CN115141651B - System and method for intensified production of chemical raw materials in aromatic fraction-rich oil region - Google Patents
System and method for intensified production of chemical raw materials in aromatic fraction-rich oil region Download PDFInfo
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- CN115141651B CN115141651B CN202210699968.2A CN202210699968A CN115141651B CN 115141651 B CN115141651 B CN 115141651B CN 202210699968 A CN202210699968 A CN 202210699968A CN 115141651 B CN115141651 B CN 115141651B
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 59
- 239000002994 raw material Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000126 substance Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 86
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 37
- 238000000926 separation method Methods 0.000 claims abstract description 32
- 238000001179 sorption measurement Methods 0.000 claims abstract description 31
- 239000002283 diesel fuel Substances 0.000 claims abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005977 Ethylene Substances 0.000 claims abstract description 7
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 4
- 239000003350 kerosene Substances 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 47
- 239000002808 molecular sieve Substances 0.000 claims description 38
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- 239000007848 Bronsted acid Substances 0.000 claims description 16
- 239000002841 Lewis acid Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 150000007517 lewis acids Chemical class 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 13
- 238000005336 cracking Methods 0.000 claims description 11
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims description 2
- 239000010724 circulating oil Substances 0.000 claims description 2
- -1 monocyclic aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- 238000009738 saturating Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 29
- 238000004517 catalytic hydrocracking Methods 0.000 description 15
- 230000008569 process Effects 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000013316 zoning Methods 0.000 description 2
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil
- C10G25/08—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil according to the "moving bed" method
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/06—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a system and a method for producing chemical raw materials in an enhanced way in an aromatic fraction oil-rich region. The method comprises the following steps: treating raw materials of catalytic cracking diesel oil, ethylene tar and DCC diesel oil by a hydrofining reactor to obtain a hydrofining product; the reformed heavy aromatic hydrocarbon is treated by a pre-hydrogenation reactor to obtain a pre-hydrogenation product; treating kerosene and straight-run diesel raw materials through a simulated moving bed adsorption separation device to obtain adsorption separated heavy aromatic hydrocarbon; and (3) transferring the hydrofining product, the pre-hydrogenation product and the adsorption separation heavy aromatic hydrocarbon to a light-weight reactor with graded catalyst filling with different physicochemical properties, and finally obtaining a high-purity product. The method can efficiently convert the aromatic-rich distillate oil into a liquid-phase product with the aromatic purity reaching 99.9wt% and a gas-phase product rich in normal paraffins, avoid excessive hydrogenation saturation of aromatic hydrocarbons, improve the light aromatic yield, reduce the reaction heat release, and realize the chemical utilization of the aromatic-rich distillate oil.
Description
Technical Field
The invention relates to the technical field of petroleum treatment, in particular to a system and a method for producing chemical raw materials in an enhanced way in an aromatic fraction-rich oil region.
Background
Along with the serious problem of the heavy quality of crude oil in the world, the processing difficulty of the oil product is gradually increased, the yield of byproduct aromatic heavy oil of refining enterprises is rapidly increased, and how to use the byproduct aromatic heavy oil is a problem to be solved in the refining industry. At present, the utilization way of the partial oil products is to separate out products with higher values through simple rectification operation, and the rest of the products are used as low-price fuel, so that the utilization rate of raw materials is low.
In recent years, the development of the light-weight technology opens up a new way for realizing the utilization of aromatic-rich heavy oil. The technology adopts single-stage equal pressureThe series reactor process comprises a pre-hydrogenation unit and a light unit, which are all fixed bed reactors. The pre-hydrogenation reactor selects a catalyst with low-temperature Gao Jiaqing activity, the aromatic ring of the polycyclic aromatic hydrocarbon is saturated with high selectivity, one aromatic ring is reserved, and simultaneously, substances easy to coke such as colloid, asphaltene and the like are removed; the light reactor uses molecular sieve catalyst to selectively crack saturated ring and alkyl side chain, and make disproportionation and alkyl transfer. The gas phase product is rich in normal alkane and is high-quality ethylene cracking material; the liquid phase product is low-carbon aromatic hydrocarbon (C) 6 ～C 10 ) Realizing the utilization of the aromatic-rich distillate oil. However, the prior aromatic-rich distillate oil lightening technology has poor raw material adaptability, and can not simultaneously treat more aromatic fractions such as catalytic diesel, ethylene tar, coke diesel, heavy aromatic hydrocarbon and the like; meanwhile, as the raw materials enter from the top of the reactor, partial aromatic hydrocarbon is saturated by excessive hydrogenation, so that the yield of light aromatic hydrocarbon is low, and the heat release is large and difficult to control. If the light catalyst with different functions is developed and organic grading is carried out, different types of raw materials enter from different beds, and partition reaction is enhanced, the adaptability of the technical raw materials can be greatly improved, the aromatic hydrocarbon loss is reduced, the reaction heat release is controlled, and the economic benefit and the competitiveness of the technology are further improved.
Chinese patent CN20131054092.6 discloses a low energy hydrocracking process for producing high quality jet fuel. In the method, after the raw oil is mixed with hydrogen, the mixture passes through a pre-hydrogenation reaction zone and a hydrocracking reaction zone in sequence after twice heat exchange; the hydrocracking reaction zone comprises at least two hydrocracking catalysts, wherein the upstream is filled with a catalyst I, and the downstream is filled with a catalyst II; wherein the catalyst I contains 15-50wt% of modified Y molecular sieve, the catalyst II contains 3-30wt% of modified Y molecular sieve, and the content of the modified Y molecular sieve in the catalyst I is 10-25 percent higher than that in the catalyst II. The method organically combines the high-temperature high-pressure countercurrent heat transfer technology and the hydrocracking catalyst grading technology, comprehensively utilizes the hydrocracking reaction heat, fully plays the characteristics of two different types of hydrocracking catalysts, improves the quality of target products while maintaining the selectivity of the catalysts, and reduces engineering investment and operation energy consumption.
Chinese patent CN02144959.7 discloses a full cycle hydrocracking process. The process adopts a process of cracking before refining, unconverted oil is recycled to a cracking section for hydrocracking, and the process is used for producing clean fuel in a maximum amount. Compared with the prior art, the process has the advantages of high overall activity, good product quality, low operation cost and the like, and is mainly used for producing high-quality clean fuel.
Chinese patent CN201610252798.8 discloses a catalyst grading process for catalyzing diesel oil conversion. The method comprises the following steps: (1) The mixed material of the catalytic cracking diesel oil and the hydrogen enters a hydrogenation reactor for pre-hydrogenation reaction; (2) The pre-hydrogenation reaction effluent directly enters a cracking reactor and is contacted and reacted with a hydrocracking catalyst bed layer which is graded and filled in the cracking reactor; wherein, two hydrocracking catalyst beds in the hydrocracking reactor are used, the upper bed uses a hydrocracking catalyst with Mo/Co as an active metal component, and the lower bed uses a hydrocracking catalyst with Mo/Ni or W/Ni as an active metal component; (3) And (3) separating and fractionating the hydrocracking reaction effluent obtained in the step (2) to obtain a naphtha component and a diesel component. The method provided by the invention provides device liquid recovery on the premise of meeting the conversion rate of catalytic diesel, reduces the hydrogenation saturation of the generated gasoline component, and improves the octane number of the gasoline component.
The above methods or processes achieve improvement of product properties to some extent, but at the same time have the following problems: (1) single raw material types are treated, and the raw material adaptability is poor; (2) The catalyst has simple grading mode, no targeted zoning strengthening conversion according to material properties, serious excessive hydrogenation saturation of aromatic hydrocarbon, limited purity and yield improvement degree of light aromatic hydrocarbon, difficult control of heat release, large cold hydrogen consumption and high energy consumption; (3) The conversion depth is limited, partial diesel oil fraction can be generated, and the overall economy is poor.
Disclosure of Invention
The invention provides a system and a method for producing chemical raw materials in an enhanced mode in an aromatic fraction-rich oil region.
In a first aspect, the present application provides a system for enhancing production of chemical raw materials in an aromatic-rich fraction oil region, which is implemented by adopting the following technical scheme.
A system for strengthening production of chemical raw materials in an aromatic-rich fraction oil region comprises an aromatic-rich fraction oil I treatment system, an aromatic-rich fraction oil II treatment system and an aromatic-rich fraction oil III treatment system; the aromatic-enriched distillate oil I treatment system comprises a hydrofining reactor and a first stripping tower connected with the hydrofining reactor, wherein the first stripping tower is connected with a top feed inlet of the light-weight reactor; the aromatic-rich distillate oil II treatment system comprises a pre-hydrogenation reactor, wherein the pre-hydrogenation reactor is connected with a feed inlet in the middle of the light-weight reactor; the aromatic-enriched fraction oil III treatment system comprises a simulated moving bed adsorption separation device, and the simulated moving bed adsorption separation device is connected with a feed inlet in the middle of the light-weight reactor; the light-weight reactor is connected with a second stripping tower, and the second stripping tower is connected with a separation system; and the heavy component discharge port of the separation system is connected with the top feed port of the light-weight reactor.
Further, the aromatic-rich distillate I treatment system also comprises a first feed pump and a second feed pump, wherein the first feed pump is connected with the hydrofining reactor; the second feed pump is disposed between the first stripping column and the light-weight reactor.
Further, the aromatic-rich distillate II treatment system also comprises a third feed pump, and the third feed pump is connected with the pre-hydrogenation reactor.
Further, the aromatic-enriched fraction oil III treatment system also comprises a fourth feed pump, and the fourth feed pump is connected with the simulated moving bed adsorption separation device.
In a second aspect, the present application provides a method for producing chemical raw materials in an enhanced manner in an aromatic-rich fraction oil region, which is implemented by adopting the following technical scheme.
A method for producing chemical raw materials in an enhanced manner in an aromatic-rich fraction oil region comprises the following steps:
s1, removing sulfur nitrogen, colloid and asphaltene from aromatic-rich distillate I through a hydrofining reactor under certain reaction conditions, hydrogenating and saturating aromatic rings of polycyclic aromatic hydrocarbon, and removing acid gas through a first stripping tower to obtain a hydrofining product;
s2, the aromatic-rich distillate II enters a pre-hydrogenation reactor, colloid, asphaltene and other easily coked components are removed under the action of a pre-hydrogenation catalyst, and aromatic rings of polycyclic aromatic hydrocarbon are selectively saturated to generate monocyclic aromatic hydrocarbon, so that a pre-hydrogenation product is obtained;
s3, enabling the aromatic-rich distillate III to enter a simulated moving bed adsorption separation device to obtain adsorption-separation heavy aromatic hydrocarbon and adsorption-separation non-aromatic hydrocarbon, and discharging the adsorption-separation non-aromatic hydrocarbon serving as ethylene pyrolysis materials;
s4, mixing the hydrofining product obtained in the step S1, the pre-hydrogenation product obtained in the step S2 and the adsorption separation heavy aromatic hydrocarbon obtained in the step S3 with hydrogen at different positions, and then entering a light-weight reactor; hydrofining products enter a lightening reactor from the top of the reactor; the pre-hydrogenation product and the adsorption separation heavy aromatic hydrocarbon enter a lightening reactor from different positions in the middle of the reactor, and the feeding position is determined by the hydrogenation activity and the cracking activity of the lightening catalyst in the bed layer which is contacted firstly along the material flow direction; the light product is obtained after the light reaction;
s5, removing acid gas from the light product through a second stripping tower, and then entering a separation system to obtain dry gas, liquefied gas, light naphtha and C 6 ～C 10 Light aromatic hydrocarbon and tower bottom heavy components; and mixing the heavy components at the bottom of the tower as circulating oil with the hydrofining product and entering a light-weight reactor or discharging.
Further, the aromatic-rich distillate oil I comprises one or more of catalytic cracking diesel oil, ethylene tar and DCC diesel oil; the aromatic-rich distillate II is reformed heavy aromatic hydrocarbon; the aromatic-rich distillate oil III comprises one or two of kerosene and straight-run diesel oil.
Further, in step S1, the operation conditions of the hydrofining reactor are as follows: the reaction pressure is 4.0-10.0 MPa, and the hydrogen-oil volume ratio is 600:1 to 1500:1, the mass airspeed is 1.0 to 3.0h -1 The reaction temperature is 300-380 ℃. Preferably, the reaction pressure is 5-8 MPa, and the hydrogen-oil volume ratio is 600: 1-800: 1, the mass airspeed is 1.5-2 h -1 The reaction temperature is 320-360 ℃.
Further, in step S2, the operating conditions of the pre-hydrogenation reactorThe method comprises the following steps: the reaction pressure is 4.0-10.0 Mpa, and the hydrogen-oil volume ratio is 600:1 to 1500:1, the mass airspeed is 1.0 to 3.0h -1 The reaction temperature is 130-280 ℃. Preferably, the reaction pressure is 5-8 MPa, and the hydrogen-oil volume ratio is 800:1 to 1000:1, the mass airspeed is 1.5 to 2.5 hours -1 The reaction temperature is 140-240 ℃.
Further, in the step S2, the pre-hydrogenation catalyst is formed by mixing a noble metal pre-hydrogenation catalyst and a non-noble metal pre-hydrogenation catalyst according to a certain mass ratio, wherein the noble metal catalyst accounts for 60-95%; the active metal of the noble metal pre-hydrogenation catalyst is Pt and/or Pd, and the carrier is alumina or amorphous silicon-aluminum; the active metal of the non-noble metal pre-hydrogenation catalyst is Ni, and the carrier is alumina or amorphous silicon-aluminum.
Further, a fixed bed reactor is adopted as the pre-hydrogenation reactor.
In the step S3, the adsorbent filled in the simulated moving bed adsorption separation device is Zn/Y; the operation conditions of the simulated moving bed adsorption separation device are as follows: the adsorption and desorption temperature is 50-150 ℃, the mass ratio of the desorbent to the aromatic-rich distillate III is 0.8:1-2.0:1, the number of adsorption beds is 8-24, and the bed switching time is 100-1000 s.
Further, in step S4, the operating conditions of the light-weight reactor are as follows: the reaction pressure is 4.0-10.0 Mpa, and the hydrogen-oil volume ratio is 600:1 to 1500:1, the mass airspeed is 0.5 to 5.0h -1 The reaction temperature is 350-460 ℃, and the temperature of each bed layer is increased by 5-15 ℃ from top to bottom. Preferably, the reaction pressure is 5.0-8.0 MPa, and the hydrogen-oil volume ratio is 800:1 to 1000:1, the mass airspeed is 1.0 to 3.0h -1 The reaction temperature is 380-440 ℃, and the temperature of each bed layer is increased by 10-12 ℃ from top to bottom.
Further, in step S4, a lightening catalyst is filled in the lightening reactor in a grading manner along the material flow direction, the lightening catalyst mainly comprises a molecular sieve a, a molecular sieve B, alumina and metal oxides of groups vi and viii, wherein the molecular sieve a, the molecular sieve B and the alumina are mechanically compounded according to a certain dry basis weight ratio and then extruded to form, and the active metals are loaded in a co-impregnation or step-by-step impregnation manner; the weight ratio of the components is as follows: a molecule0 to 90 weight percent of sieve, 0 to 90 weight percent of molecular sieve B and 10 to 50 weight percent of alumina; 5 to 30wt% of the total loading (calculated as metal oxide) of the group VIB metal and the group VIII metal; the total acid amount of the catalyst is 0.25-0.55 mmol/g, and the ratio of Bronsted acid to Lewis acid is 0.5-20. Wherein the specific surface area of the molecular sieve A is 500-700 m 2 Per gram, the total acid amount is 0.20-0.60 mmol/g, and the ratio of Bronsted acid to Lewis acid is 1-5; the specific surface area of the molecular sieve B is 300-600 m 2 Per gram, the total acid amount is 0.30-0.50 mmol/g, and the ratio of Bronsted acid to Lewis acid is 15-30. The hydrogenation activity and the cracking activity of the catalyst are regulated by regulating the compound proportion of the molecular sieve and the active metal loading.
Preferably, the weight of the molecular sieve is 40-60 wt% of the molecular sieve A, the weight of the molecular sieve B is 15-30 wt% of the molecular sieve B and the weight of the alumina is 10-30 wt% of the molding carrier; 7-20wt% of total loading (calculated by metal oxide) of VIB group metal and VIII group metal; the total acid amount of the catalyst is 0.30-0.50 mmol/g, and the ratio of Bronsted acid to Lewis acid is 1-15; wherein the specific surface area of the molecular sieve A is 550-650 m 2 Per gram, the total acid amount is 0.30-0.55 mmol/g, and the ratio of Bronsted acid to Lewis acid is 2-3; the specific surface area of the molecular sieve B is 400-550 m 2 Per gram, the total acid amount is 0.35-0.45 mmol/g, and the ratio of Bronsted acid to Lewis acid is 20-25.
Further, the A molecular sieve comprises one of a Y molecular sieve, a beta molecular sieve, an MCM-22 molecular sieve and an MCM-41 molecular sieve; the molecular sieve B is one of mordenite, ZSM-5 molecular sieve and ZSM-11 molecular sieve.
Further, according to the contact sequence of the materials and the catalyst, the catalyst filled in each bed layer is graded and filled in a mode that the hydrogenation activity is gradually reduced from top to bottom and the cracking activity is gradually increased; the grading method of the light catalyst comprises the following steps: the number of the catalyst grading layers is 2-10, the total acid amount of each catalyst is reduced by 5-30% in sequence along the material flow direction by taking the property of the first catalyst layer as a reference, and the ratio of Bronsted acid to Lewis acid is 1-10 times that of the first catalyst layer; keeping the ratio of the VIB metal to the VIII metal (calculated by metal oxide) unchanged, and sequentially reducing the total load (calculated by metal oxide) by 3-20%; the first layer catalyst properties were as follows: the total acid amount of the catalyst is 0.40-0.55 mmol/g, the ratio of Bronsted acid to Lewis acid is 1-6, and the active metal loading (calculated by metal oxide) is 10-20wt%.
Preferably, the number of the catalyst grading layers is 4-6, the total acid amount of each catalyst is reduced by 8-20% in sequence along the material flow direction by taking the property of the first layer of catalyst as a reference, and the ratio of Bronsted acid to Lewis acid is 2-6 times that of the first layer; keeping the ratio of the VIB metal to the VIII metal (calculated by metal oxide) unchanged, and sequentially reducing the total load (calculated by metal oxide) by 5-15%; the first layer catalyst properties were as follows: the total acid amount of the catalyst is 0.45-0.50 mmol/g, the ratio of Bronsted acid to Lewis acid is 1-3, and the active metal loading (calculated by metal oxide) is 12-18 wt%.
Further, the position of the pre-hydrogenation product entering the light-weight reactor is determined by the property of the catalyst which is contacted first, the total acid amount of the catalyst is 0.35-0.45 mmol/g, the ratio of Bronsted acid to Lewis acid is 4-8, and the active metal loading (calculated by metal oxide) is 8-14 wt%. Preferably, the position of the prehydrogenation product entering the light ends reactor is determined by the nature of the catalyst contacted first in the direction of flow, the total acid content is 0.38-0.42 mmol/g, the ratio of Bronsted acid to Lewis acid is 5-7, the active metal loading (calculated as metal oxide) is 10-12 wt%.
Further, the position of the heavy aromatic hydrocarbon which is absorbed and separated and enters the light-weight reactor is determined by the property of the catalyst which is firstly contacted, the total acid amount of the catalyst is 0.28-0.35 mmol/g, the ratio of Bronsted acid to Lewis acid is 6-18, and the active metal loading (calculated by metal oxide) is 4-10wt%. Preferably, the position of the heavy aromatic hydrocarbon which is absorbed and separated into the light-weight reactor is determined by the property of the catalyst which is contacted firstly, the total acid amount of the catalyst is 0.30-0.32 mmol/g, the ratio of Bronsted acid to Lewis acid is 8-15, and the active metal loading (calculated by metal oxide) is 5-8wt%.
Further, a fixed bed reactor is used as the light-weight reactor.
The separation system is obtained by integrating a gas-liquid separator and a rectifying tower.
The present application has the following advantageous effects.
1. The raw materials treated by the method are various in types and high in raw material adaptability;
2. according to different material properties, the conversion is intensified by targeted zoning through catalyst grading, aromatic hydrocarbon saturation is avoided to the greatest extent while aromatic hydrocarbon rich distillate oil is efficiently converted, the aromatic hydrocarbon yield is improved, the reaction heat release is effectively controlled, meanwhile, the heat release of an upper catalyst is fully utilized, the cold hydrogen consumption is reduced, and the energy consumption is obviously reduced;
3. the raw material conversion rate is high, and the product light aromatic hydrocarbon has high purity and value; the single pass conversion rate of the aromatic-rich distillate reaches more than 85wt%, the purity of light aromatic hydrocarbon in the light liquid phase product can reach 99.9wt%, the gas phase product is rich in normal alkane and is high-quality ethylene cracking material, the overall economy is high, and the utilization of the aromatic-rich distillate is realized.
Drawings
FIG. 1 is a schematic illustration of the process flow of the present invention.
1, a first feed pump; 2. a hydrofining reactor; 3. a first stripping column; 4. a second feed pump; 5. a third feed pump; 6. a fourth feed pump; 7. a pre-hydrogenation reactor; 8. a simulated moving bed adsorption separation device; 9. a light reactor; 10. a second stripping column; 11. a separation system; 12. a hydrogen compressor.
Detailed Description
The invention will be further described with reference to the drawings and examples.
As shown in fig. 1, the aromatic-rich distillate I is mixed with hydrogen (provided by a hydrogen compressor 12) by a first raw material pump 1 and then enters a hydrofining reactor 2, the obtained hydrofining product enters a first stripping tower 3 to remove acid gas, then enters a light-weight reactor 9 by a second raw material pump 4 and is mixed with hydrogen (provided by the hydrogen compressor 12); the aromatic-rich distillate II is mixed with hydrogen (provided by a hydrogen compressor 12) through a third raw material pump 5 and then enters a pre-hydrogenation reactor 7, and the obtained pre-hydrogenation product enters a light-weight reactor 9; the aromatic-rich distillate III enters a simulated moving bed adsorption separation device 8 through a fourth raw material pump 6, non-aromatic hydrocarbon and heavy aromatic hydrocarbon are separated and obtained through adsorption separation, and the heavy aromatic hydrocarbon and hydrogen (provided by a hydrogen compressor 12) are mixed and enter a light-weight reactor 9; the light product is removed of acid gas by a second stripping tower 10 and then enters a separation system 11 to obtain dry gas, liquefied gas and lightNaphtha, C 6 ～C 10 The major part of the aromatic hydrocarbon and heavy components are used as recycled oil and products obtained after hydrofining and acid gas removal are mixed and enter a light-weight reactor 9, and a small amount of the heavy components are thrown outwards.
Example 1
The hydrofining reactor is filled with a traditional hydrofining catalyst, the reaction pressure is 6MPa, and the hydrogen-oil volume ratio is 600:1, mass space velocity of 1.5h -1 The reaction temperature was 340 ℃.
Pre-hydrogenation reactor packing Pt/Al 2 O 3 Ni/Al 2 O 3 Mixed catalyst, pt/Al 2 O 3 The catalyst accounts for 85%, the Pt loading is 0.28% by weight, and the Ni loading is 10% by weight. The reaction temperature is 180 ℃, the pressure is 5MPa, and the hydrogen-oil volume ratio is 800:1, mass space velocity 2.0h -1 ；
The simulated moving bed adsorption separation device is filled with Zn/Y molecular sieve, and the Zn loading amount is 6wt%; the adsorption and desorption temperature is 80 ℃, the mass ratio of the desorbent to the pre-hydrogenation product is 0.8:1, the number of adsorption beds is 16, and the bed switching time is 300s;
the reaction pressure of the light-weight reactor is 5.0MPa, and the hydrogen-oil volume ratio is 800:1, mass space velocity 1.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the The raw material composition and catalyst grading loading scheme are shown in table 1, and the material balance is shown in table 2.
TABLE 1 raw material composition and light catalyst gradation loading scheme
Table 2 material balance
Example 2
The hydrofinishing unit operating conditions were the same as in example 1;
the pre-hydrogenation reactor is filled with Pd/silicon aluminum and Ni/Al 2 O 3 Mixed catalyst, pd/silicon-aluminum catalyst with a ratio of 85%, ni loading of 10wt% and Pd loading of 0.23wt%. The reaction temperature is 240 ℃, the pressure is 6MPa, and the hydrogen-oil volume ratio is 800:1, mass space velocity 2.0h -1 ；
The simulated moving bed adsorption separation device is filled with Zn/Y molecular sieve, and the Zn loading amount is 6wt%; the adsorption and desorption temperature is 90 ℃, the mass ratio of the desorbent to the pre-hydrogenation product is 1.2:1, the number of adsorption beds is 16, and the bed switching time is 600s;
the reaction pressure of the light reactor is 6.0MPa, and the hydrogen-oil volume ratio is 1000:1, mass space velocity 1.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the The raw material composition and catalyst grading loading scheme are shown in Table 3, and the material balance is shown in Table 4.
TABLE 3 raw material composition and light catalyst gradation loading scheme
Table 4 material balance
Example 3
The catalyst and reaction conditions for each reactor were the same as in example 1, the feed composition and catalyst loading schedule were as shown in Table 5, and the material balance was as shown in Table 6.
TABLE 5 raw material composition and light catalyst gradation loading scheme
TABLE 6 Material balance
As can be seen from the experimental data of examples 1-3, the invention can treat various raw materials, flexibly adjust the feeding position according to different raw material properties, avoid excessive hydrogenation saturation of aromatic hydrocarbon, remarkably improve the yield and purity of light aromatic hydrocarbon, and simultaneously produce a gas phase component rich in normal alkane as a byproduct; in addition, the invention can effectively control the reaction heat release, fully utilize the reaction heat release, reduce the cold hydrogen consumption, reduce the energy consumption, and has stronger technical competitiveness and excellent economy.
The embodiments of the present invention are all preferred embodiments of the present invention, and are not intended to limit the scope of the present invention in this way, therefore: all equivalent changes in structure, shape and principle of the invention should be covered in the scope of protection of the invention.
Claims (6)
1. A method for producing chemical raw materials in an enhanced manner in an aromatic fraction-rich oil region is characterized by comprising the following steps: the method comprises the following steps:
s1, removing sulfur, nitrogen, colloid and asphaltene from aromatic-rich distillate I through a hydrofining reactor (2) under certain reaction conditions, hydrogenating and saturating aromatic rings of polycyclic aromatic hydrocarbon, and removing acid gas through a first stripping tower (3) to obtain a hydrofining product;
s2, the aromatic-rich distillate II enters a pre-hydrogenation reactor (7), easily coked components are removed under the action of a pre-hydrogenation catalyst, and aromatic rings of polycyclic aromatic hydrocarbons are selectively saturated to generate monocyclic aromatic hydrocarbons, so that a pre-hydrogenation product is obtained;
s3, enabling the aromatic-rich distillate oil III to enter a simulated moving bed adsorption separation device (8) to obtain heavy aromatic hydrocarbon and non-aromatic hydrocarbon through adsorption separation, and discharging the non-aromatic hydrocarbon through adsorption separation;
s4, mixing the hydrofining product obtained in the step S1, the pre-hydrogenation product obtained in the step S2 and the adsorption separation heavy aromatic hydrocarbon obtained in the step S3 with hydrogen at different positions, and then feeding the mixture into a light-weight reactor (9); hydrofining products enter a lightening reactor (9) from the top of the reactor; the pre-hydrogenation product and the adsorption separation heavy aromatic hydrocarbon enter a lightening reactor (9) from different positions in the middle of the reactor, and the feeding position is determined by the hydrogenation activity and the cracking activity of the lightening catalyst in the bed layer which is firstly contacted along the material flow direction; the light product is obtained after the light reaction;
the main components of the light catalyst are a molecular sieve A, a molecular sieve B, alumina and metal oxides of VIB and VIII; the A molecular sieve comprises one of a Y molecular sieve, a beta molecular sieve, an MCM-22 molecular sieve and an MCM-41 molecular sieve; the molecular sieve B is one of mordenite, ZSM-5 molecular sieve and ZSM-11 molecular sieve;
according to the contact sequence of the materials and the catalyst, the catalyst filled in each bed layer is graded and filled in a mode that the hydrogenation activity is gradually reduced from top to bottom and the cracking activity is gradually increased; the grading method of the light catalyst comprises the following steps: the number of the catalyst grading layers is 2-10, the total acid amount of each catalyst is reduced by 5-30% in sequence along the material flow direction by taking the property of the first catalyst layer as a reference, and the ratio of Bronsted acid to Lewis acid is 1-10 times that of the first catalyst layer; keeping the ratio of VIB metal to VIII metal unchanged, and sequentially reducing the total load by 3-20%; the first layer catalyst properties were as follows: the total acid amount of the catalyst is 0.40-0.55 mmol/g, the ratio of Bronsted acid to Lewis acid is 1-6, and the active metal loading is 10-20wt%;
s5, removing acid gas from the light product through a second stripping tower (10), and then entering a separation system (11) to obtain dry gas, liquefied gas, light naphtha and C 6 ～C 10 Light aromatic hydrocarbon and tower bottom heavy components; the heavy components at the bottom of the tower are used as circulating oil and are mixed with hydrofining products to enter a lightening reactor (9) or are discharged;
the aromatic-rich distillate oil I comprises one or more of catalytic cracking diesel oil, ethylene tar and DCC diesel oil; the aromatic-rich distillate II is reformed heavy aromatic hydrocarbon; the aromatic-rich distillate oil III comprises one or two of kerosene and straight-run diesel oil.
2. The method for the enhanced production of chemical raw materials in an aromatic-rich fraction oil zone according to claim 1, which is characterized in that: in step S1, the operating conditions of the hydrofining reactor (2) are: reactionThe pressure is 4.0-10.0 MPa, and the hydrogen-oil volume ratio is 600:1 to 1500:1, the mass airspeed is 1.0 to 3.0h -1 The reaction temperature is 300-380 ℃.
3. The method for the enhanced production of chemical raw materials in an aromatic-rich fraction oil zone according to claim 1, which is characterized in that: in step S2, the operating conditions of the pre-hydrogenation reactor (7) are: the reaction pressure is 4.0-10.0 Mpa, and the hydrogen-oil volume ratio is 600:1 to 1500:1, the mass airspeed is 1.0 to 3.0h -1 The reaction temperature is 130-280 ℃.
4. The method for the enhanced production of chemical raw materials in an aromatic-rich fraction oil zone according to claim 1, which is characterized in that: in the step S2, the pre-hydrogenation catalyst is formed by mixing a noble metal pre-hydrogenation catalyst and a non-noble metal pre-hydrogenation catalyst according to a certain mass ratio, wherein the noble metal catalyst accounts for 60-95%; the active metal of the noble metal pre-hydrogenation catalyst is Pt and/or Pd, and the carrier is alumina or amorphous silicon-aluminum; the active metal of the non-noble metal pre-hydrogenation catalyst is Ni, and the carrier is alumina or amorphous silicon-aluminum.
5. The method for the enhanced production of chemical raw materials in an aromatic-rich fraction oil zone according to claim 1, which is characterized in that: in the step S3, the adsorbent filled in the simulated moving bed adsorption separation device (8) is Zn/Y; the operation conditions of the simulated moving bed adsorption separation device (8) are as follows: the adsorption and desorption temperature is 50-150 ℃, the mass ratio of the desorbent to the aromatic-rich distillate III is 0.8:1-2.0:1, the number of adsorption beds is 8-24, and the bed switching time is 100-1000 s.
6. The method for the enhanced production of chemical raw materials in an aromatic-rich fraction oil zone according to claim 1, which is characterized in that: in step S4, the operating conditions of the lightening reactor (9) are: the reaction pressure is 4.0-10.0 Mpa, and the hydrogen-oil volume ratio is 600:1 to 1500:1, the mass airspeed is 0.5 to 5.0h -1 The reaction temperature is 350-460 ℃, and the temperature of each bed layer is increased by 5-15 ℃ from top to bottom.
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