gas-liquid linkage type bubble crusher 3 and a pneumatic type bubble crusher 15 which are arranged on the side surface of the shell of the bubbling reactor 4 through a liquid-phase inlet 1 of the gas-liquid linkage type bubble crusher according to process requirements and are continuously used for bubble crushing.
The reaction pressure in the bubble breaker is 16MPa, and the reaction temperature is 440 ℃. The bubbling reactor 4 adopts a carbon-supported iron catalyst with the grain diameter of 100nm-1000 μm. The airspeed is controlled to be 0.5h-1. The sulfur content in the raw material residual oil is 0.2 wt.%, and is reduced to 0.05 wt.% after treatment.
Example 5
The difference between the embodiment and the embodiment 4 is that the standard volume ratio of the fresh hydrogen and the residual oil entering the gas-liquid linkage type bubble crusher 3 is 1200: 1; the standard volume ratio of fresh hydrogen and residual oil entering the pneumatic bubble crusher is 800: 1. the hydrogen gas is broken into microbubbles having an average diameter of 100 to 400 μm.
The reaction pressure in the bubble breaker is 8MPa, and the reaction temperature is 400 ℃. The bubbling reactor 4 adopts a carbon-supported iron catalyst with the grain diameter of 100nm-1000 μm. The airspeed is controlled to be 1.0h-1. The sulfur content in the raw material residual oil is 0.4 wt.%, and is reduced to 0.07 wt.% after treatment.
Claims (10)
1. A side-mounted micro-interface strengthening reaction device for residual oil hydrogenation reaction is characterized by comprising:
the top of the bubbling reactor is provided with a second discharge hole;
the gas inlet device comprises a hydrogen buffer tank, a compressor and a first preheater which are connected in sequence and is used for conveying raw material gas;
the liquid inlet device comprises a residual oil raw material tank, a feeding pump and a second preheater which are connected in sequence and is used for conveying raw material liquid;
the bubble crusher is arranged laterally at the lower part of the bubbling reactor, and is provided with a gas phase inlet, a liquid phase inlet and a first discharge port, and the first discharge port is connected with the bubbling reactor; the gas phase inlet is connected with a first preheater of the gas inlet device, and the liquid phase inlet is connected with a second preheater of the liquid inlet device;
the gas-liquid separator is provided with a second feed inlet, a gas-phase outlet and a liquid-phase outlet; the second feed port is connected with a second discharge port at the top of the bubbling reactor;
and the circulating pump is connected with the liquid phase outlet of the gas-liquid separator.
2. The device according to claim 1, characterized in that the bubble breaker is a pneumatic bubble breaker or a gas-liquid linkage bubble breaker.
3. The apparatus according to claim 1, wherein the bubble breaker is provided in plurality; the bubble breakers are connected in series to form a bubble breaker group and then connected with the bubbling reactor, or connected with the bubbling reactor in parallel, or connected with the bubbling reactor in a series-parallel mixed mode.
4. An apparatus according to claim 3, wherein a plurality of bubble breakers or groups of bubble breakers connected in parallel with the bubbling reactor are connected vertically to the bubbling reactor in an opposed arrangement.
5. An apparatus according to claim 3, wherein a plurality of bubble breakers or groups of bubble breakers connected in parallel with the bubble reactor are arranged tangentially to the bubble reactor, in a tangential arrangement.
6. The device of claim 1, wherein part of the liquid output by the circulating pump is produced as a finished oil product, and the rest part of the liquid is circulated into the bubble breaker for bubble breaking according to process requirements.
7. A process for the hydrogenation of residuum according to any of claims 1 to 6, comprising:
preheating hydrogen and residual oil raw materials with catalysts, then respectively entering a bubble breaker from a gas phase inlet and a liquid phase inlet to form a micron-sized bubble system, then entering a bubbling reactor from a first discharge port of the bubble breaker, flowing from bottom to top, and carrying out hydrogenation reaction under the action of the catalysts;
and the reacted product enters a gas-liquid separator for separation, gas is discharged from a gas-phase outlet, liquid with the catalyst enters a circulating pump from a liquid-phase outlet for subsequent conveying, part of the liquid is extracted as the hydrogenated oil product, and the rest of the liquid circularly enters a bubble breaker for bubble breaking according to process requirements.
8. The method as claimed in claim 7, wherein the standard volume ratio of the gas feedstock to the liquid feedstock entering the bubble breaker is 300-.
9. The method of claim 7, wherein the operating pressure within the bubble breaker is 1-16 MPa.
10. The method of claim 7, wherein the catalyst is selected from powder type catalysts with a particle size of 100nm to 1000 μm.
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| CN201910087882.2A CN111495287A (en) | 2019-01-30 | 2019-01-30 | Side-mounted micro-interface enhanced reaction device and method for residual oil hydrogenation reaction |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112023833A (en) * | 2020-08-11 | 2020-12-04 | 南京延长反应技术研究院有限公司 | Micro-interface strengthening system and method for preparing N-methyl sodium taurate |
| CN114425279A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Feeding distributor and reactor |
-
2019
- 2019-01-30 CN CN201910087882.2A patent/CN111495287A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112023833A (en) * | 2020-08-11 | 2020-12-04 | 南京延长反应技术研究院有限公司 | Micro-interface strengthening system and method for preparing N-methyl sodium taurate |
| CN114425279A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Feeding distributor and reactor |
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Application publication date: 20200807 |