CN116554919B - Method for strengthening heavy oil slurry bed hydrogenation and lightening through micro bubbles - Google Patents
Method for strengthening heavy oil slurry bed hydrogenation and lightening through micro bubbles Download PDFInfo
- Publication number
- CN116554919B CN116554919B CN202210114234.3A CN202210114234A CN116554919B CN 116554919 B CN116554919 B CN 116554919B CN 202210114234 A CN202210114234 A CN 202210114234A CN 116554919 B CN116554919 B CN 116554919B
- Authority
- CN
- China
- Prior art keywords
- raw material
- heavy oil
- slurry bed
- gas
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000295 fuel oil Substances 0.000 title claims abstract description 144
- 239000002002 slurry Substances 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- 238000005728 strengthening Methods 0.000 title claims description 6
- 239000002994 raw material Substances 0.000 claims abstract description 131
- 239000000047 product Substances 0.000 claims abstract description 125
- 239000007789 gas Substances 0.000 claims abstract description 96
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 71
- 239000001257 hydrogen Substances 0.000 claims abstract description 71
- 239000007791 liquid phase Substances 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000012071 phase Substances 0.000 claims abstract description 42
- 239000003921 oil Substances 0.000 claims abstract description 40
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 40
- 238000004062 sedimentation Methods 0.000 claims description 23
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims description 20
- 239000011733 molybdenum Substances 0.000 claims description 20
- 230000001174 ascending effect Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 3
- 239000011280 coal tar Substances 0.000 claims description 3
- 239000003027 oil sand Substances 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims 2
- 239000010779 crude oil Substances 0.000 claims 1
- 230000002708 enhancing effect Effects 0.000 abstract description 5
- 239000000571 coke Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004939 coking Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
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
- C10G47/24—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
-
- 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
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- 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
- B01J8/22—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a method for enhancing hydrogenation and lightening of a heavy oil slurry bed by micro bubbles, which comprises the following steps: after the raw material hydrogen and the circulating gas are mixed, a part of the mixture flows to a bubble crushing unit after being preheated, hydrogen is crushed into micro bubbles and uniformly dispersed in the raw material heavy oil, the raw material heavy oil coming out of the bubble crushing unit enters a riser of a slurry bed reactor after being preheated to undergo a hydrocracking reaction, the generated reaction product flows to a high-pressure separator from the slurry bed reactor to undergo gas-liquid separation, a first gas phase product and a first liquid phase product are obtained, the first liquid phase product then enters a low-pressure separator to undergo gas-liquid separation again, a second gas phase product and a second liquid phase product are obtained, the second liquid phase product further enters a stabilizing tower to undergo gas-liquid separation, and a gas phase product and a light oil product are obtained.
Description
Technical Field
The invention relates to the technical field of heavy oil hydrogenation, in particular to a method for enhancing hydrogenation and lightening of a heavy oil slurry bed by micro-bubbles.
Background
At present, petroleum resources tend to be heavy and poor, the demand for petroleum products is increasing, and the environmental protection requirement is becoming severe, and great challenges are brought to the petrochemical industry, so that the development of the deep processing technology of poor heavy oil is widely focused in the industry. The heavy oil is light, and the heavy oil is mainly subjected to two process routes of decarburization and hydrogenation, wherein the liquid phase yield of the decarburization route is lower, and the coke yield is higher; the hydrogenation route has high liquid phase yield and good product property. Therefore, the hydrogenation process is a better heavy oil light-weight process route at present, and has good development prospect.
Along with the heavy and poor quality of petroleum resources, the fixed bed hydrogenation technology has obvious defects. The boiling bed technology has serious catalyst abrasion, high cost and complex process. The heavy oil slurry bed hydrogenation technology is an emerging technical route, wherein the slurry bed reactor can well solve the problems of heavy and poor quality of petroleum resources. The catalyst in the slurry reactor is dispersed in heavy oil to form catalytic slurry with the heavy oil, and the hydrocracking reaction is carried out under the condition of hydrogen. In general, the catalyst concentration in the slurry bed reactor is low and the dispersion is good, so that on one hand, the abrasion of the catalyst and the abrasion of the catalyst to equipment are reduced; on the other hand, the use cost of the catalyst is reduced. The slurry bed reactor is generally of a hollow barrel structure, and has no complex internal components, so that the equipment is simple, and the equipment investment cost is reduced. Thus, slurry bed reactors are one of the more desirable reactors in heavy oil hydrogenation and light weight processes.
The liquid phase back mixing in the slurry bed reactor has important significance on uniform temperature distribution in the slurry bed reactor, and the liquid phase back mixing prolongs the residence time of heavy components in the reactor, so that the reaction depth is increased, the conversion rate is improved, but along with the prolonged residence time of the heavy components in the reactor, the coking tendency is also enhanced, especially the coking matters cannot be timely removed from the reactor, a coking carrier is provided for coking reaction, and the stable operation of the heavy oil hydrogenation and lightening process is not facilitated. In addition, the solubility of hydrogen in heavy oil is extremely low, the heavy oil hydrogenation and lightening process is generally carried out under the conditions of higher reaction pressure and higher hydrogen-oil ratio, the reaction condition is high in severity, and coke formation is easy to form, so that the investment cost of reactor equipment is higher, the hydrogen utilization rate is low and the energy consumption is higher.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for strengthening the hydrogenation and the lightening of a heavy oil slurry bed by micro bubbles so as to achieve the purposes of reducing the reaction condition severity of the heavy oil slurry bed hydrocracking process, improving the liquid phase yield of the heavy oil hydrocracking process, slowing down coke generation and prolonging the equipment operation period.
In order to achieve the above purpose, the present invention provides the following technical solutions:
A method for strengthening the hydrogenation and the lightening of a heavy oil slurry bed by micro bubbles is characterized in that: the method comprises the following steps:
S1, preheating a part of raw material hydrogen and recycle gas which are mixed on a pipeline and raw material heavy oil containing a catalyst with a certain concentration from a raw material tank, flowing to a bubble crushing unit, crushing the hydrogen into micro bubbles, uniformly dispersing the micro bubbles in the raw material heavy oil, preheating the raw material heavy oil from the bubble crushing unit, and entering a riser of a slurry bed reactor to perform hydrocracking reaction to generate a reaction product;
S2, enabling a reaction product flowing out of the slurry bed reactor to flow into a high-pressure separator from the slurry bed reactor, and performing primary gas-liquid separation to obtain a first gas-phase product and a first liquid-phase product;
S3, the first liquid phase product from the high-pressure separator enters the low-pressure separator for secondary gas-liquid separation to obtain a second gas phase product and a second liquid phase product;
s4, the second liquid phase product obtained by the low-pressure separator further enters a stabilizing tower for gas-liquid separation to obtain a gas phase product and a light oil product, and the light oil product flows into a product tank.
In some embodiments, the volume ratio of the raw material hydrogen to the recycle gas in the step S1 is 5:1-1:2.
In some embodiments, the raw material hydrogen and the recycle gas in the step S1 are mixed in a pipeline, and the other part of the mixture is preheated by a preheating furnace and then directly enters the riser of the slurry bed reactor.
In some embodiments, the volume ratio of the raw material gas to the raw material heavy oil entering the slurry reactor at the bottom of the riser of the slurry bed reactor in the step S1 is 400-2000.
In some embodiments, part of the raw material hydrogen enters the slurry bed reactor from the bottom of the settling section of the slurry bed reactor after being preheated in the step S1.
In some of these embodiments, the ratio of total feed gas to heavy oil feedstock volume entering the slurry bed reactor is 600 to 2200; the total feed gas is the sum of the feed hydrogen and the recycle gas.
In some embodiments, after the first gas-liquid separation in step S2, a part of the gas phase product is purified and light oil components are removed, and then enters a circulation system to be mixed with raw material hydrogen on a pipeline.
In some embodiments, the raw heavy oil in the raw oil tank in the step S1 may be a mixture of one or more of atmospheric residuum, vacuum residuum, heavy oil, oil sand asphalt, coal tar, etc., or may be a mixture of the raw heavy oil and a certain fraction of the raw heavy oil or a hydrogenated product oil or a certain fraction of a hydrogenated product oil thereof.
In some embodiments, when the mixture of the raw heavy oil and the raw heavy oil or the hydrogenated product oil of the raw heavy oil in the raw material tank in step S1 is a mixture of the raw heavy oil and the raw heavy oil or the hydrogenated product oil of the raw heavy oil in the raw material tank, the mass ratio of the raw heavy oil to the raw heavy oil or the hydrogenated product oil of the raw heavy oil is 5:1-1:5.
In some of these embodiments, the catalyst in the raw heavy oil in step S1 is an oil-soluble molybdenum catalyst, and the catalyst concentration is 10-1000ppm based on the molybdenum content.
In some embodiments, the reaction temperature in the slurry bed reactor in the step S1 is 400-480 ℃, the reaction pressure is 6-22MPa, and the liquid hourly space velocity is 0.1-1.2h -1.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the reaction severity is reduced. The hydrogen is crushed into micro bubbles and uniformly dispersed in the heavy oil, so that the contact area of the hydrogen and the heavy oil is remarkably increased, and the mass transfer process of the hydrogen to the heavy oil is enhanced, thereby enhancing the heavy oil hydrogenation reaction process.
2. The liquid phase yield is improved. Part of the gas phase product is recycled to be mixed with raw material hydrogen to enter a slurry bed reactor, so that the partial pressure of the gas phase product in the gas phase is improved, the cracking process of heavy oil to small molecular compounds (C1-C5) is further inhibited, and the liquid phase yield is improved.
3. Slow down the coke formation and prolong the running period of the equipment. Modifying a slurry bed reactor adopted in the process of the microbubble reinforced heavy oil slurry bed hydrogenation and lightening method, adding a sedimentation section for sedimentation of tailings, and separating most of tailings from a liquid phase circulating from the middle upper part of the sedimentation section to the bottom of a slurry bed riser, thereby reducing a coke precursor and a coke center in a reaction system and slowing down coke generation; further, part of hydrogen enters the reactor from the bottom of the sedimentation section to supplement the partial pressure of hydrogen in the reaction system, so as to further slow down coke generation.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic view of a slurry bed reactor apparatus according to an embodiment of the present invention;
FIG. 2 is a flow chart of a micro-bubble enhanced heavy oil external circulation slurry bed hydrocracking process according to an embodiment of the invention;
wherein:
1-a riser;
2-a downcomer;
3-a sedimentation section;
4-a first connection tube;
5-a second connection tube;
6-reactor feed inlet;
7-a make-up gas inlet;
8-a recycle inlet;
9-another make-up air inlet;
10-reducing section;
11-reactor product outlet;
12-a slag fixing outlet;
13-a one-way valve;
14-first make-up hydrogen inlet
15-A second make-up hydrogen inlet.
Detailed Description
The following detailed description of the present invention is provided in connection with specific embodiments to further understand the objects, aspects and effects of the present invention, but is not intended to limit the scope of the invention as defined in the appended claims.
The method for enhancing the hydrogenation and the lightening of the heavy oil slurry bed by using the micro bubbles comprises the following steps:
S1, preheating a part of raw material hydrogen and recycle gas which are mixed on a pipeline and raw material heavy oil containing a catalyst with a certain concentration from a raw material tank, flowing to a bubble crushing unit, crushing the hydrogen into micro bubbles, uniformly dispersing the micro bubbles in the raw material heavy oil, preheating the raw material heavy oil from the bubble crushing unit, and entering a riser of a slurry bed reactor to perform hydrocracking reaction to generate a reaction product;
S2, enabling a reaction product flowing out of the slurry bed reactor to flow into a high-pressure separator from the slurry bed reactor, and performing primary gas-liquid separation to obtain a first gas-phase product and a first liquid-phase product;
S3, the first liquid phase product from the high-pressure separator enters the low-pressure separator for secondary gas-liquid separation to obtain a second gas phase product and a second liquid phase product;
s4, the second liquid phase product obtained by the low-pressure separator further enters a stabilizing tower for gas-liquid separation to obtain a gas phase product and a light oil product, and the light oil product flows into a product tank.
The method for strengthening the heavy oil slurry bed hydrogenation and lightening through the microbubbles reduces the reaction severity, breaks hydrogen into microbubbles which are uniformly dispersed in the heavy oil, remarkably improves the contact area of the hydrogen and the heavy oil, and enhances the mass transfer process of the hydrogen to the heavy oil, thereby enhancing the heavy oil hydrogenation reaction process. The liquid phase yield is improved, and part of gas phase products are recycled to be mixed with raw material hydrogen to enter a slurry bed reactor, so that the partial pressure of the gas phase products in the gas phase is improved, the cracking process of heavy oil to small molecular compounds (C1-C5) is further inhibited, and the liquid phase yield is improved.
Wherein the volume ratio of raw material hydrogen to recycle gas in the step S1 is 5:1-1:2.
Wherein, in the step S1, raw material hydrogen and recycle gas are mixed on a pipeline, and the other part of the mixture is preheated by a preheating furnace and then directly enters into a riser of the slurry bed reactor.
Specifically, in the step S1, the volume ratio of the raw material gas to the raw material heavy oil entering the slurry reactor from the bottom of the riser of the slurry bed reactor is 400-2000.
Wherein, in the step S1, part of raw material hydrogen enters the slurry bed reactor from the bottom of the sedimentation section of the slurry bed reactor after being preheated.
Specifically, the volume ratio of the total raw material gas to the raw material heavy oil entering the slurry bed reactor is 600-2200; the total feed gas is the sum of the feed hydrogen and the recycle gas.
After the first gas-liquid separation in the step S2, part of gas phase products are purified and light oil components are removed, and then enter a circulation system to be mixed with raw material hydrogen on a pipeline.
The raw material heavy oil in the raw oil tank in the step S1 can be one or a mixture of a plurality of atmospheric residuum, vacuum residuum, heavy oil, oil sand asphalt, coal tar and the like, and can also be a mixture of the raw material heavy oil and a certain fraction of the raw material heavy oil or a hydrogenated product oil or a certain fraction of the hydrogenated product oil.
When the mixture of the raw material heavy oil and the raw material heavy oil or the hydrogenated product oil of the raw material heavy oil is in the raw material tank in the step S1, the mass ratio of the raw material heavy oil to the raw material heavy oil or the hydrogenated product oil of the raw material heavy oil is 5:1-1:5.
Wherein the catalyst in the raw material heavy oil in the step S1 is an oil-soluble molybdenum catalyst, and the concentration of the catalyst is 10-1000ppm based on the molybdenum content.
Wherein the reaction temperature in the slurry bed reactor in the step S1 is 400-480 ℃, the reaction pressure is 6-22MPa, and the liquid hourly space velocity is 0.1-1.2h -1.
The slurry bed reactor provided in the present embodiment comprises a riser 1, a downcomer 2 and a settling section 3; the side outlet at the top of the ascending pipe 1 is communicated with the middle upper part of the descending pipe 2 through a first connecting pipe 4; the bottom of the downcomer 2 is communicated with the top of the sedimentation section 3 through a reducing section 10; the first connecting pipe 4 extends into the middle lower part of the sedimentation section 3; the bottom of the riser 1 is provided with a reactor raw material inlet 6, at least 1 make-up gas inlet 7 and 1 circulating material inlet 8; the second connecting pipe 5 at the middle upper part of the sedimentation section is connected to the circulating material inlet 8 at the bottom of the ascending pipe 1 through a tee joint and is connected to the other supplementary gas inlet 9; the side surface of the top of the downcomer 2 is provided with a reactor product outlet 11; the bottom of the sedimentation section 3 is provided with a slag fixing outlet 12 and at least 2 supplementary hydrogen inlets. It should be understood that the ratio of the diameter of the ascending pipe 1 to the diameter of the descending pipe 2 of the slurry bed in this embodiment is 2:1-5:1; the ratio of the diameter of the slurry bed downcomer 2 to the diameter of the first connecting pipe 4 is 2:1-5:1; the ratio of the height of the downcomer 2 to the height of the sedimentation section 3 of the slurry bed reactor is 2:1-5:1.
The reaction temperature in the slurry bed reactor provided in the embodiment is 420-450 ℃, the reaction pressure is 8-20MPa, and the liquid hourly space velocity is 0.2-1.0h -1. The volume ratio of the raw material gas to the raw material heavy oil entering the reactor from the bottom of the rising pipe 1 of the slurry bed reactor is 600-1600. The volume ratio of the total raw material gas to the raw material heavy oil entering the slurry bed reactor is 800-1800. The catalyst concentration is 100-1000ppm in terms of metal content. The volume ratio of the raw material inlet air inflow at the bottom of the rising pipe 1 of the slurry bed reactor to the air inflow of the supplementary air inlet (comprising the other supplementary air inlet 9) is 4:1-8:1. The volume ratio of the air inflow of the supplementary air inlet 7 at the bottom of the slurry bed to the air inflow of the supplementary air inlet 9 is 5:1-2:1.
In the hydrogenation and lightening process of the micro-bubble reinforced heavy oil slurry bed provided by the embodiment, a slurry bed reactor is adopted, and a supplementary gas inlet is arranged at the bottom of a rising pipe of the slurry bed reactor, so that the turbulence effect at the inlet is enhanced, the flowing dead zone is prevented, and the coking is delayed; secondly, the slurry bed reactor is provided with a sedimentation section for sedimentation of tailings, and the tailings are discharged from an outlet at the bottom of the sedimentation section, and further, most of tailings can be separated from a liquid phase circulating from the middle upper part of the sedimentation section to the bottom of the slurry bed riser, so that a coke precursor and a coke center in a reaction system are reduced, and coke generation is slowed down; moreover, the bottom of the sedimentation section of the slurry bed is provided with a supplementary hydrogen inlet, so that on one hand, the turbulence at the bottom of the sedimentation section is further enhanced, and the coking is prevented; in another aspect, additional hydrogen is provided to the settling section and downcomer of the slurry bed reactor to supplement the hydrogen consumed in the slurry bed riser to slow down coke formation.
Raw material or equipment source: heavy oil with high sulfur and high metal content.
Evaluation analysis method: heavy oil hydrocracking.
Specific examples:
Example 1
The micro-bubble intensified heavy oil external circulation slurry bed hydrocracking process provided by the embodiment is characterized in that raw oil is typical high-sulfur and high-metal vacuum residuum.
The slurry bed reactor device adopted in this embodiment is shown in fig. 1, and the micro-bubble reinforced heavy oil external circulation slurry bed hydrocracking process flow adopted in this embodiment is shown in fig. 2, and specific process steps are as follows:
The catalyst in the raw material heavy oil is an oil-soluble molybdenum catalyst, and the concentration of the catalyst is 300ppm based on the molybdenum content; raw material hydrogen and recycle gas are mixed according to the proportion of 2:1, controlling the ratio of the raw material gas to the fresh raw material oil to be 1000 after mixing; wherein, 4/5 of the raw material heavy oil is preheated and then enters a microbubble generating device, hydrogen is crushed into microbubbles, the raw material heavy oil with the microbubbles is formed, and enters a slurry bed reactor from a raw material inlet to generate hydrocracking reaction; 1/5 is fed into the slurry bed reactor through a supplementary gas inlet at the bottom of the slurry bed reactor, wherein the ratio of the air inflow of the supplementary gas inlet 7 to the air inflow of the other supplementary gas inlet 9 is 2:1, a step of; the volume ratio of the supplementary hydrogen to the raw oil is 400; the liquid hourly space velocity in the slurry bed reactor is controlled to be 0.3h －1, the reaction pressure is 16MPa, and the reaction temperature is 430 ℃.
The reaction product flowing out from the outlet of the slurry bed reactor firstly enters a high-pressure separator to obtain a gas-phase product and a liquid-phase product, wherein part of the gas-phase product is mixed with raw material hydrogen as circulating gas and enters a subsequent flow path;
The liquid phase product from the high pressure separator enters the low pressure separator to obtain gas phase product and liquid phase product, wherein the liquid phase product further enters the stabilizing tower for further separation, and the obtained liquid phase product flows into the product tank.
Example 2
The present example provided a micro-bubble enhanced heavy oil external circulation slurry bed hydrocracking process, using the same high sulfur, high metal vacuum residuum as in example 1 as the heavy oil feedstock.
The micro-interface enhanced heavy oil hydrocracking process provided by the example comprises the following specific steps of
The catalyst in the raw material heavy oil is an oil-soluble molybdenum catalyst, and the concentration of the catalyst is 300ppm based on the molybdenum content; raw material hydrogen and recycle gas are mixed according to the proportion of 2:1, controlling the ratio of the raw material gas to the fresh raw material oil to be 1000 after mixing; wherein, 4/5 of the raw material heavy oil is preheated and then enters a bubble crushing unit to crush hydrogen into micro bubbles to form the raw material heavy oil with micro bubbles, and the raw material heavy oil enters a slurry bed reactor from a raw material inlet to carry out hydrocracking reaction; 1/5 is fed into the slurry bed reactor through a supplementary gas inlet at the bottom of the slurry bed reactor, wherein the ratio of the air inflow of the supplementary gas inlet 7 to the air inflow of the other supplementary gas inlet 9 is 2:1, a step of; the volume ratio of the supplementary hydrogen to the raw oil is 400; the liquid hourly space velocity in the slurry bed reactor is controlled to be 0.3h －1, the reaction pressure is 10MPa, and the reaction temperature is 430 ℃.
The reaction product flowing out from the outlet of the slurry bed reactor firstly enters a high-pressure separator to obtain a gas-phase product and a liquid-phase product, wherein part of the gas-phase product is mixed with raw material hydrogen as circulating gas and enters a subsequent flow path;
The liquid phase product from the high pressure separator enters the low pressure separator to obtain gas phase product and liquid phase product, wherein the liquid phase product further enters the stabilizing tower for further separation, and the obtained liquid phase product flows into the product tank.
Example 3
The present example provided a micro-bubble enhanced heavy oil external circulation slurry bed hydrocracking process, using the same high sulfur, high metal vacuum residuum as in example 1 as the heavy oil feedstock.
The micro-interface enhanced heavy oil hydrocracking process provided by the example comprises the following specific steps of
The catalyst in the raw material heavy oil is an oil-soluble molybdenum catalyst, and the concentration of the catalyst is 300ppm based on the molybdenum content; raw material hydrogen and circulating gas are mixed according to the proportion of 1:1, controlling the ratio of the raw material gas to the fresh raw material oil to be 1200; wherein, 4/5 of the raw material heavy oil is preheated and then enters a bubble crushing unit to crush hydrogen into micro bubbles to form the raw material heavy oil with micro bubbles, and the raw material heavy oil enters a slurry bed reactor from a raw material inlet to carry out hydrocracking reaction; 1/5 is fed into the slurry bed reactor through a supplementary gas inlet at the bottom of the slurry bed reactor, wherein the ratio of the air inflow of the supplementary gas inlet 7 to the air inflow of the other supplementary gas inlet 9 is 2:1, a step of; the volume ratio of the supplementary hydrogen to the raw oil is 400; the liquid hourly space velocity in the slurry bed reactor is controlled to be 0.3h －1, the reaction pressure is 20MPa, and the reaction temperature is 440 ℃.
The reaction product flowing out from the outlet of the slurry bed reactor firstly enters a high-pressure separator to obtain a gas-phase product and a liquid-phase product, wherein part of the gas-phase product is mixed with raw material hydrogen as circulating gas and enters a subsequent flow path;
The liquid phase product from the high pressure separator enters the low pressure separator to obtain gas phase product and liquid phase product, wherein the liquid phase product further enters the stabilizing tower for further separation, and the obtained liquid phase product flows into the product tank.
Comparative example 1
The present example provided a micro-bubble enhanced heavy oil external circulation slurry bed hydrocracking process, using the same high sulfur, high metal vacuum residuum as in example 1 as the heavy oil feedstock.
The micro-interface enhanced heavy oil hydrocracking process provided by the example comprises the following specific steps of
The catalyst in the raw material heavy oil is an oil-soluble molybdenum catalyst, and the concentration of the catalyst is 300ppm based on the molybdenum content; raw material hydrogen and recycle gas are mixed according to the proportion of 2:1, controlling the ratio of the raw material gas to the fresh raw material oil to be 1000 after mixing; wherein, 4/5 of the heavy oil and the raw material are directly fed into the slurry bed reactor from the raw material inlet after being preheated, and the hydrocracking reaction is carried out; 1/5 is fed into the slurry bed reactor through a supplementary gas inlet at the bottom of the slurry bed reactor, wherein the ratio of the air inflow of the supplementary gas inlet 7 to the air inflow of the other supplementary gas inlet 9 is 2:1, a step of; the volume ratio of the supplementary hydrogen to the raw oil is 400; the liquid hourly space velocity in the slurry bed reactor is controlled to be 0.3h －1, the reaction pressure is 16MPa, and the reaction temperature is 430 ℃.
The reaction product flowing out from the outlet of the slurry bed reactor firstly enters a high-pressure separator to obtain a gas-phase product and a liquid-phase product, wherein part of the gas-phase product is mixed with raw material hydrogen as circulating gas and enters a subsequent flow path;
The liquid phase product from the high pressure separator enters the low pressure separator to obtain gas phase product and liquid phase product, wherein the liquid phase product further enters the stabilizing tower for further separation, and the obtained liquid phase product flows into the product tank.
Comparative example 2
The present example provided a micro-bubble enhanced heavy oil external circulation slurry bed hydrocracking process, using the same high sulfur, high metal vacuum residuum as in example 1 as the heavy oil feedstock.
The micro-interface enhanced heavy oil hydrocracking process provided by the embodiment comprises the following specific steps:
The catalyst in the raw material heavy oil is an oil-soluble molybdenum catalyst, and the concentration of the catalyst is 300ppm based on the molybdenum content; raw material hydrogen and recycle gas are mixed according to the proportion of 2:1, controlling the ratio of the raw material gas to the fresh raw material oil to be 1000 after mixing; wherein, 4/5 of the heavy oil and the raw material are directly fed into the slurry bed reactor from the raw material inlet after being preheated, and the hydrocracking reaction is carried out; 1/5 is fed into the slurry bed reactor through a supplementary gas inlet at the bottom of the slurry bed reactor, wherein the ratio of the air inflow of the supplementary gas inlet 7 to the air inflow of the other supplementary gas inlet 9 is 2:1, a step of; the volume ratio of the supplementary hydrogen to the raw oil is 400; the liquid hourly space velocity in the slurry bed reactor is controlled to be 0.3h －1, the reaction pressure is 10MPa, and the reaction temperature is 430 ℃.
The reaction product flowing out from the outlet of the slurry bed reactor firstly enters a high-pressure separator to obtain a gas-phase product and a liquid-phase product, wherein part of the gas-phase product is mixed with raw material hydrogen as circulating gas and enters a subsequent flow path;
The liquid phase product from the high pressure separator enters the low pressure separator to obtain gas phase product and liquid phase product, wherein the liquid phase product further enters the stabilizing tower for further separation, and the obtained liquid phase product flows into the product tank.
Comparative example 3
The present example provided a micro-bubble enhanced heavy oil external circulation slurry bed hydrocracking process, using the same high sulfur, high metal vacuum residuum as in example 1 as the heavy oil feedstock.
The micro-interface enhanced heavy oil hydrocracking process provided by the example comprises the following specific steps of
The catalyst in the raw material heavy oil is an oil-soluble molybdenum catalyst, and the concentration of the catalyst is 300ppm based on the molybdenum content; raw material hydrogen and recycle gas are mixed according to the proportion of 2:1, controlling the ratio of the raw material gas to the fresh raw material oil to be 1000 after mixing; wherein, 4/5 of the raw material heavy oil is preheated and then enters a bubble crushing unit to crush hydrogen into micro bubbles to form the raw material heavy oil with micro bubbles, and the raw material heavy oil enters a slurry bed reactor from a raw material inlet to carry out hydrocracking reaction; 1/5 is fed into the slurry bed reactor through a supplementary gas inlet at the bottom of the slurry bed reactor, wherein the ratio of the air inflow of the supplementary gas inlet 7 to the air inflow of the other supplementary gas inlet 9 is 2:1, a step of; no supplementary hydrogen is introduced; the liquid hourly space velocity in the slurry bed reactor is controlled to be 0.3h －1, the reaction pressure is 16MPa, and the reaction temperature is 430 ℃.
The reaction product flowing out from the outlet of the slurry bed reactor firstly enters a high-pressure separator to obtain a gas-phase product and a liquid-phase product, wherein part of the gas-phase product is mixed with raw material hydrogen as circulating gas and enters a subsequent flow path;
The liquid phase product from the high pressure separator enters the low pressure separator to obtain gas phase product and liquid phase product, wherein the liquid phase product further enters the stabilizing tower for further separation, and the obtained liquid phase product flows into the product tank.
Comparative example 4
The present example provided a micro-bubble enhanced heavy oil external circulation slurry bed hydrocracking process, using the same high sulfur, high metal vacuum residuum as in example 1 as the heavy oil feedstock.
The micro-interface enhanced heavy oil hydrocracking process provided by the example comprises the following specific steps of
The catalyst in the raw material heavy oil is an oil-soluble molybdenum catalyst, and the concentration of the catalyst is 300ppm based on the molybdenum content; the ratio of raw material hydrogen to fresh raw material oil is controlled to be 1000 without circulating gas; wherein, 4/5 of the raw material heavy oil is preheated and then enters a bubble crushing unit to crush hydrogen into micro bubbles to form the raw material heavy oil with micro bubbles, and the raw material heavy oil enters a slurry bed reactor from a raw material inlet to carry out hydrocracking reaction; 1/5 is fed into the slurry bed reactor through a supplementary gas inlet at the bottom of the slurry bed reactor, wherein the ratio of the air inflow of the supplementary gas inlet 7 to the air inflow of the other supplementary gas inlet 9 is 2:1, a step of; the volume ratio of the supplementary hydrogen to the raw oil is 400; the liquid hourly space velocity in the slurry bed reactor is controlled to be 0.3h －1, the reaction pressure is 16MPa, and the reaction temperature is 430 ℃.
The reaction product flowing out from the outlet of the slurry bed reactor firstly enters a high-pressure separator to obtain a gas-phase product and a liquid-phase product;
The liquid phase product from the high pressure separator enters the low pressure separator to obtain gas phase product and liquid phase product, wherein the liquid phase product further enters the stabilizing tower for further separation, and the obtained liquid phase product flows into the product tank.
The hydrocracking process of each example and comparative example was evaluated, and the results are shown in table 1.
Table 1 evaluation of hydrocracking process for each of the examples and comparative examples
From the above examples, it can be seen that when hydrogen in heavy oil as a raw material is broken into microbubbles, the coke formation during heavy oil hydrogenation is not significantly increased when the reaction pressure is reduced from 16MPa to 10MPa under the condition of unchanged reaction temperature; it can be seen from the comparative examples that the recycling of the gas phase product into the slurry bed reactor can effectively improve the liquid yield; the addition of supplemental hydrogen to the bottom of the settling section also helps to slow down coke formation.
The present invention is not limited to the above-mentioned embodiments, and any equivalent embodiments which can be changed or modified by the technical content disclosed above can be applied to other fields, but any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical substance of the present invention without departing from the technical content of the present invention still belong to the protection scope of the technical solution of the present invention.
Claims (7)
1. A method for strengthening the hydrogenation and the lightening of a heavy oil slurry bed by micro bubbles is characterized in that: the method comprises the following steps:
S1, preheating a part of raw material hydrogen and recycle gas which are mixed on a pipeline and raw material heavy oil containing a catalyst with a certain concentration from a raw material tank, flowing to a bubble crushing unit, crushing the hydrogen into micro bubbles, uniformly dispersing the micro bubbles in the raw material heavy oil, preheating the raw material heavy oil from the bubble crushing unit, and entering a riser of a slurry bed reactor to perform hydrocracking reaction to generate a reaction product;
S2, enabling a reaction product flowing out of the slurry bed reactor to flow into a high-pressure separator from the slurry bed reactor, and performing primary gas-liquid separation to obtain a first gas-phase product and a first liquid-phase product;
S3, the first liquid phase product from the high-pressure separator enters the low-pressure separator for secondary gas-liquid separation to obtain a second gas phase product and a second liquid phase product;
S4, the second liquid phase product obtained by the low-pressure separator further enters a stabilizing tower for gas-liquid separation to obtain a gas phase product and a light oil product, and the light oil product flows into a product tank;
The slurry bed reactor comprises a riser, a downcomer and a sedimentation section; the side outlet of the top of the ascending pipe is communicated with the middle upper part of the descending pipe through a first connecting pipe; the bottom of the downcomer is communicated with the top of the sedimentation section through the reducing section; the first connecting pipe opening extends into the middle lower part of the sedimentation section; the bottom of the rising pipe is provided with a reactor raw material inlet, at least 1 make-up gas inlet and 1 circulating material inlet; the second connecting pipe at the middle upper part of the sedimentation section is connected to the circulating material inlet at the bottom of the ascending pipe through a tee joint and is connected to the other supplementary gas inlet; the side surface of the top of the downcomer is provided with a reactor product outlet; the bottom of the sedimentation section is provided with a tail slag fixing outlet and at least 2 supplementary hydrogen inlets;
In the step S1, part of raw material hydrogen enters the slurry bed reactor from at least 2 supplementary hydrogen inlets at the bottom of a sedimentation section of the slurry bed reactor after being preheated;
In the step S1, the volume ratio of the raw material gas to the raw material heavy oil entering the slurry reactor from the bottom of the ascending pipe of the slurry bed reactor is 400-2000;
the catalyst in the raw material heavy oil in the step S1 is an oil-soluble molybdenum catalyst, and the concentration of the catalyst is 10-1000ppm based on the molybdenum content;
In the step S1, the reaction temperature in the slurry bed reactor is 400-480 ℃, the reaction pressure is 6-22MPa, and the liquid hourly space velocity is 0.1-1.2h -1.
2. The process for the hydrolightening of a microbubble enhanced heavy oil slurry bed according to claim 1, characterized by: in the step S1, the volume ratio of raw material hydrogen to circulating gas is 5:1-1:2.
3. The process for the hydrolightening of a microbubble enhanced heavy oil slurry bed according to claim 1, characterized by: in the step S1, raw material hydrogen and recycle gas are mixed on a pipeline, and the other part of the mixture is preheated by a preheating furnace and then directly enters a riser of the slurry bed reactor.
4. The process for the hydrolightening of a microbubble enhanced heavy oil slurry bed according to claim 1, characterized by: the volume ratio of the total raw material gas to the raw material heavy oil entering the slurry bed reactor is 600-2200; the total feed gas is the sum of the feed hydrogen and the recycle gas.
5. The process for the hydrolightening of a microbubble enhanced heavy oil slurry bed according to claim 1, characterized by: after the first gas-liquid separation in the step S2, part of gas phase products are purified and light oil components are removed, and then enter a circulating system to be mixed with raw material hydrogen on a pipeline.
6. The process for the hydrolightening of a microbubble enhanced heavy oil slurry bed according to claim 1, characterized by: in the step S1, the raw material heavy oil in the crude oil tank is one or a mixture of a plurality of atmospheric residuum, vacuum residuum, heavy oil, oil sand asphalt and coal tar, or is a mixture of the raw material heavy oil and a certain distillation section of the raw material heavy oil or a hydrogenation product oil or a certain distillation section of the hydrogenation product oil.
7. The process for the hydrolightening of a microbubble-enhanced heavy oil slurry bed according to claim 1 or 6, characterized in that: when the mixture of the raw material heavy oil and the raw material heavy oil or the hydrogenated product oil of the raw material heavy oil is in the raw material tank in the step S1, the mass ratio of the raw material heavy oil to the raw material heavy oil or the hydrogenated product oil of the raw material heavy oil is 5:1-1:5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210114234.3A CN116554919B (en) | 2022-01-30 | 2022-01-30 | Method for strengthening heavy oil slurry bed hydrogenation and lightening through micro bubbles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210114234.3A CN116554919B (en) | 2022-01-30 | 2022-01-30 | Method for strengthening heavy oil slurry bed hydrogenation and lightening through micro bubbles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116554919A CN116554919A (en) | 2023-08-08 |
| CN116554919B true CN116554919B (en) | 2024-07-16 |
Family
ID=87500651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210114234.3A Active CN116554919B (en) | 2022-01-30 | 2022-01-30 | Method for strengthening heavy oil slurry bed hydrogenation and lightening through micro bubbles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116554919B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203451487U (en) * | 2013-09-17 | 2014-02-26 | 李方 | Raw oil suspended bed hydrogenation device |
| CN104549067A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Heavy oil hydrogenation slurry bed reactor and heavy oil hydrogenation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105617950B (en) * | 2014-10-29 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of heavy-oil hydrogenation paste state bed reactor and its application process |
-
2022
- 2022-01-30 CN CN202210114234.3A patent/CN116554919B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203451487U (en) * | 2013-09-17 | 2014-02-26 | 李方 | Raw oil suspended bed hydrogenation device |
| CN104549067A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Heavy oil hydrogenation slurry bed reactor and heavy oil hydrogenation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116554919A (en) | 2023-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106190278B (en) | Cracking intermediate liquid product returns to the hydrocarbon heat from hydrogenation cracking method inferior of pre-add hydrogen | |
| CN110484296A (en) | A kind of adverse current type multiphase flow hydrocracking heavy oil technique | |
| CN1038118A (en) | Obtain the high conversion of mink cell focus hydrocracking with kilfoam | |
| CN102596386A (en) | Fluidized-bed reactor and hydrotreating method thereof | |
| CN105462610B (en) | A kind of anthracene oil hydrogenation method | |
| CN104755596A (en) | Hydrovisbreaking process for feedstock containing dissolved hydrogen | |
| CN106635138B (en) | A kind of slurry bed system method for hydrogen cracking | |
| CN110066687A (en) | Liquid product recycle hydrogenates the hydrocarbon material expanded bed method of hydrotreating of Jia Fufang material among grade | |
| OA12695A (en) | Fischer-tropsch process. | |
| CN116554919B (en) | Method for strengthening heavy oil slurry bed hydrogenation and lightening through micro bubbles | |
| CN106221792A (en) | A kind of anthracene oil hydrogenation method | |
| CN109957416A (en) | With the hydrocarbon material process for selective hydrogenation of liquid material product circulation formula counter-current reactor | |
| US6921778B2 (en) | Process for converting synthesis gas in reactors that are arranged in series | |
| CN108659882A (en) | A kind of Heavy oil hydrogenation method and its hydrogenation system | |
| CN108865253A (en) | The method of coal Direct Hydrogenation liquefaction richness production aromatic hydrocarbons | |
| CN100489064C (en) | Method for refining circulating hydrogen in hydrocracking process | |
| CN111686645A (en) | Micro-interface reinforced wax oil hydrogenation reaction system and method | |
| CN110819383A (en) | Process for the upflow hydrogenation of poor quality hydrocarbons using reactors with internal parallel reaction zones | |
| CN111482145A (en) | Upper-mounted micro-interface enhanced reaction device and method for residual oil hydrogenation reaction | |
| CN112552964B (en) | Micro-interface-based system and process for strengthening coal indirect liquefaction | |
| CN106635160A (en) | Coal-coal tar mixed hydrogenation system and process | |
| CN108148624B (en) | Short-flow circulation method for solvent oil used in reaction process of directly preparing oil by coal hydrogenation | |
| CN109456794A (en) | Floating bed hydrogenation and adverse current the bed supplement of the material containing heavy hydrocarbon plus the combined method of hydrogen | |
| CN213506770U (en) | System for strengthening indirect coal liquefaction based on micro-interface | |
| CN116550240A (en) | Heavy oil hydrogenation slurry bed reactor and heavy oil hydrogenation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |