CN115108878B - Separation method for ethylene oligomerization products and catalysts - Google Patents
Separation method for ethylene oligomerization products and catalysts Download PDFInfo
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- 238000000926 separation method Methods 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000005977 Ethylene Substances 0.000 title claims abstract description 31
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 57
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000047 product Substances 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 238000000605 extraction Methods 0.000 claims abstract description 27
- 238000005192 partition Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract 2
- 238000010992 reflux Methods 0.000 claims description 29
- 238000000895 extractive distillation Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 22
- 238000004821 distillation Methods 0.000 abstract description 6
- 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 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
- 238000004458 analytical method Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010206 sensitivity analysis Methods 0.000 description 3
- 238000001179 sorption measurement 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
- 238000004364 calculation method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 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
- 230000004580 weight loss Effects 0.000 description 1
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
Abstract
The invention discloses a separation method for ethylene oligomerization products and catalysts, which comprises the steps that a feed stream containing ethylene oligomerization reaction products, catalysts and organic solvents passes through a heavy removal tower, C8, C7, C6 and organic solvent fractions extracted from the top of the heavy removal tower enter a partition tower, the organic solvents and C7 azeotropic fractions are distributed to the middle part of the partition tower to an extraction rectifying tower, an extractant and the organic solvents enter a solvent separation tower, the C6 fraction at the top of the partition tower is extracted to enter a hexene rectifying tower, and the heavy components containing the catalysts, namely C10 and more than C10, from the bottom of the heavy removal tower enter a catalyst separation tower. The separation method of the invention uses fewer distillation towers, adopts an extractant to assist in separating the solvent from the components in the product, can recycle the catalyst and the solvent to obtain 1-octene and 1-hexene with higher purity, and simultaneously reduces the equipment cost, and can save energy by 10% and save investment by about 25% compared with the method without using a partition tower.
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% of the global alpha-olefins are produced by adopting an ethylene oligomerization process. Due to catalyst, synthesis conditions, etcThe ethylene oligomerization can form a range of homologous alpha-olefins (C) 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 large proportion, and unreacted ethylene, an organic solvent used, a terminator, etc. may be present in the product, and the components are relatively complicated, and it is necessary to conduct separation, distillation, etc. for obtaining the desired carbon number of the target product. Since the distillation tower is an expensive device, excessive distillation towers can affect the cost of target products, and thus, the research on separation and distillation of the target products is of great significance. Patent CN201980080126.5 provides a process for separating olefins comprising c8+ alpha-olefins using a divided wall column which uses a plurality of divided wall columns, although separating a series of homologs, is costly.
Disclosure of Invention
In order to overcome the technical defects, the invention provides a separation method for recovering an ethylene oligomerization product and a catalyst, wherein the separation method has high purity and low cost.
The technical scheme of the invention is that the separation method for the ethylene oligomerization product and the catalyst comprises the following steps:
passing a feed stream comprising ethylene oligomerization products, catalyst, and organic solvent through a de-heavies column, distributing C8, C7, C6, and organic solvent fractions to the top portion of the de-heavies column, distributing catalyst, C10 and above C10 heavy components to the bottom portion of the de-heavies column, and entering a catalyst separation column to separate catalyst;
c8, C7, C6 and organic solvent fractions extracted from the top of the heavy ends removing tower enter a dividing wall tower; distributing the C6 fraction to the top part of the dividing wall column, distributing the C8 fraction to the bottom part of the dividing wall column and finally entering a C8 product tank, and distributing the organic solvent and the C7 azeotropic fraction to the middle part of the dividing wall column to the extractive distillation column; the organic solvent and the C7 are added with the extractant to generate azeotropic fraction, the C7 fraction is obtained at the top of the extraction rectifying tower, and the extractant at the bottom of the extraction rectifying tower and the organic solvent enter a solvent separating tower; obtaining an organic solvent product at the top of the solvent separation tower, and recycling the extractant at the bottom of the solvent separation tower and the supplementary extractant back to the extraction rectifying tower to serve as the extractant; extracting the organic solvent fraction from the top of the solvent separation tower, refining, deoxidizing and drying, and recycling the organic solvent fraction into the ethylene tetramerization reaction kettle;
extracting C6 fraction at the top of the partition tower, entering a hexene rectifying tower, entering C6 fraction of the hexene rectifying tower, distributing impurity C6 fraction containing impurities to the top of the hexene rectifying tower, distributing refined C6 fraction to the bottom of the hexene rectifying tower, and entering a product tank;
and (3) introducing the C10 and more than C10 heavy components containing the catalyst, which are discharged from the bottom of the heavy component removing tower, into a catalyst separating tower, extracting the C10-C14 components from the top of the catalyst separating tower, extracting the catalyst from the catalyst-rich fraction extracted from the side line, and introducing the C16+ heavy components extracted from the bottom of the catalyst separating tower into a heavy component tank.
Further, the tray number of the heavy removal tower is 35-45, the 15 th-20 th pedals are feeding trays, the pressure of the heavy removal tower is 30-40 KpaA, the tower top temperature is 60-80 ℃, the tower bottom temperature is 60-150 ℃, the ratio of feeding flow to top flow is 1-2:1, and the mass reflux ratio is 2-3:1.
Further, the total number of the tower plates of the partition tower is 100-140, wherein the number of the middle tower plates is 60-70, the 75-85 pedal is a feeding tower plate, the pressure of the partition tower is normal pressure, the temperature of the tower top is 50-70 ℃, the side line temperature is 110-130 ℃, the temperature of the tower bottom 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 tower plates of the hexene rectifying tower is 70-90, the 30-40 th pedal is a feeding tower plate, the pressure of the hexene rectifying tower is normal pressure, the temperature of the tower top is 50-80 ℃, the temperature of the tower bottom 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 tower plates of the extraction rectifying tower is 20-30, the 2 nd-5 th or 15 th-20 th pedal is a feeding tower plate, the pressure of the extraction rectifying tower is 30-40 KpaG, the temperature of the tower top is 80-120 ℃, the temperature of the tower bottom is 170-190 ℃, the ratio of a feeding flow to a 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 of the extractant to the organic solvent in the feed is 5-7:1, and C7 fraction with the content of 99.5% can be obtained at the top of the extractive distillation column.
Further, the number of tower plates of the solvent separation tower is 20-40, the 30-50 th pedal is a feeding tower plate, the pressure of the solvent separation tower is 5-15 KpaG, the temperature of the tower top is 100-130 ℃, the temperature of the tower bottom 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-40 th pedal is a feeding tower plate, the pressure of the catalyst separation tower is 2-4 KpaA, the temperature of the tower top is 80-110 ℃, the temperature of the tower bottom is 160-180 ℃, the ratio of a feeding stream to a top stream is 3-4:1, and the mass reflux ratio is 2-4:1.
The technical scheme has the following beneficial effects:
1. the separation method of the invention uses fewer distillation towers, adopts an extractant to assist in separating the solvent from the components in the product, can recycle the catalyst and the solvent, and obtain 1-octene (the purity can reach 99.9994%) and 1-hexene (the purity can reach 99%), simultaneously reduces the equipment cost, saves energy by 10% and saves the investment by about 25% compared with the method without using a partition tower;
2. by comparing the two solvents, the load of reboiler of different solvents is different by 10.8%, and compared with that of the reboiler without using a partition tower, the load of reboiler of different solvents is different by 22.3%, and the energy consumption and equipment investment of the separation process are also affected by the different solvents;
3. through extractive distillation, 97.3% recovery and use of the solvent are realized.
Drawings
FIG. 1 is a flow chart of a separation process for ethylene oligomerization products and catalysts according to the present invention;
FIG. 2 is a graph of tray number-reflux ratio of example 1;
FIG. 3 is a graph of feed position versus reflux ratio for example 1;
FIG. 4 is a graph of operating pressure versus reflux ratio versus heat load for example 1;
FIG. 5 is a flow chart of comparative example 1;
FIG. 6 is a flow chart of comparative example 2.
Detailed Description
The separation process for ethylene oligomerization products and catalyst as shown in fig. 1 comprises:
the feed containing ethylene oligomerization reaction products (namely H2, C8, C7, C6, C10 and above C10 heavy components), catalyst and organic solvent is flashed to obtain most of H by a flash tank 2 Then, C8, C7, C6 and organic solvent fractions are distributed to the top part of the heavy-removal tower a1 through the heavy-removal tower a1, and the catalyst, heavy components above C10 and C10 are distributed to the bottom part of the heavy-removal tower a1 and enter a catalyst separation tower a6 to separate the catalyst;
c8, C7, C6, organic solvent fractions withdrawn from the top of the de-heavies column a1 enter a dividing wall column a2; distributing the C6 fraction to the top part of the dividing wall column a2, distributing the C8 fraction to the bottom part of the dividing wall 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 dividing wall column a2 to the extractive distillation column a4; the organic solvent and the C7 fraction are azeotroped and difficult to be directly separated, an extractant is added, the C7 fraction is obtained at the top of the extractive distillation column a4, and the extractant at the bottom of the extractive distillation column and the organic solvent enter a solvent separation column a5; obtaining an organic solvent product at the top of the solvent separation tower a5, and recycling the extractant at the bottom of the solvent separation tower and the supplementary extractant back to the extraction rectifying tower a4 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 an ethylene tetramerization reaction kettle.
C6 fraction at the top of the partition tower a2 is extracted and enters a hexene rectifying tower a3, C6 fraction entering the hexene rectifying tower a3, impurity C6 fraction containing impurities is distributed to the top of the hexene rectifying tower a3, refined C6 fraction is distributed to the bottom of the hexene rectifying tower a3 and enters a product tank.
And (3) introducing the C10 and more than C10 heavy components containing the catalyst, which are discharged from the bottom of the heavy removal tower a1, into a catalyst separation tower a6, extracting the C10-C14 components from the top of the catalyst separation tower, extracting the catalyst after further purifying the catalyst-rich fraction from the side-draw line, and introducing the C16+ heavy components from the bottom of the catalyst separation tower into 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 number of tower plates of the heavy-removal tower a1 is 35-45, the 15 th-20 th pedals are feeding tower plates, the pressure of the heavy-removal tower a1 is 30-40 KpaA, the temperature of the tower top is 60-80 ℃, the temperature of the tower bottom is 60-150 ℃, the ratio of feeding flow to top flow is 1-2:1, and the mass reflux ratio is 2-3:1;
the total number of tower plates of the partition tower a2 is 100-140, wherein the number of the middle tower plates is 60-70, the 75-85 pedal plates are feeding tower plates, the pressure of the partition tower a2 is normal pressure, the temperature of the tower top is 50-70 ℃, the lateral line temperature is 110-130 ℃, the temperature of the tower bottom 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 the hexene rectifying tower a3 is 70-90, the 30-40 th pedal is a feeding tower plate, the pressure of the hexene rectifying tower a3 is normal pressure, the temperature of the tower top is 50-80 ℃, the temperature of the tower bottom 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 tower plates of the extraction rectifying tower a4 is 20-30, the 2 nd-5 th or 15-20 th pedal is a feeding tower plate, the pressure of the extraction rectifying tower a4 is 30-40 KpaG, the temperature of the tower top is 80-120 ℃, the temperature of the tower bottom is 170-190 ℃, the ratio of the feeding 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 of the extractant to the organic solvent in the feed in the extractive distillation column a4 is 5-7:1, and C7 fraction with the content of 99.5% can be obtained at the top of the extractive distillation column a4;
the number of tower plates of the solvent separation tower a5 is 20-40, the 30-50 th pedal is a feeding tower plate, the pressure of the solvent separation tower a5 is 5-15 KpaG, the temperature of the tower top is 100-130 ℃, the temperature of the tower bottom is 180-210 ℃, the ratio of a feeding flow to a top flow is 1-2:1, and the mass reflux ratio is 4-6:1;
the number of the tower plates of the catalyst separation tower a6 is 30-50, the 20 th-40 th pedal is a feeding tower plate, the pressure of the catalyst separation tower a6 is 2-4 KpaA, the temperature of the tower top is 80-110 ℃, the temperature of the tower bottom 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 weight loss column a1, the relationship between the number of trays and the reflux was analyzed by the sensitivity analysis function in ASPEN after the separation requirement was determined, and the curve of fig. 2 was obtained. As can be seen from FIG. 2, after 35 to 40 trays, the reflux ratio change is no longer obvious, so the number of the selected trays is 35 to 40. As can be seen from the analysis of the relation between the feeding position and the reflux ratio and the heat load energy consumption of the tower top and the tower bottom by the sensitivity analysis, the feeding position is at the position where 15 th to 20 th tower plates are feeding tower plates, and the reflux ratio and the heat load are lower, so that 15 th to 20 th tower plates are selected as the feeding position.
As can be seen from fig. 4, the slope change was relatively gentle at 30 to 40kpa as a result of the analysis of the change curve of the operating pressure, the reflux ratio and the heat load at the top and bottom of the column by the sensitivity analysis, and thus 30 to 40kpa was selected as the top pressure. After the optimal tower top operating pressure, the tower plate number and the optimal feeding position are determined, a proper reflux ratio of 2-3:1 can be obtained, and the feeding flow and top flow ratio can be obtained after material balance according to the component content and separation requirements in the feeding. The typical process of mass balance is as follows:
F＝D+W
f: a feed flow rate; d: overhead flow; w: bottom flow;
Fx Fi ＝Dy i +Wx i (i＝1～n-1)
x Fi : the content of component i in the feed; y is i : the content of i in the overhead fraction; x is x i : content of i in bottom fraction
The fraction of the liquid phase product W in the total feed amount F is recorded as q, the gasification rate D/F= (1-q), and the material balance formula can be expressed as follows:
x Fi ＝(1-q)y i +qx i (i＝1～n)
obviously, the components are divided into x Fi When the material of (2) is divided into q and (1-q) two streams, the compositions of the two streams yi, x i The material balance formula is necessarily satisfied.
The above analysis was also performed for several other columns to obtain the appropriate operating parameters for the examples, and will not be described in detail here.
Example 1
Simulation calculations of the procedure were performed using ASPEN PLUS. The reaction product enters an ethylene separation tank, most unreacted light components such as ethylene and the like are flashed out under the pressure of 0.5Mpa, and a chilled water cooler is arranged at the top of the flash tank, so that the loss of effective components is reduced. The ethylene oligomerization reaction product, the catalyst and the organic solvent after flash evaporation are pumped and pressed, and then exchange heat with the bottom product of the heavy-removal tower to 58 ℃ to enter the heavy-removal tower. In a heavy component removing tower, cutting and separating octene from heavy components with the temperature of C10 and more than C10 are realized, the operating pressure of the heavy component removing tower is 30kpa, the temperature of the tower top is 72 ℃, the temperature of the tower bottom is 147 ℃, the heavy component at the tower bottom enters a catalyst separating tower, the operating pressure of the catalyst separating tower is 2kpa A, the temperature of the tower top is 90 ℃, the temperature of the tower bottom is 172 ℃, C10-C14 fractions are extracted from the tower top, catalysts are obtained after adsorption refining of fractions rich in catalysts are extracted from a side line, and after the heat exchange between C16+ heavy component extracted from the tower bottom and feed is carried out to 60 ℃, the mixture is cooled to 40 ℃ by a water cooler and then discharged from a device; and the octenes at the top of the heavy-removal tower and the light components below enter a dividing wall tower. In the partition tower, the cutting separation of C6, organic solvent and octene is realized, the C6 light component extracted from the tower top enters a hexene rectifying tower, the azeotrope of the organic solvent and the C7 component is extracted from the side line of the auxiliary tower, and the octene product is extracted from the tower bottom; the operation pressure of the bulkhead column is normal, the temperature of the top of the column is 64 ℃, the lateral line is 114 ℃, and the temperature of the bottom of the column is 123 ℃. In the hexene rectifying tower, the separation of hexene and impurity C6 is realized, the 1-hexene product with 99 percent purity is obtained at the top of the tower, the operating pressure of the hexene rectifying tower is normal pressure, the temperature at the top of the tower is 63 ℃, and the temperature at the bottom of the tower is 82 ℃. C7 and organic solvent enter the lower part of an extraction rectifying tower, phenol is adopted 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 enter an organic solvent separating tower from the bottom of the extraction rectifying tower, the operating pressure of the extraction rectifying tower 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 organic solvent is extracted from the top of the organic solvent separating tower, deoxidized and dried and then recycled to the reaction system, the extractant is extracted from the bottom of the tower, and the extractant with small loss is supplemented and recycled to the upper part of the extraction rectifying tower, so that 97.3% recycling of the organic solvent can be realized, the operating pressure of the organic solvent separating tower is 110Kpa A, the top of the tower is 110 ℃, the bottom of the tower is 190 ℃, and the molar ratio of the extractant to the C7 fraction is 5-7, thereby realizing that the C7 fraction reaches 99.5% of purity. 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 FIG. 5, the reaction product enters an ethylene separation tank, and most of unreacted ethylene and other light components are flashed off under the pressure of 0.5Mpa, and a chilled water cooler is arranged at the top of the flash tank, so that the loss of effective components is reduced. The reaction product after flash evaporation and the organic solvent are subjected to pumping and pressure increasing, and then exchange heat with the bottom product of the heavy-duty removing tower to 58 ℃ and enter the heavy-duty removing tower.
In the heavy component removal tower b1, the cutting separation of octene and heavy component is realized, the operating pressure of the heavy component removal tower b1 is 30kpa (A), the temperature of the tower top is 72 ℃, the temperature of the tower bottom is 147 ℃, the heavy component at the tower bottom enters the catalyst separation tower b7, a chilled water cooler is arranged on a reflux tank of the heavy component removal tower b1, and the temperature is cooled to 20 ℃, so that the loss of effective components is reduced; the operating pressure of the catalyst separation tower b7 is 2Kpa (A), the temperature of the tower top is 90 ℃, the temperature of the tower bottom is 172 ℃, the C10-C14 fraction is extracted from the tower top, the catalyst is obtained after the catalyst-rich fraction is extracted from the side line and is subjected to adsorption refining, and the C16+ heavy component and the feed are extracted from the tower bottom and are subjected to heat exchange to 60 ℃, and then are cooled to 40 ℃ by a water cooler to be extracted from the device; the octenes at the top of the heavy-removal column b1 and the following light components enter a C6-C8 separation column b2. In a C6-C8 separation tower b2, cutting separation of C6, an organic solvent and heavier components is realized, the light components enter a hexene rectifying tower, and the heavy components enter an organic solvent-octene rectifying tower b4; in the organic solvent-octene rectifying column b4, the top distillate is C7 and azeotropic organic solvent, the bottom of the tower is 99.99% of high-purity 1-octene product, the operating pressure of the organic solvent-octene rectifying column b4 is 30Kpa (A), the top temperature is 74 ℃, and the bottom temperature is 104 ℃. In the hexene rectifying tower b3, the separation of hexene and impurity C6 is realized, the 1-hexene product with 99 percent purity is obtained at the top of the tower, the operating pressure of the hexene rectifying tower b3 is normal pressure, the temperature at the top of the tower is 63 ℃, and the temperature at the bottom of the tower is 82 ℃. C7 and organic solvent enter the lower part of an extraction rectifying tower b5, phenol is adopted as an extractant and enters the upper part of the extraction rectifying tower b5, C7 fractions are extracted from the top of the extraction rectifying tower b5, the extractant and the organic solvent enter a solvent separation tower b6 at the bottom of the extraction rectifying tower b5, the operation 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 organic solvent is extracted from the top of the organic solvent separation tower, deoxidized and dried and then recycled to the reaction system, the extractant is extracted from the bottom of the tower, and the extractant with small loss is supplemented and recycled to the upper part of the extraction rectifying tower, so that 97.3% recycling of the organic solvent can be realized, 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 extractant to the C7 fraction is 5-7, thereby realizing that the C7 fraction reaches 99.5% of purity. The purity of 1-octene was 99.9994% and the purity of 1-hexene was 99.9%.
TABLE 2
Example 1 was compared with comparative example 1: in example 1, the dividing wall column technology is used, the load of the overhead condenser is reduced by 6.9%, the load of the reboiler is reduced by 9.1%, and the investment is saved by about 25%. Of the solvents, 2.7% entered other products, and 97.3% was recovered for use. In the extractive distillation process, 0.0375% of the extractant needs to be supplemented so as to ensure the stable circulation of the extractive distillation process.
Comparative example 2
In example 1, the solvent used in the reaction section was toluene or other similar boiling point solvent, if a solvent lighter than C7 and not azeotroping with C7 or other reaction product fractions, such as dimethyl carbonate (DMC), was used, and the procedure was simulated as follows:
simulation calculations of the procedure were performed using ASPEN PLUS. The reaction product enters an ethylene separation tank as shown in fig. 6, and most of unreacted ethylene and other light components are flashed off under the pressure of 0.5Mpa, and a chilled water cooler is arranged at the top of the flash tank, so that the loss of effective components is reduced. The reaction product after flash evaporation and the solvent are subjected to pumping and pressure increasing, and then exchange heat with the bottom product of the heavy-duty removing tower to 70 ℃ and enter the heavy-duty removing tower. In the heavy component removing tower c1, the cutting separation of octene and heavy component is realized, the operating pressure of the heavy component removing tower c1 is 110kpa (A), the temperature of the tower top is 104 ℃, the temperature of the tower bottom is 205 ℃, the heavy component at the tower bottom enters the catalyst separating tower c6, a chilled water cooler is arranged on a reflux tank of the heavy component removing tower c1, and the temperature is cooled to 20 ℃, so that the loss of effective components is reduced; the operation pressure of the catalyst separation tower C6 is 2Kpa (A), the temperature of the tower top is 90 ℃, the temperature of the tower bottom is 172 ℃, the C10-C14 fraction is extracted from the tower top, the catalyst is obtained after the catalyst-rich fraction is extracted from the side line and is subjected to adsorption refining, and the C16+ heavy component and the feed are extracted from the tower bottom and are subjected to heat exchange to 60 ℃, and then are cooled to 40 ℃ by a water cooler to be extracted from the device; the octenes at the top of the heavy ends removing tower C1 and the following light components enter a C6-C7 separating tower C2. In a C6-C7 separation tower C2, cutting and separating C6, C7 and octene are realized, C6 light components and organic solvent extracted from the tower top enter a hexene rectifying tower C3, C7 and C8 products extracted from the tower bottom enter an octene rectifying tower C5, the operating pressure of the C6-C7 separation tower C2 is normal pressure, the temperature of the tower top is 84 ℃, and the temperature of the tower bottom is 131 ℃; the top of a hexene rectifying tower C3 is provided with a hexene product with 99 percent purity, the bottom of the hexene rectifying tower C3 is provided with a mixed C6 and a solvent, the mixed C6 and the solvent enter an organic solvent rectifying tower C4, the top pressure of the hexene rectifying tower C3 is 120Kpa (A), the top temperature is 68 ℃, and the bottom temperature is 103 ℃; the mixed C6 product is obtained at the top of the organic solvent rectifying tower C4, the organic solvent is arranged at the bottom of the tower, the mixed C6 product is recycled to the reaction system after deoxidization and drying, the operating pressure of the solvent separating tower is 110Kpa (A), the temperature of the top of the tower is 84 ℃, and the temperature of the bottom of the tower is 96 ℃. In the octene rectifying column, C7 fraction is obtained at the top of the column, 99.9994% of octene product is obtained at the bottom of the column, the operating pressure of the octene rectifying column is 30Kpa (A), the temperature of the top of the column is 74 ℃, and the temperature of the bottom of the column is 104 ℃.
TABLE 3 Table 3
Comparative example 2 compared to example 1, the same separation was achieved using 6 columns, comparative example 2 increased overhead condenser duty by 3.5% but reduced reboiler duty by 10.8% compared to example 1; compared with comparative example 1, comparative example 2 reduces the load of the condenser at the top of the tower by 3.25% and the load of the reboiler by 22.3% by 1 tower compared with comparative example 1, thereby achieving better energy-saving effect.
Claims (6)
1. A process for separating an ethylene oligomerization product from a catalyst, characterized by: the separation method comprises the following steps:
passing a feed stream comprising ethylene oligomerization reaction product, catalyst, and organic solvent through a deentrainment column (a 1), distributing C8, C7, C6, and organic solvent fractions to a top portion of the deentrainment column (a 1), distributing the catalyst, C10, and more than C10 heavy components to a bottom portion of the deentrainment column (a 1), and entering a catalyst separation column (a 6) to separate the catalyst;
c8, C7, C6, organic solvent fractions withdrawn from the top of the de-heavies column (a 1) enter a dividing wall column (a 2); distributing the C6 fraction to the top part of the partition tower (a 2), distributing the C8 fraction to the bottom part of the partition tower (a 2) and finally entering a C8 product tank, and distributing the organic solvent and the C7 azeotropic fraction to the middle part of the partition tower (a 2) to the extractive distillation tower (a 4); the organic solvent and the C7 are added with the extractant to generate azeotropic fraction, the C7 fraction is obtained at the top of the extraction rectifying tower (a 4), and the extractant at the bottom of the extraction rectifying tower and the organic solvent enter a solvent separating tower (a 5); obtaining an organic solvent product at the top of the solvent separation tower (a 5), and recycling the extractant at the bottom of the solvent separation tower and the supplementary extractant back to the extraction rectifying tower (a 4) to serve as the extractant; extracting the organic solvent fraction from the top of the solvent separation tower (a 5), refining, deoxidizing and drying, and recycling the organic solvent fraction into an ethylene tetramerization reaction kettle;
extracting C6 fraction at the top of the partition tower (a 2) into a hexene rectifying tower (a 3), feeding C6 fraction into the hexene rectifying tower (a 3), distributing impurity C6 fraction containing impurities to the top of the hexene rectifying tower (a 3), distributing refined C6 fraction to the bottom of the hexene rectifying tower (a 3), and feeding into a product tank;
the catalyst-containing C10 and more than C10 heavy components from the bottom of the heavy component removal tower (a 1) enter a catalyst separation tower (a 6), C10-C14 components are extracted from the top of the catalyst separation tower, the catalyst is extracted from the catalyst-rich fraction extracted from the side line after further purification, and C16+ heavy components are extracted from the bottom of the catalyst separation tower and enter a heavy component tank;
the total number of the tower plates of the partition tower (a 2) is 100-140, wherein the number of the middle tower plates is 60-70, the 75-85 pedal plates are feeding tower plates, the pressure of the partition tower (a 2) is normal pressure, the temperature of the tower top is 50-70 ℃, the side line temperature is 110-130 ℃, the temperature of the tower bottom 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.
2. The process for the separation of ethylene oligomerization products and catalysts according to claim 1, characterized in that: the number of the tower plates of the heavy removal tower (a 1) is 35-45, the 15 th-20 th pedal is a feeding tower plate, the pressure of the heavy removal tower (a 1) is 30-40 KpaA, the temperature of the tower top is 60-80 ℃, the temperature of the tower bottom 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 ethylene oligomerization products and catalysts according to claim 1, characterized in that: the number of the tower plates of the hexene rectifying tower (a 3) is 70-90, the 30-40 th pedal is a feeding tower plate, the pressure of the hexene rectifying tower (a 3) is normal pressure, the temperature of the tower top is 50-80 ℃, the temperature of the tower bottom 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.
4. The process for the separation of ethylene oligomerization products and catalysts according to claim 1, characterized in that: the number of the tower plates of the extraction rectifying tower (a 4) is 20-30, the 2 nd-5 th or 15 th-20 th pedal is a feeding tower plate, the pressure of the extraction rectifying tower (a 4) is 30-40 KpaG, the temperature of the tower top is 80-120 ℃, the temperature of the tower bottom is 170-190 ℃, the ratio of the feeding 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 extractant in the extraction rectifying tower (a 4) to the organic solvent in the feed is 5-7:1.
5. The process for the separation of ethylene oligomerization products and catalysts according to claim 1, characterized in that: the number of the tower plates of the solvent separation tower (a 5) is 20-40, the 30-50 th pedal is a feeding tower plate, the pressure of the solvent separation tower (a 5) is 5-15 KpaG, the temperature of the tower top is 100-130 ℃, the temperature of the tower bottom 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.
6. The process for the separation of ethylene oligomerization products and catalysts according to claim 1, characterized in that: the number of the tower plates of the catalyst separation tower (a 6) is 30-50, the 20-40 th pedal is a feeding tower plate, the pressure of the catalyst separation tower (a 6) is 2-4 KpaA, the temperature of the tower top is 80-110 ℃, the temperature of the tower bottom 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.
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