WO2023217303A1 - Method for separating alpha-olefin from fischer-tropsch light distillate by using adsorption and distillation to couple olefin - Google Patents

Method for separating alpha-olefin from fischer-tropsch light distillate by using adsorption and distillation to couple olefin Download PDF

Info

Publication number
WO2023217303A1
WO2023217303A1 PCT/CN2023/106403 CN2023106403W WO2023217303A1 WO 2023217303 A1 WO2023217303 A1 WO 2023217303A1 CN 2023106403 W CN2023106403 W CN 2023106403W WO 2023217303 A1 WO2023217303 A1 WO 2023217303A1
Authority
WO
WIPO (PCT)
Prior art keywords
adsorption
olefin
distillation
tower
fischer
Prior art date
Application number
PCT/CN2023/106403
Other languages
French (fr)
Chinese (zh)
Inventor
于海斌
胡智中
李犇
汲银平
范景新
刘凯隆
汪洋
赵云
赵闯
马明超
李佳
刘洋
王克富
张博宇
Original Assignee
中海油天津化工研究设计院有限公司
中海油能源发展股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中海油天津化工研究设计院有限公司, 中海油能源发展股份有限公司 filed Critical 中海油天津化工研究设计院有限公司
Publication of WO2023217303A1 publication Critical patent/WO2023217303A1/en

Links

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
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
    • 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
    • C10G2300/1022—Fischer-Tropsch products
    • 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
    • C10G2400/22—Higher olefins

Definitions

  • the invention relates to the field of olefin preparation, and specifically relates to a separation method for separating ⁇ -olefins from Fischer-Tropsch synthesis light distillate oil through adsorption distillation coupled separation technology.
  • Alpha-olefin refers to a monoolefin with a double bond at the end of the molecular chain. It is an important raw material in the petrochemical industry and can be used as comonomers, surfactant synthesis intermediates, plasticizer alcohols, synthetic lubricants and oil additives, etc. Wide range of applications. At present, ⁇ -olefins are mainly produced through ethylene oligomerization. The process is simple, but it has many by-products, high energy consumption and poor economic efficiency. There are a large amount of ⁇ -olefins in the Fischer-Tropsch synthetic light distillate.
  • Fischer-Tropsch oil is mostly hydrotreated to produce oil or directly used as primary chemical materials, and the olefin components are utilized at low values. Therefore, the present invention is proposed to separate ⁇ -olefins in Fischer-Tropsch oil through adsorption and distillation to produce high value-added olefin products, thereby improving the economic benefits of the enterprise.
  • Industrial Fischer-Tropsch synthetic oils have complex components, including ⁇ -olefins, n-alkanes, and oxygen-containing compounds such as alcohols, ketones, aldehydes, and esters. Oxygen-containing compounds are toxic substances in the adsorption distillation process. Therefore, the present invention adds a deoxygenation process before the adsorption distillation step to completely remove oxygen-containing compounds in the Fischer-Tropsch oil. At the same time, the Fischer-Tropsch oil components have an azeotrope, which makes it difficult to achieve accurate separation by conventional distillation and requires high energy consumption.
  • This invention uses the principle of adsorption coupled distillation to combine high-boiling point olefin components and low-boiling point alkane components in the same bed. The flow out is followed by rectification to achieve accurate and efficient separation of alkenes.
  • the technology of the present invention is highly advanced and the separated olefins have high purity and high yield.
  • Patent CN111100683A describes a method for separating long-chain alkanes and alkenes in Fischer-Tropsch synthetic oil.
  • the method adsorbs oxygenated compounds through a pre-adsorption tower, and then selectively separates ⁇ -olefins and alkanes through a simulated moving bed system to obtain ⁇ -rich ⁇ -olefins.
  • -Olefin components and alkane-rich components are fed separately to the distillation unit. After distillation and separation, the desorbent is recycled and reused to obtain ⁇ -olefins and alkanes.
  • Patent CN106753546A describes a method for refining Fischer-Tropsch synthetic light distillate. The method first removes metal ion impurities and some oxygen-containing compounds through a solid-phase adsorption unit; and then sequentially removes the remaining oxygen-containing compounds in the Fischer-Tropsch synthesis light distillate through extraction and refining, separation and extraction agent refining, and a recovery unit to achieve Refining Fischer-Tropsch synthetic light distillate.
  • Patent CN109652111A describes a device and method for separating olefins from Fischer-Tropsch synthetic oil.
  • the method uses an extractive distillation partition column device to separate alkanes, olefins and oxygenated compounds in Fischer-Tropsch synthetic oil at one time.
  • the extraction agent N,N-dimethylformamide is used. After separation in the partition tower, the extractant and oxygenated compounds are mixed and entered into the solvent recovery tower for distillation and separation, and the extractant is recovered and reused.
  • the present invention provides a method for Fischer-Tropsch synthesis of light distillate oil coupled with adsorption distillation to separate ⁇ -olefins.
  • This method does not require the use of desorbents in the olefin separation section, simplifies the process flow, and reduces industrialization costs. , which can achieve efficient separation of ⁇ -olefins in Fischer-Tropsch synthesis light distillate oil.
  • the present invention is a method for coupling olefin adsorption distillation of Fischer-Tropsch light distillate oil to separate ⁇ -olefins, including one or more adsorption distillation towers, and the filler inside the adsorption distillation tower is an adsorption filler with olefin adsorption capacity;
  • the adsorption filler adopts one or more of molecular sieve, modified molecular sieve, silica, modified silica, alumina, and modified alumina; the operating temperature at the top of the tower is 50-180°C, and at the bottom of the tower is 100°C-200 °C, the operating pressure at the top of the tower is 0.01-0.5MPa, and the number of theoretical plates is 5-80. It performs continuous or batch Fischer-Tropsch synthesis of light distillate oil separation.
  • the top of the tower is a saturated hydrocarbon product with low olefin content, and the tower still is of high purity. of ⁇ -olef
  • the adsorption packing inside the adsorption distillation tower is a structured packing, preferably one or more of Raschig ring, ⁇ ring, and Pall ring packing.
  • the adsorption distillation tower is preferably an adsorption distillation tower containing multiple side lines to take out products from different fractions, preferably two side lines are taken out.
  • the material of the adsorption filler is preferably one or more of molecular sieves with acid centers, silica, and alumina.
  • the material of the adsorption filler preferably has an acid center desorption temperature of 120-300°C in NH 3 -TPD analysis, preferably 200-250°C.
  • the product obtained from the adsorption distillation tower enters the olefin refining unit.
  • the olefin refining unit is composed of multiple olefin refining distillation towers.
  • the olefin product is obtained at the top of the tower and the alkane product is obtained from the tower still.
  • the top temperature of the adsorption distillation tower is 80-150°C
  • the bottom temperature is 180-200°C
  • the top pressure is 0.01-0.2MPa
  • the number of theoretical plates is 40-60.
  • the ⁇ -olefin product purity is ⁇ 99%, preferably ⁇ 99.2%, and the ⁇ -olefin yield is ⁇ 85%, preferably ⁇ 90%.
  • the beneficial effects of the present invention are reflected in: coupling the adsorption and distillation processes, eliminating the need for the use of desorbents in the olefin separation section, simplifying the process flow, reducing industrialization costs, and realizing Fischer-Tropsch synthesis of ⁇ in light distillate oils.
  • - Efficient separation of olefins, and the adsorbent packing in the present invention has a long service life, low distillation energy consumption, and high olefin separation efficiency, which provides a more economical, simple and feasible method for deep processing of Fischer-Tropsch synthetic oil ⁇ -olefins and other applications. Methods.
  • Figure 1 is a schematic process flow diagram of a Fischer-Tropsch light distillate adsorption distillation coupled olefin separation method of the present invention; in the figure: 1 is a simulated moving bed; 2 is an extract liquid distillation tower; 3 is a raffinate distillation tower; 4 is an adsorption distillation tower; 5 is a distillation tower for a mixture of C4 to C7 alkanes and ene; 6 is a distillation tower for a mixture of C6 to C10 alkanes and ene.
  • Figure 2 is a process flow of an adsorption distillation tower in a Fischer-Tropsch light distillate adsorption distillation coupled olefin separation method of the present invention; in the figure: 401 is the proprietary packing of the adsorption distillation tower.
  • the invention is a separation method for separating ⁇ -olefins from Fischer-Tropsch synthesis light distillate oil.
  • the method completes the Fischer-Tropsch synthesis light distillate oil through four units of distillation cutting, adsorption deoxygenation, adsorption distillation and deep distillation. Separation of ⁇ -olefins with different carbon numbers.
  • Fischer-Tropsch synthetic light distillate is used as raw material, which is composed of C4-C10 alkanes, ⁇ -olefins, other olefins and oxygen-containing compounds.
  • the Fischer-Tropsch synthesis light distillate oil needs to be distilled and cut first to obtain the C4-C10 fraction, whose olefin mass fraction cannot be less than 10%.
  • the preferred mass fraction is 30% to 70%.
  • Fischer-Tropsch synthetic light oil generally contains 1% to 10% oxygenated compounds.
  • the polarity of oxygenated compounds is much greater than that of alkanes and olefins, and is preferentially adsorbed in the adsorption distillation tower, affecting the separation performance of the adsorption distillation tower.
  • the oxygen-containing compounds are mainly alcohol, which can be recycled after simulated moving bed adsorption separation. Therefore, the C4-C10 fraction needs to be sent to the adsorption deoxygenation unit to deeply remove oxygenated compounds to ensure that the oxygenated compounds in the oil after deoxidation are ⁇ 10 ⁇ g/g.
  • the material from which oxygen-containing organic compounds are removed is sent to an adsorption distillation unit to selectively separate alkene components with different carbon numbers.
  • a total of four streams are extracted from the adsorption distillation tower, the C4-C5 alkane-rich component is extracted from the top of the tower, and the C8-C10 ⁇ -olefin-rich component is extracted from the tower kettle, wherein the ⁇ -olefin purity is ⁇ 99%, preferably ⁇ 99.5% .
  • Two mixtures of alkanes and olefins with different carbon numbers are extracted and sent to the distillation and refining unit to obtain C4-C5 ⁇ -olefin-rich components and C6-C7 ⁇ -olefin-rich components.
  • the purity of ⁇ -olefins is ⁇ 99%. Preferably ⁇ 99.5%.
  • the alkane-rich components obtained after distillation can be used to produce fuel oil, lubricating oil or special solvent oil.
  • a method for separating ⁇ -olefins by adsorption distillation of Fischer-Tropsch light distillate coupled with olefins includes the following steps:
  • the Fischer-Tropsch synthetic oil in the C4-C10 fraction section passes through a deoxygenated simulated moving bed to deeply remove oxygenated compounds from the Fischer-Tropsch synthetic oil in the C4-C10 fraction section to provide qualified raw materials for olefin separation;
  • adsorption distillation towers saturated hydrocarbon products with low olefin content are obtained from the top of the tower, and high-purity ⁇ -olefin products are obtained from the tower bottom;
  • the packing inside the adsorption distillation tower is an adsorption packing with olefin adsorption capacity;
  • the adsorption filler is selected from one or more of molecular sieves, modified molecular sieves, silica, modified silica, alumina and modified alumina; the top temperature of the adsorption distillation tower is 50-180 °C, the bottom temperature of the tower is 100°C-200°C, the top pressure is 0.01-0.5MPa, and the number of theoretical plates is 5-80.
  • the number of adsorption distillation towers is 1 to 4, preferably 1 to 2.
  • the purity requirements are higher.
  • it is greater than 99.5% the number of plates in the adsorption distillation tower is higher.
  • more than two distillation towers are needed to meet the separation needs.
  • one adsorption distillation tower can meet the requirements.
  • the adsorption filler is a structured filler.
  • the adsorption distillation tower is an adsorption distillation tower containing multiple side lines to take out products from different fractions.
  • the adsorption filler is one or more of molecular sieves with acid centers, silica with acid centers, and alumina with acid centers.
  • the acid center desorption temperature of the adsorption filler in NH 3 -TPD analysis is 120-300°C.
  • products from different fractions obtained from the adsorption distillation tower enter an olefin refining unit.
  • the olefin refining unit is composed of multiple olefin refining distillation towers. Olefin products are obtained at the top of the tower, and alkanes are obtained from the tower stills. .
  • the top temperature of the adsorption distillation tower is 80-150°C
  • the bottom temperature is 180-200°C
  • the top pressure is 0.01-0.2MPa
  • the number of theoretical plates is 40-60.
  • the ⁇ -olefin product has a purity of ⁇ 99% and an ⁇ -olefin yield of ⁇ 85%.
  • the morphology type of the adsorption filler is selected from one or more of Raschig ring, ⁇ ring, and Pall ring fillers.
  • the acid center desorption temperature of the adsorption filler in NH 3 -TPD analysis is 200 to 250°C.
  • the process flow of ⁇ -olefin separation from C4-C10 Fischer-Tropsch light distillate is shown in Figure 1.
  • the Fischer-Tropsch light distillate raw material is passed into the simulated moving bed 1 in the adsorption deoxygenation unit for adsorption separation.
  • the oxygen-depleted group The raffinate is sent to the distillation tower 3, and the circulating desorbent and C4-C10 alkane are obtained after distillation and separation.
  • the concentration of oxygenated compounds of the olefin mixture and the C4-C10 alkane-olefin mixture is reduced to less than 10 ⁇ g/g and sent to the adsorption distillation tower 4.
  • Figure 2 shows the process flow of the adsorption distillation tower, in which 401 is the adsorption distillation tower.
  • the proprietary filler and circulating desorbent are sent to the simulated moving bed 1 for recycling.
  • the oxygen-rich components are sent to the extracted liquid distillation tower 2, and the circulating desorbent and oxides are obtained through distillation and separation.
  • the oxides are directly sent out for subsequent processing and utilization, and the circulating desorbent is sent to the simulated moving bed 1 for recycling.
  • the C4-C10 alkanes and olefins mixture is pressurized by a pump and sent to the adsorption distillation tower 4.
  • a C4-C5 alkane-rich component is obtained from the top of the tower, and a C8-C10 ⁇ -olefin-rich component is obtained from the tower kettle.
  • the side line 1 The C6-C7 alkane and C4-C5 olefin mixture is extracted and enters the C4 ⁇ C7 alkene mixture distillation tower 5 for separation.
  • the side line 2 extracts the C8-C10 alkane and C6-C7 olefin mixture and enters the C6 ⁇ C10 alkene mixture distillation tower. 6 separation.
  • C4-C5 and C6-C7 high-purity ⁇ -olefin components are obtained, as well as C6-C7 and C8-C10 rich alkane components.
  • the adsorption deoxygenation process uses a simulated moving bed, which is composed of 12 columns connected in series. The columns are filled with deoxygenation adsorbent, and the adsorbent is silica gel material.
  • the 12th column and the 1st column are connected through a circulation pump to form a material circulation. Materials can be introduced or discharged at the joints of each column.
  • the desorbent is a mixture of 1-decanol and n-tetradecane.
  • C4-C10 light distillate enters the simulated moving bed for adsorption and deoxygenation.
  • the operating temperature is 80°C.
  • the ratio of desorbent to raw material is 1.5.
  • the position of the inlet and outlet is switched every 800 seconds, that is, along the raw material inlet to the raffinate. In the direction of the outlet, push each inlet and outlet by one pillar.
  • the extract liquid and raffinate liquid enter the extract liquid rectification tower and raffinate rectification tower respectively for desorbent recycling.
  • the liquid extraction tower is a packed tower, the packing is Pall ring, the total number of trays is 30, and the feed
  • the position is on the 15th tray, the operating pressure is 1atm, the mass reflux ratio is 0.9;
  • the raffinate tower is also a packed tower, with a total number of trays of 70, the feed position is on the 30th tray, the operating pressure is 1atm, the mass Reflow ratio 1.8.
  • the composition of the product separated through the adsorption deoxygenation process is shown in Table 1.
  • the content of oxygenated compounds in C4-C10 alkanes and olefins is less than 10 ⁇ g/g, and the yield reaches 99%.
  • C4-C10 alkanes enter the adsorption distillation tower for further separation.
  • the adsorption distillation tower is filled with adsorption packing to ensure full separation of light and heavy components.
  • the adsorption packing is theta ring type and uses 13X molecular sieve. Its physical and chemical properties are as shown in the table 2 shown.
  • the total number of plates in the adsorption distillation tower is 85, including 35 plates in the adsorption section, 20 plates in the rectification section, and 25 plates in the stripping section.
  • the C4-C10 alkene olefin raw material enters the 35th tray (middle of the adsorption section).
  • the operating pressure at the top of the tower is 1 atm, the mass reflux ratio is 2.5, the top temperature is 45°C, and the tower still temperature is 200°C.
  • a stream is extracted from the side line at the 12th tray and named side line 1. It is mainly composed of a mixture of C6-C7 alkanes and C4-C5 olefins.
  • Another stream is extracted from the side line at the 72nd tray and is named side line 2.
  • the main composition is a mixture of C8-C10 alkanes and C6-C7 olefins.
  • Table 3 The purity of C8-C10 ⁇ -olefins in the column reactor reaches over 99.8wt.%, and the yield reaches 95%.
  • the two streams extracted from the side line directly enter the distillation and refining unit for further processing.
  • the distillation and refining unit uses two distillation towers to process the two streams of side line 1 and side line 2 respectively.
  • the side line 1 stream enters the C4 ⁇ C7 alkene mixture distillation tower 5, which uses a packed tower with a ⁇ ring packing type.
  • the C4-C7 alkene mixture distillation tower 5 has a total number of 45 plates, the operating pressure at the top of the tower is 1 atm, the feed position is the 20th plate, and the mass reflux ratio is 1.5.
  • the side stream 2 flows into the C6-C10 alkane-ene mixture distillation tower 6, which adopts a packed tower, and the packing type is theta ring.
  • C6 ⁇ C10 Alkane Mixture C6 ⁇ C10 Alkene Mixture Distillation Tower 6 has a total number of plates of 55, the operating pressure is 1 atm, the feed position is the 30th plate, and the mass reflux ratio is 2.3. After distillation and purification, the purity of the product stream components is shown in Table 4 and Table 5. The purity of the C4-C5 ⁇ -olefin product can reach 99.8wt.%, and the yield reaches 94%. The purity of the C6-C7 ⁇ -olefin product can reach 99.8wt.%, and the yield reaches 92%.
  • the deoxidation section of this embodiment is the same as that of Embodiment 1.
  • the physical and chemical properties of silicon oxide used as adsorption filler are shown in Table 6, and the filler type is Pall ring.
  • the total number of plates in the adsorption distillation tower is 90, including 40 plates in the adsorption section, 23 plates in the rectification section, and 26 plates in the stripping section.
  • the C4-C10 alkane olefin raw material enters the 40th tray (middle of the adsorption section).
  • the operating pressure at the top of the tower is 1 atm, the mass reflux ratio is 2.5, the top temperature is 45°C, and the tower still temperature is 200°C.
  • a stream is produced from the side line at the 14th tray and is named side line 1.
  • the distillation and refining unit uses two distillation towers to process the two streams of side line 1 and side line 2 respectively.
  • the side line 1 stream enters the C4 ⁇ C7 alkene mixture distillation tower 5, which uses a packed tower with a ⁇ ring packing type.
  • the C4-C7 alkene mixture distillation tower 5 has a total number of 45 plates, the operating pressure at the top of the tower is 1 atm, the feed position is the 20th plate, and the mass reflux ratio is 1.5.
  • the side stream 2 flows into the C6-C10 alkane-ene mixture distillation tower 6, which adopts a packed tower, and the packing type is theta ring.
  • Distillation column C6 ⁇ C10 alkene mixture rectification column 6 has a total number of plates of 55, the operating pressure is 1 atm, the feed position is the 30th plate, and the mass reflux ratio is 2.3.
  • the purity of the product stream components is shown in Table 8 and Table 9.
  • the purity of C4-C5 ⁇ -olefin products can reach 99.7wt.%, and the yield can reach 95%.
  • the purity of C6-C7 ⁇ -olefin products can reach 99.7wt.%, and the yield can reach 95%. Reaching 99.8wt.%, the yield reached 93%.
  • the deoxidation section of this embodiment is the same as that of Embodiment 1.
  • the adsorption filler is alumina, its physical and chemical properties are shown in Table 10, and the filler type is Raschig ring.
  • the total number of plates in the adsorption distillation tower is 95, including 43 plates in the adsorption section, 26 plates in the rectification section, and 30 plates in the stripping section.
  • the C4-C10 alkene olefin raw material enters the 43rd tray (middle of the adsorption section).
  • the operating pressure at the top of the tower is 1 atm, the mass reflux ratio is 2.6, the top temperature is 45°C, and the tower still temperature is 200°C.
  • side line 1 which is mainly composed of a mixture of C6-C7 alkanes and C4-C5 olefins.
  • Another stream is taken out from the side line at the 76th tray and is named side line 2, which is mainly composed of C8-C10 alkane and C4-C5 olefins. C6-C7 olefin mixture.
  • side line 2 which is mainly composed of C8-C10 alkane and C4-C5 olefins.
  • C6-C7 olefin mixture After separation by adsorption distillation, the purity of each product is shown in Table 11. The purity of C8-C10 ⁇ -olefins in the column reactor reaches over 99.8wt.%, and the yield reaches 95%.
  • the two streams extracted from the side line directly enter the distillation and refining unit for further processing.
  • the distillation and refining unit uses two distillation towers to process the two streams of side line 1 and side line 2 respectively.
  • the side line 1 stream enters the C4 ⁇ C7 alkene mixture distillation tower 5, which uses a packed tower with a ⁇ ring packing type.
  • the C4-C7 alkene mixture distillation tower 5 has a total number of 45 plates, the operating pressure at the top of the tower is 1 atm, the feed position is the 20th plate, and the mass reflux ratio is 1.5.
  • the side stream 2 flows into the C6 ⁇ C10 alkene mixture.
  • Distillation column 6 adopts a packed tower, and the packing type is ⁇ ring.
  • the C6-C10 alkene mixture distillation column 6 has a total number of plates of 55, the operating pressure is 1 atm, the feed position is the 30th plate, and the mass reflux ratio is 2.3. After distillation and purification, the purity of the product stream components is shown in Table 12 and Table 13. The purity of the C4-C5 ⁇ -olefin product can reach 99.5wt.%, and the yield reaches 94%. The purity of the C6-C7 ⁇ -olefin product can reach 99.6wt.%, and the yield reaches 94%.
  • the adsorption deoxygenation process uses the simulated moving bed in Example 1, which is composed of 12 columns connected in series.
  • the container is filled with deoxidation adsorbent, and the adsorbent is silica gel material.
  • the C4-C10 light distillate enters the simulated moving bed for adsorption and deoxygenation.
  • the operating temperature is 100°C.
  • the ratio of desorbent to raw material is 2.5.
  • the position of the inlet and outlet is switched every 360 seconds.
  • the desorbent is 1-decane. A mixture of alcohol and n-tetradecane.
  • the raffinate distillation tower is a packed tower, the packing is Pall ring, the total number of trays is 40, the feed position is on the 20th tray, the operating pressure is 1 atm, and the mass reflux ratio is 1.1; the raffinate distillation tower is also It is a packed tower with a total number of trays of 80, the feed position is the 40th tray, the operating pressure is 1 atm, and the mass reflux ratio is 2.2.
  • the composition of the product separated through the adsorption deoxygenation process is shown in Table 14.
  • the content of oxygenated compounds in C4-C10 alkanes and olefins is less than 10 ⁇ g/g, and the yield reaches 97%.
  • C4-C10 alkanes enter the adsorption distillation tower for further separation.
  • the adsorption distillation tower is filled with adsorption packing to ensure full separation of light and heavy components.
  • the adsorption packing is Pall ring type and Y molecular sieve is used. Its physical and chemical properties are as shown in the table 15 shown.
  • the total number of plates in the adsorption distillation tower is 95, including 45 plates in the adsorption section, 20 plates in the rectification section, and 30 plates in the stripping section.
  • the C4-C10 alkene olefin raw material enters the 45th tray (middle of the adsorption section).
  • the operating pressure at the top of the tower is 1 atm, the mass reflux ratio is 3, the temperature at the top of the tower is 48°C, and the temperature of the tower still is 205°C.
  • a stream is produced from the side line at the 14th tray and is named side line 1. It is mainly composed of a mixture of C6-C7 alkanes and C4-C5 olefins.
  • Another stream is produced from the side line at the 80th tray and is named side line 2.
  • the main composition is a mixture of C8-C10 alkanes and C6-C7 olefins. After separation by adsorption distillation, the purity of each product is shown in Table 16.
  • the purity of C8-C10 ⁇ -olefin in the column reactor reaches 99.7wt.%, and the yield reaches 95%.
  • the two streams of logistics extracted from the side line are straight It then enters the distillation and refining unit for further processing.
  • the distillation and refining unit uses two distillation towers to process the two streams of side line 1 and side line 2 respectively.
  • the side line 1 stream enters the C4 ⁇ C7 alkene mixture distillation tower 5, which uses a packed tower with a ⁇ ring packing type.
  • the C4-C7 alkene mixture distillation tower 5 has a total number of plates of 35, the operating pressure at the top of the tower is 1 atm, the feed position is the 15th plate, and the mass reflux ratio is 1.7.
  • the side stream 2 flows into the C6-C10 alkane-ene mixture distillation tower 6, which adopts a packed tower, and the packing type is theta ring.
  • the C6-C10 alkene mixture distillation tower 6 has a total number of plates of 60, the operating pressure is 1 atm, the feed position is the 35th plate, and the mass reflux ratio is 2.0. After distillation and purification, the purity of the product stream components is shown in Table 17 and Table 18. The purity of the C4-C5 ⁇ -olefin product reaches 99.6wt.%, and the yield reaches 92%; the purity of the C6-C7 ⁇ -olefin product reaches 99.6wt.%, and the yield reaches 93%.

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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method for separating alpha-olefin from a Fischer-Tropsch light distillate by using adsorption and distillation to couple the olefin. The Fischer-Tropsch synthesized light distillate is cut to obtain a C4-C10 fraction section by means of fraction cutting. then, by means of a simulated moving bed, fixed bed or other adsorption separation processes, deep removal of organic oxygen-containing compound of the C4-C10 fraction section carried out. last, by means of an adsorption rectification technique, the alkane and olefin in the C4-C10 fraction after deoxidation are accurately separated, so as to obtain a high-purity alpha-olefin. The adsorption and distillation technique combines the advantages of distillation and adsorption separation, so as to have a synergistic adsorption effect in the distillation process, resulting in the separation of similar fractions of alkane and olefin, and then a high-purity target product alpha-olefin is obtained by means of deep distillation. The present method achieves accurate separation of similar fraction products, improves the separation purity of the alpha-olefin, and improves the product added value.

Description

一种费托轻馏分油吸附精馏耦合烯烃分离α-烯烃的方法A method for separating α-olefins from Fischer-Tropsch light distillate oil by adsorption distillation coupled with olefins
相关申请的交叉引用Cross-references to related applications
本申请要求2022年05月09日提交的中国专利申请202210479559.1的权益，该申请的内容通过引用被合并于本文。This application claims the rights and interests of Chinese patent application 202210479559.1 submitted on May 9, 2022. The contents of this application are incorporated herein by reference.
技术领域Technical field
本发明涉及烯烃制备领域，具体涉及一种从费托合成轻质馏分油中通过吸附精馏耦合分离技术分离α-烯烃的分离方法。The invention relates to the field of olefin preparation, and specifically relates to a separation method for separating α-olefins from Fischer-Tropsch synthesis light distillate oil through adsorption distillation coupled separation technology.
背景技术Background technique
α-烯烃是指双键在分子链端部的单烯烃，是石油化工的重要原料，可作为共聚单体、表面活性剂合成中间体、增塑剂醇、合成润滑油和油品添加剂等，应用广泛。目前，α-烯烃主要通过乙烯齐聚反应生产，工艺流程简单，但副产物多，能耗较高，经济性差。费托合成轻质馏分油中存在大量α-烯烃，目前费托油多采用加氢处理产油或直接做初级化工料，烯烃组分低值利用。因此，提出本发明，将费托油中α-烯烃经吸附精馏分离，作高附加值烯烃产品，提高企业经济效益。Alpha-olefin refers to a monoolefin with a double bond at the end of the molecular chain. It is an important raw material in the petrochemical industry and can be used as comonomers, surfactant synthesis intermediates, plasticizer alcohols, synthetic lubricants and oil additives, etc. Wide range of applications. At present, α-olefins are mainly produced through ethylene oligomerization. The process is simple, but it has many by-products, high energy consumption and poor economic efficiency. There are a large amount of α-olefins in the Fischer-Tropsch synthetic light distillate. At present, Fischer-Tropsch oil is mostly hydrotreated to produce oil or directly used as primary chemical materials, and the olefin components are utilized at low values. Therefore, the present invention is proposed to separate α-olefins in Fischer-Tropsch oil through adsorption and distillation to produce high value-added olefin products, thereby improving the economic benefits of the enterprise.
工业费托合成油品中成分复杂，包括了α-烯烃、正构烷烃以及醇、酮、醛和酯等含氧化合物。含氧化合物是吸附精馏工艺中毒性物质，因此，本发明在吸附精馏步骤前增设脱氧工艺，完全除去费托油中含氧化合物。同时，费托油组分存在共沸，常规精馏难以实现精确分离、且能耗较高，本发明利用吸附耦合精馏原理，将高沸点烯烃组分与低沸点烷烃组分在同一床层流出，后续经过精馏实现烷烯精确、高效分离，本发明技术先进性强，分离烯烃纯度高、收率高。Industrial Fischer-Tropsch synthetic oils have complex components, including α-olefins, n-alkanes, and oxygen-containing compounds such as alcohols, ketones, aldehydes, and esters. Oxygen-containing compounds are toxic substances in the adsorption distillation process. Therefore, the present invention adds a deoxygenation process before the adsorption distillation step to completely remove oxygen-containing compounds in the Fischer-Tropsch oil. At the same time, the Fischer-Tropsch oil components have an azeotrope, which makes it difficult to achieve accurate separation by conventional distillation and requires high energy consumption. This invention uses the principle of adsorption coupled distillation to combine high-boiling point olefin components and low-boiling point alkane components in the same bed. The flow out is followed by rectification to achieve accurate and efficient separation of alkenes. The technology of the present invention is highly advanced and the separated olefins have high purity and high yield.
专利CN111100683A描述了一种费托合成油中长链烷烃-烯烃的分离方法，所述方法通过预吸附塔吸附含氧化合物，后通过模拟移动床系统选择性分离α-烯烃和烷烃，得到富α-烯烃组分和富烷烃组分分别送入精馏单元。 经精馏分离，解吸剂循环回收利用，得到α-烯烃和烷烃产品。Patent CN111100683A describes a method for separating long-chain alkanes and alkenes in Fischer-Tropsch synthetic oil. The method adsorbs oxygenated compounds through a pre-adsorption tower, and then selectively separates α-olefins and alkanes through a simulated moving bed system to obtain α-rich α-olefins. -Olefin components and alkane-rich components are fed separately to the distillation unit. After distillation and separation, the desorbent is recycled and reused to obtain α-olefins and alkanes.
专利CN106753546A描述了一种费托合成轻质馏分油精制的方法。所述方法首先通过固相吸附单元脱除金属离子杂质和部分含氧化合物；而后依次经过萃取精制、分离和萃取剂精制、回收单元脱除费托合成轻质馏分油中剩余含氧化合物，实现了费托合成轻质馏分油的精制。Patent CN106753546A describes a method for refining Fischer-Tropsch synthetic light distillate. The method first removes metal ion impurities and some oxygen-containing compounds through a solid-phase adsorption unit; and then sequentially removes the remaining oxygen-containing compounds in the Fischer-Tropsch synthesis light distillate through extraction and refining, separation and extraction agent refining, and a recovery unit to achieve Refining Fischer-Tropsch synthetic light distillate.
专利CN109652111A描述了一种费托合成油中分离烯烃的装置和方法，所述方法通过萃取精馏隔壁塔的装置，一次性将费托合成油中的烷烃、烯烃和含氧化合物分开，萃取剂采用的是N,N-二甲基甲酰胺。经过隔壁塔分离后萃取剂和含氧化合物混合进入溶剂回收塔进行精馏分离，得到萃取剂回收再利用。Patent CN109652111A describes a device and method for separating olefins from Fischer-Tropsch synthetic oil. The method uses an extractive distillation partition column device to separate alkanes, olefins and oxygenated compounds in Fischer-Tropsch synthetic oil at one time. The extraction agent N,N-dimethylformamide is used. After separation in the partition tower, the extractant and oxygenated compounds are mixed and entered into the solvent recovery tower for distillation and separation, and the extractant is recovered and reused.
可见，目前分离烯烃的现有技术存在工艺流程长，工业化成本较高的问题。It can be seen that the current existing technology for separating olefins has the problems of long process flow and high industrialization cost.
发明内容Contents of the invention
为解决现有技术的问题，本发明提供了一种费托合成轻质馏分油吸附精馏耦合分离α-烯烃的方法，该方法烯烃分离工段无需解吸剂的使用，简化工艺流程，降低工业化成本，可实现费托合成轻馏分油中α-烯烃的高效分离。In order to solve the problems of the prior art, the present invention provides a method for Fischer-Tropsch synthesis of light distillate oil coupled with adsorption distillation to separate α-olefins. This method does not require the use of desorbents in the olefin separation section, simplifies the process flow, and reduces industrialization costs. , which can achieve efficient separation of α-olefins in Fischer-Tropsch synthesis light distillate oil.
本发明一种费托轻馏分油吸附精馏耦合烯烃分离α-烯烃的方法，包括一个或多个吸附精馏塔，在吸附精馏塔内部的填料为具有烯烃吸附能力的吸附填料；所述的吸附填料采用分子筛、改性分子筛、氧化硅、改性氧化硅、氧化铝、改性氧化铝中的一种或几种；操作温度塔顶为50-180℃，塔底为100℃-200℃，操作压力塔顶为0.01-0.5MPa，理论板数为5-80块，进行连续或间歇费托合成轻质馏分油分离，塔顶为低烯烃含量的饱和烃产品，塔釜为高纯度的α-烯烃产品。The present invention is a method for coupling olefin adsorption distillation of Fischer-Tropsch light distillate oil to separate α-olefins, including one or more adsorption distillation towers, and the filler inside the adsorption distillation tower is an adsorption filler with olefin adsorption capacity; The adsorption filler adopts one or more of molecular sieve, modified molecular sieve, silica, modified silica, alumina, and modified alumina; the operating temperature at the top of the tower is 50-180℃, and at the bottom of the tower is 100℃-200 ℃, the operating pressure at the top of the tower is 0.01-0.5MPa, and the number of theoretical plates is 5-80. It performs continuous or batch Fischer-Tropsch synthesis of light distillate oil separation. The top of the tower is a saturated hydrocarbon product with low olefin content, and the tower still is of high purity. of α-olefin products.
优选地，所述吸附精馏塔内部的吸附填料为规整填料，优选拉西环、θ环、鲍尔环填料中的一种或多种。 Preferably, the adsorption packing inside the adsorption distillation tower is a structured packing, preferably one or more of Raschig ring, θ ring, and Pall ring packing.
优选地，所述吸附精馏塔优选为一个含有多股侧线采出的吸附精馏塔，采出不同馏分段的产品，优选侧线采出为两股。Preferably, the adsorption distillation tower is preferably an adsorption distillation tower containing multiple side lines to take out products from different fractions, preferably two side lines are taken out.
优选地，所述的吸附填料的材料优选为具有酸中心的分子筛、氧化硅、氧化铝中的一种或几种。Preferably, the material of the adsorption filler is preferably one or more of molecular sieves with acid centers, silica, and alumina.
优选地，所述的吸附填料的材料优选为在NH3-TPD分析中酸中心脱附温度在120-300℃，优选200～250℃。Preferably, the material of the adsorption filler preferably has an acid center desorption temperature of 120-300°C in NH 3 -TPD analysis, preferably 200-250°C.
优选地，吸附精馏塔所得产品进入烯烃精制单元，烯烃精制单元由多个烯烃精制精馏塔组成，塔顶得到烯烃产品，塔釜得到烷烃产品。Preferably, the product obtained from the adsorption distillation tower enters the olefin refining unit. The olefin refining unit is composed of multiple olefin refining distillation towers. The olefin product is obtained at the top of the tower and the alkane product is obtained from the tower still.
优选地，所述吸附精馏塔的塔顶温度为80～150℃，塔底温度为180～200℃，塔顶压力为0.01～0.2MPa，理论塔板数为40～60。Preferably, the top temperature of the adsorption distillation tower is 80-150°C, the bottom temperature is 180-200°C, the top pressure is 0.01-0.2MPa, and the number of theoretical plates is 40-60.
优选地，所述α-烯烃产品纯度≥99％，优选≥99.2％，α-烯烃收率≥85％，优选≥90％。Preferably, the α-olefin product purity is ≥99%, preferably ≥99.2%, and the α-olefin yield is ≥85%, preferably ≥90%.
本发明与现有技术相比，其有益效果体现在：将吸附与精馏工艺耦合，烯烃分离工段无需解吸剂的使用，简化工艺流程，降低工业化成本，可实现费托合成轻馏分油中α-烯烃的高效分离，且本发明中的吸附剂填料使用周期长，精馏能耗低，烯烃分离效率高，为费托合成油α-烯烃进行深加工及其他应用提供了更加经济、简便易行的方法。Compared with the existing technology, the beneficial effects of the present invention are reflected in: coupling the adsorption and distillation processes, eliminating the need for the use of desorbents in the olefin separation section, simplifying the process flow, reducing industrialization costs, and realizing Fischer-Tropsch synthesis of α in light distillate oils. - Efficient separation of olefins, and the adsorbent packing in the present invention has a long service life, low distillation energy consumption, and high olefin separation efficiency, which provides a more economical, simple and feasible method for deep processing of Fischer-Tropsch synthetic oil α-olefins and other applications. Methods.
附图说明Description of the drawings
图1是本发明一种费托轻馏分油吸附精馏耦合烯烃分离方法的工艺流程示意图；图中：1为模拟移动床；2为抽出液精馏塔；3为抽余液精馏塔；4为吸附精馏塔；5为C4～C7烷烯混合物精馏塔；6为C6～C10烷烯混合物精馏塔。Figure 1 is a schematic process flow diagram of a Fischer-Tropsch light distillate adsorption distillation coupled olefin separation method of the present invention; in the figure: 1 is a simulated moving bed; 2 is an extract liquid distillation tower; 3 is a raffinate distillation tower; 4 is an adsorption distillation tower; 5 is a distillation tower for a mixture of C4 to C7 alkanes and ene; 6 is a distillation tower for a mixture of C6 to C10 alkanes and ene.
图2是本发明一种费托轻馏分油吸附精馏耦合烯烃分离方法中吸附精馏塔的工艺流程；图中：401为吸附精馏塔专有填料。Figure 2 is a process flow of an adsorption distillation tower in a Fischer-Tropsch light distillate adsorption distillation coupled olefin separation method of the present invention; in the figure: 401 is the proprietary packing of the adsorption distillation tower.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚明白，以下结合具体实 施例，并参照附图，对本发明作进一步的详细说明。In order to make the purpose, technical solutions and advantages of the present invention more clear, the following is combined with specific practice Examples and with reference to the accompanying drawings, the present invention will be described in further detail.
本发明一种从费托合成轻质馏分油中分离α-烯烃的分离方法，该方法通过精馏切割、吸附脱氧、吸附精馏和深度精馏四个单元完成费托合成轻质馏分油到不同碳数α-烯烃的分离。在此过程，以费托合成轻质馏分油为原料，组成为C4-C10的烷烃、α-烯烃、其他烯烃和含氧化合物等。The invention is a separation method for separating α-olefins from Fischer-Tropsch synthesis light distillate oil. The method completes the Fischer-Tropsch synthesis light distillate oil through four units of distillation cutting, adsorption deoxygenation, adsorption distillation and deep distillation. Separation of α-olefins with different carbon numbers. In this process, Fischer-Tropsch synthetic light distillate is used as raw material, which is composed of C4-C10 alkanes, α-olefins, other olefins and oxygen-containing compounds.
若要将α-烯烃从费托合成轻质馏分油中分离，需要首先将费托合成轻质馏分油进行精馏切割，得到其中C4-C10的馏分，其烯烃质量分数不能低于10％，优选质量分数30％～70％。To separate α-olefins from Fischer-Tropsch synthesis light distillate oil, the Fischer-Tropsch synthesis light distillate oil needs to be distilled and cut first to obtain the C4-C10 fraction, whose olefin mass fraction cannot be less than 10%. The preferred mass fraction is 30% to 70%.
切割后费托合成轻质油一般含有1％～10％含氧化合物，一方面，含氧化合物极性远大于烷烃、烯烃，在吸附精馏塔中优先吸附，影响吸附精馏塔的分离性能；另一方面，含氧化合物中主要以醇为主，经模拟移动床吸附分离后可以回收利用。因此，需将C4-C10的馏分段送入吸附脱氧单元深度脱除含氧化合物，保证脱氧后油品含氧化合物＜10μg/g。After cutting, Fischer-Tropsch synthetic light oil generally contains 1% to 10% oxygenated compounds. On the one hand, the polarity of oxygenated compounds is much greater than that of alkanes and olefins, and is preferentially adsorbed in the adsorption distillation tower, affecting the separation performance of the adsorption distillation tower. On the other hand, the oxygen-containing compounds are mainly alcohol, which can be recycled after simulated moving bed adsorption separation. Therefore, the C4-C10 fraction needs to be sent to the adsorption deoxygenation unit to deeply remove oxygenated compounds to ensure that the oxygenated compounds in the oil after deoxidation are <10 μg/g.
后续，将脱除含氧有机化合物的物料送入吸附精馏单元中，选择性地将不同碳数烷烯组分分离。从吸附精馏塔共采出四股物流，塔顶采出C4-C5富烷烃组分，塔釜采出C8-C10富α-烯烃组分，其中α-烯烃纯度≥99％，优选≥99.5％。中间采出两股不同碳数烷烃和烯烃组成的混合物送入精馏精制单元，得到C4-C5富α-烯烃组分和C6-C7富α-烯烃组分，α-烯烃纯度≥99％，优选≥99.5％。精馏后得到的富烷烃组分可以用于生产燃料油、润滑油或者特种溶剂油。Subsequently, the material from which oxygen-containing organic compounds are removed is sent to an adsorption distillation unit to selectively separate alkene components with different carbon numbers. A total of four streams are extracted from the adsorption distillation tower, the C4-C5 alkane-rich component is extracted from the top of the tower, and the C8-C10 α-olefin-rich component is extracted from the tower kettle, wherein the α-olefin purity is ≥99%, preferably ≥99.5% . Two mixtures of alkanes and olefins with different carbon numbers are extracted and sent to the distillation and refining unit to obtain C4-C5 α-olefin-rich components and C6-C7 α-olefin-rich components. The purity of α-olefins is ≥99%. Preferably ≥99.5%. The alkane-rich components obtained after distillation can be used to produce fuel oil, lubricating oil or special solvent oil.
在本发明的一些实施方式中，一种费托轻馏分油吸附精馏耦合烯烃分离α-烯烃的方法，包括如下步骤：In some embodiments of the present invention, a method for separating α-olefins by adsorption distillation of Fischer-Tropsch light distillate coupled with olefins includes the following steps:
首先，C4-C10馏分段费托合成油经过脱氧模拟移动床，进行C4-C10馏分段费托合成油含氧化合物的深度脱除，为烯烃分离提供合格原料；First, the Fischer-Tropsch synthetic oil in the C4-C10 fraction section passes through a deoxygenated simulated moving bed to deeply remove oxygenated compounds from the Fischer-Tropsch synthetic oil in the C4-C10 fraction section to provide qualified raw materials for olefin separation;
后续，通过一个或多个吸附精馏塔进行连续或间歇费托轻质馏分油分离，从塔顶得到低烯烃含量的饱和烃产品，从塔釜得到高纯度的α-烯烃产品；其中，所述吸附精馏塔内部的填料为具有烯烃吸附能力的吸附填料； 所述的吸附填料选自分子筛、改性分子筛、氧化硅、改性氧化硅、氧化铝和改性氧化铝中的一种或几种；所述吸附精馏塔的塔顶温度为50-180℃，塔底温度为100℃-200℃，塔顶压力为0.01-0.5MPa，理论板数为5-80块。Subsequently, continuous or intermittent Fischer-Tropsch light distillate separation is performed through one or more adsorption distillation towers, saturated hydrocarbon products with low olefin content are obtained from the top of the tower, and high-purity α-olefin products are obtained from the tower bottom; where, The packing inside the adsorption distillation tower is an adsorption packing with olefin adsorption capacity; The adsorption filler is selected from one or more of molecular sieves, modified molecular sieves, silica, modified silica, alumina and modified alumina; the top temperature of the adsorption distillation tower is 50-180 ℃, the bottom temperature of the tower is 100℃-200℃, the top pressure is 0.01-0.5MPa, and the number of theoretical plates is 5-80.
在本发明中，吸附精馏塔为1～4个，优选1～2个。对于α-烯烃纯度要求更高，大于99.5％时，吸附精馏塔塔板数要求更高，此时需要2个以上精馏塔以满足分离需求。普遍的，1个吸附精馏塔能够满足要求。In the present invention, the number of adsorption distillation towers is 1 to 4, preferably 1 to 2. For α-olefins, the purity requirements are higher. When it is greater than 99.5%, the number of plates in the adsorption distillation tower is higher. At this time, more than two distillation towers are needed to meet the separation needs. Generally, one adsorption distillation tower can meet the requirements.
在一些实施方式中，所述的吸附填料为规整填料。In some embodiments, the adsorption filler is a structured filler.
在一些实施方式中，所述吸附精馏塔为一个含有多股侧线采出的吸附精馏塔，采出不同馏分段的产品。In some embodiments, the adsorption distillation tower is an adsorption distillation tower containing multiple side lines to take out products from different fractions.
在一些实施方式中，所述的吸附填料为具有酸中心的分子筛、具有酸中心的氧化硅和具有酸中心的氧化铝中的一种或几种。In some embodiments, the adsorption filler is one or more of molecular sieves with acid centers, silica with acid centers, and alumina with acid centers.
在一些实施方式中，所述的吸附填料在NH3-TPD分析中的酸中心脱附温度为120-300℃。In some embodiments, the acid center desorption temperature of the adsorption filler in NH 3 -TPD analysis is 120-300°C.
在一些实施方式中，所述吸附精馏塔所得的不同馏分段的产品进入烯烃精制单元，所述烯烃精制单元由多个烯烃精制精馏塔组成，塔顶得到烯烃产品，塔釜得到烷烃产品。In some embodiments, products from different fractions obtained from the adsorption distillation tower enter an olefin refining unit. The olefin refining unit is composed of multiple olefin refining distillation towers. Olefin products are obtained at the top of the tower, and alkanes are obtained from the tower stills. .
在一些实施方式中，所述吸附精馏塔的塔顶温度为80～150℃，塔底温度为180～200℃，塔顶压力为0.01～0.2MPa，理论塔板数为40～60。In some embodiments, the top temperature of the adsorption distillation tower is 80-150°C, the bottom temperature is 180-200°C, the top pressure is 0.01-0.2MPa, and the number of theoretical plates is 40-60.
在一些实施方式中，所述α-烯烃产品的纯度≥99％，α-烯烃收率≥85％。In some embodiments, the α-olefin product has a purity of ≥99% and an α-olefin yield of ≥85%.
在一些实施方式中，所述的吸附填料形貌类型选自拉西环、θ环、鲍尔环填料中的一种或多种。In some embodiments, the morphology type of the adsorption filler is selected from one or more of Raschig ring, θ ring, and Pall ring fillers.
在一些实施方式中，所述的吸附填料在NH3-TPD分析中的酸中心脱附温度为200～250℃。In some embodiments, the acid center desorption temperature of the adsorption filler in NH 3 -TPD analysis is 200 to 250°C.
下面结合附图详细说明本发明。The present invention will be described in detail below with reference to the accompanying drawings.
C4-C10费托轻质馏分油分离α-烯烃工艺流程，如图1所示，将费托合成轻质馏分油原料通入吸附脱氧单元中的模拟移动床1中进行吸附分离，贫氧组分送入抽余液精馏塔3，经精馏分离后得到循环解吸剂和C4～C10烷 烯烃混合物，C4～C10烷烯烃混合物含氧化合物浓度降低至10μg/g以下，送入吸附精馏塔4，如图2所示为吸附精馏塔的工艺流程，其中，401为吸附精馏塔专有填料，循环解吸剂送入模拟移动床1循环利用。富氧组分送入抽出液精馏塔2，经精馏分离得到循环解吸剂和氧化物，氧化物直接送出进行下步加工利用，循环解吸剂送入模拟移动床1循环利用。The process flow of α-olefin separation from C4-C10 Fischer-Tropsch light distillate is shown in Figure 1. The Fischer-Tropsch light distillate raw material is passed into the simulated moving bed 1 in the adsorption deoxygenation unit for adsorption separation. The oxygen-depleted group The raffinate is sent to the distillation tower 3, and the circulating desorbent and C4-C10 alkane are obtained after distillation and separation. The concentration of oxygenated compounds of the olefin mixture and the C4-C10 alkane-olefin mixture is reduced to less than 10 μg/g and sent to the adsorption distillation tower 4. Figure 2 shows the process flow of the adsorption distillation tower, in which 401 is the adsorption distillation tower. The proprietary filler and circulating desorbent are sent to the simulated moving bed 1 for recycling. The oxygen-rich components are sent to the extracted liquid distillation tower 2, and the circulating desorbent and oxides are obtained through distillation and separation. The oxides are directly sent out for subsequent processing and utilization, and the circulating desorbent is sent to the simulated moving bed 1 for recycling.
C4～C10烷烯烃混合物经泵加压送入吸附精馏塔4，经吸附精馏分离后，塔顶得到C4-C5富烷烃组分，塔釜得到C8-C10富α-烯烃组分，侧线1采出C6-C7烷烃与C4-C5烯烃混合物进入C4～C7烷烯混合物精馏塔5分离，侧线2采出C8-C10烷烃和C6-C7烯烃混合物进入C6～C10烷烯混合物精馏塔6分离。经过精馏后得到的C4-C5和C6-C7高纯度α-烯烃组分，以及C6-C7和C8-C10富烷烃组分。The C4-C10 alkanes and olefins mixture is pressurized by a pump and sent to the adsorption distillation tower 4. After separation by adsorption and rectification, a C4-C5 alkane-rich component is obtained from the top of the tower, and a C8-C10 α-olefin-rich component is obtained from the tower kettle. The side line 1 The C6-C7 alkane and C4-C5 olefin mixture is extracted and enters the C4~C7 alkene mixture distillation tower 5 for separation. The side line 2 extracts the C8-C10 alkane and C6-C7 olefin mixture and enters the C6~C10 alkene mixture distillation tower. 6 separation. After rectification, C4-C5 and C6-C7 high-purity α-olefin components are obtained, as well as C6-C7 and C8-C10 rich alkane components.
下面通过实施例进一步说明本发明，但本发明并不限于此。The present invention will be further described below through examples, but the present invention is not limited thereto.
实施例1Example 1
吸附脱氧工艺采用模拟移动床，由12根柱子串联构成，柱子内装填脱氧吸附剂，吸附剂为硅胶材料。第12根柱子与第1根柱子通过循环泵连接，形成物料循环，各柱子的连接处均可引入或排出物料。按下述方法设置吸附分离各阶段所需的吸附柱数：原料入口和抽余液出口之间有3根吸附柱，为吸附区；抽余液出口和解吸剂入口之间有2根吸附柱，为隔离区；解吸剂入口和抽出液出口之间有3根吸附柱，为解吸区；抽出液出口和原料入口之间有1根吸附柱，为精制区。每隔一定的时间，沿原料入口向抽余液出口的方向将各进出料口推移1根柱子，依次类推，其中解吸剂为1-癸醇和正十四烷的混合物。The adsorption deoxygenation process uses a simulated moving bed, which is composed of 12 columns connected in series. The columns are filled with deoxygenation adsorbent, and the adsorbent is silica gel material. The 12th column and the 1st column are connected through a circulation pump to form a material circulation. Materials can be introduced or discharged at the joints of each column. Set the number of adsorption columns required for each stage of adsorption separation according to the following method: There are 3 adsorption columns between the raw material inlet and the raffinate outlet, which are the adsorption areas; there are 2 adsorption columns between the raffinate outlet and the desorbent inlet. , is the isolation area; there are three adsorption columns between the desorbent inlet and the extractant outlet, which are the desorption area; there is one adsorption column between the extractant outlet and the raw material inlet, which is the refining area. At certain intervals, move each inlet and outlet one column along the direction from the raw material inlet to the raffinate outlet, and so on. The desorbent is a mixture of 1-decanol and n-tetradecane.
C4-C10的轻质馏分油进入模拟移动床中吸附脱氧，操作温度为80℃，解吸剂和原料的比例为1.5，每隔800秒切换一次进出料口位置，即沿原料入口向抽余液出口的方向将各进出料口推移1根柱子。经模拟移动床吸附脱氧后，抽出液和抽余液分别进入抽出液精馏塔和抽余液精馏塔进行解吸剂回收利用。抽出液塔为填料塔，填料为鲍尔环，总塔板数为30块，进料 位置在第15块塔板，操作压力为1atm，质量回流比0.9；抽余液塔也为填料塔，总塔板数70块，进料位置为第30块塔板，操作压力为1atm，质量回流比1.8。C4-C10 light distillate enters the simulated moving bed for adsorption and deoxygenation. The operating temperature is 80°C. The ratio of desorbent to raw material is 1.5. The position of the inlet and outlet is switched every 800 seconds, that is, along the raw material inlet to the raffinate. In the direction of the outlet, push each inlet and outlet by one pillar. After simulated moving bed adsorption deoxygenation, the extract liquid and raffinate liquid enter the extract liquid rectification tower and raffinate rectification tower respectively for desorbent recycling. The liquid extraction tower is a packed tower, the packing is Pall ring, the total number of trays is 30, and the feed The position is on the 15th tray, the operating pressure is 1atm, the mass reflux ratio is 0.9; the raffinate tower is also a packed tower, with a total number of trays of 70, the feed position is on the 30th tray, the operating pressure is 1atm, the mass Reflow ratio 1.8.
经吸附脱氧过程分离得到的产品组成如表1所示，得到C4-C10烷烃和烯烃中的含氧化合物含量小于10μg/g，收率达到99％。The composition of the product separated through the adsorption deoxygenation process is shown in Table 1. The content of oxygenated compounds in C4-C10 alkanes and olefins is less than 10 μg/g, and the yield reaches 99%.
表1吸附脱氧后各物流组分纯度
Table 1 Purity of each stream component after adsorption deoxygenation
吸附脱氧后C4-C10烷烯烃进入吸附精馏塔进一步分离，吸附精馏塔装填吸附填料以保证轻重组分实现充分分离，吸附填料为θ环型，采用的是13X分子筛，其物化性质如表2所示。吸附精馏塔总板数为85块，吸附段35块塔板，精馏段20块塔板，提馏段25块塔板。C4-C10烷烯烃原料在第35块塔板(吸附段中部)进入，塔顶操作压力为1atm，质量回流比为2.5，塔顶温度为45℃，塔釜温度为200℃。在第12块塔板处侧线采出一股物流命名为侧线1，主要组成为C6-C7烷烃与C4-C5烯烃混合物，在第72块塔板处侧线采出另一股物流命名为侧线2，主要组成为C8-C10烷烃和C6-C7烯烃混合物。经过吸附精馏分离后，各产品纯度如表3所示。塔釜C8-C10α-烯烃纯度达到99.8wt.％以上，收率达到95％。侧线采出的两股物流直接进入精馏精制单元，进行进一步的加工。After adsorption and deoxygenation, C4-C10 alkanes enter the adsorption distillation tower for further separation. The adsorption distillation tower is filled with adsorption packing to ensure full separation of light and heavy components. The adsorption packing is theta ring type and uses 13X molecular sieve. Its physical and chemical properties are as shown in the table 2 shown. The total number of plates in the adsorption distillation tower is 85, including 35 plates in the adsorption section, 20 plates in the rectification section, and 25 plates in the stripping section. The C4-C10 alkene olefin raw material enters the 35th tray (middle of the adsorption section). The operating pressure at the top of the tower is 1 atm, the mass reflux ratio is 2.5, the top temperature is 45°C, and the tower still temperature is 200°C. A stream is extracted from the side line at the 12th tray and named side line 1. It is mainly composed of a mixture of C6-C7 alkanes and C4-C5 olefins. Another stream is extracted from the side line at the 72nd tray and is named side line 2. , the main composition is a mixture of C8-C10 alkanes and C6-C7 olefins. After separation by adsorption distillation, the purity of each product is shown in Table 3. The purity of C8-C10 α-olefins in the column reactor reaches over 99.8wt.%, and the yield reaches 95%. The two streams extracted from the side line directly enter the distillation and refining unit for further processing.
表2 13X分子筛物化性质

Table 2 Physicochemical properties of 13X molecular sieve

表3吸附精馏后各物流组分纯度
Table 3 Purity of each stream component after adsorption distillation
精馏精制单元采用两个精馏塔分别处理侧线1和侧线2两股物流，侧线1物流进入C4～C7烷烯混合物精馏塔5，采用填料塔，填料类型为θ环。C4～C7烷烯混合物精馏塔5总塔板数45块，塔顶操作压力为1atm，进料位置为第20块板，质量回流比为1.5。侧线2物流进入C6～C10烷烯混合物精馏塔6，采用填料塔，填料类型为θ环。C6～C10烷烯混合物C6～C10烷烯混合物精馏塔6总塔板数55块，操作压力为1atm，进料位置为第30块板，质量回流比为2.3。经过精馏精制后，产品流股组分纯度如表4和表5所示。C4-C5α-烯烃产品纯度能达到99.8wt.％，收率达到94％，C6-C7α-烯烃产品纯度能达到99.8wt.％，收率达到92％。The distillation and refining unit uses two distillation towers to process the two streams of side line 1 and side line 2 respectively. The side line 1 stream enters the C4 ~ C7 alkene mixture distillation tower 5, which uses a packed tower with a θ ring packing type. The C4-C7 alkene mixture distillation tower 5 has a total number of 45 plates, the operating pressure at the top of the tower is 1 atm, the feed position is the 20th plate, and the mass reflux ratio is 1.5. The side stream 2 flows into the C6-C10 alkane-ene mixture distillation tower 6, which adopts a packed tower, and the packing type is theta ring. C6~C10 Alkane Mixture C6~C10 Alkene Mixture Distillation Tower 6 has a total number of plates of 55, the operating pressure is 1 atm, the feed position is the 30th plate, and the mass reflux ratio is 2.3. After distillation and purification, the purity of the product stream components is shown in Table 4 and Table 5. The purity of the C4-C5α-olefin product can reach 99.8wt.%, and the yield reaches 94%. The purity of the C6-C7α-olefin product can reach 99.8wt.%, and the yield reaches 92%.
表4 C4～C7烷烯混合物精馏塔5各物流组分纯度

Table 4 Purity of each stream component in C4~C7 alkene-ene mixture distillation tower 5

表5 C6～C10烷烯混合物精馏塔6各物流组分纯度
Table 5 Purity of each stream component in C6~C10 alkene mixture distillation tower 6
实施例2Example 2
本实施例脱氧工段与实施例1相同，吸附填料采用的氧化硅，其物化性质如表6所示，填料类型为鲍尔环。吸附精馏塔总板数为90块，吸附段40块塔板，精馏段23块塔板，提馏段26块塔板。C4-C10烷烯烃原料在第40块塔板(吸附段中部)进入，塔顶操作压力为1atm，质量回流比为2.5，塔顶温度为45℃，塔釜温度为200℃。在第14块塔板处侧线采出一股物流命名为侧线1，主要组成为C6-C7烷烃与C4-C5烯烃混合物，在第74块塔板处侧线采出另一股物流命名为侧线2，主要组成为C8-C10烷烃和C6-C7烯烃混合物。经过吸附精馏分离后，各产品纯度如表7所示。塔釜C8-C10α-烯烃纯度达到99.7wt.％以上，收率达到96％。侧线采出的两股物流直接 进入精馏精制单元，进行进一步的加工。The deoxidation section of this embodiment is the same as that of Embodiment 1. The physical and chemical properties of silicon oxide used as adsorption filler are shown in Table 6, and the filler type is Pall ring. The total number of plates in the adsorption distillation tower is 90, including 40 plates in the adsorption section, 23 plates in the rectification section, and 26 plates in the stripping section. The C4-C10 alkane olefin raw material enters the 40th tray (middle of the adsorption section). The operating pressure at the top of the tower is 1 atm, the mass reflux ratio is 2.5, the top temperature is 45°C, and the tower still temperature is 200°C. A stream is produced from the side line at the 14th tray and is named side line 1. It is mainly composed of a mixture of C6-C7 alkanes and C4-C5 olefins. Another stream is produced from the side line at the 74th tray and is named side line 2. , the main composition is a mixture of C8-C10 alkanes and C6-C7 olefins. After separation by adsorption distillation, the purity of each product is shown in Table 7. The purity of C8-C10 α-olefin in the column reactor reaches more than 99.7wt.%, and the yield reaches 96%. The two logistics streams extracted from the side line are directly Enter the distillation and refining unit for further processing.
表6氧化硅物化性质
Table 6 Physical and chemical properties of silicon oxide
表7吸附精馏后各物流组分纯度
Table 7 Purity of each stream component after adsorption distillation
精馏精制单元采用两个精馏塔分别处理侧线1和侧线2两股物流，侧线1物流进入C4～C7烷烯混合物精馏塔5，采用填料塔，填料类型为θ环。C4～C7烷烯混合物精馏塔5总塔板数45块，塔顶操作压力为1atm，进料位置为第20块板，质量回流比为1.5。侧线2物流进入C6～C10烷烯混合物精馏塔6，采用填料塔，填料类型为θ环。精馏塔C6～C10烷烯混合物精馏塔6总塔板数55块，操作压力为1atm，进料位置为第30块板，质量回流比为2.3。经过精馏精制后，产品流股组分纯度如表8和表9所示。C4-C5α-烯烃产品纯度能达到99.7wt.％，收率达到95％，C6-C7α-烯烃产品纯度能 达到99.8wt.％，收率达到93％。The distillation and refining unit uses two distillation towers to process the two streams of side line 1 and side line 2 respectively. The side line 1 stream enters the C4 ~ C7 alkene mixture distillation tower 5, which uses a packed tower with a θ ring packing type. The C4-C7 alkene mixture distillation tower 5 has a total number of 45 plates, the operating pressure at the top of the tower is 1 atm, the feed position is the 20th plate, and the mass reflux ratio is 1.5. The side stream 2 flows into the C6-C10 alkane-ene mixture distillation tower 6, which adopts a packed tower, and the packing type is theta ring. Distillation column C6~C10 alkene mixture rectification column 6 has a total number of plates of 55, the operating pressure is 1 atm, the feed position is the 30th plate, and the mass reflux ratio is 2.3. After distillation and purification, the purity of the product stream components is shown in Table 8 and Table 9. The purity of C4-C5α-olefin products can reach 99.7wt.%, and the yield can reach 95%. The purity of C6-C7α-olefin products can reach 99.7wt.%, and the yield can reach 95%. Reaching 99.8wt.%, the yield reached 93%.
表8 C4～C7烷烯混合物精馏塔5各物流组分纯度
Table 8 Purity of each stream component in C4~C7 alkene-ene mixture distillation tower 5
表9 C6～C10烷烯混合物精馏塔6各物流组分纯度
Table 9 Purity of each stream component in C6~C10 alkene mixture distillation tower 6
实施例3Example 3
本实施例脱氧工段与实施例1相同，吸附填料采用的是氧化铝，其物化性质如表10所示，填料类型为拉西环。吸附精馏塔总板数为95块，吸附段43块塔板，精馏段26块塔板，提馏段30块塔板。C4-C10烷烯烃原料在第43块塔板(吸附段中部)进入，塔顶操作压力为1atm，质量回流比为2.6，塔顶温度为45℃，塔釜温度为200℃。在第17块塔板处侧线采 出一股物流命名为侧线1，主要组成为C6-C7烷烃与C4-C5烯烃混合物，在第76块塔板处侧线采出另一股物流命名为侧线2，主要组成为C8-C10烷烃和C6-C7烯烃混合物。经过吸附精馏分离后，各产品纯度如表11所示。塔釜C8-C10α-烯烃纯度达到99.8wt.％以上，收率达到95％。侧线采出的两股物流直接进入精馏精制单元，进行进一步的加工。The deoxidation section of this embodiment is the same as that of Embodiment 1. The adsorption filler is alumina, its physical and chemical properties are shown in Table 10, and the filler type is Raschig ring. The total number of plates in the adsorption distillation tower is 95, including 43 plates in the adsorption section, 26 plates in the rectification section, and 30 plates in the stripping section. The C4-C10 alkene olefin raw material enters the 43rd tray (middle of the adsorption section). The operating pressure at the top of the tower is 1 atm, the mass reflux ratio is 2.6, the top temperature is 45°C, and the tower still temperature is 200°C. Mining the side line at the 17th tray One stream is taken out and named side line 1, which is mainly composed of a mixture of C6-C7 alkanes and C4-C5 olefins. Another stream is taken out from the side line at the 76th tray and is named side line 2, which is mainly composed of C8-C10 alkane and C4-C5 olefins. C6-C7 olefin mixture. After separation by adsorption distillation, the purity of each product is shown in Table 11. The purity of C8-C10 α-olefins in the column reactor reaches over 99.8wt.%, and the yield reaches 95%. The two streams extracted from the side line directly enter the distillation and refining unit for further processing.
表10氧化铝物化性质
Table 10 Physical and chemical properties of alumina
表11吸附精馏后各物流组分纯度
Table 11 Purity of each stream component after adsorption distillation
精馏精制单元采用两个精馏塔分别处理侧线1和侧线2两股物流，侧线1物流进入C4～C7烷烯混合物精馏塔5，采用填料塔，填料类型为θ环。C4～C7烷烯混合物精馏塔5总塔板数45块，塔顶操作压力为1atm，进料位置为第20块板，质量回流比为1.5。侧线2物流进入C6～C10烷烯混合物 精馏塔6，采用填料塔，填料类型为θ环。C6～C10烷烯混合物精馏塔6总塔板数55块，操作压力为1atm，进料位置为第30块板，质量回流比为2.3。经过精馏精制后，产品流股组分纯度如表12和表13所示。C4-C5α-烯烃产品纯度能达到99.5wt.％，收率达到94％，C6-C7α-烯烃产品纯度能达到99.6wt.％，收率达到94％。The distillation and refining unit uses two distillation towers to process the two streams of side line 1 and side line 2 respectively. The side line 1 stream enters the C4 ~ C7 alkene mixture distillation tower 5, which uses a packed tower with a θ ring packing type. The C4-C7 alkene mixture distillation tower 5 has a total number of 45 plates, the operating pressure at the top of the tower is 1 atm, the feed position is the 20th plate, and the mass reflux ratio is 1.5. The side stream 2 flows into the C6~C10 alkene mixture. Distillation column 6 adopts a packed tower, and the packing type is θ ring. The C6-C10 alkene mixture distillation column 6 has a total number of plates of 55, the operating pressure is 1 atm, the feed position is the 30th plate, and the mass reflux ratio is 2.3. After distillation and purification, the purity of the product stream components is shown in Table 12 and Table 13. The purity of the C4-C5α-olefin product can reach 99.5wt.%, and the yield reaches 94%. The purity of the C6-C7α-olefin product can reach 99.6wt.%, and the yield reaches 94%.
表12 C4～C7烷烯混合物精馏塔5各物流组分纯度
Table 12 Purity of each stream component in C4~C7 alkene-ene mixture distillation tower 5
表13 C6～C10烷烯混合物精馏塔6各物流组分纯度
Table 13 Purity of each stream component in C6~C10 alkene mixture distillation tower 6
实施例4Example 4
吸附脱氧工艺采用实例1中的模拟移动床，由12根柱子串联构成，柱 子内装填脱氧吸附剂，吸附剂为硅胶材料。C4-C10的轻质馏分油进入模拟移动床中吸附脱氧，操作温度为100℃，解吸剂和原料的比例为2.5，每隔360秒切换一次进出料口位置，其中，解吸剂为1-癸醇和正十四烷的混合物。经模拟移动床吸附脱氧后，抽出液和抽余液分别进入精馏塔进行解吸剂回收利用。抽出液精馏塔为填料塔，填料为鲍尔环，总塔板数为40块，进料位置在第20块塔板，操作压力为1atm，质量回流比1.1；抽余液精馏塔也为填料塔，总塔板数80块，进料位置为第40块塔板，操作压力为1atm，质量回流比2.2。The adsorption deoxygenation process uses the simulated moving bed in Example 1, which is composed of 12 columns connected in series. The container is filled with deoxidation adsorbent, and the adsorbent is silica gel material. The C4-C10 light distillate enters the simulated moving bed for adsorption and deoxygenation. The operating temperature is 100°C. The ratio of desorbent to raw material is 2.5. The position of the inlet and outlet is switched every 360 seconds. The desorbent is 1-decane. A mixture of alcohol and n-tetradecane. After simulated moving bed adsorption and deoxygenation, the extract liquid and raffinate liquid enter the distillation tower respectively for desorbent recycling. The raffinate distillation tower is a packed tower, the packing is Pall ring, the total number of trays is 40, the feed position is on the 20th tray, the operating pressure is 1 atm, and the mass reflux ratio is 1.1; the raffinate distillation tower is also It is a packed tower with a total number of trays of 80, the feed position is the 40th tray, the operating pressure is 1 atm, and the mass reflux ratio is 2.2.
经吸附脱氧过程分离得到的产品组成如表14所示，得到C4-C10烷烃和烯烃中的含氧化合物含量小于10μg/g，收率达到97％。The composition of the product separated through the adsorption deoxygenation process is shown in Table 14. The content of oxygenated compounds in C4-C10 alkanes and olefins is less than 10 μg/g, and the yield reaches 97%.
表14吸附脱氧后各物流组分纯度
Table 14 Purity of each stream component after adsorption deoxygenation
吸附脱氧后C4-C10烷烯烃进入吸附精馏塔进一步分离吸附精馏塔装填吸附填料以保证轻重组分实现充分分离，吸附填料为鲍尔环型，采用的是Y分子筛，其物化性质如表15所示。吸附精馏塔总板数为95块，吸附段45块塔板，精馏段20块塔板，提馏段30块塔板。C4-C10烷烯烃原料在第45块塔板(吸附段中部)进入，塔顶操作压力为1atm，质量回流比为3，塔顶温度为48℃，塔釜温度为205℃。在第14块塔板处侧线采出一股物流命名为侧线1，主要组成为C6-C7烷烃与C4-C5烯烃混合物，在第80块塔板处侧线采出另一股物流命名为侧线2，主要组成为C8-C10烷烃和C6-C7烯烃混合物。经过吸附精馏分离后，各产品纯度如表16所示。塔釜C8-C10α-烯烃纯度达到99.7wt.％，收率达到95％。侧线采出的两股物流直 接进入精馏精制单元，进行进一步的加工。After adsorption and deoxygenation, C4-C10 alkanes enter the adsorption distillation tower for further separation. The adsorption distillation tower is filled with adsorption packing to ensure full separation of light and heavy components. The adsorption packing is Pall ring type and Y molecular sieve is used. Its physical and chemical properties are as shown in the table 15 shown. The total number of plates in the adsorption distillation tower is 95, including 45 plates in the adsorption section, 20 plates in the rectification section, and 30 plates in the stripping section. The C4-C10 alkene olefin raw material enters the 45th tray (middle of the adsorption section). The operating pressure at the top of the tower is 1 atm, the mass reflux ratio is 3, the temperature at the top of the tower is 48°C, and the temperature of the tower still is 205°C. A stream is produced from the side line at the 14th tray and is named side line 1. It is mainly composed of a mixture of C6-C7 alkanes and C4-C5 olefins. Another stream is produced from the side line at the 80th tray and is named side line 2. , the main composition is a mixture of C8-C10 alkanes and C6-C7 olefins. After separation by adsorption distillation, the purity of each product is shown in Table 16. The purity of C8-C10 α-olefin in the column reactor reaches 99.7wt.%, and the yield reaches 95%. The two streams of logistics extracted from the side line are straight It then enters the distillation and refining unit for further processing.
表15 Y分子筛物化性质
Table 15 Physicochemical properties of Y molecular sieve
精馏精制单元采用两个精馏塔分别处理侧线1和侧线2两股物流，侧线1物流进入C4～C7烷烯混合物精馏塔5，采用填料塔，填料类型为θ环。C4～C7烷烯混合物精馏塔5总塔板数35块，塔顶操作压力为1atm，进料位置为第15块板，质量回流比为1.7。侧线2物流进入C6～C10烷烯混合物精馏塔6，采用填料塔，填料类型为θ环。C6～C10烷烯混合物精馏塔6总塔板数60块，操作压力为1atm，进料位置为第35块板，质量回流比为2.0。经过精馏精制后，产品流股组分纯度如表17和表18所示。C4-C5α-烯烃产品纯度达到99.6wt.％，收率达到92％；C6-C7α-烯烃产品纯度达到99.6wt.％，收率达到93％。The distillation and refining unit uses two distillation towers to process the two streams of side line 1 and side line 2 respectively. The side line 1 stream enters the C4 ~ C7 alkene mixture distillation tower 5, which uses a packed tower with a θ ring packing type. The C4-C7 alkene mixture distillation tower 5 has a total number of plates of 35, the operating pressure at the top of the tower is 1 atm, the feed position is the 15th plate, and the mass reflux ratio is 1.7. The side stream 2 flows into the C6-C10 alkane-ene mixture distillation tower 6, which adopts a packed tower, and the packing type is theta ring. The C6-C10 alkene mixture distillation tower 6 has a total number of plates of 60, the operating pressure is 1 atm, the feed position is the 35th plate, and the mass reflux ratio is 2.0. After distillation and purification, the purity of the product stream components is shown in Table 17 and Table 18. The purity of the C4-C5α-olefin product reaches 99.6wt.%, and the yield reaches 92%; the purity of the C6-C7α-olefin product reaches 99.6wt.%, and the yield reaches 93%.
表16吸附精馏后各物流组分纯度
Table 16 Purity of each stream component after adsorption distillation
表17 C4～C7烷烯混合物精馏塔5各物流组分纯度
Table 17 Purity of each stream component in C4~C7 alkene-ene mixture distillation tower 5
表18 C6～C10烷烯混合物精馏塔6各物流组分纯度
Table 18 Purity of each stream component in C6~C10 alkene mixture distillation tower 6

Claims (10)

  1. 一种费托轻馏分油吸附精馏耦合烯烃分离α-烯烃的方法，其特征在于：包括一个或多个吸附精馏塔，在吸附精馏塔内部的填料为具有烯烃吸附能力的吸附填料；所述的吸附填料采用分子筛、改性分子筛、氧化硅、改性氧化硅、氧化铝、改性氧化铝中的一种或几种；操作温度塔顶为50-180℃，塔底为100℃-200℃，操作压力塔顶为0.01-0.5MPa，理论板数为5-80块，进行连续或间歇费托轻质馏分油分离，塔顶为低烯烃含量的饱和烃产品，塔釜为高纯度的α-烯烃产品。A method for coupling olefin adsorption distillation of Fischer-Tropsch light distillate oil to separate α-olefins, which is characterized in that it includes one or more adsorption distillation towers, and the packing inside the adsorption distillation tower is an adsorption packing with olefin adsorption capacity; The adsorption filler adopts one or more of molecular sieve, modified molecular sieve, silica, modified silica, alumina, and modified alumina; the operating temperature at the top of the tower is 50-180°C, and at the bottom of the tower is 100°C -200℃, the operating pressure at the top of the tower is 0.01-0.5MPa, the number of theoretical plates is 5-80, continuous or intermittent Fischer-Tropsch light distillate separation is carried out, the top of the tower is a saturated hydrocarbon product with low olefin content, and the tower kettle is high Purity of alpha-olefin products.
  2. 根据权利要求1所述的方法，其特征在于，所述的吸附填料为规整填料。The method according to claim 1, characterized in that the adsorption filler is a structured filler.
  3. 根据权利要求1所述的方法，其特征在于，吸附精馏塔为一个含有多股侧线采出的吸附精馏塔，采出不同馏分段的产品。The method according to claim 1, characterized in that the adsorption distillation tower is an adsorption distillation tower containing multiple side lines to extract products from different fractions.
  4. 根据权利要求1所述的方法，其特征在于，所述的吸附填料为具有酸中心的分子筛、氧化硅、氧化铝中的一种或几种。The method according to claim 1, characterized in that the adsorption filler is one or more selected from the group consisting of molecular sieves with acid centers, silica, and alumina.
  5. 根据权利要求1所述的方法，其特征在于，所述的吸附填料在NH3-TPD分析中酸中心脱附温度在120-300℃。The method according to claim 1, characterized in that the acid center desorption temperature of the adsorption filler in NH 3 -TPD analysis is 120-300°C.
  6. 根据权利要求3所述的方法，其特征在于，吸附精馏塔所得的不同馏分段的产品进入烯烃精制单元，烯烃精制单元由多个烯烃精制精馏塔组成，塔顶得到烯烃产品，塔釜得到烷烃产品。The method according to claim 3, characterized in that the products of different fractions obtained from the adsorption distillation tower enter the olefin refining unit. The olefin refining unit is composed of a plurality of olefin refining distillation towers, and the olefin products are obtained at the top of the tower. Alkane products are obtained.
  7. 根据权利要求1所述的方法，其特征在于，所述吸附精馏塔的塔顶温度为80～150℃，塔底温度为180～200℃，塔顶压力为0.01～0.2MPa，理论塔板数为40～60。The method according to claim 1, characterized in that the top temperature of the adsorption distillation tower is 80-150°C, the bottom temperature is 180-200°C, the top pressure is 0.01-0.2MPa, and the theoretical plate The number is 40 to 60.
  8. 根据权利要求1所述的方法，其特征在于，所述α-烯烃产品纯度≥99％，α-烯烃收率≥85％。The method according to claim 1, characterized in that the α-olefin product purity is ≥99% and the α-olefin yield is ≥85%.
  9. 根据权利要求2所述的方法，其特征在于，所述的吸附填料形貌类型为拉西环、θ环、鲍尔环填料中的一种或多种。The method according to claim 2, characterized in that the morphology type of the adsorption filler is one or more of Raschig ring, θ ring, and Pall ring fillers.
  10. 根据权利要求2所述的方法，其特征在于，所述的吸附填料在NH3-TPD分析中酸中心脱附温度在200～250℃。 The method according to claim 2, characterized in that the desorption temperature of the acid center of the adsorption filler in NH 3 -TPD analysis is between 200 and 250°C.
PCT/CN2023/106403 2022-05-09 2023-07-07 Method for separating alpha-olefin from fischer-tropsch light distillate by using adsorption and distillation to couple olefin WO2023217303A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210479559.1A CN115011376B (en) 2022-05-09 2022-05-09 Method for separating alpha-olefin by Fischer-Tropsch light distillate oil adsorption and rectification coupled olefin
CN202210479559.1 2022-05-09

Publications (1)

Publication Number Publication Date
WO2023217303A1 true WO2023217303A1 (en) 2023-11-16

Family

ID=83066849

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/106403 WO2023217303A1 (en) 2022-05-09 2023-07-07 Method for separating alpha-olefin from fischer-tropsch light distillate by using adsorption and distillation to couple olefin

Country Status (2)

Country Link
CN (1) CN115011376B (en)
WO (1) WO2023217303A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115011376B (en) * 2022-05-09 2023-12-12 中海油天津化工研究设计院有限公司 Method for separating alpha-olefin by Fischer-Tropsch light distillate oil adsorption and rectification coupled olefin

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5173173A (en) * 1990-09-28 1992-12-22 Union Oil Company Of California Trace contaminant removal in distillation units
CN109652111A (en) * 2019-01-16 2019-04-19 北京三聚环保新材料股份有限公司 A kind of device and method separating alkene from Fischer-Tropsch synthesis oil
CN111647427A (en) * 2019-03-04 2020-09-11 内蒙古伊泰煤基新材料研究院有限公司 Method for increasing carbon chain length of Fischer-Tropsch alpha-olefin
CN114395416A (en) * 2021-12-17 2022-04-26 中海油天津化工研究设计院有限公司 Method for producing polymer grade high carbon alpha-olefin by coal-based Fischer-Tropsch synthetic oil
CN114409496A (en) * 2021-12-31 2022-04-29 国家能源集团宁夏煤业有限责任公司 Method and device for separating 1-octene from Fischer-Tropsch synthetic oil
CN115011376A (en) * 2022-05-09 2022-09-06 中海油天津化工研究设计院有限公司 Method for separating alpha-olefin by coupling adsorption distillation and olefin of Fischer-Tropsch light fraction oil

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1032532C (en) * 1991-04-01 1996-08-14 中国石油化工总公司石油化工科学研究院 Method of purifying low-carbon alpha-olefin
CN105777467B (en) * 2016-04-13 2018-06-26 上海兖矿能源科技研发有限公司 A kind of method that oxygenatedchemicals and 1- hexenes are detached from oil from Fischer-Tropsch synthesis
WO2020073853A1 (en) * 2018-10-08 2020-04-16 中国石油化工股份有限公司 Method and system for separating light hydrocarbons
CN113198519B (en) * 2021-04-27 2022-09-20 万华化学集团股份有限公司 Method for producing high-purity alpha-olefin by adopting backpack type reaction rectification device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5173173A (en) * 1990-09-28 1992-12-22 Union Oil Company Of California Trace contaminant removal in distillation units
CN109652111A (en) * 2019-01-16 2019-04-19 北京三聚环保新材料股份有限公司 A kind of device and method separating alkene from Fischer-Tropsch synthesis oil
CN111647427A (en) * 2019-03-04 2020-09-11 内蒙古伊泰煤基新材料研究院有限公司 Method for increasing carbon chain length of Fischer-Tropsch alpha-olefin
CN114395416A (en) * 2021-12-17 2022-04-26 中海油天津化工研究设计院有限公司 Method for producing polymer grade high carbon alpha-olefin by coal-based Fischer-Tropsch synthetic oil
CN114409496A (en) * 2021-12-31 2022-04-29 国家能源集团宁夏煤业有限责任公司 Method and device for separating 1-octene from Fischer-Tropsch synthetic oil
CN115011376A (en) * 2022-05-09 2022-09-06 中海油天津化工研究设计院有限公司 Method for separating alpha-olefin by coupling adsorption distillation and olefin of Fischer-Tropsch light fraction oil

Also Published As

Publication number Publication date
CN115011376A (en) 2022-09-06
CN115011376B (en) 2023-12-12

Similar Documents

Publication Publication Date Title
RU2279421C2 (en) Method for production of crude 1,3-butadiene by extractive distillation of c4-cut and device therefor
EP1803699B1 (en) Method for fine cleaning of 1-buten flows
US20080312481A1 (en) Propylene production
WO2023217303A1 (en) Method for separating alpha-olefin from fischer-tropsch light distillate by using adsorption and distillation to couple olefin
CN100513365C (en) Method of double solvents, benzene substitutive rectification for separating c9 aromatics
CN1143623A (en) Separation of (meth) acrylic acid from reaction gas mixture formed in catalytic gas phase oxidation of C3/C4 compounds
CN1285707C (en) Naphtha optimized utilization method
CN109627137B (en) A kind of separation method for coal base Fischer-Tropsch olefins
CN102781891A (en) Process for removing oxygenated contaminants from a hydrocarbon stream
CN103664446A (en) Technology for separating n-hexane-methylcyclopentane through extractive distillation
CN103086823A (en) Method and device for separating n-hexane, isohexane and benzene
CN111100683A (en) Separation method of long-chain alkane-olefin in Fischer-Tropsch synthetic oil
CN113372953A (en) Method for adsorbing and separating saturated hydrocarbon and unsaturated hydrocarbon by FCC (fluid catalytic cracking) gasoline
CN111073677A (en) Separation and purification device and separation and purification process for C8-C20 normal paraffin mixed fraction
CN103664489B (en) Produce the rectificating method of para-xylene product
CN114395416A (en) Method for producing polymer grade high carbon alpha-olefin by coal-based Fischer-Tropsch synthetic oil
CN1309691C (en) Method for working up crude 1,3-butadiene
CN109704907B (en) Method for preparing hexane from raffinate oil
JPH049774B2 (en)
CN101468938B (en) Composite solvent for extracting, distilling and separating styrene in hydrocarbons mixture, and method therefor
CN111548816A (en) Separation and purification device for C8-C20 normal paraffin mixed fraction and thermal coupling process
WO2022042508A1 (en) Composite adsorbent for separating ethylbenzene by adsorptive rectification and use thereof
CN113354502B (en) Method for separating low-carbon hydrocarbon from unsaturated dry gas by combined absorption and recovery
CN104557409B (en) The method of the amylene of high-purity 1
CN101962311B (en) Method and device for increasing service life of extractant in hydrofining process of crude benzene

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23803071

Country of ref document: EP

Kind code of ref document: A1