CN116969809A - Method and device for separating 1-octene from ethylene oligomerization reactant - Google Patents
Method and device for separating 1-octene from ethylene oligomerization reactant Download PDFInfo
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 title claims abstract description 465
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000005977 Ethylene Substances 0.000 title claims abstract description 51
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 33
- 239000000376 reactant Substances 0.000 title claims abstract description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 340
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 52
- 230000008569 process Effects 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000007670 refining Methods 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 238000006298 dechlorination reaction Methods 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000006477 desulfuration reaction Methods 0.000 claims description 5
- 230000023556 desulfurization Effects 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 description 14
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 12
- NFJPEKRRHIYYES-UHFFFAOYSA-N methylidenecyclopentane Chemical compound C=C1CCCC1 NFJPEKRRHIYYES-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229940069096 dodecene Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ILPBINAXDRFYPL-UHFFFAOYSA-N cis-octene-2 Natural products CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- ILPBINAXDRFYPL-HWKANZROSA-N (E)-2-octene Chemical compound CCCCC\C=C\C ILPBINAXDRFYPL-HWKANZROSA-N 0.000 description 2
- ILPBINAXDRFYPL-HYXAFXHYSA-N (Z)-2-octene Chemical compound CCCCC\C=C/C ILPBINAXDRFYPL-HYXAFXHYSA-N 0.000 description 2
- IRUCBBFNLDIMIK-BQYQJAHWSA-N (e)-oct-4-ene Chemical compound CCC\C=C\CCC IRUCBBFNLDIMIK-BQYQJAHWSA-N 0.000 description 2
- IRUCBBFNLDIMIK-FPLPWBNLSA-N (z)-oct-4-ene Chemical compound CCC\C=C/CCC IRUCBBFNLDIMIK-FPLPWBNLSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- YCTDZYMMFQCTEO-UHFFFAOYSA-N 3-octene Chemical compound CCCCC=CCC YCTDZYMMFQCTEO-UHFFFAOYSA-N 0.000 description 1
- FCOUHTHQYOMLJT-UHFFFAOYSA-N 6-methylheptan-2-ol Chemical compound CC(C)CCCC(C)O FCOUHTHQYOMLJT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for separating 1-octene from an ethylene oligomerization reactant, which comprises the following steps: step a, enabling a material flow extracted from an ethylene oligomerization reaction termination kettle to enter an octene removal tower system, extracting an octene-rich material flow from the tower top of the octene removal tower system, enabling the material flow to enter a hexene removal tower system, and then extracting a material flow containing octene and toluene from the tower bottom of the hexene removal tower system; b, feeding a tower kettle extract stream of the hexene removal tower system into an octene rectifying tower system, extracting a toluene-rich stream containing 1-octene and 1-octene isomers from the tower top, and extracting a crude 1-octene stream from the tower kettle; and c, feeding the tower top produced stream of the octene rectifying tower system into a toluene rectifying tower system, and extracting a stream containing 1-octene and 1-octene isomer from a tower kettle. Because the material extracted from the top of the octene rectifying tower system contains 1-octene, most of 1-octene isomer can be extracted from the top of the tower, so that the isomer in the system is removed, and the 1-octene is ensured to reach high purity.
Description
Technical Field
The invention relates to a separation method of alpha-olefin, in particular to a method and a device for separating 1-octene from an ethylene oligomerization reactant.
Background
1-octene is an important organic chemical raw material and chemical intermediate, and has wide application in the fields of high-end polyolefin, high-grade lubricating oil, synthetic detergent and the like. Compared with the polyethylene produced by the traditional comonomer 1-butene and 1-hexene, the polyethylene has obvious advantages in the aspects of mechanical processing, heat resistance, flexibility and the like. The replacement of lower alpha-olefins with 1-octene has become a necessary trend in future development. With the increasing use of linear low density polyethylene, the demand for 1-octene for the synthesis of linear low density polyethylene is increasing. The ethylene selective oligomerization has the characteristics of high catalyst activity, high selectivity of target products, good economical efficiency and the like, and is a main production method of the 1-octene at present.
At present, the related patent of 1-octene is mostly focused on the research and development of a catalyst for producing 1-octene and a device for producing 1-octene by oligomerization of ethylene. CN109331880a discloses a phosphorus-nitrogen coordinated metal catalyst for producing alpha-olefin by oligomerization of ethylene and its use. The invention can realize the selective preparation of 1-hexene and 1-octene, the sum of the mass fractions of two linear alpha-olefins can be up to more than 95%, and different yield ratios can be realized through the modulation of the phosphorus-nitrogen groups. CN115040833a discloses a reaction device for producing 1-octene by ethylene oligomerization and a reaction product separation method. The liquid phase output end of the tubular reactor is connected with a separation system, and the separation system is provided with an ethylene circulation system connected with a raw material pretreatment unit. Ethylene, C6, solvent, C8 and C10+ are separated sequentially by adopting a sequential separation method, but the technology does not further rectify the 1-octene component in C8.
In the ethylene oligomerization reactant, the octene contains 1-octene isomer besides 1-octene, however, the 1-octene and the isomer thereof are difficult to separate, so that the difficulty of ensuring the 1-octene to have higher purity is how to remove the isomer.
No solution has been proposed in the prior art for how to remove the isomers and obtain high quality 1-octene.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a process for separating 1-octene from ethylene oligomerization reactants.
In a first aspect of the present invention there is provided a process for the separation of 1-octene from an ethylene oligomerization reactant, the process comprising:
step a, enabling a material flow extracted from an ethylene oligomerization reaction termination kettle to enter an octene removal tower system, extracting an octene-rich material flow from the tower top of the octene removal tower system, enabling the material flow to enter a hexene removal tower system, and then extracting a material flow containing octene and toluene from the tower bottom of the hexene removal tower system;
b, enabling a material flow extracted from a tower kettle of the hexene removal tower system to enter an octene rectifying tower system, extracting a toluene-rich material flow containing 1-octene and 1-octene isomerides from the tower top of the octene rectifying tower system, and extracting a crude 1-octene material flow from the tower kettle of the octene rectifying tower system;
and c, feeding a material flow extracted from the top of the octene rectifying tower system into a toluene rectifying tower system, and extracting a material flow containing 1-octene and 1-octene isomerides from a tower kettle of the toluene rectifying tower system.
In some embodiments of the invention, the toluene content in the toluene-rich stream withdrawn from the top of the octene rectifying column system is 90% wt to 99% wt, the 1-octene content is 1% wt to 10% wt, and the 1-octene isomer content is 0.5% wt to 5% wt. For example, the toluene-rich stream may have a 1-octene content of 5% wt to 10% wt.
In some embodiments of the invention, the 1-octene isomer content is 5% wt to 20% wt and the 1-octene content is 80% wt to 95% wt in the stream withdrawn from the bottoms of the toluene rectifying column system.
In some embodiments of the invention, the octene rectifying column system operates at a pressure of-90 kPa (g) to-60 kPa (g) and at a column top temperature of 70 ℃ to 80 ℃.
In some embodiments of the invention, the toluene rectifying column system operates at a pressure of 0kPa (g) to 50kPa (g) and a column bottoms temperature of 120 ℃ to 130 ℃.
In some embodiments of the invention, the operating pressure of the octene rectifying column system is-80 kPa (g) to-70 kPa (g) and the operating pressure of the toluene rectifying column system is 10kPa (g) to 20kPa (g).
In some embodiments of the invention, the octene removal column system includes a column bottoms pump that is a slurry pump for withdrawing solid particulates from the ethylene oligomerization reactant stream.
In some embodiments of the invention, the octene removal column system comprises a reboiler, and the reactant stream enters the bottoms of the octene removal column system through an inlet of the reboiler.
In some embodiments of the invention, the reboiler is a forced heat extraction heat exchange mode.
In some embodiments of the invention, the operating pressure of the octene removal column system is-80 kPa (g) to-60 kPa (g), the column top temperature is 75-85 ℃, and the column bottom temperature is 140-160 ℃; the operating pressure of the hexene removing tower system is 0kPa (g) to 50kPa (g), the tower top temperature is 63 ℃ to 73 ℃, and the tower bottom temperature is 115 ℃ to 125 ℃.
In some embodiments of the invention, the step b further comprises: refining a crude 1-octene stream extracted from a tower kettle of an octene rectifying tower system, so that the crude 1-octene stream sequentially passes through a desulfurization unit, a dechlorination unit, a deoxidization unit and a dehydration unit to obtain a refined 1-octene stream, wherein the content of 1-octene in the refined 1-octene stream is more than 99.5% wt, the toluene content is less than 1ppm (wt), the sulfur content is less than 1ppm (wt), the chlorine content is less than 1ppm (wt), the oxygen content is less than 1ppm (wt) and the water content is less than 1ppm (wt).
In some embodiments of the invention, the step c further comprises: and (3) extracting a crude toluene stream from the top of the toluene rectifying tower system, refining the crude toluene stream, and sequentially passing through a deoxidizing unit and a dehydrating unit to obtain a refined toluene stream, wherein the toluene content in the refined toluene stream is more than 99.9% wt, the oxygen content is less than 1ppm (wt), and the water content is less than 1ppm (wt).
In some embodiments of the invention, the method further comprises: and d, feeding a part of a stream containing 1-octene and 1-octene isomers extracted from the tower bottom of the toluene rectifying tower system into the octene rectifying tower system so as to recover the 1-octene extracted from the tower bottom of the toluene rectifying tower system.
In a second aspect of the invention there is provided an apparatus suitable for use in the separation method of the first aspect of the invention, the apparatus comprising: a octene removal column system: the method is used for allowing a stream extracted from an ethylene oligomerization reaction termination kettle to pass through, and extracting an octene-rich stream from the top of the tower; hexene removal tower system: passing an octene-rich stream withdrawn from the top of the octene removal column to remove hexene and withdrawing a stream comprising octene and toluene from the bottoms; octene rectifying column system: the method comprises the steps of allowing a stream extracted from a tower kettle of a hexene removal tower system to pass, extracting a crude 1-octene stream from the tower kettle, and extracting a toluene-rich stream containing 1-octene and 1-octene isomers from the tower top; toluene rectifying column system: for passing a stream withdrawn from the top of the octene rectifying column system and withdrawing a stream comprising 1-octene isomers from the bottom of the column.
Compared with the prior art, the invention has the following beneficial technical effects:
in the invention, a material flow containing 1-octene, 1-octene isomerides (cis-2-octene, trans-2-octene, cis-4-octene, trans-4-octene and the like) and toluene is extracted from the top of the octene rectifying tower in an excessive evaporation mode, so that most of the 1-octene isomerides are separated from the crude product of the 1-octene, and then the 1-octene isomerides are extracted from the tower bottom of the toluene rectifying tower system, so that the 1-octene isomerides in the system are removed, and the 1-octene is ensured to reach high purity.
By controlling the content of 1-octene in the toluene-rich stream extracted from the top of the octene rectifying tower to be 1-10wt%, most of 1-octene isomers can be ensured to be separated, and too much 1-octene is not lost, so that the energy cost can be saved as much as possible on the premise of achieving the purposes of effectively separating the 1-octene isomers and improving the purity of the 1-octene final product.
In addition, because the ethylene oligomerization reactant contains solid particles, if the ethylene oligomerization reactant is directly separated by distillation of a tower, the tower packing or a tower tray can be blocked by the solid particles for a long time. According to the invention, a stripping section is omitted by feeding at the bottom of the tower, so that no particle blockage exists on the filler or the tower tray.
Meanwhile, a tower bottom pump of the octene removal tower adopts a slurry pump mode, a heat siphon heat exchange mode is canceled by a reboiler of the octene removal tower, and a forced heat taking heat exchange mode is adopted to strengthen the flow of the material flow in the reboiler, so that the blockage of an internal tube bundle is prevented.
Drawings
FIG. 1 is a schematic view of a 1-octene separation unit according to an embodiment of the invention.
Reference numerals: 1-ethylene oligomerization reactant, 2-isooctanol, 3-termination kettle, 4-termination kettle produced stream, 5-octene removal tower system, 6-octene removal tower kettle pump, 7-octene removal tower kettle stream I, 8-octene removal tower kettle stream II, 9-octene removal tower reboiler, 10-octene removal tower top octene rich stream, 11-hexene removal tower top ethylene rich stream, 12-hexene removal tower system, 13-hexene removal tower kettle stream, 14-hexene removal tower top stream, 15-octene rectification tower system, 16-octene rectification tower kettle crude 1-octene stream, 17-refined 1-octene stream, 18-octene rectification tower top stream, 19-toluene rectification tower system, 20-toluene rectification tower kettle stream I, 21-toluene rectification tower kettle stream II, 22-toluene rectification tower top crude toluene stream, 23-refined toluene stream.
Detailed Description
The various aspects of the present invention will now be described in detail with reference to the following examples, which are intended to illustrate the invention and are not intended to limit the scope and spirit of the invention.
In a specific embodiment of the present invention, a schematic diagram of an apparatus for separating 1-octene from an ethylene oligomerization reactant is shown in FIG. 1, the apparatus comprising: octene removal tower system (5): the method is used for allowing a stream extracted from an ethylene oligomerization reaction termination kettle (3) to pass through, and extracting an octene-rich stream from the top of the tower; hexene removal column system (12): passing an octene-rich stream withdrawn from the top of the octene removal column to remove hexene and withdrawing a stream comprising octene and toluene from the bottoms; octene rectifying column system (15): the method comprises the steps of allowing a stream extracted from a tower kettle of a hexene removal tower system to pass, extracting a crude 1-octene stream from the tower kettle, and extracting a toluene-rich stream containing 1-octene and 1-octene isomers from the tower top; toluene rectifying column system (19): for passing a stream withdrawn from the top of the octene rectifying column system and withdrawing a stream comprising 1-octene isomers from the bottom of the column.
With reference to fig. 1, the separation method in the embodiment of the present invention includes the following steps:
and a, enabling a material flow extracted from an ethylene oligomerization reaction termination kettle to enter an octene removal tower system, extracting an octene-rich material flow from the top of the octene removal tower system, enabling the material flow to enter a hexene removal tower system, and then extracting a material flow containing octene and toluene from the tower kettle of the hexene removal tower system.
Feeding the stream extracted from the tower bottom of the hexene removal tower system into an octene rectifying tower system, and extracting a toluene-rich stream containing 1-octene and 1-octene isomer from the tower top of the octene rectifying tower system through excessive evaporation, wherein the toluene-rich stream contains 90-99% wt of toluene, 1-octene is 1-10% wt and 1-octene isomer is 0.5-5% wt; a crude 1-octene stream is extracted from a tower kettle of an octene rectifying tower system, and the crude 1-octene stream is refined to be sequentially subjected to a desulfurization unit, a dechlorination unit, a deoxidization unit and a dehydration unit to obtain a refined 1-octene stream, wherein the refined 1-octene stream contains more than 99.5% wt of 1-octene, less than 1ppm (wt) of toluene, less than 1ppm (wt) of sulfur, less than 1ppm (wt) of chlorine, less than 1ppm (wt) of oxygen and less than 1ppm (wt) of water.
C, feeding a stream extracted from the top of the octene rectifying tower system into a toluene rectifying tower system, and extracting a stream containing 1-octene isomers from the tower kettle of the toluene rectifying tower system, wherein the content of the 1-octene isomers in the stream is 5-20% wt and the content of the 1-octene is 80-95% wt; and (3) extracting a crude toluene stream from the top of the toluene rectifying tower system, refining the crude toluene stream, and sequentially passing through a deoxidizing unit and a dehydrating unit to obtain a refined toluene stream, wherein the toluene content in the refined toluene stream is more than 99.9% wt, the oxygen content is less than 1ppm (wt), and the water content is less than 1ppm (wt).
And d, merging part of the material flow containing 1-octene and 1-octene isomer extracted from the tower kettle of the toluene rectifying tower system with the material flow extracted from the tower kettle of the hexene removing tower system, and returning the material flow to the octene rectifying tower system again for recovering the extracted 1-octene.
Wherein in step a, a octene removal column system (5) and a hexene removal column system (12) are involved.
Specifically, ethylene oligomerization reaction adopts ethylene and hydrogen as reaction raw materials, toluene is used as a reaction solvent, reactants rich in 1-octene are generated under the action of a catalyst, the ethylene oligomerization reactants (1) generated by ethylene oligomerization and isooctanol (2) enter a termination kettle (3) together to terminate the reaction, and a material flow (4) extracted from the bottom of the termination kettle is a heterogeneous mixture of hydrogen, ethylene, butene, hexene, methylcyclopentane, methylene cyclopentane, toluene, octene, n-octane, isooctanol, decene, dodecene, ethylene oligomers and deactivated catalyst. This stream (4) enters a octene removal column reboiler (9) of a octene removal column system (5). Because the material flow (4) contains ethylene oligomer, deactivated catalyst and other solid matters, a tray or a filler of the octene removal tower can be blocked, a stripping section of the octene removal tower is eliminated, and the material flow (4) enters the octene removal tower (5) from an inlet of a reboiler (9), so that the separation effect of a rectifying section of the octene removal tower can be improved, components with boiling points close to that of 1-octene such as n-octane and the like are removed from the material flow (10), and the purity of the 1-octene in a product can be effectively improved. And after the tower kettle extract stream of the octene removal tower is pressurized by a tower kettle pump (6), part of the octene removal tower kettle stream I (7) is extracted from the system, and part of the octene removal tower kettle stream II (8) and the stream (4) are converged and returned to the octene removal tower system again.
Wherein, the tower bottom material flow I (7) and the tower bottom material flow II (8) of the octene removing tower are a mixture of n-octane, isooctanol, decene, dodecene, ethylene oligomer and deactivated catalyst. Since the ethylene oligomer is present in the stream either as a solid or as a melt, the deactivated catalyst is present as a solid, the deoctena column bottoms stream I (7) and the column bottoms stream II (8) are heterogeneous solid-liquid mixtures. In order to prevent the pump and the heat exchanger from being blocked, in the invention, a tower bottom pump (6) of the octene removal tower adopts a slurry pump type, and meanwhile, a reboiler (9) of the octene removal tower cancels a thermosiphon heat exchange mode and adopts a forced heat-taking heat exchange mode so as to strengthen the flow of a material flow in the reboiler (9) and prevent the internal tube bundle from being blocked.
The 1-octene-rich material flow (10) is extracted from the reflux tank bottom of the octene removal tower and enters a hexene removal tower system (12). The 1-octene rich stream (10) is a mixture of butene, hexene, methylcyclopentane, methylenecyclopentane, toluene, octene, wherein the toluene content is 40% wt-50% wt and the octene content is 35% wt-45% wt.
An ethylene-rich stream (11) is produced at the top of a reflux tank of the octene removal tower, the ethylene-rich stream (11) is a mixture of hydrogen and ethylene, wherein the ethylene content is more than 99% wt, and the ethylene is recovered and then is participated in ethylene oligomerization.
The operating pressure of the octene removal column system (5) is-80 kPa (g) to-60 kPa (g), preferably-75 kPa (g) to-65 kPa (g). The operation temperature of the tower top is 75-85 ℃, and the temperature of the tower bottom is 140-160 ℃. The top of the tower adopts circulating water as a condensing medium, and the bottom of the tower adopts superheated steam of 1.2MPa as a heating medium. Under the operating pressure, the temperature of the tower kettle is generally kept at 140-160 ℃, at this time, the ethylene oligomer in the material flow (4) entering the octene removal tower system can be kept in a molten state, a large number of side reactions can not be generated due to high temperature, and the blockage of the tower kettle pump (6) can be effectively prevented.
A hexene removal column system (12) is used to remove hexene from the stream. After the tower top material flow (10) of the octene removal tower system enters the hexene removal tower system (12), a material flow (13) is extracted from the tower bottom of the hexene removal tower system. The stream (13) is a mixture of octenes and toluene, wherein the toluene content is 50% wt to 60% wt and the 1-octene content is 40% wt to 50% wt. Stream (13) then enters octene rectifying column system (15). The top stream (14) of the hexene removal column system is taken, the stream (14) is a mixture of butene, hexene, methylcyclopentane and methylenecyclopentane, wherein the content of 1-hexene is more than 85% wt, and the refined 1-hexene can be obtained by continuing the multistage rectification of the stream (14).
The operating pressure of the hexene removal column system (12) is from 0kPa (g) to 50kPa (g), preferably from 10kPa (g) to 20kPa (g). The operation temperature of the tower top is 63-73 ℃, and the temperature of the tower bottom is 115-125 ℃. The top of the tower adopts circulating water as a condensing medium, and the bottom of the tower adopts 0.4MPa superheated steam as a heating medium.
In step b, an octene rectifying column system (15) is involved.
Specifically, after the bottoms take-off stream (13) of the hexene removal column system (12) enters the octene rectifying column system, a toluene-rich stream (18) is taken from the top of the octene rectifying column system by excessive evaporation, the stream (18) contains octene and toluene, wherein the toluene content is 90-99% wt, the 1-octene content is 1-10% wt, and the 1-octene isomer content is 0.5-5% wt. The overhead stream (18) of the octene rectifying column system contains 1-10% wt 1-octene (e.g., 5-10% wt) to effectively remove 1-octene isomers present in octene, allowing a substantial portion of the isomers to be withdrawn overhead, thereby increasing the purity of 1-octene in the bottoms stream (16). And, when the 1-octene content in the toluene-rich stream (18) is higher than 10% by weight, the improvement in the separation effect of the 1-octene isomers is not significant, the improvement in the purity of the 1-octene product is not significant, but more 1-octene is lost in the process. Therefore, the control stream (18) contains 1-10wt% of 1-octene, so that not only can most of isomers be ensured to be extracted from the top of the tower, but also excessive loss of 1-octene can be avoided, the separation requirement of an octene rectifying tower system (15) is reduced, and the purity of 1-octene in the crude 1-octene stream (16) extracted from the tower kettle is ensured.
A crude 1-octene stream (16) is withdrawn from the bottoms of an octene rectifying column system, the stream (16) comprising 1-octene and minor amounts of isomers thereof (e.g., cis-2-octene, trans-2-octene, cis-4-octene, trans-4-octene, etc.), the stream (16) having a toluene content of <1ppm (wt), an octene content of >99.9 wt, a 1-octene content of >99.5 wt, and a 1-octene isomer content of <0.5 wt.
And refining the crude 1-octene stream (16) to obtain a refined 1-octene stream (17) after the crude 1-octene stream (16) sequentially passes through a desulfurization unit, a dechlorination unit, a deoxidization unit and a dehydration unit, wherein in the stream (17), the 1-octene content is more than 99.5% wt, the 1-octene isomer content is less than 0.5% wt, the toluene content is less than 1ppm (wt), the sulfur content is less than 1ppm (wt), the chlorine content is less than 1ppm (wt), the oxygen content is less than 1ppm (wt) and the water content is less than 1ppm (wt).
The operating pressure of the octene rectifying column system (15) is-90 kPa (g) to-60 kPa (g), preferably-80 kPa (g) to-70 kPa (g). The operation temperature of the tower top is 70-80 ℃, and the temperature of the tower bottom is 80-90 ℃. The top of the tower adopts circulating water as a condensing medium, and the bottom of the tower adopts 0.4MPa superheated steam as a heating medium. The octene rectifying tower system (15) can select the operation pressure of-80 kPa (g) to-70 kPa (g), under the pressure, the relative volatility of 1-octene and toluene is larger, and the separation capacity of the octene rectifying tower system (15) can be increased.
In step c, a toluene rectifying column system (19) is involved.
Specifically, a toluene-rich stream (18) extracted from the top of the octene rectifying tower system enters the toluene rectifying tower system (19), and then a stream I (20) and a stream II (21) are extracted from the bottom of the toluene rectifying tower. Stream I (20) and stream II (21) are both streams comprising 1-octene and 1-octene isomers, wherein the content of 1-octene isomers is 5% wt to 20% wt, the 1-octene content is 80% wt to 95% wt, and the toluene content is <1% wt.
Therefore, a large amount of 1-octene isomers in the 1-octene can be extracted from the system through the tower kettle of the toluene rectifying tower, so that the 1-octene in the tower kettle extracted material flow of the octene removing rectifying tower system is ensured to have higher purity.
A crude toluene stream (22) was taken from the top of the toluene rectifying column, the toluene content in stream (22) being >99.9% wt. The crude toluene stream (22) is then further refined and passed sequentially through a deoxygenation unit and a dehydration unit to produce a refined toluene stream (23). In stream (23) the toluene content is >99.9% wt, the oxygen content is less than 1ppm (wt) and the water content is less than 1ppm (wt).
The toluene rectifying column system (19) is operated at a pressure of 0kPa (g) to 50kPa (g), preferably at a pressure of 10kPa (g) to 20kPa (g). The operation temperature of the tower top is 110-120 ℃, and the temperature of the tower bottom is 120-130 ℃. Air is used as a condensing medium at the top of the tower, and 0.4MPa superheated steam is used as a heating medium at the bottom of the tower. The toluene rectifying tower system (19) adopts air as a condensing medium due to overhigh temperature at the top of the tower, so that the corrosion phenomenon caused by overhigh heat exchange temperature difference due to the use of a circulating water heat exchanger is prevented.
Thus, the tower top extract stream (18) of the octene rectifying tower system can be separated to obtain toluene after passing through the toluene rectifying tower system (19), so that the side reaction of the upstream ethylene oligomerization reaction is ensured to be as few as possible; and the 1-octene isomer can be separated as much as possible, thereby ensuring that the high-quality 1-octene can be produced from the tower bottom of the octene rectifying tower.
In step d, the extracted material flow I (20) of the tower kettle of the toluene rectifying tower is converged with the tower kettle extracted material flow (13) of the hexene removing tower system, and enters the octene rectifying tower system (15) for further rectification, so that part of 1-octene is recovered.
Example 1
In this example there is provided a process for the separation of 1-octene from ethylene oligomerization reactants involving apparatus as described in figure 1 hereinbefore. In this embodiment, the method comprises the steps of:
step a: toluene is used as a reaction solvent, isooctanol is used as a reaction terminator, a material flow after ethylene oligomerization is terminated enters an octene removal tower system, an octene-rich material flow extracted from the tower top of the octene removal tower system enters a hexene removal tower system, and a material flow (13) is extracted from the tower bottom of the hexene removal tower system.
Wherein the total content of hydrogen and ethylene in the stop stream (4) is 22% wt, the total content of butene, hexene, methylcyclopentane and methylenecyclopentane is 11% wt, the total content of toluene is 30% wt, the total content of octene is 27% wt, and the total content of n-octane, isooctanol, decene, dodecene, ethylene oligomer and deactivated catalyst is 10% wt.
The octene-rich stream (10) withdrawn from the top of the octene-removal column system comprises butene, hexene, methylcyclopentane, methylenecyclopentane, toluene and octene, with a toluene content of 45% wt, octene content of 40.5% wt and hexene content of 13.2% wt. The stream (7) extracted from the tower bottom of the octene removal tower system is a mixture of n-octane, isooctanol, decene, dodecene, ethylene oligomer and deactivated catalyst.
The stream (13) withdrawn from the bottom of the hexene removal column system contained octene together with toluene in an amount of 52.6% wt and 1-octene in an amount of 47.4% wt. The stream (14) taken off at the top of the hexene removal column system was a mixture of butene, hexene, methylcyclopentane, and methylenecyclopentane, with a 1-hexene content of 91.0% wt.
Wherein, the operating pressure of the octene removing tower is-70 kPa (g), the temperature of the tower top is 77 ℃, and the temperature of the tower bottom is 151 ℃. The operating pressure of the hexene removing tower is 20kPa (g), the temperature of the tower top is 67 ℃, and the temperature of the tower bottom is 119 ℃.
Step b: and (3) enabling a tower bottom extraction stream of the hexene removal tower system to enter an octene rectifying tower system, extracting a toluene-rich stream (18) containing 1-octene isomerides from the tower top of the octene rectifying tower system through excessive evaporation, and extracting a crude 1-octene stream (16) from the tower bottom of the octene rectifying tower system. Wherein the toluene-rich stream (18) withdrawn from the top of the column has a toluene content of 95% by weight, a 1-octene content of 4.68% by weight, a 1-octene isomer content of 0.32% by weight and a ratio of 1-octene to 1-octene isomer of 14.625. In the crude 1-octene stream withdrawn from the bottom of the column, the octene content is >99.9% wt, the 1-octene content is >99.5% wt, and the 1-octene isomer content is <0.5% wt. The operating pressure of the octene rectifying tower is-70 kPa (g), the temperature of the tower top is 75 ℃, and the temperature of the tower bottom is 87 ℃.
Step c: the top product stream of the octene rectifying tower system is fed into the toluene rectifying tower system, and a stream I (20) and a stream II (21) containing 1-octene and 1-octene isomers are extracted from the tower bottom of the toluene rectifying tower system. Stream I (20) and stream II (21) both comprise toluene, 1-octene and 1-octene isomers, with a 1-octene content of 93% wt, a toluene content of 0.4% wt and a 1-octene isomer content of 6.6% wt. The operating pressure of the toluene rectifying column system was 20kPa (g), the column top temperature was 115℃and the column bottom temperature was 126 ℃.
Step d: the stream I (20) containing 1-octene extracted from the tower kettle of the toluene rectifying tower system is converged with the stream (13) extracted from the tower kettle of the hexene removing tower system, and enters the octene rectifying tower system for further rectification, so that part of 1-octene is recovered.
In step c, a crude toluene stream (22) is taken out from the top of the toluene rectifying tower system, the crude toluene stream (22) is refined, and is sequentially subjected to a deoxidizing unit and a dehydrating unit to obtain a refined toluene stream (23), wherein the oxygen content in the refined toluene stream (23) is less than 1ppm (wt), the water content is less than 1ppm (wt), and the mass fraction is 99.95%.
In the step b, the crude 1-octene material flow (16) extracted from the tower kettle of the octene rectifying tower system is refined, so that the crude 1-octene material flow is sequentially subjected to a desulfurization unit, a dechlorination unit, a deoxidization unit and a dehydration unit to obtain a refined 1-octene material flow (17), wherein in the refined 1-octene material flow (17), the toluene content is 0.3ppm (wt), the sulfur content is less than 1ppm (wt), the chlorine content is less than 1ppm (wt), the oxygen content is less than 1ppm (wt), the water content is less than 1ppm (wt), the 1-octene isomer content is 0.3% wt, and the 1-octene purity reaches 99.70%.
Example 2
This example differs from example 1 in that the 1-octene content of the toluene-rich stream withdrawn from the top of the octene rectifying column system is different.
Specifically, in this example, the operating pressure of the octene rectifying column system was-70 kPa (g), the overhead temperature 76 ℃, and the bottoms temperature 87 ℃ so that the 1-octene content in the toluene-rich stream withdrawn overhead of the octene rectifying column system was 9.2% wt. At this time, in the toluene-rich stream (18), the toluene content was 90.25% by weight, the 1-octene content was 9.2% by weight, the 1-octene isomer content was 0.55% w, and the ratio of 1-octene to 1-octene isomer was 16.7.
Thus, in the refined 1-octene stream (17) obtained after the same refining step as in example 1, toluene content was 0.25ppm (wt), sulfur content was less than 1ppm (wt), chlorine content was less than 1ppm (wt), oxygen content was less than 1ppm (wt), water content was less than 1ppm (wt), 1-octene isomer content was 0.28% wt, and 1-octene purity was 99.72%.
Comparative example
This comparative example differs from example 1 in that the 1-octene content of the overhead product stream of the octene rectifying column system is more than 10% wt.
Specifically, in this comparative example, the operating pressure of the octene rectifying column system was-70 kPa (g), the overhead temperature was 76.4 ℃, the bottoms temperature was 87 ℃, and the toluene-rich stream withdrawn from the top of the octene rectifying column system contained more than 10% by weight of 1-octene. At this time, in the toluene-rich stream (18), the toluene content was 79.2% by weight, the 1-octene content was 20% by weight, the 1-octene isomer content was 0.8% by weight, and the ratio of 1-octene to 1-octene isomer was 25.
Thus, in the refined 1-octene stream (17) obtained after the same refining step as in example 1, toluene content was 0.2ppm (wt), sulfur content was less than 1ppm (wt), chlorine content was less than 1ppm (wt), oxygen content was less than 1ppm (wt), water content was less than 1ppm (wt), 1-octene isomer content was 0.26% wt, and 1-octene purity was 99.74%.
As can be seen from this, the purity of 1-octene in this comparative example was improved to a limited extent as compared with example 1, but the ratio of 1-octene to 1-octene isomers in the toluene-rich stream taken from the top of the octene rectifying column system was large and the loss of 1-octene was relatively large.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above embodiments are only for illustrating the technical solution of the present invention, and the protection scope of the present invention is not limited thereby; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by others without departing from the spirit and scope of the present invention; while such modifications and equivalents are intended to fall within the scope of the invention.
Claims (14)
1. A process for separating 1-octene from an ethylene oligomerization reactant, said process comprising:
step a, enabling a material flow extracted from an ethylene oligomerization reaction termination kettle to enter an octene removal tower system, extracting an octene-rich material flow from the tower top of the octene removal tower system, enabling the material flow to enter a hexene removal tower system, and then extracting a material flow containing octene and toluene from the tower bottom of the hexene removal tower system;
b, enabling a material flow extracted from a tower kettle of the hexene removal tower system to enter an octene rectifying tower system, extracting a toluene-rich material flow containing 1-octene and 1-octene isomerides from the tower top of the octene rectifying tower system, and extracting a crude 1-octene material flow from the tower kettle of the octene rectifying tower system;
and c, feeding a material flow extracted from the top of the octene rectifying tower system into a toluene rectifying tower system, and extracting a material flow containing 1-octene and 1-octene isomerides from a tower kettle of the toluene rectifying tower system.
2. The process of claim 1, wherein the toluene content in the toluene-rich stream withdrawn from the top of the octene rectifying column system is from 90% wt to 99% wt, the 1-octene content is from 1% wt to 10% wt, and the 1-octene isomer content is from 0.5% wt to 5% wt.
3. The process of claim 2, wherein the 1-octene isomer content is from 5% wt to 20% wt and the 1-octene content is from 80% wt to 95% wt in the stream withdrawn from the bottoms of the toluene rectifying column system.
4. The process of claim 1 wherein the octene rectifying column system operates at a pressure of from-90 kPa (g) to-60 kPa (g) and at a column top temperature of from 70 ℃ to 80 ℃.
5. The process of claim 4 wherein the toluene rectifying column system is operated at a pressure of from 0kPa (g) to 50kPa (g) and a column bottoms temperature of from 120 ℃ to 130 ℃.
6. The process of claim 5 wherein the octene rectifying column system operates at a pressure of from-80 kPa (g) to-70 kPa (g) and the toluene rectifying column system operates at a pressure of from 10kPa (g) to 20kPa (g).
7. The process of claim 1 wherein the octene removal column system comprises a bottoms pump which is a slurry pump for withdrawing solid particulates from the ethylene oligomerization reactant stream.
8. The method of claim 7, wherein the octene removal column system comprises a reboiler and the reactant stream enters a bottoms of the octene removal column system through an inlet of the reboiler.
9. The method of claim 8, wherein the reboiler is a forced heat transfer mode.
10. The method of claim 1, wherein the operating pressure of the octene removal column system is-80 kPa (g) to-60 kPa (g), the column top temperature is 75 ℃ to 85 ℃, and the column bottom temperature is 140 ℃ to 160 ℃; the operating pressure of the hexene removing tower system is 0kPa (g) to 50kPa (g), the tower top temperature is 63 ℃ to 73 ℃, and the tower bottom temperature is 115 ℃ to 125 ℃.
11. The method of claim 1, wherein step b further comprises:
refining a crude 1-octene stream extracted from a tower kettle of an octene rectifying tower system, and sequentially passing the crude 1-octene stream through a desulfurization unit, a dechlorination unit, a deoxidization unit and a dehydration unit to obtain a refined 1-octene stream, wherein the content of 1-octene in the refined 1-octene stream is more than 99.5% wt, the toluene content is less than 1ppm (wt), the sulfur content is less than 1ppm (wt), the chlorine content is less than 1ppm (wt), the oxygen content is less than 1ppm (wt) and the water content is less than 1ppm (wt).
12. The method of claim 1, wherein step c further comprises:
and (3) extracting a crude toluene stream from the top of the toluene rectifying tower system, and refining the crude toluene stream, wherein the crude toluene stream sequentially passes through a deoxidizing unit and a dehydrating unit to obtain a refined toluene stream, and the refined toluene stream contains more than 99.9% wt of toluene, less than 1ppm (wt) of oxygen and less than 1ppm (wt) of water.
13. The method of claim 1, wherein the method further comprises:
and d, introducing part of a stream containing 1-octene and 1-octene isomerides extracted from the tower bottom of the toluene rectifying tower system into the octene rectifying tower system.
14. An apparatus suitable for use in the process for separating 1-octene from ethylene oligomerization reactants according to any of claims 1-13, said apparatus comprising:
a octene removal column system: the method is used for allowing a stream extracted from an ethylene oligomerization reaction termination kettle to pass through, and extracting an octene-rich stream from the top of the tower;
hexene removal tower system: passing an octene-rich stream withdrawn from the top of the octene removal column to remove hexene and withdrawing a stream comprising octene and toluene from the bottoms;
octene rectifying column system: the method comprises the steps of allowing a stream extracted from a tower kettle of a hexene removal tower system to pass, extracting a crude 1-octene stream from the tower kettle, and extracting a toluene-rich stream containing 1-octene and 1-octene isomers from the tower top;
toluene rectifying column system: for passing a stream withdrawn from the top of an octene rectifying column system and withdrawing a stream comprising 1-octene and 1-octene isomers from the bottom of the column.
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