CN110938465B - Method for multi-component adsorption separation of gasoline - Google Patents
Method for multi-component adsorption separation of gasoline Download PDFInfo
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- CN110938465B CN110938465B CN201911134942.8A CN201911134942A CN110938465B CN 110938465 B CN110938465 B CN 110938465B CN 201911134942 A CN201911134942 A CN 201911134942A CN 110938465 B CN110938465 B CN 110938465B
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
- B01D15/1814—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns recycling of the fraction to be distributed
- B01D15/1821—Simulated moving beds
- B01D15/1828—Simulated moving beds characterized by process features
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
- B01D15/1864—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns using two or more columns
- B01D15/1871—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns using two or more columns placed in series
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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
- 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
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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
- 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
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- 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
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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Abstract
The invention relates to a method for multi-component adsorption separation of gasoline, which comprises the steps of firstly, enabling a gasoline raw material to enter a selective hydrogenation device to remove impurities such as dialkene, sulfur, nitrogen, colloid and the like in the gasoline, enabling the hydrogenated gasoline to enter a pretreatment tower to remove strong polar substances in the gasoline, enabling the pretreated gasoline to enter a five-zone simulated moving bed device, and adsorbing and separating saturated hydrocarbon, olefin and aromatic hydrocarbon components in the gasoline; the separated saturated hydrocarbon component is a high-quality raw material for ethylene cracking, and can increase the yield of low-carbon olefin; the olefin component is a high-quality raw material for catalytic cracking, so that the load of the device is reduced; the aromatic hydrocarbon component is fractionated to obtain BTX which is a high value-added product, and the fractionated C9 +Aromatic hydrocarbon is a high octane product and can be blended into high aromatic solvent oil for sale. The method carries out classification management on the gasoline components, reasonably utilizes the resources of the gasoline components and creates objective economic benefits.
Description
Technical Field
The invention relates to a method for multi-component adsorption separation of gasoline.
Background
At the present stage, the oil refining capacity in China is seriously surplus, the surplus capacity is expected to be maintained at 1.1 hundred million tons/year, and the speed increase of the finished oil is greatly slowed down; however, the basic organic chemical raw materials such as aromatic hydrocarbon and olefin are still in shortage, and the transformation and upgrading from fuel type to chemical type in oil refining enterprises in China is in great trend.
Gasoline is one of the most used light petroleum products and is mainly produced by the processes of crude oil distillation, catalytic cracking, coking, hydrocracking and the like; wherein the contents of sulfur, nitrogen, olefin and aromatic hydrocarbon in the catalytic cracking gasoline, the coking gasoline and the like are higher. The main methods for processing gasoline traditionally are hydrofinishing and upgrading techniques. The two methods can realize the purposes of deep desulfurization and denitrification and great olefin reduction; but on the one hand, the problems of high octane number loss rate, high hydrogen consumption, high operation cost, difficult achievement of the quality requirement of the finished product oil of the product and the like exist. On the other hand, by adopting the traditional gasoline processing technology, a large amount of saturated hydrocarbon, olefin and aromatic hydrocarbon resources in the gasoline cannot be utilized, and serious resource waste is caused.
Separating all components in the gasoline by an adsorption separation method to obtain a high-purity saturated hydrocarbon component, an olefin component and an aromatic hydrocarbon component; wherein the saturated hydrocarbon is a high-quality raw material for ethylene cracking; the olefin affects the stability in the gasoline fraction, but the olefin is a high-quality raw material for increasing the yield of the low-carbon olefin by catalytic cracking, and the load of a device is reduced; BTX obtained by adsorbing and separating aromatic hydrocarbon components is not only an aromatic hydrocarbon product with high added value, but also C after rectification9 +Aromatic hydrocarbon is a high-octane product, and can be added into high aromatic solvent oil for direct sale, so that the aim of classification management of gasoline components is fulfilled; the method not only achieves the purpose of deep treatment of the gasoline, but also improves the economic benefit and social benefit of enterprises.
CN106929098A discloses a method for hydro-upgrading catalytic gasoline, catalytic gasoline and hydrogen are mixed and enter a pre-hydrogenation reactor, and the product enters a fractionating tower to be cut into light, medium and heavy gasoline components; the light gasoline component coming out of the top of the fractionating tower is used as a modified gasoline blending component, and the middle gasoline component coming out of the lateral line and hydrogen are mixed, enter the first hydrodesulfurization reactor, react and then return to the fractionating tower; and (3) allowing the fractionation product to enter a second hydrodesulfurization reactor for reaction, cooling the product, allowing the product to enter a product separator for gas-liquid separation, recycling the hydrogen at the top, allowing the liquid phase at the bottom to enter a stabilizing tower for removing sulfur-containing gas, and mixing the liquid phase with light gasoline to obtain a modified gasoline product. The method has the problems of high energy consumption, low liquid yield, high aromatic hydrocarbon loss rate in the produced gasoline, incapability of directly meeting the national standard requirement of octane number and the like.
CN102382678A discloses a method for producing aromatic hydrocarbons from coker gasoline, which comprises extracting aromatic hydrocarbons from coker gasoline raw material, subjecting raffinate oil obtained by separating raffinate oil phase at the top of extraction tower to aromatization reaction, returning liquid product of aromatization reaction as feed for aromatic hydrocarbon extraction, subjecting solvent phase at the bottom of extraction tower to hydrogenation refining, and subjecting refined mixed aromatic hydrocarbons to aromatic hydrocarbon rectification to obtain aromatic hydrocarbon products such as benzene, toluene and xylene. The mixed aromatic hydrocarbon component produced by the method has low aromatic hydrocarbon purity (the aromatic hydrocarbon content is less than 85 wt%), and has the problems of high energy consumption of aromatization reaction and the like.
CN102295955A discloses a hydro-upgrading method for selective hydrodesulfurization of inferior gasoline, substantial olefin reduction and octane number recovery. The method adopts a process flow of connecting two agents and two devices in series. The first reactor is filled with a selective hydrodesulfurization catalyst, and the second reactor is filled with an octane number recovery catalyst. The sulfur content in the modified gasoline product is less than 30 mug/g, compared with the raw material, the olefin is reduced by 20 percent, the best effect can be achieved without loss of octane number basically, and the total liquid yield is more than 99 wt%. The method has the problems of complex process flow, high investment cost, high hydrogen consumption and the like, and the modified product has high contents of olefin and sulfur and can not meet the quality requirement of the finished oil.
CN102051223A discloses a method for hydrorefining catalytically cracked gasoline, which comprises the steps of fractionating a gasoline full-cut raw material into three fractions, namely a light fraction, a middle fraction and a heavy fraction, carrying out deep hydrodesulfurization, hydrodenitrogenation and olefin saturation reaction on the heavy fraction in a first reaction zone, mixing the effluent of the first reaction zone and the middle fraction, and allowing the mixture to enter a second reaction zone for selective hydrodesulfurization reaction; and mixing the hydrogenated gasoline fraction separated from the reaction effluent of the second reaction zone with the light fraction for alkali-free deodorization to obtain a gasoline product with low sulfur and a higher octane number. The method has the problems of high energy consumption, low liquid yield and the like.
CN106118728A discloses a method for hydrofining coker gasoline, wherein the process adopts a fixed bed reactor, and a hydrodesulfurization and denitrification catalyst is filled in the fixed bed reactor. The reaction temperature is 240-350 ℃, the hydrogen partial pressure is 2-3.5 MPa, the hydrogen-oil volume ratio is 450-700, and the volume airspeed is 1-2 h-1. The process can control the total sulfur content of the coking gasoline to be lower than 5ppm and prolong the service life of the catalyst to be more than 8 years. But the method has the defects of high aromatic hydrocarbon loss rate and octane number which can not directly meet the requirements of national standards.
The processing method for upgrading the gasoline, which is a hydrorefining or hydroupgrading technology, has the problems of resource waste, high octane number loss rate, high olefin loss rate, high hydrogen consumption, large equipment investment and the like.
Disclosure of Invention
The invention aims to overcome the defects of the existing gasoline processing and utilizing technology and provide a method for multi-component adsorption separation of gasoline. The method can effectively separate the gasoline components into saturated hydrocarbon, olefin and aromatic hydrocarbon, provides a necessary and feasible means for molecular utilization and high-value utilization of gasoline, and further improves the economic benefit and social benefit of enterprises.
The invention provides a method for multi-component adsorption separation of gasoline, which comprises the following steps:
firstly, a gasoline raw material enters a selective hydrogenation device to remove impurities such as diene, sulfur nitrogen, colloid and the like, the hydrogenated gasoline enters a pretreatment adsorption tower (the pretreatment adsorption tower adopts two parallel towers, one is opened and the other is prepared), pretreatment is carried out, and strong polar substances in the gasoline are removed through a pretreatment adsorbent (the content of alkaline nitrogen and oxide after removal is not more than 1 ppm); the pretreated gasoline enters a five-zone simulated moving bed device for adsorption separation;
the selective hydrogenation device, the pretreatment adsorption tower and the five-zone simulated moving bed adsorption device are connected in series, the pretreatment adsorption tower is formed by connecting two opened towers in parallel, adsorption columns of the five-zone simulated moving bed device are connected end to end side by side and form a closed loop through a circulating pump, the device is divided into five regions, a double-extraction-outlet structure is adopted, an adsorption I region, an isolation IV region, a desorption 0 region, a desorption III region and a refining II region are sequentially arranged along the flowing direction of a liquid material (a 0 region is additionally arranged in front of a desorption region of a conventional four-zone simulated moving bed for desorbing strongest adsorption components), and at least 1 adsorption column is distributed in each region; each adsorption column comprises six feeding and discharging pipelines and a periodic switching valve, and forms a closed loop through a circulating pump, wherein a desorption 0 area is arranged in front of the desorption III area and is used for desorbing the strongest adsorption component;
wherein, the adsorption I area adsorbs olefin and aromatic hydrocarbon components through a complexing adsorbent to obtain saturated hydrocarbon components; desorbing the olefin in the desorption III zone through D1 to obtain an olefin component; in the desorption 0 zone, the aromatic hydrocarbon is desorbed through a desorbent D0 to obtain an aromatic hydrocarbon component; finally, the separation of saturated hydrocarbon components, olefin components and aromatic hydrocarbon components in the gasoline is realized.
The pretreatment adsorbent adopts a high-silicon or pure-silicon molecular sieve with high specific surface area and large adsorption capacity; such as one of MCM-41 molecular sieve, MCM-48 molecular sieve, SBA-3 molecular sieve and SBA-15-4.2 molecular sieve; the specific surface area is more than or equal to 600m2Per g, pore volume is more than or equal to 0.55cm3(ii)/g, the average pore diameter is 2-5 nm;
the complexing adsorbent is a metal modified molecular sieve; the modified metal is one or more of K, Cs, Mg, Ca, Ba, Co, Ni, Cu, Zn and Mo, and the content is 0.1-10 wt%; the molecular sieve carrier is one of MCM-22, a beta molecular sieve, a 13X molecular sieve and a Y molecular sieve;
the desorbent D1 is one or more of n-tridecene, n-tetradecene and methylnaphthalene;
the desorbent D0 is one or two of reformed heavy aromatic hydrocarbon or long-chain alkylbenzene.
The method for the multi-component adsorption separation of the gasoline comprises the step of optimizing the temperature of an adsorbent bed layer of a pretreatment adsorption tower in the adsorption device of the pretreatment adsorption tower to be 30-150 ℃, wherein the mass space velocity is 0.1-3.0 h-1The adsorption pressure is 0.1-5.0 MPa, and the preferred mass space velocity is 0.5-1.5 h-1The temperature of the adsorbent bed is 30-70 ℃ and the adsorption pressure is 0.3-0.5 MPa.
In the five-zone simulated moving bed adsorption device, the temperature of each adsorption column is preferably 40-150 ℃, the adsorption pressure is 0.5-2.0 MPa, and the switching time is 100-2000; more preferably, the switching time is 150-700 s, the temperature of the adsorbent bed is 50-90 ℃, and the adsorption pressure is 0.5-1.5 MPa.
In the five-zone simulated moving bed adsorption device, the mass flow rate ratio of the gasoline raw material to the desorbent is preferably 1: 1-1: 4, more preferably 1: 1.8-1: 2.5, and the volume flow rate ratio of the gasoline raw material to the circulation volume is 1: 1-1: 5, more preferably 1: 4-1: 4.5.
The saturated adsorption capacity of the pretreatment adsorbent is 10-40%; the saturated adsorption capacity of the complexing adsorbent is 5-20%.
Compared with the existing gasoline processing technology, the process has the following advantages:
1) the invention adopts a simulated moving bed process, belongs to a green and efficient separation technology, and can realize the purposes of efficient conversion of gasoline and classified management of each component;
2) the adsorption separation technology separates multiple components in the gasoline at low pressure and low temperature without hydrogen, adopts a multi-tower series process, and has the characteristics of environmental protection, no pollution, mild reaction conditions, less investment, low energy consumption, easy control and the like;
3) the adsorption separation technology realizes the high-efficiency separation of gasoline multi-components with lower cost and simple process, and has high separation purity, saturated hydrocarbon content of saturated hydrocarbon component is more than 95%, olefin content of olefin component is more than 90%, and aromatic hydrocarbon content of aromatic hydrocarbon component is more than 90%;
4) the saturated hydrocarbon separated by the adsorption separation technology can be used asHigh-quality raw materials for ethylene cracking are adopted, and the yield of low-carbon olefin is increased; the separated olefin can be used as a high-quality raw material for catalytic cracking, so that the load of the device is reduced; wherein BTX obtained from aromatic hydrocarbon component is high value-added product, C9 +Aromatic hydrocarbon is a high octane number product and can be blended into high aromatic solvent oil for direct sale.
Drawings
FIG. 1 is a schematic diagram of a process flow for adsorptive separation of three components in a five-zone simulated moving bed device;
FIG. 2 is a schematic diagram of a process flow of gasoline multicomponent adsorption separation;
in fig. 1: f (A, B, C) -gasoline feedstock; r (a) -a saturated hydrocarbon component and D1+ D0 mixed desorbent; e (B) -olefin component and D1+ D0 mixed desorbent; t (c) -an aromatic hydrocarbon component and D1+ D0 mixed desorbent; a-saturated hydrocarbons; a B-olefin; a C-aromatic hydrocarbon; fluid flow-liquid flow direction; solid flow-direction of flow of solids;
in fig. 2: d0-desorbent D0, D1-desorbent D1; 1-a selective hydrogenation unit; 2 and 3-pretreatment adsorption tower; 4-a five-zone simulated moving bed device; 5, 6, 7 and 8-fractionation columns.
Detailed Description
The technical scheme and technical effect of the method of the invention are further explained by combining the drawings in the specification and the concrete embodiment.
The method is used for the multi-component adsorption separation of gasoline and comprises a pretreatment adsorbent, a complexing adsorbent, pretreatment device process parameters and five-zone simulated moving bed device process parameters. As shown in fig. 2, a gasoline raw material firstly enters a selective hydrogenation device 1 to remove impurities such as dialkene, sulfur and nitrogen, colloid and the like in the gasoline; the hydrogenated gasoline enters a pretreatment adsorption tower (2, 3, two towers which are arranged in parallel and are opened and prepared one by one) to remove strong polar substances in the gasoline, the content of alkaline nitrogen and oxide after removal does not exceed 1ppm, the pretreated gasoline enters a five-zone simulated moving bed adsorption device 4 to be subjected to an adsorption separation process, the separated saturated hydrocarbon component enters a fractionating tower 5 to be fractionated to obtain a saturated hydrocarbon component and a mixed desorbent; the separated olefin component enters a fractionating tower 6 to obtain an olefin component and a mixed desorbent; the separated aromatic hydrocarbon component enters a fractionating tower 7 to obtain an aromatic hydrocarbon component and a mixed desorbent; the three mixed desorbents are converged and then enter a fractionating tower 8, and are fractionated to obtain the desorbents D1 and D0, and the two desorbents are respectively recycled after fractionation. The invention relates to a gasoline multi-component adsorption separation process, belonging to a simulated moving bed process, which operates according to the process parameters provided by the invention.
The following examples will further illustrate the invention.
The composition of the gasoline raw material used in the examples is shown in Table 1, the process conditions of the pretreatment column are shown in Table 2, and the process conditions of the five-zone 12-column simulated moving bed are shown in Table 3.
The yield of saturated hydrocarbon is equal to the mass of saturated hydrocarbon in the product/mass of saturated hydrocarbon in the feed gasoline x 100%
Olefin yield-product olefin mass/olefin mass in feed gasoline x 100%
Saturated hydrocarbon content ═ saturated hydrocarbon mass of saturated hydrocarbon component/total mass of saturated hydrocarbon component × 100%
Olefin content ═ olefin mass of olefin component/total mass of olefin component × 100%
Aromatic hydrocarbon content ═ aromatic hydrocarbon content of aromatic hydrocarbon component/total mass of aromatic hydrocarbon component × 100%
Example 1
(1) The pretreatment adsorbent adopts MCM-41 molecular sieve, belongs to pure silicon molecular sieve, and has specific surface area of 900m2Per g, pore volume of 0.8cm3(ii)/g, average pore diameter 4.2 nm;
the complexing adsorbent is metal modified molecular sieve, and the modified metal is K, Mg and Co, wherein K is2O content of 0.5 wt%, MgO content of 0.5 wt%, Co3O4The content is 1.0 wt%; the carrier adopts MCM-22 molecular sieve, SiO2/Al2O3Is 30, Na2O content is less than or equal to 0.1 percent, and the specific surface area is 600m2Per g, pore volume of 0.5cm3Per g, the average pore diameter is 0.95nm, and the relative crystallinity is more than or equal to 95 percent; the D1 desorbent used was n-tridecene and the D0 desorbent used was long chain alkylbenzene.
(2) The mass flow rate ratio of the raw gasoline to the desorbent is 1:1.8 (the mass flow rates of the two desorbents are the same), and the volume flow rate ratio of the raw gasoline to the circulating volume is 1: 4;
(3) the composition analysis of the gasoline raw material is shown in No. 1 catalytic gasoline in Table 1, the process conditions of the pretreatment adsorption tower are shown in Table 2, the process conditions of the five-zone simulated moving bed adsorption separation are shown in Table 3, and the evaluation results are shown in Table 4.
Example 2
(1) The pretreatment adsorbent adopts MCM-48 molecular sieve and SiO2/Al2O3Is 580, Na2O content is less than or equal to 0.1 percent and specific surface area is 785m2Per g, pore volume of 0.65cm3(ii)/g, the average pore diameter is 2.5nm, and the relative crystallinity is more than or equal to 90%;
the complexing adsorbent is metal modified molecular sieve, and the modified metal is K, Ba and Ni, wherein K is2The O content is 0.5 wt%, the MgO content is 0.5 wt%, and the NiO content is 1.0 wt%; the carrier adopts MCM-22 molecular sieve, SiO2/Al2O3Is 30, Na2O content is less than or equal to 0.1 percent, and the specific surface area is 800m2Per g, pore volume of 0.34cm3(ii)/g, the average pore diameter is 0.62nm, and the relative crystallinity is more than or equal to 95%; the D1 desorbent used was n-tridecene and the D0 desorbent used was long chain alkylbenzene.
(2) The mass flow rate ratio of the raw material gasoline to the desorbent is 1:2 (the mass flow rates of the two desorbents are the same), and the volume flow rate ratio of the raw material gasoline to the circulating volume is 1: 4.2;
(3) the composition analysis of the gasoline raw material is shown in No. 1 catalytic gasoline in Table 1, the process conditions of the pretreatment adsorption tower are shown in Table 2, the process conditions of the five-zone simulated moving bed adsorption separation are shown in Table 3, and the evaluation results are shown in Table 4.
Example 3
(1) The pretreatment adsorbent adopts SBA-3 molecular sieve, belongs to pure silicon molecular sieve, Na2O content is less than or equal to 0.05 percent, and the specific surface area is 850m2Per g, pore volume of 0.7cm3(ii)/g, the average pore diameter is 3.2nm, and the relative crystallinity is more than or equal to 85%;
the complexing adsorbent is metal modified molecular sieve, and the modified metal is Cs, Mg and Cu, wherein Cs2The O content is 0.5 wt%, the MgO content is 0.5 wt%, and the CuO content is 1.0 wt%; the carrier adopts beta molecular sieve, SiO2/Al2O3Is 40, Na2O content is less than or equal to 0.05 percent, and the specific surface area is 680m2Per g, mean pore diameter0.6nm and relative crystallinity not less than 95%; the D1 desorbent used was n-tridecene and the D0 desorbent used was long chain alkylbenzene.
(2) The mass flow rate ratio of the raw gasoline to the desorbent is 1:2.5 (the mass flow rates of the two desorbents are the same), and the volume flow rate ratio of the raw gasoline to the circulating volume is 1: 4.5;
(3) the composition analysis of the gasoline raw material is shown in No. 1 catalytic gasoline in Table 1, the process conditions of the pretreatment adsorption tower are shown in Table 2, the process conditions of the five-zone simulated moving bed adsorption separation are shown in Table 3, and the evaluation results are shown in Table 4.
Example 4
(1) The pretreatment adsorbent adopts SBA-15-4.2 molecular sieve, belongs to pure silicon molecular sieve, and is Na2O content is less than or equal to 0.1 percent, relative crystallinity is more than or equal to 90 percent, and specific surface area is 600m2Per g, pore volume of 0.7cm3(ii)/g, average pore diameter 4.2 nm;
the complexing adsorbent is metal modified molecular sieve, and the modified metal is Cs, Ca and Zn, wherein Cs2The O content is 0.5 wt%, the CaO content is 0.5 wt%, and the ZnO content is 1.0 wt%; the carrier adopts 13X molecular sieve, SiO2/Al2O3Is 2.56, and the specific surface area is 500m2Per g, the average pore diameter is 2.8nm, and the relative crystallinity is more than or equal to 95 percent; the D1 desorbent used was n-tetradecene and the D0 desorbent used was reformed heavy aromatics.
(2) The mass flow rate ratio of the raw material gasoline to the desorbent is 1:2 (the mass flow rates of the two desorbents are the same), and the volume flow rate ratio of the raw material gasoline to the circulating volume is 1: 4;
(3) the composition analysis of the gasoline raw material is shown in No. 2 coker gasoline in Table 1, the process conditions of the pretreatment adsorption tower are shown in Table 2, the process conditions of the five-zone simulated moving bed adsorption separation process are shown in Table 3, and the evaluation results are shown in Table 4.
Example 5
(1) The pretreatment adsorbent was the same as in example 1;
the complexing adsorbent is metal modified molecular sieve, and the modified metal is Cs, Ba and Mo, wherein Cs20.5 wt% of O, 0.5 wt% of BaO, and MoO3The content is 1.0 wt%; the carrier adopts NaY molecular sieve and SiO2/Al2O32.56 to 5.2, specific surfaceProduct 640m2Per g, the average pore diameter is 2.1nm, and the relative crystallinity is more than or equal to 95 percent; the D1 desorbent used was n-tetradecene and the D0 desorbent used was reformed heavy aromatics.
(2) The mass flow rate ratio of the raw gasoline to the desorbent is 1:2.5 (the mass flow rates of the two desorbents are the same), and the volume flow rate ratio of the raw gasoline to the circulating volume is 1: 4.5;
(3) the composition analysis of the gasoline raw material is shown in No. 2 coker gasoline in Table 1, the process conditions of the pretreatment adsorption tower are shown in Table 2, the process conditions of the five-zone simulated moving bed adsorption separation process are shown in Table 3, and the evaluation results are shown in Table 4.
TABLE 1 gasoline feed composition
TABLE 2 adsorption separation Process conditions of the pretreatment adsorption column
TABLE 3 FIVE-ZONE 12-COLUMN SIMULATED MOVING BED ADSORPTION SEPARATION PROCESS CONDITIONS
TABLE 4 results of five-zone 12-column simulated moving bed evaluation
| Examples | 1 | 2 | 3 | 4 | 5 |
| Yield of saturated hydrocarbons,% | 42.79 | 43.05 | 44.37 | 53.25 | 55.62 |
| Saturated hydrocarbon component saturated hydrocarbon content% | 96.64 | 95.56 | 95.06 | 96.85 | 95.72 |
| Olefin yield% | 41.17 | 39.95 | 38.05 | 35.81 | 34.21 |
| Olefin component olefin content% | 90.49 | 92.85 | 93.17 | 92.05 | 92.65 |
| Aromatic component aromatic content% | 90.25 | 92.89 | 93.78 | 92.85 | 93.17 |
Claims (8)
1. A method for multi-component adsorptive separation of gasoline, comprising the steps of:
the method comprises the following steps that a gasoline raw material firstly enters a selective hydrogenation device to remove dialkene, sulfur and nitrogen and colloid impurities in the gasoline, the hydrogenated gasoline enters a pretreatment adsorption tower to be pretreated, strong polar substances in the hydrogenated gasoline are removed through a pretreatment adsorbent, the contents of alkaline nitrogen and oxides are not more than 1ppm after removal, and the pretreated gasoline enters a five-zone simulated moving bed adsorption device to be adsorbed and separated;
the selective hydrogenation device, the pretreatment adsorption tower and the five-zone simulated moving bed adsorption device are connected in series, the pretreatment adsorption tower is formed by connecting two towers in parallel, the two towers are opened and prepared, the five-zone simulated moving bed adsorption device is of a double-extraction-port structure and comprises an adsorption I zone, an isolation zone IV zone, a desorption 0 zone, a desorption III zone and a refining II zone, and each zone is at least distributed with 1 adsorption column; each adsorption column comprises six feeding and discharging pipelines and a periodic switching valve, and forms a closed loop through a circulating pump, wherein a desorption 0 area is arranged in front of the desorption III area and is used for desorbing the strongest adsorption component;
wherein, the adsorption I area adsorbs olefin and aromatic hydrocarbon in the gasoline through a complexing adsorbent to obtain a saturated hydrocarbon component, and the desorption III area desorbs the olefin through a desorbent D1 to obtain an olefin component; in the desorption 0 zone, the aromatic hydrocarbon is desorbed through a desorbent D0 to obtain an aromatic hydrocarbon component, and finally, the separation of saturated hydrocarbon, olefin and aromatic hydrocarbon in the gasoline is realized;
the pretreatment adsorbent is one of an MCM-41 molecular sieve, an MCM-48 molecular sieve, an SBA-3 molecular sieve and an SBA-15-4.2 molecular sieve;
the complexing adsorbent is a metal modified molecular sieve; the modified metal is one or more of K, Cs, Mg, Ca, Ba, Co, Ni, Cu, Zn and Mo, and the content is 0.1-10 wt%; the molecular sieve carrier is one of MCM-22, a beta molecular sieve, a 13X molecular sieve and a Y molecular sieve;
the desorbent D1 is one or more of n-tridecene, n-tetradecene and methylnaphthalene;
the desorbent D0 is one or two of reformed heavy aromatic hydrocarbon or long-chain alkylbenzene.
2. The method of claim 1, wherein the adsorbent bed temperature of the pretreatment adsorption tower is 30-150 ℃ and the mass space velocity is 0.1-3.0 h-1The adsorption pressure is 0.1-5.0 MPa.
3. The method as claimed in claim 1, wherein the temperature of each adsorption column of the five-zone simulated moving bed adsorption device is 40-150 ℃, the adsorption pressure is 0.5-2.0 MPa, and the switching time is 100-2000 s.
4. The method according to claim 1, wherein the mass flow rate ratio of the gasoline raw material to the desorbent of the five-zone simulated moving bed adsorption device is 1: 1-1: 4, wherein the mass flow rates of the desorbent D1 and the desorbent D0 are the same, and the volume flow rate ratio of the gasoline raw material to the circulating amount is 1: 1-1: 5.
5. The method of claim 2, wherein the adsorbent bed temperature of the pretreatment adsorption tower is 30-70 ℃, and the mass space velocity is 0.5-1.5 h-1The adsorption pressure is 0.3-0.5 MPa.
6. The method as claimed in claim 3, wherein the temperature of each adsorption column of the five-zone simulated moving bed adsorption device is 50-90 ℃, the adsorption pressure is 0.5-1.5 MPa, and the switching time is 150-700 s.
7. The method according to claim 4, wherein the mass flow rate ratio of the gasoline raw material to the desorbent of the five-zone simulated moving bed adsorption device is 1: 1.8-1: 2.5, wherein the mass flow rates of the desorbent D1 and the desorbent D0 are the same, and the volume flow rate ratio of the gasoline raw material to the circulating amount is 1: 4-1: 4.5.
8. The method of claim 1, wherein the pretreatment adsorbent has a saturation adsorption capacity of 10% to 40%; the saturated adsorption capacity of the complexing adsorbent is 5-20%.
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| CN113372953A (en) * | 2021-06-30 | 2021-09-10 | 中海油天津化工研究设计院有限公司 | Method for adsorbing and separating saturated hydrocarbon and unsaturated hydrocarbon by FCC (fluid catalytic cracking) gasoline |
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