CN111482145A - Upper-mounted micro-interface enhanced reaction device and method for residual oil hydrogenation reaction - Google Patents
Upper-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 28
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000007789 gas Substances 0.000 claims abstract description 45
- 239000001257 hydrogen Substances 0.000 claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 45
- 239000012071 phase Substances 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 239000007791 liquid phase Substances 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 230000009471 action Effects 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 239000007790 solid phase Substances 0.000 claims description 8
- 238000005191 phase separation Methods 0.000 claims description 4
- 238000005728 strengthening Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 49
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005501 phase interface Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 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
- 230000008859 change Effects 0.000 description 1
- 238000004581 coalescence Methods 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
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010771 distillate fuel oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960001341 troxipide Drugs 0.000 description 1
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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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- 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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- 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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- 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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Abstract
The invention discloses an overhead micro-interface enhanced reaction device and 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 suspended bed type reactor, flowing from top to bottom, and carrying out hydrogenation reaction under the action of the catalysts; and the reacted product enters a three-phase separator for separation, gas is discharged from a gas phase outlet, and liquid with the catalyst is discharged from a liquid phase outlet. 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 an overhead 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 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 a micro interface, the phase interface system formed by micro bubble groups is called a micro interface system, according to the Yang-L aplace equation, the internal pressure of the bubbles is inversely proportional to the radius of the bubbles, so the micro bubbles are favorable for improving the internal pressure of the bubbles and the solubility of the gasHas rigidity characteristic, good independence and difficult coalescence, so that gas and liquid of a 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 a reactor-1) Thereby accelerating the reaction rate.
Disclosure of Invention
The invention aims to provide an overhead micro-interface enhanced reaction device and method for residual oil hydrogenation reaction. It comprises a reactor main body, a bubble breaker, a three-phase 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:
an overhead micro-interface strengthening reaction device for residual oil hydrogenation reaction comprises:
the top of the suspension bed reactor is provided with a second discharge port, the side wall of the bottom of the suspension bed reactor is provided with a third discharge port, and the side wall of the top of the suspension bed reactor is provided with a fourth discharge port;
the gas inlet device comprises a hydrogen buffer tank, a compressor and a hydrogen 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 residual oil preheater which are connected in sequence and is used for conveying raw material liquid;
the bubble crusher is arranged at the top of the suspended bed reactor and is provided with a gas phase inlet, a liquid phase inlet and a first discharge hole, and the first discharge hole is connected with the suspended bed reactor; the gas phase inlet is connected with the hydrogen preheater of the gas inlet device and the fourth discharge hole, and the liquid phase inlet is connected with the residual oil preheater of the liquid inlet device; a first discharge port of the bubble breaker at the top is connected with the suspended bed reactor through a gas-liquid mixing pipeline;
the three-phase separator is provided with a second feed inlet, a gas phase outlet, a liquid phase outlet and a solid phase outlet; the second feed inlet is connected with a second discharge outlet at the top of the suspended bed reactor;
and the circulating pump is connected with a third discharge hole of the suspension bed reactor and pumps the feed liquid discharged from the third discharge hole into the bubble breaker at the top.
According to the reaction device, when residual oil and hydrogen respectively enter the bubble crusher from the liquid phase inlet and the gas phase inlet, the hydrogen is crushed into small-particle-size microbubbles so as to increase the contact area with an oil phase; in addition, the low-pressure area in the overhead bubble breaker can repeatedly send the unreacted hydrogen above the reactor to the bottom of the liquid layer to continue to react, so that the contact time of gas phase and liquid phase is prolonged, the two phases are more fully mixed, and the effects of strengthening mass transfer and accelerating macroscopic reaction rate can be achieved. Therefore, the pressure of the system can be reduced, and the proportion of hydrogen and oil can be reduced, so that the problem of the traditional suspension bed reactor can be effectively solved.
In the micro-interface enhanced reaction device, because bubbles are small, gas-liquid separation is slow, and a separator is required to be arranged behind the reactor to realize solid residue separation of micro bubbles, liquid, catalyst and the like.
As a further improvement of the invention, the bubble breaker is a pneumatic bubble breaker, a hydraulic bubble breaker or a gas-liquid linkage 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 enhanced 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 enhanced reaction device can improve the gas-liquid phase interface area1000m2/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 are connected with the suspended bed reactor, or are connected with the suspended bed reactor in parallel, or are connected with the suspended bed reactor in a series-parallel mixed mode.
As a further improvement of the invention, the feeding pump is a plunger pump.
The invention also provides a method for residual oil hydrogenation reaction by using the device, which comprises the following steps:
raw material residual oil is extracted from a residual oil raw material tank, a circulating liquid pumped by a feeding pump and a circulating pump is converged and then enters a micro bubble crusher through a residual oil preheater, meanwhile, raw material hydrogen is extracted from a hydrogen raw material tank, and enters the micro bubble crusher together with hydrogen extracted by a fourth discharge port after passing through a compressor and the hydrogen preheater to form a micron-sized bubble system, and then enters a suspension bed reactor from a first discharge port of the bubble crusher, flows from top to bottom, and is subjected to hydrogenation reaction under the action of a catalyst;
part of feed liquid at the lower part of the reactor enters the bubble breaker at the top through a third discharge hole through a circulating pump and circularly flows; the other part of the material is led out from a second discharge hole at the upper part of the reactor and enters a three-phase separator for gas-liquid-solid three-phase separation; gas is extracted from the gas phase outlet, liquid phase oil is extracted from the liquid phase outlet, and solid slag is extracted from the solid phase outlet.
As a further improvement of the invention, the standard volume ratio of the gas raw material and the liquid raw material entering the bubble breaker is 300-1500: 1; for example, for the hydrogenation ring-opening reaction system, the reaction ratio is generally 300-1200: 1; for the hydrodesulfurization reaction system, it is generally 500-1500: 1.
As a further improvement of the invention, the operating pressure in the bubble breaker is 1-15 MPa; for example, for a hydrogenation ring-opening reaction system, the pressure is generally 1-8 MPa; preferably 2-5 MPa; for the hydrodesulfurization reaction system, it is generally from 6 to 15 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 space velocity in the suspension bed reactor 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 the hydrogenation ring-opening reaction system, the temperature is generally 440-480 ℃; for the hydrodesulfurization reaction system, 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 suspension bed reactor, the invention has the advantages that:
1. the energy consumption is low. Traditional suspension bed reactors increase the solubility of hydrogen in atmospheric residue by high pressure (>20MPa) 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 normal pressure residual oil can be fully reacted in the traditional suspension bed reactor, the hydrogen-oil ratio is generally controlled to be more than 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 top-mounted micro-interface enhanced reaction system for residue hydrogenation;
in the figure, 1-bubble breaker gas phase inlet; 2-bubble breaker liquid phase inlet; 3-a bubble breaker; 4-a suspended bed reactor; 5-a three-phase separator; 6-gas phase outlet of three-phase separator; 7-a liquid phase outlet of the three-phase separator; 8-solid phase outlet of three-phase separator; 9. 10, 11, 13-pipes; 12-a circulation pump; 14-resid feed vessel; 15-a feed pump; 16-resid preheater; 17-a hydrogen buffer tank; 18-a compressor; 19-a hydrogen preheater; 20-gas-liquid mixing pipeline.
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 top-mounted micro-interface enhanced reactor for residue hydrogenation shown in fig. 1 comprises:
the top of the suspension bed reactor 4 is provided with a second discharge hole, and the side wall of the bottom of the suspension bed reactor 4 is provided with a third discharge hole;
the gas inlet device comprises a hydrogen buffer tank 17, a compressor 18 and a hydrogen preheater 19 which are connected in sequence and is used for conveying raw material gas;
the liquid inlet device comprises a residual oil raw material tank 14, a feeding pump 15 and a residual oil preheater 16 which are connected in sequence and used for conveying raw material liquid; in the embodiment, the feeding pump is a plunger pump;
the bubble crusher is arranged at the top of the suspended bed reactor 4, a gas phase inlet, a liquid phase inlet and a first discharge port are arranged on the bubble crusher, and the first discharge port is connected with the suspended bed reactor; the gas phase inlet is connected with a hydrogen preheater 19 of the gas inlet device, and the liquid phase inlet is connected with a residual oil preheater 16 of the liquid inlet device;
in the embodiment, a gas-liquid linkage type bubble crusher 3 is adopted, a liquid phase inlet 2 of the gas-liquid linkage type bubble crusher is connected with a residual oil preheater 16 and a circulating pump 12, and a gas phase inlet 1 of the gas-liquid linkage type bubble crusher is connected with a hydrogen preheater 14. The first discharge port of the bubble breaker at the top is connected with the suspended bed reactor through a gas-liquid mixing pipeline 20.
The bubble breakers can be a plurality of bubble breakers, and the bubble breakers are connected in series to form a bubble breaker group and then are connected with the suspended bed reactor, or are connected with the suspended bed reactor in parallel, or are connected with the suspended bed reactor in a series-parallel mixed mode.
The three-phase separator 5 is provided with a second feeding hole, a gas phase outlet 6, a liquid phase outlet 7 and a solid phase outlet 8; the second feed inlet is connected with a second discharge outlet at the top of the suspended bed reactor 4;
and the circulating pump 8 is connected with a third discharge hole of the suspension bed reactor, and the feed liquid discharged from the third discharge hole is pumped into the bubble breaker at the top.
Example 2
This example illustrates a residue hydrogenation ring-opening reaction, and describes one embodiment of the residue hydrogenation reaction using the apparatus of example 1.
Raw material residual oil is extracted from a residual oil raw material tank 14, is merged with circulating liquid in a pipeline 11 through a plunger pump 15 through a pipeline 9 and then enters a bubble crusher 3 from a liquid phase inlet 2 through a residual oil preheater 16, meanwhile, raw material hydrogen is extracted from a hydrogen raw material tank 17, is subjected to a compressor 18 and a hydrogen preheater 19, is subjected to a gas phase inlet 1, and is together with hydrogen sucked from a fourth discharge port through a pipeline 13 (the hydrogen is not reacted in a suspension bed reactor 4 and is gathered above the liquid level), and enters a micro bubble crusher 3 through a first discharge port, wherein the volume ratio of the hydrogen to the residual oil is 1200: gas-liquid two phases are fully mixed under the action of a bubble breaker 3. Under the action of the microbubble crusher, the hydrogen is crushed into microbubbles with the average diameter of 500 mu m-1mm so as to increase the contact area of the two phases. The output material of the top bubble breaker extends into the reactor 4 through the gas-liquid mixing pipeline 20, and hydrogenation ring-opening reaction is carried out under the action of the catalyst.
The feed liquid discharged from the third discharge port at the lower part of the reactor is extracted through a pipeline 10, enters the reactor through a circulating pump 12, a pipeline 11, a residual oil preheater 16 and a liquid phase inlet 2, and continuously circularly flows in the way. The other part of the materials are led out from a second discharge hole at the upper part of the reactor and enter a middle tank 5 for gas-liquid-solid three-phase separation. Unreacted H2Gas generated by the reaction is extracted from a gas phase outlet 6 at the top end of the intermediate tank 5, liquid phase oil products subjected to hydrogenation ring opening are extracted from a liquid phase outlet 7, solid residues such as catalyst and the like are extracted from a solid phase outlet 8 at the bottom end, and the solid residues are respectively collected for subsequent treatment.
Inner reverse of bubble breakerThe reaction pressure is 8MPa, and the reaction temperature is 450 ℃. A carbon-supported iron catalyst with the particle size of 100nm-1000 mu m is adopted in the suspension bed reactor 4; the airspeed is controlled to be 1.0h-1. The yield of light oil was 83%, which was substantially the same as that of the conventional suspended bed reactor at 18MPa and 480 ℃.
Example 3
The difference between this example and example 2 is that the bubble breaker 3 is a pneumatic bubble breaker, and the standard volume ratio of fresh hydrogen to residual oil entering the bubble breaker 3 is 300: 1; the hydrogen gas is broken into microbubbles having an average diameter of 200 to 600 μm.
The reaction pressure in the bubble breaker is 1MPa, and the reaction temperature is 480 ℃. The carbon-supported iron catalyst with the grain diameter of 100nm-1000 μm is adopted in the suspension bed reactor 4. The space velocity is controlled to be 1.5h-1. The yield of light oil was 81%.
Example 4
This example illustrates a residue hydrodesulfurization reaction, one embodiment of which is carried out using the apparatus of example 1.
Raw material residual oil is extracted from a residual oil raw material tank 14, is converged with circulating liquid in a pipeline 11 through a plunger pump 15 through a pipeline 9 and then enters a micro bubble crusher 3 through a residual oil preheater 16 from a liquid phase inlet 2, meanwhile, raw material hydrogen is extracted from a hydrogen raw material tank 17, is subjected to a compressor 18 and a hydrogen preheater 19, passes through a gas phase inlet 1, and together with hydrogen sucked from a fourth discharge port through a pipeline 13 (the hydrogen is not reacted in a suspension bed reactor 4 and is gathered above the liquid level), and enters the micro bubble crusher 3 through a first discharge port, wherein the volume ratio of the hydrogen to the residual oil is 600: gas-liquid two phases are fully mixed under the action of a bubble breaker 3. Under the action of the bubble breaker, the hydrogen is broken into micro-bubbles with the average diameter of 400-500 mu m so as to increase the contact area of the two phases. The output material of the top bubble breaker extends into the reactor 4 through the gas-liquid mixing pipeline 20, and the hydrodesulfurization reaction is carried out under the action of the catalyst.
The feed liquid discharged from the third discharge port at the lower part of the reactor is extracted through a pipeline 10, enters the reactor through a circulating pump 12, a pipeline 11, a residual oil preheater 16 and a liquid phase inlet 2, and is continuously discharged in the wayA circulating flow is performed. The other part of the materials are led out from the upper part of the reactor and enter an intermediate tank 5 for gas-liquid-solid three-phase separation. Unreacted H2And H formed by reaction2S and other gases are extracted from a gas phase outlet 6 at the top end of the intermediate tank 5, liquid phase oil with lower sulfur content is extracted from a liquid phase outlet 7 after hydrodesulfurization, solid residues such as catalyst and the like are extracted from a solid phase outlet 8 at the bottom end, and the solid residues are respectively collected for subsequent treatment.
The reaction pressure in the bubble breaker is 12MPa, and the reaction temperature is 440 ℃. The carbon-supported iron catalyst is adopted in the suspension bed reactor 4, and the airspeed is controlled to be 0.5h-1. The sulfur content in the raw material residual oil is 0.3wt.%, and is reduced to 0.05 wt.% after being treated by the hydrodesulfurization reaction process.
Example 5
Example 5 differs from example 4 in that the fresh hydrogen to resid standard volume ratio entering the bubble breaker 3 is 1500: 1; the hydrogen gas is broken into microbubbles having an average diameter of 1 to 300 μm. The reaction pressure in the bubble breaker is 15MPa, and the reaction temperature is 400 ℃. The carbon-supported iron catalyst is adopted in the suspension bed reactor 4, and the airspeed is controlled to be 0.2h-1. The sulfur content in the raw material residual oil is 0.3wt.%, and is reduced to 0.08wt.% after being treated by the hydrodesulfurization reaction process.
Claims (10)
1. An overhead micro-interface strengthening reaction device for residual oil hydrogenation reaction is characterized by comprising:
the top of the suspension bed reactor is provided with a second discharge port, the side wall of the bottom of the suspension bed reactor is provided with a third discharge port, and the side wall of the top of the suspension bed reactor is provided with a fourth discharge port;
the gas inlet device comprises a hydrogen buffer tank, a compressor and a hydrogen 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 residual oil preheater which are connected in sequence and is used for conveying raw material liquid;
the bubble crusher is arranged at the top of the suspended bed reactor and is provided with a gas phase inlet, a liquid phase inlet and a first discharge hole, and the first discharge hole is connected with the suspended bed reactor; the gas phase inlet is connected with the hydrogen preheater of the gas inlet device and the fourth discharge hole, and the liquid phase inlet is connected with the residual oil preheater of the liquid inlet device; a first discharge port of the bubble breaker at the top is connected with the suspended bed reactor through a gas-liquid mixing pipeline;
the three-phase separator is provided with a second feed inlet, a gas phase outlet, a liquid phase outlet and a solid phase outlet; the second feed inlet is connected with a second discharge outlet at the top of the suspended bed reactor;
and the circulating pump is connected with a third discharge hole of the suspension bed reactor and pumps the feed liquid discharged from the third discharge hole into the bubble breaker at the top.
2. The apparatus of claim 1, wherein the bubble breaker is a pneumatic bubble breaker, a hydraulic 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 are connected with the suspended bed reactor, or are connected with the suspended bed reactor in parallel, or are connected with the suspended bed reactor in a series-parallel mixed mode.
4. The apparatus of claim 1, wherein the feed pump is a plunger pump.
5. A process for the hydrogenation of residuum according to any of claims 1 to 4, comprising:
raw material residual oil is extracted from a residual oil raw material tank, a circulating liquid pumped by a feeding pump and a circulating pump is converged and then enters a micro bubble crusher through a residual oil preheater, meanwhile, raw material hydrogen is extracted from a hydrogen raw material tank, and enters a micro-scale bubble system through a compressor and a hydrogen preheater and then enters a bubble crusher together with hydrogen extracted by a fourth discharge port to form a micro-scale bubble system, and then enters a suspension bed reactor from a first discharge port of the bubble crusher, flows from top to bottom, and is subjected to hydrogenation reaction under the action of a catalyst;
part of feed liquid at the lower part of the reactor enters the bubble breaker at the top through a third discharge hole through a circulating pump and circularly flows; the other part of the material is led out from a second discharge hole at the upper part of the reactor and enters a three-phase separator for gas-liquid-solid three-phase separation; gas is extracted from the gas phase outlet, liquid phase oil is extracted from the liquid phase outlet, and solid slag is extracted from the solid phase outlet.
6. The method as claimed in claim 5, wherein the standard volume ratio of the gas feedstock to the liquid feedstock entering the bubble breaker is 300-.
7. The method of claim 5, wherein the operating pressure within the bubble breaker is 1-15 MPa.
8. The method of claim 5, wherein the catalyst is selected from powder type catalyst with particle size of 100nm-1000 μm.
9. The method of claim 5, wherein the space velocity in the suspension bed reactor is controlled to be 0.2-1.5h-1。
10. The method as claimed in claim 5, wherein the operating temperature in the bubble breaker is 400-.
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| CN201910088340.7A CN111482145A (en) | 2019-01-29 | 2019-01-29 | Upper-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 |
|---|---|---|---|---|
| CN113035285A (en) * | 2021-04-01 | 2021-06-25 | 南京延长反应技术研究院有限公司 | Method for calculating influence of microbubble size on oil product hydrodesulfurization effect |
| CN114381300A (en) * | 2020-10-19 | 2022-04-22 | 中国石油大学(北京) | Heavy oil lightening method |
-
2019
- 2019-01-29 CN CN201910088340.7A patent/CN111482145A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114381300A (en) * | 2020-10-19 | 2022-04-22 | 中国石油大学(北京) | Heavy oil lightening method |
| CN113035285A (en) * | 2021-04-01 | 2021-06-25 | 南京延长反应技术研究院有限公司 | Method for calculating influence of microbubble size on oil product hydrodesulfurization effect |
| CN113035285B (en) * | 2021-04-01 | 2023-04-11 | 南京延长反应技术研究院有限公司 | Method for calculating influence of microbubble size on oil product hydrodesulfurization effect |
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