CN114836235B - Method for separating aromatic hydrocarbon by adsorption and rectification coupling of distillate oil - Google Patents
Method for separating aromatic hydrocarbon by adsorption and rectification coupling of distillate oil Download PDFInfo
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 123
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000010168 coupling process Methods 0.000 title claims abstract description 16
- 230000008878 coupling Effects 0.000 title claims abstract description 15
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 43
- 238000000926 separation method Methods 0.000 claims abstract description 42
- 239000000945 filler Substances 0.000 claims abstract description 22
- 238000007670 refining Methods 0.000 claims abstract description 21
- 239000003921 oil Substances 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 17
- 238000012856 packing Methods 0.000 claims description 16
- 238000004458 analytical method Methods 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 32
- 239000002808 molecular sieve Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
-
- 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
-
- 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
- C10G7/00—Distillation of hydrocarbon oils
-
- 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
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- 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)
- Dispersion Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for separating aromatic hydrocarbon by coupling adsorption and rectification of distillate oil, which comprises one or more adsorption and rectification towers, wherein the filler in the adsorption and rectification towers is adsorption filler with aromatic hydrocarbon separation capacity, continuous or intermittent distillate oil aromatic hydrocarbon separation is carried out, a non-aromatic product with low aromatic hydrocarbon content is arranged at the top of the tower, an aromatic hydrocarbon product with high aromatic hydrocarbon content is arranged at the bottom of the tower, and the obtained product is subjected to an aromatic hydrocarbon refining unit to obtain a high-purity aromatic hydrocarbon product and a non-aromatic product. The method for separating aromatic hydrocarbon by adsorption and rectification coupling of the distillate oil has the characteristics of large treatment capacity, simple operation, continuous operation, low investment cost and the like, and the adsorption process has strong separation capability on aromatic hydrocarbon in the distillate oil, and the aromatic hydrocarbon content in an aromatic hydrocarbon product reaches more than 90 percent.
Description
Technical Field
The invention relates to the technical field of petroleum treatment, in particular to a method for separating aromatic hydrocarbon by adsorption, rectification and coupling of distillate oil.
Background
The distillate oil is obtained by separating by a distillate device in the oil refining process, such as gasoline, diesel oil, kerosene, lubricating oil, etc. As the demand for finished oil increases in speed and slows down, the consumption of gasoline and diesel reaches the peak gradually in recent years. Since 2015, domestic finished oil is surplus. The demands for basic chemicals such as olefins and aromatics are vigorous, and the demands for refining high-quality chemicals from distillate oils are increasing. The traditional hydrogenation process adopts a 'destructive' processing mode of macromolecule fracture and micromolecule reconstruction, and has the problems of high hydrogen consumption, selectivity, harsh reaction conditions, high production cost and the like. New distillate processing separation technology is required to be developed to produce more basic chemicals such as aromatic hydrocarbons.
The existing method for separating aromatic hydrocarbon of distillate oil mainly comprises solvent extraction and adsorption separation, the solvent extraction method needs multistage extraction and rectification separation, the process flow is long, the process energy consumption is high, the adsorption separation mainly comprises a simulated moving bed process, the operation is continuous, the stability is high, the product purity is high, but the problems of high adsorbent cost, high equipment investment and the like exist.
CA105542835A discloses a method for separating polycyclic aromatic hydrocarbon by simulated moving bed adsorption, which adopts oxide or modified oxide as adsorbent to adsorb polycyclic aromatic hydrocarbon in diesel oil, thereby realizing low temperature, low pressure, low adsorbent abrasion and high polycyclic aromatic hydrocarbon removal rate. However, the simulated moving bed adsorption separation has the defect of high investment cost of the adsorbent and equipment, and has certain difficulty in industrialized popularization.
CN101732883a discloses an adsorption rectifying tower for decolorizing aromatic hydrocarbon solvent oil and a process method thereof, wherein an adsorption device is arranged at the upper part in the rectifying tower, the upper part of the adsorption device is a tower top condensation reflux device, and the lower part is a rectifying section, thus forming the adsorption rectifying tower. The method can realize the decolorization of the aromatic hydrocarbon solvent, but has limited processing capacity, and the adsorption and the rectification are sequentially operated in series, so that the coupling of the adsorption and the rectification is not really realized.
The prior treatment technology has high separation cost of the distillate aromatic hydrocarbon, the adsorption and distillation coupling separation aromatic hydrocarbon method combines the adsorption and separation and the distillation process into a whole, and the advantages of retaining the continuity of the distillation operation on the basis of utilizing the high selectivity of the adsorption and separation are important supplements for upgrading the quality of the distillate oil product.
Disclosure of Invention
The invention aims to provide a method for separating aromatic hydrocarbon by adsorption and rectification coupling of distillate oil, which aims at overcoming the defects of the existing distillate oil aromatic hydrocarbon separation technology and can effectively separate aromatic hydrocarbon and non-aromatic components in the distillate oil.
The method realizes the separation of aromatic hydrocarbon and saturated hydrocarbon in the distillate oil by an adsorption rectification coupling process, and adopts adsorption rectification filler with aromatic hydrocarbon separation capability. The invention has the advantages of low cost, easy operation and continuous separation of aromatic hydrocarbon and saturated hydrocarbon in the distillate oil.
The invention provides a method for separating aromatic hydrocarbon by adsorption, rectification and coupling of distillate oil, which comprises the following steps: the method comprises the steps of introducing distillate oil into an adsorption rectifying tower, continuously or intermittently separating distillate oil from aromatic hydrocarbon under the action of adsorption rectifying coupling separation, obtaining a non-aromatic product with low aromatic hydrocarbon content at the tower top, and obtaining an aromatic hydrocarbon product with high aromatic hydrocarbon content at the tower bottom; wherein the filler in the adsorption rectifying tower is adsorption filler with aromatic hydrocarbon separation capability; the adsorption filler is one or more of molecular sieve, modified molecular sieve, silicon oxide, modified silicon oxide, aluminum oxide and modified aluminum oxide; the operation temperature is 50-230 ℃ at the top of the tower, 100-350 ℃ at the bottom of the tower, the operation pressure is 0.01-0.5MPa at the top of the tower, and the theoretical plate number is 5-80;
the adsorption packing in the adsorption rectifying tower is structured packing or random packing;
the adsorption rectifying tower is preferably an adsorption rectifying tower containing a plurality of side line extractions, and products of different rectifying sections are extracted;
the material of the adsorption filler is preferably one or more of modified molecular sieve with acid center, modified silicon oxide and modified aluminum oxide;
the material of the adsorption filling is preferably NH 3 -a material with an acid centre desorption temperature of 120-300 ℃ in TPD analysis.
The product obtained by the adsorption rectifying tower enters an aromatic hydrocarbon refining unit, the aromatic hydrocarbon refining unit consists of a plurality of aromatic hydrocarbon refining rectifying towers, an aromatic hydrocarbon product is obtained at the tower top, and a non-aromatic product is obtained at the tower bottom;
the aromatic hydrocarbon refining rectifying tower can be replaced by a simulated moving bed adsorption tower comprising a plurality of adsorption beds, and is uniformly filled with filler with an aromatic hydrocarbon adsorption separation function.
Compared with the existing distillate aromatic hydrocarbon separation method, the method has the following advantages:
(1) The process is simple, continuous operation is carried out, and the production capacity is high;
(2) The equipment investment cost is low;
(3) The raw material has strong adaptability, and can finish the separation of aromatic hydrocarbon and non-aromatic hydrocarbon of different distillate oil.
Drawings
FIG. 1 is a schematic diagram of the process flow for separating aromatic hydrocarbon by adsorption and rectification of distillate oil.
Fig. 2 is a schematic diagram of a process flow for separating aromatic hydrocarbons by adsorption and rectification of distillate oil in example 1 of the present invention.
Fig. 3 is a schematic diagram of a process flow for separating aromatic hydrocarbons by adsorption and rectification of distillate according to embodiment 2 of the present invention.
Fig. 4 is a schematic diagram of a process flow for separating aromatic hydrocarbons by adsorption and rectification of distillate according to embodiment 5 of the present invention.
In the figure, 101 is a distillate oil raw material, 102 is a low carbon number non-aromatic component, 103 is a high carbon number aromatic component, 104 is a low carbon number aromatic component, 105 is a medium carbon number non-aromatic component, 106 is a medium carbon number aromatic component, 107 is a high carbon number non-aromatic component, 108 is aromatic hydrocarbon, 109 is a non-aromatic component, 201 is an adsorption rectifying tower, and 202 to 203 are aromatic hydrocarbon refining rectifying towers.
Detailed Description
In order to further explain the method for separating the distillate aromatic hydrocarbon through adsorption rectification coupling according to the invention, the following is combined with the accompanying drawings.
As shown in fig. 1, distillate oil is used as a raw material, the distillate oil is introduced into an adsorption rectifying tower, continuous or intermittent distillate oil aromatic hydrocarbon separation is carried out under the action of adsorption rectifying coupling separation, a non-aromatic product with low aromatic hydrocarbon content is obtained at the tower top, and an aromatic hydrocarbon product with high aromatic hydrocarbon content is obtained at the tower bottom; wherein the filler in the adsorption rectifying tower is adsorption filler with aromatic hydrocarbon separation capability; the adsorption filler is one or more of molecular sieve, modified molecular sieve, silicon oxide, modified silicon oxide, aluminum oxide and modified aluminum oxide; the operation temperature is 50-230 ℃ at the top of the tower, 100-350 ℃ at the bottom of the tower, the operation pressure is 0.01-0.5MPa at the top of the tower, and the theoretical plate number is 5-80.
The selected adsorption rectifying tower is an adsorption rectifying tower containing a plurality of side line extractions, the side line extractions are carried out on products of different rectifying sections, the extracted products enter an aromatic hydrocarbon refining unit, the aromatic hydrocarbon refining unit consists of a plurality of aromatic hydrocarbon refining rectifying towers, aromatic hydrocarbon products are obtained at the top of the tower, and non-aromatic products are obtained at the bottom of the tower.
The adsorption filler in the adsorption rectifying tower is structured filler or random filler, and the material is preferably one or more of modified molecular sieve with acid center, modified silicon oxide and modified aluminum oxide. The material of the adsorption filling is preferably NH 3 -a material with an acid centre desorption temperature of 120-300 ℃ in TPD analysis.
The aromatic hydrocarbon refining rectifying tower can be replaced by a simulated moving bed adsorption tower comprising a plurality of adsorption beds, and is uniformly filled with filler with an aromatic hydrocarbon adsorption separation function.
The process according to the invention is further illustrated by the following examples, which are not intended to be limiting.
Example 1
The process flow is shown in fig. 2.
(1) The raw material is middle distillate oil (101) with 220-330 ℃ of hydrofining product of a certain refinery, the distillate oil is introduced into an adsorption rectifying tower (201) with 40 theoretical plates, aromatic hydrocarbon separation of the distillate oil is realized under continuous operation, and C is obtained at the top of the tower 10 -C 12 Is a non-aromatic component (102),the non-aromatic content was 90.8wt%.
(2) The mixed component (103) is extracted from the 8 th theoretical plate number side line, the extracted material enters an aromatic hydrocarbon refining rectifying tower (202), and C is obtained from the top of the tower 10 -C 12 Aromatic hydrocarbon component (106), C is obtained in the tower kettle 13 -C 15 Is a non-aromatic component (107). 106 aromatic components with an aromatic content of 90.1wt% and 107 non-aromatic components with an aromatic content of 8.6wt%.
(3) The mixed components are withdrawn at the side of the theoretical plate of block 28 (104). The extracted material enters an aromatic hydrocarbon adsorption separation simulated moving bed (203) to obtain aromatic hydrocarbon (108) with the purity of more than 95 weight percent and non-aromatic components (109).
(4) C is obtained from the tower kettle 16 -C 18 The aromatic hydrocarbon component (105) of (2) was 91.5wt%.
(5) The packing inside the adsorption rectifying tower is structured packing with aromatic adsorption separation capacity, the selected material is modified 13X molecular sieve, the tower top pressure is 0.02MPa, and the plate pressure drop is 200Pa. Wherein the modified 13X molecular sieve is NH 3 The acid center adsorption temperature in TPD analysis is about 180 ℃.
Example 2
The process flow is shown in fig. 3.
(1) The raw material is a mixture (101) of toluene and petroleum ether, and the toluene content is 30wt%. The mixed fraction is fed into an adsorption rectifying tower (201) with the theoretical plate number of 5 blocks, the separation of toluene and petroleum ether is realized under intermittent operation, and the operation pressure is 0.5MPa at the top of the tower.
(2) The packing inside the adsorption rectifying tower is random packing with arene adsorption separation capacity, the selected material is modified alumina, the tower top pressure is normal pressure, and the plate pressure drop is 300Pa. Wherein the modified alumina is NH 3 The acid center adsorption temperature in TPD analysis was around 120 ℃.
(3) The top of the adsorption rectifying tower is used for obtaining a low-carbon non-aromatic product (102) with toluene content of 5.1wt%. The product (103) obtained from the tower bottom enters a conventional rectifying device (202), the theoretical plate number is 6, the reflux ratio is 3, the toluene product (104) is obtained from the tower top product, the toluene concentration is 94.6wt%, the non-aromatic product (105) is obtained from the tower bottom, and the toluene content is 6.2wt%.
Comparative example 1
(1) The starting materials were the same as in example 2. The mixed fraction is fed into a rectifying tower with 5 theoretical plates, toluene and petroleum ether are separated under intermittent operation, and the operation pressure is 0.5MPa at the top of the tower.
(2) The packing material in the rectifying column is a random packing material with common size and void ratio as in example 2. The overhead pressure was normal pressure and the plate pressure drop was 300Pa.
(3) The top of the rectifying tower is used for obtaining a low-carbon non-aromatic product, and the toluene content is 25.6wt%. The product obtained in the tower kettle enters a rectifying device, the theoretical plate number is 6, the reflux ratio is 3, the toluene enrichment product is obtained in the tower top product, the toluene concentration is 83.2wt%, the non-aromatic product is obtained in the tower kettle, and the toluene content is 26.4wt%.
Example 3
(1) The raw material is a product of a certain refinery gasoline product, the distillate oil is fed into an adsorption rectifying tower with a theoretical plate number of 60 blocks, aromatic hydrocarbon separation of the distillate oil is realized under continuous operation, and C is obtained at the tower top 6 -C 7 The non-aromatic component of (2) was 94.5% by weight of non-aromatic content.
(2) Side draw C at theoretical plate number 18 8 -C 9 Non-aromatic components of (C) 6 -C 7 The aromatic hydrocarbon component of (2) is produced, the produced material is fed into aromatic hydrocarbon refining rectifying tower, and C is obtained from top of tower 6 -C 7 Aromatic hydrocarbon component of (C) is obtained in the tower kettle 8 -C 9 Is a non-aromatic component of (a). The aromatic hydrocarbon content of the tower top product is 96.1wt% and the aromatic hydrocarbon content of the tower bottom product is 3.6wt%.
(3) Side draw C from 45 th theoretical plate 10 -C 11 And C 8 -C 9 Is contained in the aromatic hydrocarbon component of (a). The extracted material enters an aromatic hydrocarbon refining rectifying tower, and C is obtained at the top of the tower 8 -C 9 Aromatic hydrocarbon component of (C) is obtained in the tower kettle 10 -C 11 Is a non-aromatic component of (a). The aromatic hydrocarbon content of the tower top product is 96.1wt% and the aromatic hydrocarbon content of the tower bottom product is 3.6wt%.
(4) C is obtained from the tower kettle 16 -C 18 The aromatic hydrocarbon content of (2) was 91wt%.
(5) The packing inside the adsorption rectifying tower is structured packing with arene adsorption separation capacity, the material is modified 13X molecular sieve, and the tower top pressure is0.01MPa, and a plate pressure drop of 200Pa. Wherein the modified 13X molecular sieve is NH 3 The acid center adsorption temperature in TPD analysis is about 180 ℃.
Example 4
(1) The raw material is the same as that of example 3, the distillate oil is fed into an adsorption rectifying tower with theoretical plate number of 80, the tower top pressure is 0.01MPa, and the plate pressure drop is 200Pa. Realizing aromatic hydrocarbon separation of distillate oil under continuous operation, obtaining C at the top of the tower 6 -C 7 The non-aromatic component of (2) and the non-aromatic content of 96.5wt%.
(2) Side draw C at theoretical plate number of 28 th 8 -C 9 Non-aromatic components of (C) 6 -C 7 The aromatic hydrocarbon component of (2) is produced, and the produced material enters an aromatic hydrocarbon adsorption separation simulated moving bed to obtain aromatic hydrocarbon with the purity of more than 98 weight percent and non-aromatic components.
(3) Side draw C from theoretical plate 61 10 -C 11 Non-aromatic components of (C) 8 -C 9 Is contained in the aromatic hydrocarbon component of (a). The extracted material enters an aromatic hydrocarbon adsorption separation simulated moving bed to obtain aromatic hydrocarbon and non-aromatic components with purity of more than 98 wt%.
(4) C is obtained from the tower kettle 16 -C 18 The aromatic hydrocarbon content of (2) was 93wt%.
(5) The packing inside the adsorption rectifying tower is structured packing with arene adsorption separation capacity, and the selected material is modified molecular sieve and modified silica, with tower top pressure of 0.01MPa and plate pressure drop of 200Pa. Wherein the 2 nd to 28 th theoretical plates are filled with modified silica, which is in NH 3 The acid center adsorption temperature in TPD analysis was around 120 ℃. Modified 13X molecular sieve loaded with 29 th to 60 th theoretical plates and prepared by NH 3 The acid center adsorption temperature in TPD analysis is about 180 ℃.61 theoretical plates to tower kettle are filled with modified Y molecular sieve which is prepared by NH 3 The acid center adsorption temperature in TPD analysis was around 300 ℃.
Example 5
The process flow is shown in fig. 4.
(1) The raw material is middle distillate oil (101) with 220-350 ℃ of hydrofining product of a certain refinery, the distillate oil is introduced into an adsorption rectifying tower (201) with 48 theoretical plates, aromatic hydrocarbon separation of the distillate oil is realized under continuous operation, and the tower top is obtainedC 10 -C 11 Non-aromatic component (102) of (C) and a non-aromatic content of 90.8wt%.
(2) Side draw C at theoretical plate number 7 12 -C 13 Non-aromatic and C 10 -C 11 The aromatic hydrocarbon mixed components of (2) are fed into an aromatic hydrocarbon refining rectifying tower (202), and C is obtained at the top of the tower 10 -C 11 Aromatic hydrocarbon component (104) of (2), and C is obtained in the tower kettle 12 -C 13 Is a non-aromatic component (105). The aromatic hydrocarbon content of the aromatic hydrocarbon component is 91.2wt% and the aromatic hydrocarbon content of the non-aromatic component is 7.6wt%.
(3) Side line C at theoretical plate 24 14 -C 17 Non-aromatic components of (C) 12 -C 15 Is contained in the aromatic hydrocarbon component of (a). The extracted material enters an aromatic hydrocarbon adsorption separation simulated moving bed (203) to obtain aromatic hydrocarbon (106) with the purity of more than 97 weight percent and non-aromatic components (107).
(4) Side line C at 35 th theoretical plate number 18 -C 19 Non-aromatic components and C 16 -C 17 The aromatic hydrocarbon component of (2) is produced, the produced material enters an aromatic hydrocarbon refining rectifying tower (204), and C is obtained at the top of the tower 16 -C 17 Aromatic hydrocarbon component (108) of (C) is obtained in the tower kettle 18 -C 19 Is a non-aromatic component (109). The aromatic hydrocarbon content of the aromatic hydrocarbon component is 92.2wt% and the aromatic hydrocarbon content of the non-aromatic component is 6.8wt%.
(5) C is obtained from the tower kettle 18 -C 19 Aromatic hydrocarbon component (103) of (2) and the aromatic hydrocarbon content was 92.3% by weight.
(6) The packing inside the adsorption rectifying tower is structured packing with arene adsorption separation capacity, the tower top pressure is 0.01MPa, and the plate pressure drop is 200Pa. Wherein the 2 nd to 7 th theoretical plates are filled with silicon oxide, which is in NH 3 The acid center adsorption temperature in TPD analysis was around 90 ℃. 13X molecular sieves with theoretical plate loading of 8 th to 24 th, which are NH 3 The acid center adsorption temperature in TPD analysis was around 160 ℃.25-35 theoretical plates are modified Y molecular sieve, which is in NH 3 The adsorption temperature of the acid center in TPD analysis is about 200 ℃, and the H-shaped modified Y molecular sieve is filled from 36 theoretical plates to the tower kettle and is prepared by NH 3 The acid center adsorption temperature in TPD analysis was around 300 ℃.
Claims (3)
1. A method for separating aromatic hydrocarbon by adsorption and rectification coupling of distillate oil comprises one or more adsorption and rectification towers, and is characterized in that: the adsorption rectifying tower is an adsorption rectifying tower containing a plurality of side lines for extracting products of different distillation sections, and extracting products of different distillation sections; the filler in the adsorption rectifying tower is adsorption filler with aromatic hydrocarbon separation capability; the operation temperature is 50-230 ℃ at the top of the tower, 100-350 ℃ at the bottom of the tower, 0.01-0.5MPa at the top of the operation pressure and 5-80 theoretical plates, continuous or intermittent distillate oil aromatic hydrocarbon separation is carried out, the top of the tower is a non-aromatic product with low aromatic hydrocarbon content, and the bottom of the tower is an aromatic hydrocarbon product with high aromatic hydrocarbon content;
the side-line collected product of the adsorption rectifying tower enters an aromatic hydrocarbon refining unit, the aromatic hydrocarbon refining unit consists of one or more aromatic hydrocarbon refining rectifying towers, aromatic hydrocarbon products are obtained at the top of the tower, and non-aromatic products are obtained at the bottom of the tower;
the adsorption filler is one or more of modified molecular sieve with acid center, modified silicon oxide and modified aluminum oxide; the adsorption filler is NH 3 -a material with an acid centre desorption temperature of 120-300 ℃ in TPD analysis.
2. The method for separating aromatic hydrocarbon by adsorption and rectification coupling of distillate oil according to claim 1, wherein the adsorption filler in the adsorption and rectification column is structured filler or random packing.
3. The method for separating aromatic hydrocarbon by coupling adsorption and rectification of distillate oil according to claim 1, wherein the aromatic hydrocarbon refining unit is a simulated moving bed adsorption tower comprising a plurality of adsorption beds, and is uniformly filled with filler with an aromatic hydrocarbon adsorption and separation function.
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