CN115108878A - Separation method for ethylene oligomerization product and catalyst - Google Patents
Separation method for ethylene oligomerization product and catalyst Download PDFInfo
- Publication number
- CN115108878A CN115108878A CN202210728984.XA CN202210728984A CN115108878A CN 115108878 A CN115108878 A CN 115108878A CN 202210728984 A CN202210728984 A CN 202210728984A CN 115108878 A CN115108878 A CN 115108878A
- Authority
- CN
- China
- Prior art keywords
- tower
- catalyst
- column
- temperature
- organic solvent
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 238000000926 separation method Methods 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000005977 Ethylene Substances 0.000 title claims abstract description 32
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 61
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000047 product Substances 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 238000000605 extraction Methods 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims description 29
- 238000000895 extractive distillation Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 25
- 238000004821 distillation Methods 0.000 abstract description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000005192 partition Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 241000183024 Populus tremula Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000010206 sensitivity analysis Methods 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
- C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
- C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for separating ethylene oligomerization products and a catalyst, which is characterized in that a feed stream containing ethylene oligomerization reaction products, the catalyst and an organic solvent passes through a de-heavy tower, C8, C7, C6 and organic solvent fractions extracted from the top of the de-heavy tower enter a bulkhead tower, the organic solvent and the C7 azeotropic fractions are distributed to the middle part of the bulkhead tower to an extraction rectifying tower, an extracting agent and the organic solvent enter a solvent separation tower, the C6 fractions at the top of the bulkhead tower are extracted to enter a hexene rectifying tower, and heavy components containing the catalyst and more than C10 and C10 and discharged from the bottom of the de-heavy tower enter the catalyst separation tower. The separation method of the invention uses less distillation columns, adopts an extracting agent to assist in separating the solvent and the components in the product, can recover the catalyst and the solvent, obtains the 1-octene and the 1-hexene with higher purity, and simultaneously reduces the equipment cost, and can save energy by 10 percent and investment by about 25 percent compared with the separation method without adopting a dividing wall column.
Description
Technical Field
The invention relates to the technical field of chemical separation, in particular to a separation method for an ethylene oligomerization product and a catalyst.
Background
Alpha-olefin is an important organic chemical raw material and intermediate, can be used as a monomer for producing high-performance polyolefin, and can also be used for producing high-end lubricating oil, plasticizer, surfactant and the like. At present, more than 80 percent of the alpha-olefin in the world is produced by adopting an ethylene oligomerization process. Due to the influence of catalyst, synthesis conditions and the like, the ethylene oligomerization can form a certain range of homologous alpha-olefins (C) with even number of carbon atoms 2n H 2n Where n is a positive integer of 2 or more), or 1-butene, 1-hexene, 1-octene or 1-decene may be produced in a relatively large proportion, and at the same time, unreacted ethylene, an organic solvent used, a terminator and the like may be present in the product, the composition is relatively complicated, and if the desired carbon number of the target product is to be obtained, separation, multiple distillations and the like are required. Since the distillation column is an expensive device and the cost of the target product is affected by the excessive number of distillation columns, it is important to study the separation and distillation. Patent CN201980080126.5 provides a process for the separation of C8+ alpha-olefins using a dividing wall column, which uses a plurality of dividing wall columns, and although a series of homologues are separated, it is costly.
Disclosure of Invention
In order to overcome the technical defects, the invention provides a separation method for recovering ethylene oligomerization products and catalysts with high purity and low cost.
The technical scheme of the invention is that the method for separating the ethylene oligomerization product and the catalyst comprises the following steps:
passing a feed stream containing ethylene oligomerization reaction products, a catalyst and an organic solvent through a de-heavy tower, distributing C8, C7, C6 and organic solvent fractions to the top part of the de-heavy tower, distributing the catalyst and heavy components above C10 and C10 to the bottom part of the de-heavy tower, and entering a catalyst separation tower to separate the catalyst;
c8, C7, C6 and organic solvent fractions extracted from the top of the de-heavy column enter a dividing wall column; distributing the C6 fraction to the top part of a bulkhead column, distributing the C8 fraction to the bottom part of the bulkhead column and finally entering a C8 product tank, and distributing the organic solvent and the C7 azeotropic fraction to the middle part of the bulkhead column to an extractive distillation column; adding an organic solvent and an extracting agent into C7 to generate azeotropic distillation, obtaining C7 distillation at the top of an extraction rectifying tower, and enabling the extracting agent and the organic solvent at the bottom of the tower to enter a solvent separation tower; obtaining an organic solvent product at the top of the solvent separation tower, and circulating the extractant and the supplemented extractant at the bottom of the tower to the extraction and rectification tower to be used as the extractant; extracting organic solvent fraction from the top of the solvent separation tower, refining, deoxidizing, drying, and circularly entering an ethylene tetramerization reaction kettle;
extracting the C6 fraction at the top part of the next door tower into a hexene rectifying tower, introducing the C6 fraction into the hexene rectifying tower, distributing the impurity C6 fraction containing impurities to the top part of the hexene rectifying tower, and distributing the refined C6 fraction to the bottom part of the hexene rectifying tower to enter a product tank;
the heavy components containing catalyst and more than C10 and C10 from the bottom of the de-heavy tower enter a catalyst separation tower, C10-C14 components are extracted from the top of the tower, the rich catalyst fraction extracted from the side line is further purified to extract the catalyst, and the C16+ heavy components extracted from the bottom of the tower enter a heavy component tank.
Furthermore, the number of tower plates of the de-weighting tower is 35-45, 15-20 pedals are used as feeding tower plates, the pressure of the de-weighting tower is 30-40 KpaA, the temperature of the top of the tower is 60-80 ℃, the temperature of the bottom of the tower is 60-150 ℃, the ratio of the feeding flow to the top flow is 1-2: 1, and the mass reflux ratio is 2-3: 1.
Further, the total number of tower plates of the partition tower is 100-140, wherein the number of the tower plates in the middle is 60-70, 75-85 pedals are used as feeding tower plates, the pressure of the partition tower is normal pressure, the temperature of the top of the partition tower is 50-70 ℃, the temperature of the lateral line is 110-130 ℃, the temperature of the bottom of the partition tower is 110-130 ℃, the ratio of the feeding flow to the top flow is 5-9: 1, and the mass reflux ratio is 25-35: 1.
Further, the number of the tower plates of the hexene rectifying tower is 70-90, the 30 th to 40 th pedals are feeding tower plates, the pressure of the hexene rectifying tower is normal pressure, the temperature of the top of the tower is 50-80 ℃, the temperature of the bottom of the tower is 60-90 ℃, the ratio of the feeding flow to the top flow is 1-2: 1, and the mass reflux ratio is 4-7: 1.
Further, the number of the tower plates of the extractive distillation tower is 20-30, 2-5 or 15-20 pedals are used as feeding tower plates, the pressure of the extractive distillation tower is 30-40 KpaG, the temperature of the top of the extractive distillation tower is 80-120 ℃, the temperature of the bottom of the extractive distillation tower is 170-190 ℃, the ratio of the feed stream to the top stream is 2-4: 1 or 10-20: 1, and the mass reflux ratio is 5-10: 1; and the molar ratio of the addition amount of the extracting agent in the extraction rectifying tower to the organic solvent in the feed is 5-7: 1, so that the C7 fraction with the content of 99.5% can be obtained at the top of the extraction rectifying tower.
Further, the number of tower plates of the solvent separation tower is 20-40, the 30 th to 50 th pedals are feeding tower plates, the pressure of the solvent separation tower is 5-15 KpaG, the temperature of the top of the tower is 100-130 ℃, the temperature of the bottom of the tower is 180-210 ℃, the ratio of the feeding flow to the top flow is 1-2: 1, and the mass reflux ratio is 4-6: 1.
Further, the number of tower plates of the catalyst separation tower is 30-50, the 20 th to 40 th pedals are feeding tower plates, the pressure of the catalyst separation tower is 2-4 KpaA, the temperature of the top of the tower is 80-110 ℃, the temperature of the bottom of the tower is 160-180 ℃, the ratio of the feeding flow to the top flow is 3-4: 1, and the mass reflux ratio is 2-4: 1.
This technical scheme has following beneficial effect:
1. the separation method uses less distillation columns, adopts an extracting agent to assist in separating the solvent and the components in the product, can recover the catalyst and the solvent, obtains the 1-octene (the purity can reach 99.9994%) and the 1-hexene (the purity can reach 99%) with higher purity, reduces the equipment cost, and can save 10 percent of energy and about 25 percent of investment compared with the separation method without adopting a dividing wall column;
2. by comparing the two solvents, the difference between the loads of reboilers of different solvents is 10.8 percent, and compared with a method without adopting a dividing wall tower, the difference reaches 22.3 percent, and different solvents are found to influence the energy consumption and equipment investment in the separation process;
3. through extraction and rectification, the solvent is recycled by 97.3 percent.
Drawings
FIG. 1 is a flow chart of the separation process for ethylene oligomerization products and catalyst of the present invention;
FIG. 2 is a graph of the number of trays versus reflux ratio for example 1;
FIG. 3 is a graph of feed position versus reflux ratio for example 1;
FIG. 4 is a graph of operating pressure-reflux ratio-heat load for example 1;
FIG. 5 is a flow chart of comparative example 1;
fig. 6 is a flowchart of comparative example 2.
Detailed Description
The separation method for ethylene oligomerization products and catalyst shown in fig. 1 comprises:
flash evaporating most of H from the feed containing ethylene oligomerization reaction products (namely H2, C8, C7, C6, C10 and heavy components above C10), catalyst and organic solvent by a flash tank 2 Then, the catalyst passes through a de-heavy column a1, C8, C7, C6 and organic solvent fraction are distributed to the top part of a de-heavy column a1, and the catalyst, heavy components above C10 and C10 are distributed to the bottom part of a de-heavy column a1 and enter a catalyst separation column a6 to separate the catalyst;
c8, C7, C6 and the organic solvent fraction extracted from the top of the de-heaving column a1 enter a dividing wall column a 2; distributing the C6 fraction to the top part of a bulkhead column a2, distributing the C8 fraction to the bottom part of the bulkhead column a2 and finally entering a C8 product tank, and distributing the organic solvent and the C7 azeotropic fraction to the middle part of a bulkhead column a2 to an extractive distillation column a 4; the organic solvent and the C7 fraction are subjected to azeotropic distillation and are difficult to be directly separated, an extracting agent is added, the C7 fraction is obtained at the top of the extraction rectifying tower a4, and the extracting agent and the organic solvent at the bottom of the tower enter a solvent separation tower a 5; organic solvent products are obtained at the top of the solvent separation tower a5, and the extractant and the supplementary extractant at the bottom of the tower are recycled to the extraction rectification tower a4 to be used as the extractant; the organic solvent fraction is extracted from the top of the solvent separation tower a5, refined, deoxidized and dried, and then circularly enters the ethylene tetramerization reaction kettle.
The C6 fraction in the column top part of the dividing wall column a2 was withdrawn into the hexene rectifying column a3, the C6 fraction into the hexene rectifying column a3, the impurity C6 fraction containing the impurity was distributed to the column top part of the hexene rectifying column a3, and the refined C6 fraction was distributed to the column bottom of the hexene rectifying column a3 to the product tank.
Heavy components of C10 and above C10 containing catalyst and extracted from the bottom of a heavy component removal tower a1 enter a catalyst separation tower a6, C10-C14 components are extracted from the top of the tower, catalyst is extracted from a rich catalyst fraction extracted from a side line after further purification, and C16+ heavy components extracted from the bottom of the tower enter a heavy component tank.
In this embodiment: the pressure of the flash tank is 0.3-0.75 Mpa, and the temperature is 30-45 ℃; the tower plate number of the de-heavy tower a1 is 35-45, the 15 th to 20 th pedals are feeding tower plates, the pressure of the de-heavy tower a1 is 30-40 KpaA, the tower top temperature is 60-80 ℃, the tower bottom temperature is 60-150 ℃, the ratio of the feed flow to the top flow is 1-2: 1, and the mass reflux ratio is 2-3: 1;
the total number of tower plates of the dividing wall tower a2 is 100-140, wherein the number of tower plates in the middle is 60-70, the 75-85 pedals are feeding tower plates, the pressure of the dividing wall tower a2 is normal pressure, the temperature of the top of the tower is 50-70 ℃, the temperature of the lateral line is 110-130 ℃, the temperature of the bottom of the tower is 110-130 ℃, the ratio of the feeding flow to the top flow is 5-9: 1, and the mass reflux ratio is 25-35: 1;
the number of tower plates of a hexene rectifying tower a3 is 70-90, the 30 th to 40 th pedals are feeding tower plates, the pressure of the hexene rectifying tower a3 is normal pressure, the temperature of the top of the tower is 50-80 ℃, the temperature of the bottom of the tower is 60-90 ℃, the ratio of the feeding flow to the top flow is 1-2: 1, and the mass reflux ratio is 4-7: 1;
the number of the tower plates of the extraction and rectification tower a4 is 20-30, 2-5 or 15-20 pedals are used as feeding tower plates, the pressure of the extraction and rectification tower a4 is 30-40 KpaG, the temperature of the top of the extraction and rectification tower a is 80-120 ℃, the temperature of the bottom of the extraction and rectification tower a is 170-190 ℃, the ratio of the feed flow to the top flow is 2-4: 1 or 10-20: 1, and the mass reflux ratio is 5-10: 1; the molar ratio of the addition amount of the extracting agent in the extraction rectifying tower a4 to the organic solvent in the feed is 5-7: 1, and a C7 fraction with the content of 99.5% can be obtained at the top of the extraction rectifying tower a 4;
the number of tower plates of the solvent separation tower a5 is 20-40, the 30 th to 50 th pedals are feeding tower plates, the pressure of the solvent separation tower a5 is 5-15 KpaG, the temperature of the top of the tower is 100-130 ℃, the temperature of the bottom of the tower is 180-210 ℃, the ratio of the feeding flow to the top flow is 1-2: 1, and the mass reflux ratio is 4-6: 1;
the number of tower plates of the catalyst separation tower a6 is 30-50, the 20 th to 40 th pedals are feeding tower plates, the pressure of the catalyst separation tower a6 is 2-4 KpaA, the temperature of the top of the tower is 80-110 ℃, the temperature of the bottom of the tower is 160-180 ℃, the ratio of the feeding flow to the top flow is 3-4: 1, and the mass reflux ratio is 2-4: 1.
For the heavies removal column a1, the relationship between the number of trays and reflux was analyzed by the sensitivity analysis function in ASPEN to determine the separation requirement, and the graph of fig. 2 was obtained. As can be seen from FIG. 2, after 35 to 40 trays, the change in reflux ratio is no longer significant, and therefore 35 to 40 trays are selected. The relationship between the feeding position and the reflux ratio and the relationship between the feeding position and the heat load energy consumption at the bottom of the tower top are analyzed through sensitivity analysis, as shown in figure 3, the feeding position is at the position where the 15 th to 20 th tower plates are used as the feeding tower plates, the reflux ratio and the heat load are lower, and therefore the 15 th to 20 th tower plates are selected as the feeding position.
Analysis of the change in the operating pressure with respect to the reflux ratio and the heat load at the bottom of the column top was carried out by sensitivity analysis, and as can be seen from FIG. 4, the change in the slope was relatively gentle at 30 to 40KpaA, and therefore 30 to 40KpaA was selected as the column top pressure. After the optimal tower top operation pressure, the optimal tower plate number and the optimal feeding position are determined, the appropriate reflux ratio is 2-3: 1, the ratio of the feed flow to the top flow is determined according to the component content and the separation requirement in the feeding, and the recovery ratio can be obtained after material balance. A typical process for mass balance is as follows:
F＝D+W
f: a feed rate; d: the flow rate at the top of the tower; w: flow rate at the bottom of the tower;
Fx Fi ＝Dy i +Wx i (i＝1～n-1)
x Fi : the content of i component in the feed; y is i : content of i in the overhead fraction；x i : content of i in the bottom fraction
The fraction of the liquid phase product W in the total feeding amount F is recorded as q, the gasification rate D/F is (1-q), and the material balance formula can be expressed as:
x Fi ＝(1-q)y i +qx i (i＝1～n)
obviously, the component is x Fi When the material is divided into two streams of q and (1-q), the compositions of the two streams of material are yi and x i The above material balance formula is necessarily satisfied.
For several other columns, the above analysis was also performed to obtain the appropriate operating parameters in the examples, which are not described herein again.
Example 1
Simulation calculations for the flow are performed using ASPEN PLUS. The reaction product enters an ethylene separation tank, most of unreacted ethylene and other light components are flashed out under the pressure of 0.5Mpag, and the top of the flash tank is provided with a chilled water cooler, so that the loss of effective components is reduced. And (3) pumping the flashed ethylene oligomerization reaction product, the catalyst and the organic solvent, and then exchanging heat with the bottom product of the de-weighting tower to 58 ℃ to enter the de-weighting tower. Cutting and separating octene from heavy components of C10 and above C10 in a de-heavy tower, wherein the operating pressure of the de-heavy tower is 30kpa, the temperature of the top of the de-heavy tower is 72 ℃, the temperature of the bottom of the de-heavy tower is 147 ℃, the heavy components at the bottom of the de-heavy tower enter a catalyst separation tower, the operating pressure of the catalyst separation tower is 2kpa, the temperature of the top of the de-heavy tower is 90 ℃, the temperature of the bottom of the de-heavy tower is 172 ℃, C10-C14 fractions are extracted from the top of the de-heavy tower, the catalyst is obtained after the catalyst-rich fractions extracted from the side line are adsorbed and refined, C16+ heavy components extracted from the bottom of the de-heavy tower and fed in heat exchange mode to 60 ℃, and then the catalyst is cooled to 40 ℃ by a water cooler and is discharged out of the device; and (4) introducing octene and the following light components at the top of the heavy component removal tower into a partition wall tower. Cutting and separating C6, organic solvent and octene in a bulkhead tower, extracting C6 light components from the tower top, feeding the light components into a hexene rectifying tower, extracting an azeotrope of the organic solvent and C7 components from the side line of an auxiliary tower, and extracting an octene product from the tower bottom; the operation pressure of the dividing wall tower is normal pressure, the tower top temperature is 64 ℃, the lateral line is 114 ℃, and the tower bottom temperature is 123 ℃. In a hexene rectifying tower, the separation of hexene and impurity C6 is realized, a 1-hexene product with the purity of 99 percent is obtained at the tower top, the operation pressure of the hexene rectifying tower is normal pressure, the tower top temperature is 63 ℃, and the tower bottom temperature is 82 ℃. C7 and an organic solvent enter the lower part of an extraction rectifying tower, phenol is used as an extracting agent to enter the upper part of the extraction rectifying tower, C7 fraction is extracted from the top of the extraction rectifying tower, the extracting agent and the organic solvent at the bottom of the extraction rectifying tower enter an organic solvent separation tower, the operating pressure of the extraction rectifying tower is 120kpa, the temperature at the top of the extraction rectifying tower is 105 ℃, and the temperature at the bottom of the extraction rectifying tower is 176 ℃; the method comprises the following steps of recovering an organic solvent from the top of an organic solvent separation tower, deoxidizing, drying, circulating the organic solvent back to a reaction system, recovering an extracting agent from the bottom of the organic solvent separation tower, supplementing a small amount of lost extracting agent, circulating the extracting agent back to the upper part of an extraction rectification tower, recycling the organic solvent by 97.3%, controlling the operation pressure of the organic solvent separation tower to be 110KpaA, controlling the top of the tower to be 110 ℃, controlling the bottom of the tower to be 190 ℃, and controlling the molar ratio of the extracting agent to C7 fraction to be 5-7, so that the C7 fraction has the purity of 99.5%. The purity of 1-octene was 99.9994%, and the purity of 1-hexene was 99.9%.
TABLE 1
Comparative example 1
As shown in figure 5, the reaction product enters an ethylene separation tank, most of light components such as unreacted ethylene are flashed out under the pressure of 0.5Mpag, and a chilled water cooler is arranged at the top of the flash tank, so that the loss of effective components is reduced. And (3) pumping the reaction product after flash evaporation and an organic solvent, and then exchanging heat with a product at the bottom of the de-weighting tower to 58 ℃ to enter the de-weighting tower.
Cutting and separating octene and heavy components in a de-heavy tower b1, wherein the operating pressure of the de-heavy tower b1 is 30kpa (A), the temperature of the top of the tower is 72 ℃, the temperature of the bottom of the tower is 147 ℃, the heavy components at the bottom of the tower enter a catalyst separation tower b7, a chilled water cooler is arranged on a reflux tank of the de-heavy tower b1, the cooling is carried out to 20 ℃, and the loss of effective components is reduced; the operating pressure of a catalyst separation tower b7 is 2Kpa (A), the temperature at the top of the tower is 90 ℃, the temperature at the bottom of the tower is 172 ℃, C10-C14 fractions are extracted from the top of the tower, catalyst-rich fractions are extracted from the side line and are subjected to adsorption refining to obtain a catalyst, C16+ heavy components extracted from the bottom of the tower exchange heat with feed to 60 ℃, and then the mixture is cooled to 40 ℃ by a water cooler and is taken out of the device; and the overhead octene and the following light components of the heavy component removal column b1 enter a C6-C8 separation column b 2. In a C6-C8 separation tower b2, the cutting separation of C6, an organic solvent and heavier components is realized, light components enter a hexene rectifying tower, and heavy components enter an organic solvent-octene rectifying tower b 4; in an organic solvent-octene rectifying tower b4, the overhead distillate is C7 and azeotropic organic solvent, the tower bottom is 99.99 percent of high-purity 1-octene product, the operating pressure of an organic solvent-octene rectifying tower b4 is 30Kpa (A), the tower top temperature is 74 ℃, and the tower bottom temperature is 104 ℃. In a hexene rectifying tower b3, the separation of hexene and a mixed C6 impurity is realized, a 1-hexene product with the purity of 99% is obtained at the tower top, the operation pressure of the hexene rectifying tower b3 is normal pressure, the tower top temperature is 63 ℃, and the tower bottom temperature is 82 ℃. C7 and an organic solvent enter the lower part of an extraction rectifying tower b5, phenol is used as an extracting agent to enter the upper part of an extraction rectifying tower b5, C7 fraction is extracted from the top of the extraction rectifying tower b5, the extracting agent and the organic solvent at the bottom of the tower enter a solvent separation tower b6, the operating pressure of the extraction rectifying tower b5 is 120kpa (A), the temperature of the top of the tower is 105 ℃, and the temperature of the bottom of the tower is 176 ℃; the method comprises the following steps of recovering an organic solvent from the top of an organic solvent separation tower, deoxidizing, drying, circulating the organic solvent back to a reaction system, recovering an extracting agent from the bottom of the organic solvent separation tower, supplementing a small amount of lost extracting agent, and circulating the extracting agent back to the upper part of an extraction rectification tower, wherein the organic solvent can be recycled at 97.3 percent, the operating pressure of the organic solvent separation tower is 110Kpa (A), the top of the tower is 110 ℃, the bottom of the tower is 190 ℃, and the molar ratio of the extracting agent to C7 fraction is 5-7, so that the C7 fraction can reach the purity of 99.5 percent. The purity of 1-octene was 99.9994%, and the purity of 1-hexene was 99.9%.
TABLE 2
Example 1 in comparison to comparative example 1: in example 1, the dividing wall column technology is used, the load of a condenser at the top of the tower is reduced by 6.9 percent, the load of a reboiler is reduced by 9.1 percent, and the investment is saved by about 25 percent. Of the solvents, 2.7% was incorporated into the other products, and 97.3% was recovered for use. In the extraction and rectification process, 0.0375% of extractant needs to be supplemented so as to ensure stable circulation in the extraction and rectification process.
Comparative example 2
In example 1, where the solvent used in the reaction section is toluene or other similar boiling solvent, and if a solvent that is lighter than C7 and does not azeotropically react with C7 or other reaction product cuts is used, such as dimethyl carbonate (DMC), the flow chart for the simulation calculations is as follows:
simulation calculations for the flow are performed using ASPEN PLUS. As shown in figure 6, the reaction product enters an ethylene separation tank, most of light components such as unreacted ethylene are flashed out under the pressure of 0.5Mpag, and a chilled water cooler is arranged at the top of the flash tank, so that the loss of effective components is reduced. And (3) pumping the reaction product after flash evaporation and a solvent, and then exchanging heat with a product at the bottom of the de-heavy tower to 70 ℃ to enter the de-heavy tower. Cutting and separating octene and heavy components in a de-heavy tower c1, wherein the operating pressure of the de-heavy tower c1 is 110kpa (A), the temperature of the top of the tower is 104 ℃, the temperature of the bottom of the tower is 205 ℃, the heavy components at the bottom of the tower enter a catalyst separation tower c6, a chilled water cooler is arranged on a reflux tank of the de-heavy tower c1, the cooling is carried out to 20 ℃, and the loss of effective components is reduced; the operating pressure of a catalyst separation tower C6 is 2Kpa (A), the temperature at the top of the tower is 90 ℃, the temperature at the bottom of the tower is 172 ℃, C10-C14 fractions are extracted from the top of the tower, catalyst-rich fractions are extracted from the side line and are subjected to adsorption refining to obtain a catalyst, C16+ heavy components extracted from the bottom of the tower exchange heat with feed materials to 60 ℃, and then the mixture is cooled to 40 ℃ by a water cooler and is discharged from the device; and the overhead octene and the following light components of the heavy component removal column C1 enter a C6-C7 separation column C2. Cutting and separating C6, C7 and octene in a C6-C7 separation tower C2, introducing C6 light components and an organic solvent extracted from the tower top into a hexene rectifying tower C3, introducing C7 and C8 products extracted from the tower bottom into an octene rectifying tower C5, wherein the operation pressure of the C2 of the C6-C7 separation tower is normal pressure, the temperature of the tower top is 84 ℃, and the temperature of the tower bottom is 131 ℃; a hexene product with the purity of 99 percent is obtained at the top of a hexene rectifying tower C3, the bottom of the tower is mixed C6 and a solvent which enter an organic solvent rectifying tower C4, the pressure at the top of the hexene rectifying tower C3 is 120Kpa (A), the temperature at the top of the tower is 68 ℃, and the temperature at the bottom of the tower is 103 ℃; the mixed C6 product is obtained at the top of the organic solvent rectifying tower C4, the organic solvent is at the bottom of the tower, the organic solvent is deoxidized and dried and then circulated back to the reaction system, the operating pressure of the solvent separation tower is 110Kpa (A), the temperature at the top of the tower is 84 ℃, and the temperature at the bottom of the tower is 96 ℃. In an octene rectifying tower, C7 fraction is obtained at the top of the tower, 99.9994% of octene product is obtained at the bottom of the tower, the operating pressure of the octene rectifying tower is 30Kpa (A), the temperature at the top of the tower is 74 ℃, and the temperature at the bottom of the tower is 104 ℃.
TABLE 3
Comparative example 2 compared to example 1, where the separation was also achieved using 6 columns, comparative example 2 increased the overhead condenser duty by 3.5% but the reboiler duty was reduced by 10.8% compared to example 1; compared with the comparative example 1, the comparative example 2 has the advantages that 1 tower is reduced compared with the comparative example 1, the load of a condenser at the top of the tower is reduced by 3.25%, the load of a reboiler is reduced by 22.3%, and a better energy-saving effect is achieved.
Claims (7)
1. A method for separating ethylene oligomerization products from a catalyst is characterized in that: the separation method comprises the following steps:
passing a feed stream containing ethylene oligomerization reaction products, a catalyst and an organic solvent through a de-heavy column (a1), distributing C8, C7, C6 and organic solvent fractions to the top part of the de-heavy column (a1), distributing the catalyst, the heavy components above C10 and C10 to the bottom part of the de-heavy column (a1) and entering a catalyst separation column (a6) to separate the catalyst;
c8, C7, C6 and organic solvent fraction extracted from the top of the de-heaving column (a1) enter a dividing wall column (a 2); distributing the C6 fraction to the top part of a bulkhead column (a2), distributing the C8 fraction to the bottom part of the bulkhead column (a2) and finally entering a C8 product tank, and distributing the organic solvent and the C7 azeotropic fraction to the middle part of the bulkhead column (a2) and the extractive distillation column (a 4); adding an extracting agent into the organic solvent and C7 to generate azeotropic fraction, obtaining C7 fraction at the top of the extraction rectifying tower (a4), and enabling the extracting agent and the organic solvent at the bottom of the tower to enter a solvent separation tower (a 5); organic solvent products are obtained at the top of the solvent separation tower (a5), and the extractant and the supplementary extractant at the bottom of the tower are recycled to the extractive distillation tower (a4) to be used as the extractant; extracting the organic solvent fraction from the top of a solvent separation tower (a5), refining, deoxidizing, drying, and recycling the organic solvent fraction into an ethylene tetramerization reaction kettle;
the C6 fraction in the column top part of the dividing wall column (a2) is extracted into a hexene rectifying column (a3), the C6 fraction in the hexene rectifying column (a3), the mixed C6 fraction containing impurities is distributed to the column top part of the hexene rectifying column (a3), and the refined C6 fraction is distributed to the column bottom of the hexene rectifying column (a3) and enters a product tank;
heavy components of C10 and C10 containing catalyst and coming out from the bottom of the heavy component removal tower (a1) enter a catalyst separation tower (a6), C10-C14 components are extracted from the top of the tower, catalyst is extracted from a catalyst-rich fraction extracted from a side line after further purification, and C16+ heavy components are extracted from the bottom of the tower and enter a heavy component tank.
2. The process according to claim 1 for separating ethylene oligomerization products and catalyst, wherein: the number of tower plates of the de-weighting tower (a1) is 35-45, the 15 th to 20 th pedals are feeding tower plates, the pressure of the de-weighting tower (a1) is 30-40 KpaA, the temperature of the top of the tower is 60-80 ℃, the temperature of the bottom of the tower is 60-150 ℃, the ratio of the feeding flow to the top flow is 1-2: 1, and the mass reflux ratio is 2-3: 1.
3. The process for the separation of an ethylene oligomerization product and a catalyst according to claim 1, wherein: the total number of the tower plates of the dividing wall tower (a2) is 100-140, wherein the number of the middle tower plates is 60-70, the 75-85 th pedals are used as feeding tower plates, the pressure of the dividing wall tower (a2) is normal pressure, the temperature of the top of the dividing wall tower is 50-70 ℃, the temperature of the lateral line is 110-130 ℃, the temperature of the bottom of the dividing wall tower is 110-130 ℃, the ratio of the feeding flow to the top flow is 5-9: 1, and the mass reflux ratio is 25-35: 1.
4. The process according to claim 1 for separating ethylene oligomerization products and catalyst, wherein: the number of the tower plates of the hexene rectifying tower (a3) is 70-90, the 30 th to 40 th pedals are feeding tower plates, the pressure of the hexene rectifying tower (a3) is normal pressure, the temperature of the top of the tower is 50-80 ℃, the temperature of the bottom of the tower is 60-90 ℃, the ratio of the feeding flow to the top flow is 1-2: 1, and the mass reflux ratio is 4-7: 1.
5. The process according to claim 1 for separating ethylene oligomerization products and catalyst, wherein: the number of the tower plates of the extractive distillation tower (a4) is 20-30, the 2 nd-5 th or 15 th-20 th pedal is a feeding tower plate, the pressure of the extractive distillation tower (a4) is 30-40 KpaG, the temperature of the top of the extractive distillation tower is 80-120 ℃, the temperature of the bottom of the extractive distillation tower is 170-190 ℃, the ratio of the feed flow to the top flow is 2-4: 1 or 10-20: 1, and the mass reflux ratio is 5-10: 1; and the molar ratio of the addition amount of the extracting agent in the extraction rectifying tower (a4) to the organic solvent in the feed is 5-7: 1.
6. The process for the separation of an ethylene oligomerization product and a catalyst according to claim 1, wherein: the number of the tower plates of the solvent separation tower (a5) is 20-40, the 30 th to 50 th pedals are feeding tower plates, the pressure of the solvent separation tower (a5) is 5-15 KpaG, the temperature of the top of the tower is 100-130 ℃, the temperature of the bottom of the tower is 180-210 ℃, the ratio of the feeding flow to the top flow is 1-2: 1, and the mass reflux ratio is 4-6: 1.
7. The process according to claim 1 for separating ethylene oligomerization products and catalyst, wherein: the number of tower plates of the catalyst separation tower (a6) is 30-50, the 20 th to 40 th pedals are feeding tower plates, the pressure of the catalyst separation tower (a6) is 2-4 KpaA, the temperature of the top of the tower is 80-110 ℃, the temperature of the bottom of the tower is 160-180 ℃, the ratio of the feed flow to the top flow is 3-4: 1, and the mass reflux ratio is 2-4: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210728984.XA CN115108878B (en) | 2022-06-24 | 2022-06-24 | Separation method for ethylene oligomerization products and catalysts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210728984.XA CN115108878B (en) | 2022-06-24 | 2022-06-24 | Separation method for ethylene oligomerization products and catalysts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115108878A true CN115108878A (en) | 2022-09-27 |
| CN115108878B CN115108878B (en) | 2023-12-01 |
Family
ID=83328873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210728984.XA Active CN115108878B (en) | 2022-06-24 | 2022-06-24 | Separation method for ethylene oligomerization products and catalysts |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115108878B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116969809A (en) * | 2023-07-28 | 2023-10-31 | 连云港石化有限公司 | Method and device for separating 1-octene from ethylene oligomerization reactant |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819299A (en) * | 2014-02-24 | 2014-05-28 | 上海兖矿能源科技研发有限公司 | Method for separating and purifying 1-hexene in carbon hydrogen mixture |
| CN105777467A (en) * | 2016-04-13 | 2016-07-20 | 上海兖矿能源科技研发有限公司 | Method for separating oxygenated chemicals and 1-hexene from Fischer-Tropsch synthesis oil product |
| CN106588551A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Separation method of 1-hexylene namely ethylene oligomerization product |
| CN109096033A (en) * | 2018-07-17 | 2018-12-28 | 天津大学 | Remove the method and apparatus of oxygenatedchemicals in Fischer-Tropsch synthesis oil narrow fraction |
| CN109982991A (en) * | 2016-12-19 | 2019-07-05 | 沙特基础工业全球技术有限公司 | The method of segregated linear alpha-olefin |
| CN113166001A (en) * | 2018-12-04 | 2021-07-23 | 埃克森美孚化学专利公司 | Process for separating linear alpha-olefins using a divided wall column |
| CN113511949A (en) * | 2021-08-06 | 2021-10-19 | 迈瑞尔实验设备（上海）有限公司 | Production process for co-producing 1-hexene and 1-octene through ethylene selective oligomerization |
-
2022
- 2022-06-24 CN CN202210728984.XA patent/CN115108878B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819299A (en) * | 2014-02-24 | 2014-05-28 | 上海兖矿能源科技研发有限公司 | Method for separating and purifying 1-hexene in carbon hydrogen mixture |
| CN106588551A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Separation method of 1-hexylene namely ethylene oligomerization product |
| CN105777467A (en) * | 2016-04-13 | 2016-07-20 | 上海兖矿能源科技研发有限公司 | Method for separating oxygenated chemicals and 1-hexene from Fischer-Tropsch synthesis oil product |
| CN109982991A (en) * | 2016-12-19 | 2019-07-05 | 沙特基础工业全球技术有限公司 | The method of segregated linear alpha-olefin |
| CN109096033A (en) * | 2018-07-17 | 2018-12-28 | 天津大学 | Remove the method and apparatus of oxygenatedchemicals in Fischer-Tropsch synthesis oil narrow fraction |
| CN113166001A (en) * | 2018-12-04 | 2021-07-23 | 埃克森美孚化学专利公司 | Process for separating linear alpha-olefins using a divided wall column |
| CN113511949A (en) * | 2021-08-06 | 2021-10-19 | 迈瑞尔实验设备（上海）有限公司 | Production process for co-producing 1-hexene and 1-octene through ethylene selective oligomerization |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116969809A (en) * | 2023-07-28 | 2023-10-31 | 连云港石化有限公司 | Method and device for separating 1-octene from ethylene oligomerization reactant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115108878B (en) | 2023-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2619113C2 (en) | A method of selecting hexene-1 from a mixture of products produced in the ethylene trimerization zone | |
| US7982086B2 (en) | Deisobutenizer | |
| US20060047176A1 (en) | Butane removal in C4 upgrading processes | |
| KR101115220B1 (en) | Method and Device for Extractive Distillation | |
| JP2012522047A (en) | Systems and processes for producing linear alpha olefins | |
| US5122236A (en) | Method for removal of dimethyl ether and methanol from c4 hydrocarbon streams | |
| US8252150B1 (en) | Extractive distillation process for recovering butadiene from C4 hydrocarbon mixtures | |
| CN115108878B (en) | Separation method for ethylene oligomerization products and catalysts | |
| CN109851586A (en) | The purification process of propylene oxide | |
| EP1777208B1 (en) | Method for oligomerization of ethylene and reactor system therefore with cooling device | |
| CA2965476C (en) | Breaking a methanol/methyl methacrylate azeotrope using pressure swing distillation | |
| CN100378048C (en) | Method of extracting, rectifying and separating aromatic hydrocarbons and extracting and rectifying apparatus | |
| US11401221B2 (en) | Method for producing a stream of propylene and associated facility | |
| US11591303B2 (en) | Method and system for producing epoxyalkane | |
| CN109851589B (en) | Propylene oxide purification method and purification apparatus | |
| EP3429716B1 (en) | Process for recovering aldehyde obtained by hydroformulation in two columns with increasing pressure | |
| CN103012102B (en) | Method of recovering acetic acid and water in production of aromatic carboxylic acid | |
| CN110945108A (en) | Raffinate-2 refining process | |
| CN111718256B (en) | Acetic acid dehydration method | |
| JP5863734B2 (en) | Systems and processes for producing linear alpha olefins | |
| CN109851581B (en) | Method for purifying butylene oxide | |
| CN105218342A (en) | The processing method of pimelinketone is produced in a kind of cyclohexanol dehydrogenation | |
| CN105579424A (en) | Processes and systems for separating streams to provide a transalkylation feed stream in an aromatics complex | |
| CN115491229B (en) | Separation method of high-temperature Fischer-Tropsch synthesis light oil | |
| EP2240424A1 (en) | Process for separating diisopropylbenzene (dipb) and triisopropylbenzene (tipb) from a feed comprising dipb, tipb, and polyalkylate heavies |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |