CN101113125A - Novel coupling process for isobutene oligomerisation reaction distillation - Google Patents
Novel coupling process for isobutene oligomerisation reaction distillation Download PDFInfo
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- CN101113125A CN101113125A CNA2006101041907A CN200610104190A CN101113125A CN 101113125 A CN101113125 A CN 101113125A CN A2006101041907 A CNA2006101041907 A CN A2006101041907A CN 200610104190 A CN200610104190 A CN 200610104190A CN 101113125 A CN101113125 A CN 101113125A
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Abstract
A novel coupling technique for an oligomerization reaction and a distillation of isobutene is to arrange the oligomerization reaction and the distillation of the isobutene in single tower equipment, namely to couple the oligomerization reaction and the distillation of the isobutene, and certain inert components, such as isopentane or isohexane as thermal carrier are added during the reaction process to improve vapor-liquid phase flow rate and distribution condition of temperature. The technique has simple technique process, equipment and process flow, low equipment investment, and wide market prospect.
Description
Technical field
The present invention relates to a kind of novel coupling process that is used for isobutene oligomerisation reaction distillation, it is a kind of improvement technology that belongs to petrochemical process process and device, this processing method mainly is isobutene oligomerisation reaction and rectifying separation PROCESS COUPLING to be arranged in the same tower finish, this process modification had both helped the simplification of equipment and technical process, reduce the investment of equipment again, reduced the complexity of operation.
Background technology
Over surplus in the of nearly ten year, China successively introduces and has set up several cover alkene oligomerization production equipments or olefin oligomerization production equipment, but, the technological process of all these production equipments all is to finish being arranged in respectively in reactor and a plurality of separation column oligomerisation reaction and separating of its product, and for example the mixed butene oligomerisation full scale plant of Shanghai petrochemical industry research institute exploitation and the iso-butylene polyunit (French IFP technology) of Shijiazhuang Oil Refinery all belong to this kind situation.At present, being coupled about the separation purifying technique of butene oligomerization technology and its product both at home and abroad is that the research of olefin oligomerization rectifying coupling technique does not appear in the newspapers as yet.
Because the primary product of olefin oligomerization is dipolymer, trimer and tetramer, but also often take place, as cracking and disproportionation etc., also comprise several monomeric intersection oligomerisation reactions simultaneously, thereby product is formed very complicated with side reaction.And in existing olefin oligomerization production equipment, the product of reaction fails to be separated timely, and is relatively poor as the target product selectivity of intermediate product.In addition, the oligomerisation reaction of alkene is an exothermic process, therefore the hot issue in the polymerization reactor solves effectively as can not get, not only cause the poor selectivity of target product, yield low easily, and, also caused the waste of energy simultaneously to also producing detrimentally affect the work-ing life of catalyzer and equipment.
Summary of the invention
Purpose of the present invention provides a kind of novel coupling process that is used for isobutene oligomerisation reaction distillation with regard to being to avoid the deficiencies in the prior art, this technology mainly is isobutene oligomerisation reaction and rectifying separation PROCESS COUPLING to be arranged in the equipment of same reaction fractionating tower finish, and in the process of reaction, add a certain amount of inert component, carry agent as iso-pentane or isohexane as heat, to improve the distribution situation of vapour-liquid phase flow rate and temperature in the reaction fractionating tower, the major technique characteristics of this technology be with the design of the process of the process of oligomerisation reaction and rectification process in same reaction fractionating tower, catalyzer and filler fill in this tower, and the total reflux device is set at the top of tower, the reaction raw materials iso-butylene is carried agent iso-pentane or isohexane with the middle part charging of cold conditions by conversion zone with heat, the purpose product is extracted out by the bottom of tower, and isolates behind vapour liquid separator.The catalyzer that uses in the conversion zone can be any butene oligomerization solid catalyst, and employed filler is the stainless steel dumped packing.
Description of drawings
The drawing of accompanying drawing is described as follows:
1----heating kettle 2----reactive distillation tower body 3----beds 4----condenser
5----return tank 6----thermopair 7----head tank 8----advection ram pump
9----knockout drum 10----high pressure water flat valve
Embodiment
Below in conjunction with drawings and Examples in detail technical characterstic of the present invention is described in detail:
Operating procedure is undertaken by following flow process: behind the reaction under high pressure rectifying tower sealing leak test, press certain flow to the reaction fractionating tower charging with volume pump, open reaction under high pressure rectifying micromanipulator heater switch, make system heat up, boost, unreacted iso-butylene is crossed cold total reflux after the overhead condenser condensation.After the question response distillation system was stable, from the continuous discharging of tower still, after Separate System of Water-jet was separated, gas-liquid was measured respectively mutually, is analyzed.
Embodiment 1: raw material is iso-butylene (polymerization-grade, purity 〉=99.0%).Catalyzer and filler equal-volume uniform mixing fill in
Reaction fractionating tower catalytic section (the used catalyzer of present embodiment is sial bead solid acid catalyst and stainless steel Dixon ring filler).From the charging of conversion zone top, feeding rate 8ml/min, tower still desired temperature is 100 ℃, system pressure 0.64Mpa, 27 ℃ of reflux temperatures.Reactive distillation the results are shown in Table 1:
Reactive distillation experimental data under 100 ℃ of still temperature of table 1
| Time/min | 20 | 50 | 110 | 170 | 200 | 260 | 320 | 380 | 440 |
| Transformation efficiency/% dimerization selectivity % trimerization selectivity % four poly-selectivity % | 73.37 45.99 43.82 10.19 | 76.03 65.27 27.59 7.14 | 82.03 63.75 28.89 7.35 | 77.51 61.70 30.52 7.78 | 78.73 62.13 29.84 8.03 | 78.18 63.07 29.14 7.79 | 71.89 63.72 28.75 7.52 | 76.92 62.33 30.54 7.13 | 73.58 60.80 31.86 7.34 |
Embodiment 2: raw material and catalyst loading pattern are with embodiment 1.From the charging of conversion zone top, feeding rate 8ml/min,
Tower still desired temperature is 120 ℃, system pressure 0.73Mpa, 27 ℃ of reflux temperatures.Reactive distillation the results are shown in Table 2:
Reactive distillation experimental data under 120 ℃ of still temperature of table 2
| Time/min | 60 | 120 | 180 | 240 | 300 | 360 | 420 |
| Transformation efficiency/% dimerization selectivity % trimerization selectivity % four poly-selectivity % | 54.31 35.38 53.71 10.71 | 81.94 39.24 51.44 9.32 | 85.74 38.46 53.01 8.53 | 85.80 36.45 52.12 11.43 | 86.23 36.80 52.48 10.72 | 88.89 32.03 53.44 14.53 | 85.13 35.20 55.14 9.66 |
Embodiment 3: raw material and catalyst loading pattern are with embodiment 1.From the charging of conversion zone top, feeding rate 8ml/min, tower still desired temperature is 140 ℃, system pressure 0.90Mpa, 22 ℃ of reflux temperatures.Reactive distillation the results are shown in Table 3:
Reactive distillation experimental data under 140 ℃ of still temperature of table 3
| Time/min | 110 | 140 | 170 | 200 | 260 | 320 | 380 | 440 | 500 |
| Transformation efficiency/% dimerization selectivity % trimerization selectivity % four poly-selectivity % | 68.28 36.14 50.47 13.39 | 85.88 40.38 52.03 7.59 | 87.04 40.29 49.53 10.18 | 84.02 38.53 50.44 11.03 | 89.69 37.78 53.69 8.53 | 89.64 37.39 53.50 9.11 | 89.03 37.26 53.77 8.97 | 91.51 34.56 55.52 9.92 | 87.34 39.89 51.20 8.91 |
Embodiment 4: raw material and catalyst loading pattern are with embodiment 1.From the charging of conversion zone top, feeding rate 6ml/min, tower still desired temperature is 100 ℃, system pressure 0.46Mpa, 22 ℃ of reflux temperatures.Reactive distillation the results are shown in Table 4:
Experimental data during table 4 6ml/min feeding rate
| Time/min | 40 | 70 | 100 | 150 | 210 | 270 | 330 | 390 | 450 |
| Transformation efficiency/% dimerization selectivity % trimerization selectivity % four poly-selectivity % | 81.28 19.77 66.20 14.03 | 80.22 43.61 45.35 11.04 | 86.48 49.47 41.52 9.01 | 87.49 51.71 39.66 8.63 | 85.42 55.11 36.69 8.20 | 82.08 58.19 34.26 7.55 | 83.63 58.45 34.24 7.31 | 93.80 61.48 32.12 6.40 | 88.45 55.16 37.43 7.41 |
Embodiment 5: raw material and catalyst loading pattern are with embodiment 1.From the charging of conversion zone top, feeding rate 10ml/min, tower still desired temperature is 100 ℃, system pressure 0.64Mpa, 22 ℃ of reflux temperatures.Reactive distillation the results are shown in Table 5:
Experimental data during table 5 10ml/min feeding rate
| Time/h | 0.5 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Transformation efficiency/% dimerization selectivity % trimerization selectivity % four poly-selectivity % | 68.15 54.82 37.01 8.17 | 81.28 61.52 31.48 7.00 | 76.53 64.40 29.32 6.28 | 75.19 58.34 32.88 8.78 | 79.55 56.90 35.20 7.89 | 79.83 58.09 34.10 7.81 | 81.50 57.18 34.98 7.84 | 83.68 56.98 35.08 7.94 | 83.70 57.68 34.54 7.78 |
Embodiment 6: raw material and catalyst loading pattern are with embodiment 1.From the charging of conversion zone top, feeding rate 8ml/min, tower still desired temperature is 100 ℃, system pressure 0.90Mpa, 14 ℃ of reflux temperatures.Reactive distillation the results are shown in Table 6:
Experimental data under the low reflux temperature of table 6
| Time/min | 120 | 180 | 240 | 270 | 260 | 330 | 390 |
| Transformation efficiency/% dimerization selectivity % trimerization selectivity % four poly-selectivity % | 65.26 58.15 35.88 5.97 | 58.52 61.38 32.99 5.63 | 65.65 53.90 39.79 6.31 | 68.31 51.74 40.65 7.61 | 69.64 51.86 40.77 7.38 | 75.07 47.99 44.79 7.22 | 74.26 47.98 43.82 8.21 |
Embodiment 7: raw material and catalyst loading pattern are with embodiment 1.From the conversion zone underfeed, feeding rate 8ml/min, tower still desired temperature is 100 ℃, system pressure 0.63Mpa, 22 ℃ of reflux temperatures.Reactive distillation the results are shown in Table 7:
The experimental data of table 7 during by the conversion zone underfeed
| Time/min | 20 | 50 | 90 | 120 | 210 | 270 | 345 | 405 | 465 |
| Transformation efficiency/% dimerization selectivity % trimerization selectivity % four poly-selectivity % | 66.28 52.61 38.97 8.42 | 81.51 50.83 41.08 8.09 | 78.34 48.87 42.95 8.18 | 80.28 46.55 45.01 8.44 | 84.57 44.63 46.65 8.72 | 86.84 42.94 48.02 9.04 | 76.66 44.26 46.85 8.89 | 79.16 49.72 43.36 6.92 | 84.25 50.21 41.46 8.33 |
Embodiment 8: raw material and catalyst loading pattern are with embodiment 1.From the charging of conversion zone top, feeding rate 8ml/min.Add a certain amount of inert component iso-pentane simultaneously, iso-pentane/iso-butylene (volume ratio) is 0.2: 1.0, and tower still desired temperature is 140 ℃, system pressure 0.72Mpa, 22 ℃ of reflux temperatures.Reactive distillation the results are shown in Table 8:
Table 8 adds the experimental data after the inert component
| Time/min | 30 | 60 | 90 | 120 | 150 | 180 | 240 | 300 |
| Transformation efficiency/% dimerization selectivity % trimerization selectivity % four poly-selectivity % | 78.69 66.02 29.23 4.74 | 86.01 69.91 25.37 4.718 | 87.91 69.29 25.83 4.88 | 87.23 71.33 23.91 4.76 | 89.24 70.79 24.7 4.51 | 88.22 71.92 23.58 4.498 | 86.11 72.25 23.82 3.932 | 86.83 71.58 24.14 4.275 |
Contrast experiment's result compares reaction and rectification device with the experimental result of fixed-bed reactor, when reaction conversion ratio was identical, the selectivity of dipolymer was the highest in the reactive distillation product, and three, the selectivity all minimum (seeing Table 9) of tetramer; When the yield of dipolymer is identical; the temperature of reaction fractionating tower beds is lower more than 20 ℃ than the bed temperature of fixed-bed reactor; this not only help guard catalyst activity, prolong its work-ing life, and help dipolymer and optionally improve.Take adequate measures with the prerequisite that guarantees the dipolymer selectivity and be not lowered under. temperature that can also be by suitably increasing reaction bed or height are to reach the purpose that improves transformation efficiency.
The comparison of table 9 reactive distillation and fixed-bed reactor experimental result
| Temperature/℃ | Transformation efficiency/% | The dipolymer selectivity | The trimer selectivity | The tetramer selectivity | |
| The reaction fractionating tower fixed-bed reactor | (99.4 tower still) 66.0 (conversion zones) 100.0 | 78.73 78.22 | 0.6213 0.5340 | 0.2984 0.3792 | 0.0803 0.0868 |
The invention effect
Compared with prior art, novel coupling process characteristics for isobutene oligomerisation reaction distillation of the present invention are to have utilized " coupling " technology, and bed temperature runaway or local hot spot phenomenon that polymerisation may occur in distillation process, have been controlled, suppress the generation of accessory substance, reduce the deactivation rate of catalyst; Simultaneously because the impurity composition in the product also can be in time removed in the existence of distillation process, to improve purity and the conversion rate of products of target product. Angle from technical process is coupled oligomerisation reaction and distillation process, is conducive to the simplification of equipment and technological process, reduces equipment investment, reduces the complexity of operation.
Claims (2)
1. novel coupling process that is used for isobutene oligomerisation reaction distillation, this technology is the reaction of isobutene oligomerisation and rectifying separation PROCESS COUPLING to be arranged in the same tower finish, it is characterized in that design of technological process is that the process of oligomerisation reaction and the process of rectifying separation are designed in same reaction fractionating tower, catalyzer and filler fill in this tower and at the top of this reaction fractionating tower the total reflux device are set, the reaction raw materials iso-butylene is carried agent with the middle part charging of cold conditions by conversion zone with heat, the purpose product is extracted out by the bottom of tower, and via isolating behind the vapour liquid separator.
2. a kind of novel coupling process that is used for isobutene oligomerisation reaction distillation according to claim 1, it is characterized in that employed catalyzer is the solid catalyst that is used for butene oligomerization, the filler that uses is the stainless steel dumped packing, and it is iso-pentane or isohexane that employed heat carries agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946642A (en) * | 2017-03-12 | 2017-07-14 | 山东成泰化工有限公司 | A kind of isobutene polymerisation prepares triisobutylene and the method and device of four isobutenes |
| CN114426444A (en) * | 2020-09-22 | 2022-05-03 | 中国石油化工股份有限公司 | Isobutylene polymerization reaction overtemperature treatment method |
-
2006
- 2006-08-04 CN CNA2006101041907A patent/CN101113125A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946642A (en) * | 2017-03-12 | 2017-07-14 | 山东成泰化工有限公司 | A kind of isobutene polymerisation prepares triisobutylene and the method and device of four isobutenes |
| CN114426444A (en) * | 2020-09-22 | 2022-05-03 | 中国石油化工股份有限公司 | Isobutylene polymerization reaction overtemperature treatment method |
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