CN100339342C - Method of separating refined 1-hexene from ethylene tripolymer - Google Patents
Method of separating refined 1-hexene from ethylene tripolymer Download PDFInfo
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- CN100339342C CN100339342C CNB2003101014198A CN200310101419A CN100339342C CN 100339342 C CN100339342 C CN 100339342C CN B2003101014198 A CNB2003101014198 A CN B2003101014198A CN 200310101419 A CN200310101419 A CN 200310101419A CN 100339342 C CN100339342 C CN 100339342C
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 title claims abstract description 132
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000005977 Ethylene Substances 0.000 title claims description 26
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 238000007599 discharging Methods 0.000 claims abstract description 30
- 238000005829 trimerization reaction Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000007670 refining Methods 0.000 claims abstract description 7
- 238000000605 extraction Methods 0.000 claims description 30
- 241000282326 Felis catus Species 0.000 claims description 25
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 22
- 239000006227 byproduct Substances 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 description 14
- 238000005265 energy consumption Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000012856 packing Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- IBTYIZQBUUFQNC-UHFFFAOYSA-N heptane;hex-1-ene Chemical compound CCCCC=C.CCCCCCC IBTYIZQBUUFQNC-UHFFFAOYSA-N 0.000 description 6
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Abstract
The present invention relates to a method for separating and refining 1-hexene from trimerization products of ethene. In the method, 1-hexene is refined by two serial rectifying towers, the removal of heavy fraction and the removal of light fraction are completed in a tower, wherein reaction liquid from the trimerization reaction of ethene enters a heavy and light fraction removal tower (2) from the middle part of the tower through a feeding pipeline(1), unreacted ethene is discharged through a discharging pipeline (3) at the top of the tower through the separation of the removal of heavy fraction and light fraction, components more than C8 and residual catalysts are discharged from a pipeline (4) at the bottom of the tower, the mixture of 1-hexene and the solvent is discharged in a gas phase mode from a side line (5) positioned below a feeding port of the heavy and light fraction removal tower and enters a refining tower (6) from the middle part of the tower to be separated, products (namely 1-hexene) are discharged from the top (7) of the tower, and the solvent is discharged from the bottom (8) of the tower. The method ensures the quality of products and saves production cost.
Description
Technical field
The present invention relates to the method for separation and purification 1-hexene from ethylene tripolymer.
Background technology
Linear alpha-alkene, particularly 1-hexene are mainly as the comonomer of producing high density polyethylene(HDPE) (HDPE) and linear low density polyethylene (LLDPE) resin.This comonomer produces the short carbon chain branch with linear alpha-alkene and prevents that polymer chain from closely getting together in polymkeric substance, therefore just reduced the density of product, and the density of the high more then resin of comonomer concentration is low more.In addition, comonomer also can change the processing and the mechanical characteristics of this polymkeric substance with alpha-olefin, and the carbon chain lengths of comonomer also can influence these characteristics.
At present, the technology of known highly-selective preparation 1-hexene is also few, and representational technology has three major types: the first kind be characterized in that raw materials cost is lower, but plant investment is higher for the Coal Chemical Industry legal system is equipped with the 1-hexene; Second class is the ethylene oligomerization method, is characterized in that product is to comprise from carbon four to carbon a series of alkene of ten, and selectivity is relatively poor; In recent years,, find to adopt the ethylene trimerization legal system to be equipped with the 1-hexene, have selectivity and yield preferably along with the development of catalysis technique.This three types of technology is compared, and it is abundant to be equipped with 1-hexene feed source with the ethylene trimerization legal system, and the plant investment minimum also is more suitable for the national conditions of China.
The reaction process of ethylene trimerization method is under the effect of high selectivity multiple catalyzer, ethene in varsol under certain temperature and pressure trimerization reaction, obtain the 1-hexene, reaction product is formed except the 1-hexene, comprise that also carbon number is generally 8 to 100 hydrocarbon reaction by product in unreacted ethene, the solvent that reacts use, the molecule, and remainder catalyst.
For the overwhelming majority's chemical plant installations, energy consumption and investment the best part all are the separation and purification parts of device, so, by developing advanced separation and purification technology, can effectively reduce investment, reduce cost, increase the competitive power of technology.Proposed the product separation process for refining of ethylene trimerization legal system 1-hexene in EP 168105 and EP 168106, the solvent of its reaction is a hexanaphthene, adopts three tower separation processes routes.The employing hexanaphthene is a solvent, because its boiling point and 1-hexene are approaching, so bigger with the isolating difficulty of 1-hexene, energy consumption is higher.Having proposed with heptane in JP 8-283330 and JP 8-283332 is solvent, by the placed in-line separating technology of tower, because the boiling point of heptane and 1-hexene differs far away, compares with hexanaphthene, more separate easily; Should but this separating technology be the very conventional tower separating technology that pursues, the table of equipment number is more, energy consumption is bigger.
Summary of the invention
Purpose of the present invention just provides a kind of improved method by refining 1-hexene in the ethylene tripolymer, it adopts two placed in-line rectifying tower to finish the refining of 1-hexene, adopted a side line discharging tower on stream, to take off heavy and take off light function and focus on the rectifying tower and realize the investment that reduces production costs and install.High-level efficiency reclaims unreacted ethene and solvent simultaneously, and reaction raw materials is fully utilized.
The technological process of separation and purification 1-hexene of the present invention is: enter first rectifying tower from the reaction solution of ethylene trimerization reaction through feeding line (1) and promptly take off heavy lightness-removing column (2), reaction solution mainly comprises unreacted ethene, the 1-hexene, the solvent that trimerization reaction uses and comprise that the alkene and the molecular weight that are generally C8-C100 more than the C8 are generally 5,000 to 5,000,000 poly heavy component by product and remainder catalyst, in general, therein ethylene content is 1～15% weight, 1-hexene content is 15～40% weight, solvent is 40～80% weight, heavy component by product and remainder catalyst content are 1～20% weight, temperature is generally 50 ℃ to 140 ℃, and pressure is generally 4.0-6.0MPa (pressure all is absolute pressure among the application); Through taking off the separation of heavy lightness-removing column, unreacted ethene is discharged by cat head discharging pipeline (3), not necessarily returning reactor cycles uses, heavy component that C8 is above and remainder catalyst by tower at the bottom of discharging pipeline (4) discharge, the mixture of 1-hexene and solvent is discharged by the gas phase side line (5) below the opening for feed that takes off heavy lightness-removing column, and it is treating tower (6) that the side line product that takes off heavy lightness-removing column enters second rectifying tower; Proceed separation and purification, product 1-hexene is discharged by cat head discharging pipeline (7), solvent by tower at the bottom of discharging pipeline (8) discharge, not necessarily return reactor cycles and use.
Its stage number of weight lightness-removing column (2) of taking off of the present invention is preferably between 20 to 60, and column internals can adopt for example sieve plate, float valve and other forms of column plate, according to the character of material, preferably uses sieve plate.The reaction solution that ethylene trimerization produces is by the middle part charging of tower, and its scope is that (the plate number of tower) * 1/3 is to (stage number is numbered the numbering of counting from top to bottom among the application) between the scope of (the plate number of tower) * 2/3; Discharge port is in the following gas phase extraction of the opening for feed of tower, its scope is preferably feed plate following 1 between (the plate number of tower)/3 blocks column plate, more preferably following (the plate number of tower)/5 of feed plate are to piece plate gas phase extraction between the 3* (the plate number of tower)/5, and its discharge port temperature is 100 ℃ to 200 ℃; The tower top pressure that takes off the working pressure of heavy lightness-removing column preferably is controlled between 0.1 to 2.5Mpa, and the pressure reduction at the bottom of cat head and the tower is preferably 0.02Mpa between the 0.1Mpa, and wherein tower top pressure is between 0.3 to 1.0Mpa, and effect is better.Tower top temperature is preferred 40 ℃ to 150 ℃, and column bottom temperature is preferably 100 ℃ to 300 ℃, and reflux ratio is preferably between 0.5 to 10.
The theoretical plate number for the treatment of tower of the present invention (6) is between preferred 20 to 60, column internals can adopt column plate or filler, tower diameter less than 800 millimeters situation under, can adopt the form of packing tower, as dumped packing or structured packing, be preferably efficient structured packing, tower diameter more than or equal to 800 millimeters situation under, can adopt the form of tray column, as float valve or sieve plate.The position of feed plate is at the middle part of tower, the position of feed plate is in the scope of (the plate number of tower)/2 ± 4, the tower top pressure of the working pressure for the treatment of tower (6) preferably is controlled at 0.1Mpa between the 1.0Mpa, pressure reduction at the bottom of cat head and the tower is preferably 0.02Mpa to 0.1Mpa, and working pressure has better effect between 0.1 to 0.2Mpa.Tower top temperature is preferably 60 ℃ to 100 ℃, and column bottom temperature is preferably 90 ℃ to 150 ℃.Reflux ratio preferably between 2 to 15, more preferably 2 to 10.
The solvent that is suitable among the present invention comprises paraffinic hydrocarbons, naphthenic hydrocarbon, aromatic hydrocarbon or its mixture, comprises hexane, toluene, hexene, heptane etc., and wherein heptane is more satisfactory solvent.
Characteristics of the present invention are that promptly taking off heavy lightness-removing column (2) by first treating tower adopts the following gas phase side line discharging of opening for feed, make and take off heavy and take off gently at a tower and realize, like this, just can finish the refining of 1-hexene with two placed in-line rectifying tower, compare by tower series connection separation and purification technology with existing, reduced by a cover tower system and a relevant utility appliance.Like this, for the 1-hexene device of 10,000 tons of annual outputs, compared with prior art, can reduce about 2,000,000 yuan of the construction investment of device, can also reduce about 1,000,000 yuan of energy consumption cost every year, the rate of recovery of ethene can reach more than 99%, the yield of 1-hexene is more than 97%, purity had both guaranteed quality product more than 99.9%, had saved production cost again.
Description of drawings
Fig. 1 be according to the present invention from the ethylene trimerization reaction product process flow sheet of separation and purification 1-hexene.
Fig. 2 is the process flow sheet (seeing the explanation of Comparative Examples) by tower separation and purification 1-hexene according to the flow process prior art of routine.
Embodiment
The following examples only are in order to illustrate the present invention better, but do not limit its scope.
Embodiment 1
Reaction product composition from the ethylene trimerization reaction sees the following form
| Component | Ethene | The 1-hexene | Heptane | By product and remainder catalyst |
| Form (weight %) | 1.8 | 24.2 | 70.2 | 3.8 |
Technical process is referring to accompanying drawing 1, enter through feeding line (1) from the reaction product of ethylene trimerization and to take off heavy lightness-removing column (2), 700 kilograms/hour of feed rates, feeding temperature is 90 ℃, and pressure is 0.7Mpa, and taking off heavy lightness-removing column is sieve-tray tower, 600 millimeters of tower diameters, stage number is 40, and feed plate is the 18th plate, and the side line reclaiming plate is the 26th a block of plate.Working pressure (tower top pressure) is 0.6Mpa, and tower bottom pressure is 0.67Mpa; 110 ℃ of tower top temperatures, 200 ℃ of column bottom temperatures, 167 ℃ of side line drop temperatures, discharge port pressure 0.63Mpa, reflux ratio is 4.Ethene and a spot of 1-hexene, are returned reactor cycles and use through discharging pipeline (3) extraction by cat head, and byproduct of reaction and remainder catalyst are discharged through discharging pipeline (4) at the bottom of by tower.The side line discharging enters treating tower (6) through pipeline (5), treating tower (6) is a packing tower, 450 millimeters of tower diameters adopt efficient screen waviness packings, and number of theoretical plate is 20, at theoretical stage is the charging of 10 places, working pressure (tower top pressure) is 0.12Mpa, and tower bottom pressure is 0.16Mpa, 62 ℃ of tower top temperatures, 117 ℃ of column bottom temperatures, reflux ratio are 4; Through pipeline (7) extraction, solvent through pipeline (8) extraction, returns reactor cycles and uses at the bottom of tower product 1-hexene at cat head.Separating effect is as follows:
1-hexene purity: 99.9% 1-hexene yield: 97.6%
Circulating solvent purity: the 99.6% circulating solvent rate of recovery: 99.9%
Energy consumption: 1.3 kilowatts of/kilogram 1-hexenes
Comparative Examples 1
From the reaction product of ethylene trimerization reaction form and feed conditions with embodiment 1
| Component | Ethene | The 1-hexene | Heptane | By product and remainder catalyst |
| Form (weight %) | 1.8 | 24.2 | 70.2 | 3.8 |
Technical process is referring to accompanying drawing 2, enters lightness-removing column (2) through feeding line (1), 700 kilograms/hour of feed rates from the reaction product of ethylene trimerization, feeding temperature is 90 ℃, and pressure is 0.7Mpa, and lightness-removing column is a sieve-tray tower, 600 millimeters of tower diameters, stage number are 45, and feed plate is the 19th plate.Working pressure (tower top pressure) is 0.6Mpa, and tower bottom pressure is 0.65Mpa; 86 ℃ of tower top temperatures, 165 ℃ of column bottom temperatures, reflux ratio is 1.Ethene and a spot of 1-hexene, are returned reactor cycles and use through discharging pipeline (3) extraction by cat head, and the extraction temperature is 40 ℃, and pressure is 0.6Mpa; 1-hexene, heptane, byproduct of reaction and remainder catalyst are discharged through discharging pipeline (4) at the bottom of by tower, enter weight-removing column (5), and temperature is 165 ℃, and pressure is 0.65MPa.Weight-removing column is a sieve-tray tower, 600 millimeters of tower diameters, and stage number is 45, feed plate is the 26th plate.Working pressure (tower top pressure) is 0.12Mpa, and tower bottom pressure is 0.17Mpa; 88 ℃ of tower top temperatures, 195 ℃ of column bottom temperatures, reflux ratio is 0.2.1-hexene and heptane through discharging pipeline (6) extraction, enter treating tower (8) by cat head, and the extraction temperature is 80 ℃, and pressure is 0.12Mpa; Byproduct of reaction and remainder catalyst are discharged through discharging pipeline (7) at the bottom of by tower, and temperature is 195 ℃, and pressure is 0.17MPa.Treating tower (8) is a packing tower, and 600 millimeters of tower diameters adopt efficient screen waviness packings, and number of theoretical plate is 20, at theoretical stage is the charging of 10 places, and working pressure (tower top pressure) is 0.12Mpa, and tower bottom pressure is 0.16Mpa, 62 ℃ of tower top temperatures, 117 ℃ of column bottom temperatures, reflux ratio is 4; Through pipeline (9) extraction, solvent through pipeline (10) extraction, returns reactor cycles and uses at the bottom of tower product 1-hexene at cat head.Separating effect is as follows:
1-hexene purity: 99.9% 1-hexene yield: 97.6%
Circulating solvent purity: the 99.6% circulating solvent rate of recovery: 99.9%
Energy consumption: 1.4 kilowatts of/kilogram 1-hexenes
The reaction product composition sees the following form
| Component | Ethene | The 1-hexene | Heptane | By product and remainder catalyst |
| Form (%) | 9.7 | 23.5 | 64.7 | 2.1 |
Technical process is referring to accompanying drawing 1, enter through feeding line (1) from the reaction product of ethylene trimerization and to take off heavy lightness-removing column (2), 650 kilograms/hour of feed rates, feeding temperature is 125 ℃, and pressure is 3.5Mpa, and taking off heavy lightness-removing column is sieve-tray tower, 500 millimeters of tower diameters, stage number is 45, and feed plate is the 20th plate, and the side line reclaiming plate is the 30th a block of plate.Working pressure (tower top pressure) is 1.0Mpa, and tower bottom pressure is 1.07Mpa; 140 ℃ of tower top temperatures, 250 ℃ of column bottom temperatures, 200 ℃ of side line drop temperatures, discharge port pressure 1.04Mpa, reflux ratio is 3.Ethene and a spot of 1-hexene, are returned reactor cycles and use through discharging pipeline (3) extraction by cat head, and byproduct of reaction and remainder catalyst are discharged through discharging pipeline (4) at the bottom of by tower.The side line discharging enters treating tower (6) through pipeline (5), treating tower (6) is a valve tray column, 600 millimeters of tower diameters, stage number is 30, and feed plate is the 16th a block of column plate, and working pressure (tower top pressure) is 0.12Mpa, tower bottom pressure is 0.16Mpa, 62 ℃ of tower top temperatures, 117 ℃ of column bottom temperatures, reflux ratio is 4; Through pipeline (7) extraction, solvent through pipeline (8) extraction, returns reactor cycles and uses at the bottom of tower product 1-hexene at cat head.Separating effect is as follows:
1-hexene purity: 99.9% 1-hexene yield: 97.2%
Circulating solvent purity: the 99.4% circulating solvent rate of recovery: 99.9%
Energy consumption: 1.32 kilowatts of/kilogram 1-hexenes
Comparative Examples 2
From the reaction product of ethylene trimerization reaction form and feed conditions with embodiment 2
| Component | Ethene | The 1-hexene | Heptane | By product and remainder catalyst |
| Form (weight %) | 9.7 | 23.5 | 64.7 | 2.1 |
Technical process is referring to accompanying drawing 2, enters lightness-removing column (2) through feeding line (1), 650 kilograms/hour of feed rates from the reaction product of ethylene trimerization, feeding temperature is 125 ℃, and pressure is 3.5Mpa, and lightness-removing column is a sieve-tray tower, 600 millimeters of tower diameters, stage number are 45, and feed plate is the 19th plate.Working pressure (tower top pressure) is 1.0Mpa, and tower bottom pressure is 1.05Mpa; 108 ℃ of tower top temperatures, 200 ℃ of column bottom temperatures, reflux ratio is 0.8.Ethene and a spot of 1-hexene, are returned reactor cycles and use through discharging pipeline (3) extraction by cat head, and the extraction temperature is 40 ℃, and pressure is 1.0Mpa; 1-hexene, heptane, byproduct of reaction and remainder catalyst are discharged through discharging pipeline (4) at the bottom of by tower, enter weight-removing column (5), and temperature is 200 ℃, and pressure is 1.05MPa.Weight-removing column is a sieve-tray tower, 600 millimeters of tower diameters, and stage number is 45, feed plate is the 26th plate.Working pressure (tower top pressure) is 0.12Mpa, and tower bottom pressure is 0.17Mpa; 88 ℃ of tower top temperatures, 195 ℃ of column bottom temperatures, reflux ratio is 0.2.1-hexene and heptane through discharging pipeline (6) extraction, enter treating tower (8) by cat head, and the extraction temperature is 80 ℃, and pressure is 0.12Mpa; Byproduct of reaction and remainder catalyst are discharged through discharging pipeline (7) at the bottom of by tower, and temperature is 195 ℃, and pressure is 0.17MPa.Treating tower (8) is a valve tray column, 600 millimeters of tower diameters, and stage number is 30, and feed plate is the 16th a block of column plate, and working pressure (tower top pressure) is 0.12Mpa, and tower bottom pressure is 0.16Mpa, 62 ℃ of tower top temperatures, 117 ℃ of column bottom temperatures, reflux ratio is 4; Through pipeline (9) extraction, solvent through pipeline (10) extraction, returns reactor cycles and uses at the bottom of tower product 1-hexene at cat head.Separating effect is as follows:
1-hexene purity: 99.9% 1-hexene yield: 97.3%
Circulating solvent purity: the 99.4% circulating solvent rate of recovery: 99.9%
Energy consumption: 1.45 kilowatts of/kilogram 1-hexenes
Embodiment 3
The reaction product composition sees the following form
| Component | Ethene | The 1-hexene | Heptane | By product and remainder catalyst |
| Form (%) | 3.9 | 24.8 | 68.1 | 3.2 |
Technical process is referring to accompanying drawing 1, enter through feeding line (1) from the reaction product of ethylene trimerization and to take off heavy lightness-removing column (2), 8000 kilograms/hour of feed rates, feeding temperature is 105 ℃, and pressure is 1.5Mpa, and taking off heavy lightness-removing column is sieve-tray tower, 1200 millimeters of tower diameters, stage number is 50, and feed plate is the 18th plate, and the side line reclaiming plate is the 32nd a block of plate.Working pressure (tower top pressure) is 0.8Mpa, and tower bottom pressure is 0.87Mpa; 125 ℃ of tower top temperatures, 235 ℃ of column bottom temperatures, 190 ℃ of side line drop temperatures, discharge port pressure 0.84Mpa, reflux ratio is 4.Ethene and a spot of 1-hexene, are returned reactor cycles and use through discharging pipeline (3) extraction by cat head, and byproduct of reaction and remainder catalyst are discharged through discharging pipeline (4) at the bottom of by tower.The side line discharging enters treating tower (6) through pipeline (5), treating tower (6) is a valve tray column, 800 millimeters of tower diameters, stage number is 45, and feed plate is the 22nd a block of column plate, and working pressure (tower top pressure) is 0.12Mpa, tower bottom pressure is 0.16Mpa, 62 ℃ of tower top temperatures, 117 ℃ of column bottom temperatures, reflux ratio is 3; Through pipeline (7) extraction, solvent through pipeline (8) extraction, returns reactor cycles and uses at the bottom of tower product 1-hexene at cat head.Separating effect is as follows:
1-hexene purity: 99.9% 1-hexene yield: 97.4%
Circulating solvent purity: the 99.5% circulating solvent rate of recovery: 99.9%
Energy consumption: 1.31 kilowatts of/kilogram 1-hexenes
Comparative Examples 3
From the reaction product of ethylene trimerization reaction form and feed conditions with embodiment 3
| Component | Ethene | The 1-hexene | Heptane | By product and remainder catalyst |
| Form (weight %) | 3.9 | 24.8 | 68.1 | 3.2 |
Technical process is referring to accompanying drawing 2, enters lightness-removing column (2) through feeding line (1), 8000 kilograms/hour of feed rates from the reaction product of ethylene trimerization, feeding temperature is 105 ℃, and pressure is 1.5Mpa, and lightness-removing column is a sieve-tray tower, 800 millimeters of tower diameters, stage number are 45, and feed plate is the 19th plate.Working pressure (tower top pressure) is 0.8Mpa, and tower bottom pressure is 0.85Mpa; 100 ℃ of tower top temperatures, 180 ℃ of column bottom temperatures, reflux ratio is 1.5.Ethene and a spot of 1-hexene, are returned reactor cycles and use through discharging pipeline (3) extraction by cat head, and the extraction temperature is 40 ℃, and pressure is 0.8Mpa; 1-hexene, heptane, byproduct of reaction and remainder catalyst are discharged through discharging pipeline (4) at the bottom of by tower, enter weight-removing column (5), and temperature is 180 ℃, and pressure is 0.85MPa.Weight-removing column is a sieve-tray tower, 800 millimeters of tower diameters, and stage number is 45, feed plate is the 26th plate.Working pressure (tower top pressure) is 0.12Mpa, and tower bottom pressure is 0.17Mpa; 88 ℃ of tower top temperatures, 195 ℃ of column bottom temperatures, reflux ratio is 0.2.1-hexene and heptane through discharging pipeline (6) extraction, enter treating tower (8) by cat head, and the extraction temperature is 80 ℃, and pressure is 0.12Mpa; Byproduct of reaction and remainder catalyst are discharged through discharging pipeline (7) at the bottom of by tower, and temperature is 195 ℃, and pressure is 0.17MPa.Treating tower (8) is a valve tray column, 800 millimeters of tower diameters, and stage number is 45, and feed plate is the 22nd a block of column plate, and working pressure (tower top pressure) is 0.12Mpa, and tower bottom pressure is 0.16Mpa, 62 ℃ of tower top temperatures, 117 ℃ of column bottom temperatures, reflux ratio is 3; Through pipeline (9) extraction, solvent through pipeline (10) extraction, returns reactor cycles and uses at the bottom of tower product 1-hexene at cat head.Separating effect is as follows:
1-hexene purity: 99.9% 1-hexene yield: 97.4%
Circulating solvent purity: the 99.5% circulating solvent rate of recovery: 99.9%
Energy consumption: 1.41 kilowatts of/kilogram 1-hexenes
Claims (16)
1. the method for a separation and purification 1-hexene from ethylene tripolymer, it adopts two placed in-line rectifying tower to finish the refining of 1-hexene, wherein: enter from the tower middle part through feeding line (1) from the reaction solution of ethylene trimerization reaction and to take off heavy lightness-removing column (2), reaction solution mainly comprises solvent, heavy component by product and the remainder catalyst in unreacted ethene, 1-hexene, the ethylene trimerization reaction; Separate through taking off heavy lightness-removing column (2), unreacted ethene is discharged by cat head discharging pipeline (3), by product heavy component and remainder catalyst are discharged by tower bottom tube line (4), and the mixture of 1-hexene and described solvent is discharged with gas phase from the side line (5) that is positioned at below the opening for feed that takes off heavy lightness-removing column; The side line product that takes off heavy lightness-removing column enters treating tower (6) at the tower middle part and proceeds separation and purification, and product 1-hexene is discharged by cat head (7), and described solvent is discharged (8) at the bottom of by tower.
2. method according to claim 1, the column internals that wherein takes off heavy lightness-removing column adopts column plate, and stage number is between 20 to 60.
3. method according to claim 2 is wherein taken off the position of the feed plate of heavy lightness-removing column and is arrived between the scope of (the plate number of tower) * 2/3 for (the plate number of tower) * 1/3.
4. method according to claim 2, wherein take off the discharging of heavy lightness-removing column side line below the feed plate 1 to gas phase extraction between (the plate number of tower) * 1/3 block column plate.
5. method according to claim 1, wherein taking off heavy lightness-removing column side line discharge port temperature is between 100 ℃ to 200 ℃.
6. method according to claim 2 is wherein taken off the form that heavy lightness-removing column tower plate structure adopts sieve plate.
7. method according to claim 2 takes off wherein heavily that the tower top pressure of the working pressure of dehydrogenation tower is between 0.1 to 2.5Mpa, and the pressure reduction at the bottom of cat head and the tower is between 0.02 to 0.1MPa.
8. method according to claim 1 takes off wherein heavily that the service temperature of dehydrogenation tower is cat head 40-150 ℃, at the bottom of the tower 100-300 ℃.
9. method according to claim 1, wherein taking off heavily, the reflux ratio of dehydrogenation tower is 0.5-10.
10. method according to claim 1, the column internals for the treatment of tower adopts column plate or filler, and stage number or theoretical plate number are between 20 to 60.
11. method according to claim 1, the feed plate position of wherein said treating tower are in the scope of (the plate number of tower) * 1/2 ± 4.
12. method according to claim 1, wherein the tower top pressure of the working pressure for the treatment of tower be 0.1Mpa between the 1.0Mpa, and the pressure reduction at the bottom of cat head and the tower is between the 0.02-0.1MPa.
13. method according to claim 1, the service temperature of wherein said treating tower are cat head 60-100 ℃, at the bottom of the tower 90-150 ℃.
14. method according to claim 1, the reflux ratio of wherein said treating tower are 2-15.
15. according to each described method of claim 1～14, described solvent is selected from paraffinic hydrocarbons, naphthenic hydrocarbon, aromatic hydrocarbon or its mixture.
16. according to the method for claim 15, wherein said solvent is hexane, toluene, hexene or heptane.
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| CNB2003101014198A CN100339342C (en) | 2003-10-17 | 2003-10-17 | Method of separating refined 1-hexene from ethylene tripolymer |
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| CNB2003101014198A CN100339342C (en) | 2003-10-17 | 2003-10-17 | Method of separating refined 1-hexene from ethylene tripolymer |
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| CN1609083A CN1609083A (en) | 2005-04-27 |
| CN100339342C true CN100339342C (en) | 2007-09-26 |
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| CN106588551B (en) * | 2015-10-19 | 2019-02-19 | 中国石油化工股份有限公司 | A kind of separation method of the 1- hexene for ethylene oligomerization product |
| EP3397607B1 (en) * | 2015-12-30 | 2022-12-28 | SABIC Global Technologies B.V. | Method of separating hexene |
| US11254630B2 (en) | 2016-12-19 | 2022-02-22 | Sabic Global Technologies B.V. | Method of separating linear alpha olefins |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0168105A1 (en) * | 1984-07-04 | 1986-01-15 | Koninklijke Philips Electronics N.V. | Apparatus for exposing a UV-curable coating on a filamentary body |
| JPH08283330A (en) * | 1995-04-18 | 1996-10-29 | Mitsubishi Chem Corp | Production of low alpha-olefin polymer |
| WO1999019280A1 (en) * | 1997-10-14 | 1999-04-22 | Phillips Petroleum Company | Process for the trimerization of olefins |
-
2003
- 2003-10-17 CN CNB2003101014198A patent/CN100339342C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0168105A1 (en) * | 1984-07-04 | 1986-01-15 | Koninklijke Philips Electronics N.V. | Apparatus for exposing a UV-curable coating on a filamentary body |
| JPH08283330A (en) * | 1995-04-18 | 1996-10-29 | Mitsubishi Chem Corp | Production of low alpha-olefin polymer |
| WO1999019280A1 (en) * | 1997-10-14 | 1999-04-22 | Phillips Petroleum Company | Process for the trimerization of olefins |
Non-Patent Citations (3)
| Title |
|---|
| 1-己烯产品分离工艺优化 梁爱民，马奉瑞，当代石油石化，第10卷第8期 2002 * |
| α-烯烃的生产和应用进展 姜涛 阎卫东 刘立新 李丹 吴殿义，化工进展，第3期 2001 * |
| 乙烯三聚制1-己烯研究进展 姜涛 阎卫东 刘立新 李丹 吴殿义，石化技术与应用，第5期 2000 * |
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