CN111871333A - Micro-interface reaction system and method for anthracene oil hydrogenation - Google Patents
Micro-interface reaction system and method for anthracene oil hydrogenation Download PDFInfo
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- CN111871333A CN111871333A CN202010683555.6A CN202010683555A CN111871333A CN 111871333 A CN111871333 A CN 111871333A CN 202010683555 A CN202010683555 A CN 202010683555A CN 111871333 A CN111871333 A CN 111871333A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 104
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000005336 cracking Methods 0.000 claims abstract description 69
- 238000000926 separation method Methods 0.000 claims abstract description 64
- 239000001257 hydrogen Substances 0.000 claims abstract description 53
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007789 gas Substances 0.000 claims abstract description 40
- 239000000047 product Substances 0.000 claims abstract description 19
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims description 27
- 238000005194 fractionation Methods 0.000 claims description 12
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000010406 interfacial reaction Methods 0.000 claims 3
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000003921 oil Substances 0.000 description 67
- 230000000694 effects Effects 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- 239000012071 phase Substances 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- -1 naphtha Substances 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a micro-interface reaction system and a method for anthracene oil hydrogenation, wherein the micro-interface reaction system comprises: the micro-interface generator and the hydrogenation reactor are connected in sequence; introducing hydrogen and anthracene oil into the micro-interface generator; a hydrogenation product outlet is formed in the side wall of the hydrogenation reactor, a product from the hydrogenation product outlet is introduced into the first separation tank to be used for separating hot high-temperature-distribution gas and hot high-temperature-distribution oil, and the hot high-temperature-distribution gas is sent to the second separation tank to be separated into cold high-temperature-distribution gas and cold high-temperature-distribution oil; and after the hot high-molecular oil enters a cracking reaction tower for cracking reaction, the obtained cracking reaction product is sent to a fractionating tower for fractionating, and the cold high-molecular gas and the cold high-molecular oil are respectively collected and discharged. The micro-interface reaction system provided by the invention is combined with the micro-interface generator, so that the energy consumption is reduced, the reaction temperature is reduced, the reaction yield is improved, the utilization rate of raw materials is improved, particularly the utilization rate of hydrogen is improved, and meanwhile, the productivity is effectively improved.
Description
Technical Field
The invention relates to the field of anthracene oil hydrogenation, in particular to a micro-interface reaction system and a micro-interface reaction method for anthracene oil hydrogenation.
Background
The anthracene oil is part of coal tar components, distillate at 280-360 ℃ is cut by distilling tar, is generally yellow green oily liquid, is crystallized and separated out at room temperature, is yellow and blue in fluorescence, can be dissolved in ethanol and ether, is insoluble in water, is partially dissolved in organic solvents such as hot benzene and chlorobenzene, and has strong irritation. The material is combustible by high-temperature open fire, and the main components comprise anthracene, phenanthrene, fluorene, acenaphthene, carbazole and the like.
By adopting the anthracene oil hydrogenation process, the desulfurization, unsaturated hydrocarbon saturation, denitrification reaction and aromatic hydrocarbon saturation can be effectively realized, so that the stability of the anthracene oil is improved, the sulfur nitrogen content and the aromatic hydrocarbon content are reduced, and high-quality naphtha and diesel blending components are obtained.
At present, most anthracene oil hydrogenation processes adopt hydrofining and hydrocracking or a combination of hydrofining and hydrocracking as two-stage hydrogenation processes, and although the hydrogenation process is convenient to operate and easy to industrialize, the energy consumption is high, the pressure and the temperature of a hydrogenation reactor are high, and the productivity is also low.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a micro-interface reaction system for anthracene oil hydrogenation, which combines a hydrogenation reactor and a micro-interface generator, thereby reducing energy consumption, reducing reaction temperature, improving reaction yield, improving utilization rate of raw materials, especially improving utilization rate of hydrogen, and effectively improving productivity, thereby improving product quality and yield, and further saving equipment cost and equipment floor area.
The second purpose of the invention is to provide a reaction method for hydrogenating anthracene oil by using the micro-interface reaction system, the hydrogenated anthracene oil obtained by the reaction is environment-friendly and clean, has wide application, improves the application range of anthracene oil, and is worthy of wide popularization and application.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a micro-interface reaction system for anthracene oil hydrogenation, which comprises: the micro-interface generator and the hydrogenation reactor are connected in sequence;
introducing hydrogen and anthracene oil into the micro-interface generator; a hydrogenation product outlet is formed in the side wall of the hydrogenation reactor, a product from the hydrogenation product outlet is introduced into a first separation tank to be used for separating hot high-temperature-separation gas and hot high-temperature-separation oil, and the hot high-temperature-separation gas is conveyed to a second separation tank to be separated into cold high-temperature-separation gas and cold high-temperature-separation oil; after the hot high-molecular oil enters a cracking reaction tower for cracking reaction, the obtained cracking reaction product is sent to a fractionating tower for fractionating, and the cold high-molecular gas and the cold high-molecular oil are respectively collected and discharged;
and a plurality of catalyst beds are arranged in the cracking reaction tower, each catalyst bed is filled with a catalyst, and the micro-interface generator is arranged between the adjacent catalyst beds.
According to the micro-interface reaction system for the anthracene oil hydrogenation, the micro-interface generator is arranged in the hydrogenation reactor, and the entering hydrogen is dispersed and crushed into micro bubbles, so that the mass transfer effect is improved.
Preferably, a micro-interface generator is arranged at the top of the outer side of the cracking reaction tower, hydrogen from a hydrogen main pipeline is introduced into the micro-interface generator positioned at the top of the cracking reaction tower, and hot high-fraction oil enters from the side part of the micro-interface generator positioned at the top of the cracking reaction tower.
The position of the micro-interface generator of the present invention is specifically designed. The micro interface generator is arranged outside the hydrogenation reactor, but for the cracking reaction tower, the arrangement mode of simultaneously arranging the micro interface generator outside and inside the cracking reaction tower is selected, which is equivalent to simultaneously combining and applying the micro interface generator outside and inside, and the cracking reaction tower is a fixed bed reactor, therefore, the micro interface generator inside the cracking reaction tower is preferably uniformly arranged between the adjacent fixed bed layers along a vertical direction in a straight line in sequence, the arrangement mode can ensure that the cracking hydrogenation effect of the gap between the two fixed bed layers is better when the hydrocracking reaction is carried out, the effect of cracking macromolecular substances into micromolecular substances is improved, which is equivalent to simultaneously carrying out the dispersion crushing and the reaction, the connection between the dispersion crushing operation and the reaction is tighter, and through the action of the micro interface generator arranged outside the top of the cracking reaction tower, make the feeding just can realize fully breaking into micron bubble in the source, the crushing effect after advancing the reactor inside like this will be more abundant, has played the effect of cooperateing, consequently little interface generator set up the position also obtain through the practical design, need carry out specific design according to the different characteristics of different reactions.
More preferably, the catalyst beds are preferably 4 stages, and the number of the micro-interface generators located inside the cracking reaction tower is preferably 3, such that each micro-interface generator is disposed between two adjacent catalyst beds. The number of 3 micro-interface generators already ensures the effect of dispersive disruption.
The micro-interface generator arranged in front of the hydrogenation reactor is of a pneumatic type, and hydrogen and anthracene oil are introduced into the micro-interface generator and then dispersed and crushed, so that the subsequent hydrogenation reaction is enhanced, impurities such as sulfur, nitrogen and the like are removed, and the mass transfer effect is improved.
The micro-interface generator inside and outside the cracking reaction tower is of a pneumatic type, and hydrogen is introduced into the micro-interface generator and then is directly crushed with hot low-temperature oil to form micro bubbles, so that the mass transfer effect is improved.
It will be appreciated by those skilled in the art that the micro-interface generator used in the present invention is described in the prior patents of the present inventor, such as the patents of application nos. CN201610641119.6, 201610641251.7, CN201710766435.0, CN106187660, CN105903425A, CN109437390A, CN205833127U and CN 207581700U. The detailed structure and operation principle of the micro bubble generator (i.e. micro interface generator) is described in detail in the prior patent CN201610641119.6, which describes that "the micro bubble generator comprises a body and a secondary crushing member, wherein the body is provided with a cavity, the body is provided with an inlet communicated with the cavity, the opposite first end and second end of the cavity are both open, and the cross-sectional area of the cavity decreases from the middle of the cavity to the first end and second end of the cavity; the secondary crushing member is disposed at least one of the first end and the second end of the cavity, a portion of the secondary crushing member is disposed within the cavity, and an annular passage is formed between the secondary crushing member and the through holes open at both ends of the cavity. The micron bubble generator also comprises an air inlet pipe and a liquid inlet pipe. "the specific working principle of the structure disclosed in the application document is as follows: liquid enters the micro-bubble generator tangentially through the liquid inlet pipe, and gas is rotated at a super high speed and cut to break gas bubbles into micro-bubbles at a micron level, so that the mass transfer area between a liquid phase and a gas phase is increased, and the micro-bubble generator in the patent belongs to a pneumatic micro-interface generator.
In addition, the first patent 201610641251.7 describes that the primary bubble breaker has a circulation liquid inlet, a circulation gas inlet and a gas-liquid mixture outlet, and the secondary bubble breaker communicates the feed inlet with the gas-liquid mixture outlet, which indicates that the bubble breakers all need to be mixed with gas and liquid, and in addition, as can be seen from the following drawings, the primary bubble breaker mainly uses the circulation liquid as power, so that the primary bubble breaker belongs to a hydraulic micro-interface generator, and the secondary bubble breaker simultaneously introduces the gas-liquid mixture into an elliptical rotating ball for rotation, thereby realizing bubble breaking in the rotating process, so that the secondary bubble breaker actually belongs to a gas-liquid linkage micro-interface generator. In fact, the micro-interface generator is a specific form of the micro-interface generator, whether it is a hydraulic micro-interface generator or a gas-liquid linkage micro-interface generator, however, the micro-interface generator adopted in the present invention is not limited to the above forms, and the specific structure of the bubble breaker described in the prior patent is only one of the forms that the micro-interface generator of the present invention can adopt. Furthermore, the prior patent 201710766435.0 states that the principle of the bubble breaker is that high-speed jet flows are used to achieve mutual collision of gases, and also states that the bubble breaker can be used in a micro-interface strengthening reactor to verify the correlation between the bubble breaker and the micro-interface generator; moreover, in the prior patent CN106187660, there is a related description on the specific structure of the bubble breaker, see paragraphs [0031] to [0041] in the specification, and the accompanying drawings, which illustrate the specific working principle of the bubble breaker S-2 in detail, the top of the bubble breaker is a liquid phase inlet, and the side of the bubble breaker is a gas phase inlet, and the liquid phase coming from the top provides the entrainment power, so as to achieve the effect of breaking into ultra-fine bubbles, and in the accompanying drawings, the bubble breaker is also seen to be of a tapered structure, and the diameter of the upper part is larger than that of the lower part, and also for better providing the entrainment power for the liquid phase.
Since the micro-interface generator was just developed in the early stage of the prior patent application, the micro-interface generator was named as a micro-bubble generator (CN201610641119.6), a bubble breaker (201710766435.0) and the like in the early stage, and is named as a micro-interface generator in the later stage along with the continuous technical improvement, and the micro-interface generator in the present invention is equivalent to the micro-bubble generator, the bubble breaker and the like in the prior art, and has different names.
In summary, the micro-interface generator of the present invention belongs to the prior art, although some bubble breakers belong to the type of pneumatic bubble breakers, some bubble breakers belong to the type of hydraulic bubble breakers, and some bubble breakers belong to the type of gas-liquid linkage bubble breakers, the difference between the types is mainly selected according to the different specific working conditions, and in addition, the connection between the micro-interface generator and the reactor and other equipment, including the connection structure and the connection position, is determined according to the structure of the micro-interface generator, which is not limited.
Preferably, the hydrogenation reactor for hydrogenation reaction is a fixed bed reactor, the catalyst in the fixed bed reactor is fixed on the bed layer, the catalyst for hydrogenation reaction is generally a nickel-based catalyst, preferably the catalyst can be a supported nickel-based catalyst, or more preferably a nickel-based catalyst modified by alkaline earth metal oxide or rare earth metal oxide, and the carrier is selected from silicon oxide or aluminum oxide.
Preferably, the active component of the catalyst for cracking hydrogenation reaction is oxides of nickel, cobalt and molybdenum, and the carrier is alumina, silicon-aluminum oxide or molecular sieve.
The hydrogenation reactor has the functions of removing impurities such as sulfur, nitrogen and the like and improving the quality of anthracene oil products, and the cracking reaction tower has the functions of processing heavy oil, cracking macromolecules into micromolecules under the action of a catalyst and converting most residual oil into fuel oil, liquefied gas and the like, so that the utilization rate of oil products is improved, and the olefin content in the products is higher.
The product from the hydrogenation reactor is separated by the first separating tank and the second separating tank, the separating tank can adjust the pressure according to different separated products, the separated hot high-molecular oil enters from the top of the cracking reaction tower and is cracked and hydrogenated together with hydrogen, and the hydrogenation effect is improved and the reaction depth is correspondingly improved by connecting the hydrogenation reaction and the hydrocracking circulation in parallel.
Preferably, a thermal high-pressure oil inlet and a hydrogen inlet are formed in the micro-interface generator between the adjacent catalyst beds, the thermal high-pressure oil inlet is connected with the bottom of the first separation tank, and the hydrogen inlet is connected with the hydrogen main pipeline. The inlet of the hot high-temperature-distribution oil and the inlet of the hydrogen are respectively arranged on the micro-interface generator, so that the catalytic cracking reaction can be effectively carried out after the micro-interface generator is dispersed and crushed. The number of inlets and hydrogen inlets of the hot high-pressure-separation oil and the number of the arranged micro-interface generators are in one-to-one correspondence, so that a plurality of branches can be ensured to simultaneously enter hydrogen and the hot high-pressure-separation oil for catalytic cracking.
Preferably, a cracking reaction product outlet for discharging the cracking reaction product is arranged at the bottom of the cracking reaction tower, the cracking reaction product outlet is connected with a fourth separation tank for oil-gas separation, and the oil phase separated from the bottom of the fourth separation tank goes to the fractionating tower.
Preferably, the gas phase separated from the top of the fourth separation tank is compressed by a compressor in advance and then returns to be communicated with the hydrogen main pipeline.
The hydrogen from the hydrogen main pipeline is totally divided into two parts, one part is fresh supplementary hydrogen, the other part is gas phase from the top of the fourth separation tank, the part is compressed by a compressor and then goes to a micro-interface generator positioned at the top of the cracking reaction tower from the hydrogen main pipeline, and a plurality of branches are branched to go to the micro-interface generator positioned in the cracking reaction tower.
Preferably, the cold high-pressure gas from the top of the second separation tank goes to the fourth separation tank for further separation.
Preferably, the cold high-cut oil from the bottom of the second separation tank is passed to the fractionation column for fractionation.
The cracking reaction product from the cracking reaction tower can be subjected to gas-liquid separation in different degrees through the fourth separating tank, and meanwhile, the product in the front separating tank can also enter the subsequent separating tank for re-separation, so that the separation effect is improved.
Preferably, a plurality of layers of trays are arranged in the fractionating tower, the trays are filled with packing materials which contribute to the fractionating effect, overhead gas from the top of the fractionating tower is discharged through a pipeline, tail oil from the bottom of the fractionating tower is discharged through a pipeline, and different fractions from the middle part of the tower section of the fractionating tower are respectively collected. The fractionating tower is used for collecting different fractions according to different purposes and performing corresponding application. The fraction in the middle tower section is composed of fuel oil, naphtha and liquefied gas.
The invention also provides a reaction method of the anthracene oil hydrogenation micro-interface reaction system, which comprises the following steps:
the anthracene oil and hydrogen mixed micro interface is dispersed and crushed, then hydrogenation reaction is carried out, and then separation, micro interface dispersion and crushing, then hydrocracking, gas-liquid separation and fractionation are carried out.
Preferably, the pressure of the hydrogenation reaction is 8-10MPa, and the temperature of the hydrogenation reaction is 220-230 ℃;
preferably, the hydrocracking pressure is 8-10MPa, and the temperature is 220-230 ℃.
Compared with the prior reaction, the hydrogenation reaction and the cracking hydrogenation reaction in the reaction method both reduce energy consumption, improve reaction effect and improve the utilization rate of raw materials, especially the utilization rate of hydrogen.
The oil product obtained by the anthracene oil hydrogenation reaction has good quality and high yield, and the desulfurization rate can reach 99.95%.
The reaction method for hydrogenating the anthracene oil has the advantages of low reaction temperature, greatly reduced pressure and high liquid hourly space velocity, is equivalent to improvement of productivity, and the final desulfurization rate is close to 100 percent and is improved by nearly 1 percent compared with the conventional method.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the micro-interface reaction system for the anthracene oil hydrogenation, the hydrogenation reactor and the micro-interface generator are combined, so that the energy consumption is reduced, the reaction temperature is reduced, the reaction yield is improved, and the utilization rate of raw materials is improved;
(2) the micro-interface reaction system for the hydrogenation of anthracene oil is most favorable for improving the mass transfer effect by arranging the micro-interface generator at a specific position;
(3) the reaction method for hydrogenating the anthracene oil has the advantages of low reaction temperature, greatly reduced pressure and high liquid hourly space velocity, is equivalent to improvement of productivity, and the final desulfurization rate is close to 100 percent and is improved by nearly 1 percent compared with the conventional method.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
fig. 1 is a schematic structural diagram of a micro-interface reaction system for hydrogenating anthracene oil according to an embodiment of the present invention.
Description of the drawings:
10-a hydrogen storage tank; 20-a micro-interface generator;
30-anthracene oil storage tank; 40-a hydrogen preheater;
50-a hydrogenation reactor; 60-a first separation tank;
70-a second separation tank; 80-a cracking reaction tower;
90-a fourth separation tank; 100-a fractionation column;
801-catalyst bed layer; an 802-cracked reaction product outlet;
803-hot high-pressure oil inlet; 804-a hydrogen inlet;
805-hydrogen main; 806-a compressor;
1001-tray;
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In order to more clearly illustrate the technical solution of the present invention, the following description is made in the form of specific embodiments.
Examples
Referring to fig. 1, a micro-interface reaction system for hydrogenating anthracene oil according to an embodiment of the present invention mainly includes a micro-interface generator 20, a hydrogenation reactor 50, and a cracking reactor 80;
simultaneously introducing hydrogen and anthracene oil into the micro-interface generator 20, conveying the anthracene oil from an anthracene oil storage tank 30, preheating the hydrogen from a hydrogen storage tank 10 by a hydrogen preheater 40, and then introducing the preheated hydrogen into the micro-interface generator 20, dispersing and crushing the hydrogen into small molecules in the micro-interface generator 20, and conveying the mixture of the dispersed and crushed anthracene oil and hydrogen into a hydrogenation reactor 50 for hydrogenation reaction;
the oil after hydrodesulfurization and denitrification is discharged from the hydrogenation reactor 50 and is firstly separated into hot high-molecular gas and hot high-molecular oil through the first separation tank 60, the hot high-molecular oil goes to a subsequent cracking reaction tower for hydrocracking reaction, the hot high-molecular gas is continuously separated through the second separation tank 70 and is separated into cold high-molecular gas and cold high-molecular oil, the cold high-molecular gas at the top of the second separation tank 70 goes to a subsequent fourth separation tank 90 for further separation, and the cold high-molecular oil at the bottom of the second separation tank 70 directly goes to a subsequent fractionating tower for fractionation.
The top of the cracking reaction tower 80 is provided with a micro interface generator 20, the micro interface generator is introduced with hydrogen through a hydrogen main pipe 805, one part is fresh hydrogen, the other part is a gas phase returned from the top of the fourth separation tank 90, the gas phase is compressed by a compressor 806 and then introduced into the cracking reaction tower 80, and the hot high-molecular oil from the bottom of the first separation tank 60 enters the micro interface generator at the top of the cracking reaction tower 80 for hydrocracking. Thus, the hydrogen and the hot high-molecular oil are dispersed and crushed from the micro interface generator at the top and then enter the cracking reaction tower 80 to carry out the cracking catalytic reaction.
The cracking reaction tower 80 is internally provided with a plurality of catalyst bed layers 801, preferably 4 catalyst bed layers 801, each catalyst bed layer 801 is filled with a catalyst, in order to improve the mass transfer effect, micro-interface generators 20 are respectively arranged between adjacent catalyst bed layers 801 in the cracking reaction tower 80, the number of the arranged micro-interface generators is 3, each micro-interface generator is provided with a thermal high-temperature separation oil inlet 803 and a hydrogen inlet 804, the thermal high-temperature separation oil inlet 803 is connected with the bottom of the first separation tank 60, and the hydrogen inlet 804 is connected with a hydrogen main pipeline 805.
Thus, the hot high-molecular oil from the bottom of the first separation tank 60 simultaneously enters the micro-interface generator 20 positioned at the top of the cracking reaction tower 80 and the micro-interface generator 20 positioned inside the cracking reaction tower 80, and simultaneously, the hydrogen from the hydrogen main pipe 805 enters the micro-interface generator 20 positioned at the top of the cracking reaction tower 80 and the micro-interface generator 20 positioned inside the cracking reaction tower 80, and is dispersed and crushed in advance and then undergoes the catalytic cracking reaction, so that the reaction mass transfer effect can be remarkably improved.
The type of the micro interface generator 20 is the same as the type of the micro interface generator 20 arranged in front of the hydrogenation reactor 50, the micro interface generator 20 is selected to be a pneumatic type, and the mass transfer effect of the whole reaction is improved through the cooperative action of the micro interface generators 20 arranged at different positions.
After the hydrocracking catalytic reaction, a cracking reaction product outlet 802 for discharging a cracking reaction product is arranged at the bottom of the cracking reactor, the substance discharged from the cracking reaction product outlet 802 goes to the fourth separation tank 90 for oil-gas separation, and the oil phase separated from the bottom of the fourth separation tank 90 goes to a fractionating tower for fractionation. The gas phase separated at the top of the fourth separation tank 90 is returned to the cracking reaction tower 80 again to be reused as a raw material for the cracking reaction.
The fractionating tower 100 is provided with a plurality of stages 1001, the stages 1001 are filled with packing materials for facilitating the fractionation, and the packing materials may be Raschig rings, pall rings, etc.
After the fractionation of the fractionating tower 100, the overhead gas from the top of the tower is discharged through a pipeline, the tail oil from the bottom of the fractionating tower 100 is discharged through a pipeline, and different fractions from the middle part of the tower section of the fractionating tower 100 are respectively collected, wherein the different fractions mainly comprise liquefied gas, naphtha, fuel oil and the like.
In the above embodiment, in order to increase the dispersion and mass transfer effects, an additional micro-interface generator 20 may be additionally provided, the installation position is not limited, and the micro-interface generator may be external or internal, and may be installed on the side wall inside the kettle in a manner of being arranged relatively when the micro-interface generator is installed internally, so as to realize the opposite collision of micro-bubbles coming out from the outlet of the micro-interface generator 20.
In the above embodiment, the type of the hydrogenation reactor 50 may be a fixed bed reactor, a fluidized bed reactor, or other types, and the feeding and discharging manner is not limited, and the feeding and discharging manner may be from the lower side and the upper side, or the feeding and the lower side, but the side feeding and the upper side discharging manner are more preferable.
In the above embodiment, the number of the pump bodies is not specifically required, and the pump bodies may be arranged at corresponding positions as required.
The working process and principle of the anthracene oil hydrogenation micro-interface reaction system of the invention are briefly explained as follows:
nitrogen purges each device in the micro-interface reaction system, then operation is performed by driving, hydrogen and anthracene oil are subjected to hydrogenation reaction in a hydrogenation reactor 50, before hydrogenation reaction, the hydrogen and anthracene oil are firstly introduced into a micro-interface generator 20 for dispersion and crushing so that gas forms micro bubbles, which is more beneficial to efficient reaction, after hydrogenation reaction, reaction products are separated by a separation tank and then go to a cracking reaction tower 80, the reaction products are dispersed and crushed by the micro-interface generator positioned at the top and inside of the cracking reaction tower and then are subjected to cracking reaction, and the obtained cracking reaction products are separated and then go to a fractionating tower 100 for fractionation to obtain final products.
Wherein the pressure of the hydrogenation reaction is 8-10MPa, and the temperature of the hydrogenation reaction is 220-230 ℃.
The pressure of cracking hydrogenation is 8-10MPa, and the temperature is 220-230 ℃. By arranging the micro-interface generator 20, the operating pressure and temperature are correspondingly reduced, the energy consumption is reduced, and the productivity is improved.
The above steps are repeated circularly to make the whole synthesis system run smoothly.
By adopting the hydrogenation reaction process, the removal rate of desulfurization can reach 99.95%, and compared with the prior hydrogenation reaction process, the removal rate is improved by nearly 1 percent.
In addition, the pressure and the temperature of the hydrogenation reaction kettle are reduced by laying the micro-interface generator, and the energy consumption is fully reduced.
In a word, compared with the micro-interface reaction system for the hydrogenation of anthracene oil in the prior art, the micro-interface reaction system for the hydrogenation of anthracene oil has the advantages of fewer equipment components, small occupied area, low energy consumption, low cost, high safety, controllable reaction and high raw material conversion rate, is equivalent to providing a micro-interface reaction system with higher operability for the field of the hydrogenation of anthracene oil, and is worthy of wide popularization and application.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A micro-interface reaction system for anthracene oil hydrogenation is characterized by comprising: the micro-interface generator and the hydrogenation reactor are connected in sequence;
introducing hydrogen and anthracene oil into the micro-interface generator; a hydrogenation product outlet is formed in the side wall of the hydrogenation reactor, a product from the hydrogenation product outlet is introduced into a first separation tank to be used for separating hot high-temperature-separation gas and hot high-temperature-separation oil, and the hot high-temperature-separation gas is conveyed to a second separation tank to be separated into cold high-temperature-separation gas and cold high-temperature-separation oil; after the hot high-molecular oil enters a cracking reaction tower for cracking reaction, the obtained cracking reaction product is sent to a fractionating tower for fractionating, and the cold high-molecular gas and the cold high-molecular oil are respectively collected and discharged;
and a plurality of catalyst beds are arranged in the cracking reaction tower, each catalyst bed is filled with a catalyst, and the micro-interface generator is arranged between the adjacent catalyst beds.
2. The micro-interface reaction system of claim 1, wherein the micro-interface generator is arranged at the top of the outer side of the cracking reaction tower, the micro-interface generator at the top of the cracking reaction tower is introduced with hydrogen from a hydrogen main, and the hot high-fraction oil enters from the side of the micro-interface generator at the top of the cracking reaction tower.
3. The micro-interface reaction system according to claim 2, wherein the micro-interface generators located between adjacent catalyst beds are provided with a thermal high-pressure oil inlet and a hydrogen inlet, the thermal high-pressure oil inlet is connected with the bottom of the first separation tank, and the hydrogen inlet is connected with the hydrogen main pipe.
4. The micro-interfacial reaction system of claim 1, wherein there are 4 catalyst beds and 3 micro-interfacial generators inside the cracking reactor.
5. The micro-interface reaction system according to claim 2, wherein the bottom of the cracking reaction tower is provided with a cracking reaction product outlet for discharging the cracking reaction product, the cracking reaction product outlet is connected with a fourth separation tank for oil-gas separation, and oil phase separated from the bottom of the fourth separation tank goes to the fractionating tower.
6. A micro-interface reaction system according to claim 5, wherein the gas phase separated from the top of the fourth separation tank is compressed by a compressor and then returns to be communicated with the hydrogen main pipe.
7. The micro-interfacial reaction system of claim 5, wherein the cold high-split gas coming out of the top of the second separation tank goes to the fourth separation tank for further separation.
8. The micro-interfacial reaction system of claim 5, wherein the cold high-split oil from the bottom of the second separation tank goes to the fractionation column for fractionation.
9. The reaction method of the micro-interface reaction system for hydrogenating anthracene oil according to any one of claims 1-8, comprising:
the anthracene oil and hydrogen mixed micro interface is dispersed and crushed, then hydrogenation reaction is carried out, then separation and micro interface dispersion crushing are carried out, then hydrocracking is carried out, and finally separation and fractionation treatment are carried out.
10. The reaction process as claimed in claim 9, wherein the pressure of the hydrogenation reaction is 8-10MPa, and the temperature of the hydrogenation reaction is 220-230 ℃;
preferably, the hydrocracking pressure is 8-10MPa, and the temperature is 220-230 ℃.
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