CN1785940A - Technology of ion liquid catalyzing benzene and long chain olefin alkylation reaction and its device - Google Patents
Technology of ion liquid catalyzing benzene and long chain olefin alkylation reaction and its device Download PDFInfo
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Abstract
The present invention relates to a technological process capable of utilizing ion liquor to catalyze alkylation reaction of benzene and long-chain olefin hydrocarbon and its equipment. Said equipment includes the following several portions: reactor formed from premixer and static mixing/reactor, liquid-liquid continuous deposition phase separator, liquid inlet and outlet and controller. Said invention also provides their connection mode and working principle of said equipment.
Description
Technical field
The present invention relates to a kind of ion liquid catalyzing benzene and long chain olefin alkylation reaction technology and device, particularly with chloroaluminate ionic liquid as catalyzer, catalysis benzene and long chain olefin alkylation successive reaction-separate-recirculating process and device.
Background technology
Long-chain alkyl benzene refers generally to long-chain olefin (C
10-C
30) with the general name of benzene alkylation product.The alkylated reaction of long-chain olefin and benzene belongs to typical Friedel-Crafts reaction.Industrial employing straight chain (C
10-C
14) alkylbenzene mixture that makes of alkene and benzene alkylation, as the raw material of synthetic detergent; Adopt carbon number at the alkylbenzene mixture that the alkene more than 20 and benzene alkylation make, be used to make clean disperser for lubricating oil.
The early stage detergent use alkylbenzene sulfonate of producing (ABS) has a large amount of branches on alkyl chain, because the branched structure of alkyl chain can not cause the pollution to water body rapidly by biological degradation.After recognizing that alkylation obtains based on normal olefine ABS has preferably biodegradable, industry member turns to its attention and produces unbranched alkene and be used to produce linear alkylbenzene (LAB).
The traditional technology of producing LAB adopts sulfuric acid, hydrofluoric acid and anhydrous AlCl
3Deng as catalyzer, it is low to be easy to biodegradable 2-phenyl isomer content in the product; Catalyzer is difficult to recycle, and equipment corrosion and environmental pollution are serious.From the sixties in last century, carried out big quantity research around little, nuisanceless, the reproducible solid acid catalyst of corrodibility, mainly concentrate on molecular sieve, unformed aluminium, clay and carried heteropoly acid etc.But solid acid catalyst ubiquity inactivation is fast, and benzene feed alkene is bigger than very, and the catalyzer cycle of operation is short, and regeneration is frequent, the shortcoming that energy consumption is big.
Ionic liquid at room temperature provides new selection as novel green catalyst and solvent for the exploitation of " green process ".Adopt the alkylated reaction of chloroaluminate ionic liquid catalysis benzene and long-chain olefin because ionic liquid low temperature active height, under the condition that itself and reaction mixture fully mix alkene can be fast, conversion fully; The 2-phenyl isomer selectivity of readily biodegradable is apparently higher than traditional catalyst; Dissolve each other hardly between ionic liquid and the product stream and density difference bigger, this helps the loss that separates and reduce catalyzer of catalyzer and product stream.Yet, ionic-liquid catalyst has certain requirement to reaction process, as: 1, to realize the recycle of operate continuously and ionic-liquid catalyst, should make catalyzer and reaction mixture high efficient mixed, increase phase contact area and strengthen interphase mass transfer, and efficient, the sharp separation of the milk sap that organic phase and ionic liquid are formed; 2, because the chloro-aluminate ionic liquid at room temperature to moisture-sensitive, contains at feeding liquid under the operational condition of minor amount of water, how the easy inactivation of catalyzer guarantees that the catalyzer long-term operation remains a problem demanding prompt solution.
WO 98/03454 (1998) discloses BP company carries out synthesizing ethyl benzene in the recirculation reactor of a cover pilot scale experiment (see figure 1), between ionic liquid and the reaction mixture with real two phase reaction pattern operation.But this flow process all circulates the ionic liquid of adding, can not conditioned reaction thing and ionic liquid molecules ratio, though the use of nozzle can realization response feed liquid and ion liquid short mix in this technology in addition, but because of alkylating agent (alkene) once adds system in same point, can cause exothermic heat of reaction too concentrated, local temperature is higher, and degree of depth side reaction is uncontrollable, and reaction preference is lower; Settling process in the gravity separator is not reinforced, and the volume of separator may be bigger;
US 6284937 (2001) discloses the biliquid phase technology of a kind of Difasol of being called.This technique unit is reduced to a continuously stirring jar reactor and a follow-up phase separator (see figure 2) basically, raw material enters continuously and is equipped with in ionic liquid and catalyzer and the well-mixed agitator tank reactor, carry out alkylated reaction, reaction mass is through the sedimentation phase separator, isolated ionic liquid returns mixing reactor, and add fresh ionic liquid and remedy the catalyst activity forfeiture that causes because of the poisonous substance of carrying secretly in the charging, directly discharging of a reaction mass part after the separation, another part is got back to the reactor cycles reaction via water cooler, and water cooler is used to remove reaction heat.The characteristics of this technology be need not add special part catalyzer can be fixed on ionic liquid mutually in, Ni salt and aluminum alkyls derivative react in ionic liquid directly and to generate catalyzer, thereby can utilize stirred pot to realize biliquid phase successive reaction.In this system, improve the ratio of mixing efficiency and ionic liquid and organic phase, can quicken the dimerization of the olefinic monomer of enrichment in the charging, but when the ionic liquid ratio is too high, will make the sedimentation segregation time longer, cause dimeric selectivity to reduce, so realize the operation of this technology continous-stable, need make the material circular flow, ionic liquid adds speed and sepn process is coordinated mutually, and this patent technology and device can not independent regulation to the ratio of reaction mass and ionic liquid flow, are difficult to be implemented in the rational Match of hybrid reaction and sepn process in the big operating restraint; Adopt in addition general settling separation device because of be difficult to effectively to overcome feed liquid into and out of the time disturbance, can not satisfy the industry requirement of cyclical operation continuously; Though this technology is under the operate continuously condition in addition, catalyzer is retained in conversion zone effectively,, this operator scheme does not suppress the inactivation of acidic chloroaluminate ionic liquid catalyst.Major cause is ionic-liquid catalyst to water and moisture-sensitive and contains minor amount of water in the stock liquid that acidic chloroaluminate ionic liquid catalyst has kept AlCl
3As some character of catalyzer, promptly it removes the generation HCl after meeting water, also forms some oxygenated species, and most probable oxygenated species is [Al
3Cl
9OH]
-[Al
2Cl
6OH]
-, cause problems such as reactive system intermediate ion liquid catalyst effective constituent minimizing.
Summary of the invention
The present invention solves in ion liquid catalyzing benzene and long chain olefin alkylation biliquid catalysis successive reaction mutually-separate-process recycling, material circular flow, ionic liquid adding speed independent regulation reach the mutual coordination problem with sepn process, have realized that ionic-liquid catalyst reacts, separates continuously and effectively recirculation with high dispersing, the high efficient mixed of reactant; Solved the room-temperature ion liquid body catalyst by benefit aluminium in addition moisture-sensitive is caused the problem of rapid inactivation, a kind of ion liquid catalyzing benzene is efficient with long chain olefin alkylation, stable continuous is reacted-separated-recirculating process and device thereby provide.
Main technical schemes of the present invention: the present invention adopts the technology of continuous biliquid phase catalytic reaction, comprise: fresh feed, recycle stock and ionic liquid add mixing/reactor and carry out alkylated reaction, reaction back feed liquid is separated in phase separator with ionic liquid, partial material after the separation is drawn as product stream, and most of material and ionic liquid recirculation respectively return reactor.Wherein, the material that loops back reactor in premixed device, converge earlier with ionic-liquid catalyst and carry out pre-dispersed-mix-react, carry out alkylated reaction then in static mixing/reactor, the volumetric ratio of intense mixing/reaction zone and non-intense mixing/reaction zone is between 0.5: 1～5: 1 in the reactor; And in the maintenance reactor the up blank pipe linear velocity of feed liquid greater than 0.16ms
-1Reacted compound is after water cooler shifts out reaction heat, importing liquid-liquid sedimentation phase separator separates continuously, by overflow box outlet and the upper and lower outlet of circulation feed liquid are set on separator, the separator separated space is divided into heavy clear district, main negative area and ionic liquid leading-out zone, to realize the stable continuous high efficiency separation, adjust the separated space capacity that is complementary with the cyclic reaction mixture flow by the position of regulating overflow port and the upper and lower outlet of feed liquid, to guarantee separating effect; The settlement separate ionic liquid that goes out imports the ionic liquid collector from the separator bottom, switching the ionic liquid collector that makes two parallel connections by valve is in liquid collecting respectively and injects working order, according to the operation operating mode, the control ionic liquid loops back the flow of reactor, and the ratio of feed liquid and ionic liquid circular flow is remained between 300: 1～1000: 1.
In addition, the reacted mixed solution of above-mentioned ionic-liquid catalyst and feed liquid is before cooling heat transferring, taked original position to mend the aluminium measure, be used to prolong the life-span of ionic-liquid catalyst, its principle is the mixture that will leave static mixing/reactor by a packed bed that aluminium wire is housed, and realizes mending aluminium according to following chemical principle:
When the benzene alkene mol ratio of charging is hanged down, for fear of the selectivity that reduces main reaction because of the alkene autohemagglutination, can adopt along the mode of reaction tubes side line distribution charging, guarantee that the entire reaction district all is in high benzene/alkene than operation, to suppress side reaction.
The present invention is applicable to common ion liquid catalyzing benzene and long chain olefin alkylation reaction system, as ionic liquid is the imidazole type chloro-aluminate ionic liquid at room temperature that different alkyl replace, different alkylammonium type chloro-aluminate ionic liquid at room temperature, through the imidazole type chloro-aluminate ionic liquid at room temperature of modification or the replacement of compound alkyl, through modification or compound alkylammonium type chloro-aluminate ionic liquid at room temperature etc.; Long-chain olefin is the alkene of C10-C14, as: 1-laurylene etc.
Realize the device of technology of the present invention:
Device of the present invention is linked in sequence by valve and pipeline and forms with lower member: feed liquid recycle pump, pipeline flowmeter, premixed device, static mixing/reactor, high-performance heat exchanger, liquid-liquid continuous sedimentation phase separator, and the ionic liquid collector is characterized in that:
(1) reactor is formed by premixed device and static mixing/reactors in series, and static mixing/reactor is a unitized construction, and inner member can optionally draw off or reequip, and static mixing/reactor one side is provided with side line and connects into and out of the arm and the circulation line of feed liquid;
(2) liquid-liquid continuous sedimentation phase separator its top feed pipe lower end is equipped with liquid distributor, is made two-phase mixture be assigned on the phase separator total cross section evenly, imperturbably; Separator has upper and lower two circulation material liquid outlets, lay respectively on the above and following sidewall of feed liquid ingress pipe outlet, and connect mutually by outer communicating pipe between upper and lower material liquid outlet, be positioned on the above wall of feed liquid ingress pipe outlet and also have overflow port, be used to discharge the product feed liquid;
(3) on the ionic liquid recirculating line after phase separator, be connected to two ionic liquid collectors in parallel, each ionic liquid collector is equipped with the ionic liquid import and export, and is provided with logical nitrogen and blow-down pipe and control corresponding valve respectively on two collector tops.
In the circulation line of said apparatus, also be parallel with the branch road of the packed bed of filling aluminium wire on the circulation line between mixing/reactor and the high-effect cooling device, switch by valve, feed liquid can be carried out the ionic liquid original position through this packed bed and be mended reactive aluminum, delays catalyst deactivation.
Below above-mentioned phase separator feed-pipe liquid distributor, tilt to place one group of parallel baffle, separated liquid mixture is flowed down along baffle plate.Above-mentioned liquid liquid phase separator also can adopt the spinning liquid settling vessel.
Effect of the present invention:
Processing method of the present invention owing to take pre-mixing/reaction and static mixing/reaction to unite, under the little situation of power consumption, has realized rapidly and efficiently mixing and reaction of ionic-liquid catalyst and reaction mass with device; The side entry feed mode that is provided with even still can reach 100% per pass conversion when hanging down benzene alkene than charging, and effectively suppresses side reaction; The subregion subsidence style of sepn process has been realized stable, effectively separation continuously; The ratio of reaction mixture flow and ionic liquid flow can independent regulation, making mixing, separation and material circular flow and ionic liquid add speed is complementary, realized continuous, the efficient and smooth running of system, and catalyzer is retained in the system effectively, has obtained the stable more and reaction result efficiently than periodical operation; In addition, the present invention will mend the aluminium measure first and be used for the chloroaluminate ionic liquid catalystic converter system, make that under the condition that metallic aluminium exists, original position generates AlCl
3, to replenish the AlCl that is lost because of the dissolving and the water decomposition of ionic liquid chance of benzene
3Thereby, prolonged catalyst life; B acid is the amount of HCl in the minimizing catalystic converter system, makes the selectivity of 2-phenyl isomer in product maintain higher level, and has reduced the corrodibility that exists because of HCl.
Description of drawings:
Fig. 1 is the BP company device flow process of WO 98/03454 (1998)
Fig. 2 is existing biliquid phase reaction process unit schematic flow sheet
Fig. 3 is a biliquid phase reaction process unit schematic flow sheet of the present invention
Fig. 4 is a liquid liquid sedimentation phase separator structural representation of the present invention
Fig. 5 is static mixing/structure of reactor synoptic diagram that the present invention uses
Embodiment:
Technology of the present invention is realized by device as shown in Figure 3, Figure 4, reactor assembly is in series by premixed device Venturi tube 1 and a static mixing/reactor 2, Venturi tube sucks ionic liquid, and circulation feed liquid and circulation ionic liquid are converged, and brings into play the effect of pre-dispersed-mixing-reaction simultaneously.The inner member of static mixing/reactor is that a plurality of dismountable mixed cells combine, as: several left and right alternative Kenics type flights that revolve make up, and can optionally draw off; Mixing/reactor one side is provided with axial equally distributed side line arm 3a, 3b, 3c, 3d, 3e, 3f, 3g, 3h, 3i, can be respectively applied for thermometric, sampling and side line turnover reaction mass.When benzene feed alkene is relatively lower, if all once adding affiliation, alkene make Reactor inlet place benzene alkene smaller, thereby alkene may reduce the main reaction selectivity by the catalysis autohemagglutination, can adopt part along reaction tubes side entry feed mode, guarantee that the entire reaction district all is in high benzene/alkene than operation, to suppress side reaction, this moment is because the pre-dispersed-mixing-reactivity of Venturi tube, also avoided forming by product in the polymerization that causes alkene that contacts of side line fresh feed with ionic liquid stream thigh.
Circulation loop parallel connection behind static mixing/reactor is equipped with and is filled out aluminium wire packed bed 8, and packed bed carries out ionic liquid original position benefit aluminium can to make reacted mixed liquor switch so far, delays catalyst deactivation, enters high-performance heat exchanger again, shifts out reaction heat.
Connect a continuous liquid liquid sedimentation phase separator 6 behind the interchanger, the separator its top feed is taken over 9 and is inserted separator body certain depth, and its pipe end is connected with sieve plate liquid distributor 10, both can make charging uniform at total cross section, also increased the charging damping action, reduced settlement separate interference.The position of feed liquid ingress pipe outlet is adjustable up and down, in order to according to the settlement separate space of regulating working conditions; Be positioned on the above wall of feed liquid ingress pipe outlet and have overflow port 11, be positioned at more than the feed liquid ingress pipe outlet position and also to have the upper and lower outlet 12,13 of circulation feed liquid on the lower wall, separator is divided into three parts, that is: the feed liquid ingress pipe is above regional for sinking clear district H1 to overflow port and feed liquid upper outlet, feed liquid derive the mouth of pipe following to the feed liquid exit region be main negative area H2, the following subregion of outlet is ionic liquid leading-out zone H3 under the feed liquid; Through connecting mutually outer communicating pipe 14, the circular flow of part has been shared in the setting that exports under the feed liquid, thereby reduces the disturbance of flowing and produce because of near the feed liquid cocycle discharge port in the above heavy clear district of feed liquid ingress pipe pelvic outlet plane.The syphonic effect that may form because of the lower discharge port pipeline structure has been avoided in the setting of feed liquid upper outlet; In addition, the perforation pipe section of the upper and lower outlet of feed liquid can continue settling process; Derive through settlement separate feed liquid to recycle pump 4 from upper outlet; The separator bottom is ionic liquid outlet 15.In order to improve settlement separate efficient, below liquid distributor, to the cylindrical shell of sedimentation phase separator garden post part lower rim, adorned one group of parallel and tilted-putted dividing plate 16, the clear liquid part on sedimentation phase separator top flows out reactive system as product from overflow port 11, and most of clear liquid enters circulating reaction system along cocycle liquid outlet 12 circulations on right side.According to the needs of separated space, the local amplification of the perforation pipeline middle portion between the upper and lower outlet of feed liquid can be formed the zone that flow velocity reduces relatively, make settlement separate more thorough.In addition, the following outlet of circulation feed liquid can be for a plurality of, outlet down of every increase, because shared circular flow, following outlet near zone will reduce because of the disturbance that produces of flowing, and has also therefore increased the residence time of circulation feed liquid simultaneously, has strengthened separating power.By regulating the position of the outlet of phase separator feed liquid ingress pipe, overflow outlet and the upper and lower outlet of feed liquid, regulate the capacity of different zones in the settlement separate space.Such as: rising overflow port position, can increase the volume space in the above zone of feed liquid ingress pipe pelvic outlet plane, improve clarity.
Be connected with two ionic liquid collectors 7 in parallel in liquid liquid sedimentation phase separator 6 bottom interface, settlement separate ionic liquid is exported to the ionic liquid collector through by-pass valve control, ionic liquid collector configuration ionic liquid import and export, and be provided with logical nitrogen and blow-down pipe and corresponding switch valve respectively on two collector tops, can make two ionic liquid collectors be in liquid collecting and ionic liquid injection state respectively by adjusting corresponding valve, and can be by the ratio of valve difference conditioned reaction mixture with the ionic liquid flow.
Complete assembly is except that the small part flow passage components use the tetrafluoroethylene material, and all the other all are transparent glass, and the observation experiment phenomenon is convenient in protection against corrosion.
The said apparatus circulating reaction technology both can move according to andnon-continuous operation manner, also can move: under the periodical operation condition according to the operate continuously mode, should at first add benzene, begin circulation, add a certain amount of 1-laurylene again in recycle stock, add ionic-liquid catalyst at last, just can realize that alkylated reaction, reaction mixture separate with ionic liquid with recirculation carries out simultaneously, stop sampling analysis behind the circulation certain hour.
Under the operate continuously condition, before the operation, at first open the high-effect cooling device cooling water valve on the circulation process, in advance a certain amount of ionic liquid is added in the ionic liquid collector wherein, in system, add reaction mixture and start recycle pump, the circulation of beginning feed liquid, ionic-liquid catalyst is injected in normal back, reaction mixture and ionic-liquid catalyst be earlier pre-dispersed in venturi mixer-and mix-react, enter in static mixing/reactor again, as the ionic liquid of disperse phase with feed liquid by redispersion-mixing-reaction, strengthened dispersion-mixing and heat, matter is transmitted.After injecting ionic-liquid catalyst and stable feed liquid and ionic liquid circular flow continuously, with certain flow benzene and 1-laurylene stock liquid are pressed the certain molar ratio injected system with another pump again.Open the overflow outlet valve of liquid liquid sedimentation phase separator simultaneously and discharge feed liquid automatically, and it is constant to keep system's feed liquid cubic capacity.The circulation feed liquid enters continuous liquid liquid sedimentation phase separator through high-effect cooling device, by regulating overflow outlet valve, the operation capacity of regulator solution liquid sedimentation phase separator.Settlement separate ionic liquid is exported to the ionic liquid collector through valve control, adjusting corresponding valve makes two ionic liquid collectors be in liquid collecting and logical nitrogen pressure injection working order respectively, export to the feed liquid recycle pump through settlement separate feed liquid from separator feed liquid upper outlet, enter recirculation; When low benzene alkene during than charging, adopt fresh feed along the distributed feeding manner of reaction tubes side line arm, guarantee that the entire reaction district all is in high benzene/alkene than operation, to suppress side reaction.
In addition, technology of the present invention has taked original position to mend the aluminium measure, is used to prolong the life-span of ionic-liquid catalyst, and its principle is the mixture that will leave static mixing/reactor by a packed bed that aluminium wire is housed, and realizes mending aluminium according to following chemical principle:
Embodiment 1: ion liquid synthetic
1-Methylimidazole, 1-n-propylcarbinyl chloride mix by a certain percentage with toluene, use exsiccant N
2After air-blowing is swept 20 minutes, stir intensification and maintain 80～85 ℃, react 36 hours postcooling to room temperature.Get chlorination-3-butyl-1-Methylimidazole (BMIC) through freezing and crystallizing, solvent wash, recrystallization and vacuum-drying then; At N
2In the glove box of gas shiled, under agitation slowly add AlCl to BMIC
3Vacuumize under 70 ℃ and got the light brown transparent liquid in 1 hour, by 2.0 moles of AlCl
3The synthetic chlorine aluminic acid of the ratio of corresponding 1.0 moles of BMIC-3-butyl-1-Methylimidazole ([BMIM] [AlCl
4]) ionic liquid.AlCl in the ionic liquid
3Mole fraction (X
AlCl3) be defined as:
Embodiment 2: with the alkylated reaction of device periodical operation of the present invention
Under the periodical operation condition, at first add a certain amount of benzene, begin circulation, in recycle stock, add a certain amount of 1-laurylene again, the ionic-liquid catalyst that adds a certain amount of embodiment 1 preparation at last just can realize that alkylated reaction, reaction mixture separate with ionic liquid and circulate.Table 1 has provided the result of alkylated reaction example and performance test under two kinds of periodical operation conditions.
The experimental result of table 1. ion liquid catalyzing benzene and the periodical operation of 1-laurylene alkylated reaction
| The cumulative volume of feed liquid (L) in the system | Dosage (the cm of 1-laurylene 3) | Feed liquid and ionic liquid round-robin volume ratio | Reaction times (min) | The transformation efficiency of 1-laurylene (%) | 2-Ph selectivity (%) |
| 15.0 | 500.0 | 850∶1 | 5.0 | 100.0 | 40.8 |
| 15.0 | 500.0 | 700∶1 | 10.0 | 100.0 | 41.7 |
Embodiment 3: with the alkylated reaction of device operate continuously of the present invention
Under the operate continuously condition, open the water cooler Cold water tap on the circulation process, add stock liquid, the circulation of beginning feed liquid, and inject the ionic-liquid catalyst of embodiment 1 preparation continuously, stablize after the circulation of feed liquid and ionic liquid, inject the stock liquid of certain benzene and 1-laurylene mol ratio again with given reinforced flow from the fresh material inlet, open the overflow outlet valve of liquid liquid sedimentation phase separator simultaneously and discharge the feed liquid and the total feed liquid constancy of volume of the system that keeps, after after a while, in-system concentration and temperature distribution are kept constant the most at last.
Table 2 has provided the result of alkylated reaction example and performance test under the operate continuously condition.
The experimental result of table 2. ion liquid catalyzing benzene and the operate continuously of 1-laurylene alkylated reaction
| The cumulative volume of feed liquid (L) in the system | Feed liquid circular flow (L/min) | Fresh feed benzene alkene mol ratio | Fresh feed speed (ml/min) | Ionic liquid rate of injection (ml/min) | Sampling spot | Probe temperature (℃) | The transformation efficiency of 1-laurylene (%) | 2-Ph selectivity (%) |
| 15.0 | 11.5 | 6∶1 | 40.0 | 19.2 | 3h | 30.2 | 100.0 | 41.8 |
| 15.0 | 11.5 | 6∶1 | 80.0 | 9.7 | 3h | 29.8 | 100.0 | 40.7 |
| 15.0 | 11.5 | 2∶1 | 80.0 | 9.3 | 3h | 35.5 | 100.0 | 37.7 |
Embodiment 4-12: illustrated that mixing of the present invention, separation and material circular flow and ionic liquid add the relation of rate-matched, as following table 3:
| Feed liquid circular flow (Lmin -1) | Blank pipe linear velocity (the ms of feed liquid in mixing tank -1) | Ionic liquid flow (mlmin -1) | Ionic liquid and feed liquid troubled water | Settlement separate situation |
| 3.5 | 0.054 | 40 | Ionic liquid sinks | - |
| 5.5 | 0.085 | 40 | Ionic liquid rises, poor dispersion | - |
| 7.5 | 0.116 | 40 | Ionic liquid rises, and mixes relatively poor | - |
| 9.0 | 0.396 | 40 | Ionic liquid rises, mix through behind 6-7 mixed cell, almost do not observe tangible drop | Effective * |
| 10.5 | 0.163 | 40 | Ionic liquid rises, mix through behind 3-4 mixed cell, almost do not observe tangible drop | Effective * |
| 12.25 | 0.190 | 40 | Ionic liquid rises, mix through behind 2-3 mixed cell, almost do not observe tangible drop | Effective * |
| 15.0 | 0.233 | 40 | Ionic liquid rises, mix through behind 1-2 mixed cell, almost do not observe tangible drop | Effective * |
| 15.0 | 0.233 | 80 | Ionic liquid rises, mix through behind 1-2 mixed cell, almost do not observe tangible drop and do not observe drop | Local variation |
| 19.0 | 0.295 | 30 | Ionic liquid rises, mix through behind 1-2 mixed cell, almost do not observe tangible drop and do not observe drop | Bad |
As can be seen from Table 3, when the material circular flow was low, heavier ionic-liquid catalyst can not rise with feed liquid in static mixer relatively, even sank; At the material circular flow greater than 10.0Lmin
-1The time, can realize more satisfactory mixing.Separating effect and material circular flow and ionic liquid add speed all relation, and separating effect is retraining the material circular flow and ionic liquid adds speed, but has also determined the operation domain of device.It can also be seen that from table 3 the material circular flow is at 10～15Lmin
-1, the ionic liquid rate of injection is≤50.0cm
3Min
-1Condition under, all can realize comparatively ideal mixing, separation and ionic liquid recirculation.
Embodiment 13: mend the aluminium test: benzene (about 15 liters) is as the simulation mixture.The used ionic liquid scale of construction is 1500 milliliters.The load weighted aluminium wire of packing in mending the aluminium packed bed starts recycle pump and makes liquid mixture at system's internal recycle.Water injects the reaction mixture material from the side line arm of static mixing/reactor bottom.Ejector priming also makes material through passage 17 circulations, benzene and ionic liquid mix fully and circulate normal after, from the separator upper organic phase, get a clear liquid sample, note is made ICP 1, within an hour 25.0 ml waters are being injected the circulating system of benzene and ionic liquid mixture, get the clear liquid sample then from isolating organic phase, note is made ICP 2.Allow benzene and ionic liquid through passage 18 circulations 1 hour, get clear liquid sample 3 from separation.So, got clear liquid sample 4 through 1 hour again, recycle stock switches to passage 17 then, annotates second 25.0 ml water, gets clear liquid sample 5.After second and the 3rd 25.0 ml water inject, obtain 9 clear liquid samples altogether, detect wherein aluminium content by the ICP-AES method.Table 4 has provided the detected result of aluminium content in the different samples, and the interior Al content of organic phase significantly increases after the water filling, but reduces to again and original being on close level after mending aluminium, proves that the aluminium that disappears from organic phase enters into ionic liquid.After 3 water fillings and the operation of benefit aluminium, ion liquid activity is still very high.The measure of proof benefit aluminium is very effective thus.
Table 4 is mended the ICP-AES detected result of sample aluminium content in the aluminium experiment
| Sample number | Aluminium content (mgL -1) | Sample number. | Aluminium content (mgL -1) |
| ICP 1 | 40.4 | ICP 6 | 95.8 |
| ICP 2 | 251.5 | ICP 7 | 56.6 |
| ICP 3 | 43.5 | ICP 8 | 189.7 |
| ICP 4 | 47.6 | ICP 9 | 54.0 |
| ICP 5 | 266.2 |
Claims (9)
1, a kind of ion liquid catalyzing benzene and long chain olefin alkylation reaction technology, comprise: material and the ionic liquid that adds carries out alkylated reaction in static mixing/reactor continuously, reacted feed liquid is separated in phase separator with ionic liquid, separate back material and ionic liquid and be recycled to reactor respectively, it is characterized in that: material and ionic-liquid catalyst in premixed device, converge earlier and carry out pre-dispersed-mix, import static mixing/reactor then; The volumetric ratio of intense mixing/reaction zone and non-intense mixing/reaction zone is between 0.5: 1～5: 1 in the reactor, and keeps the up blank pipe linear velocity of feed liquid in the reactor greater than 0.16ms
-1When reacted feed liquid is separated in liquid-liquid sedimentation phase separator with ionic-liquid catalyst, adjust the separated space capacity that is complementary with the cyclic reaction mixture flow by regulating the overflow box outlet and the upper and lower outlet position of circulation feed liquid that are provided with on the separator; The settlement separate ionic liquid that goes out imports the ionic liquid collector, switching the ionic liquid collector that makes two parallel connections by valve is in liquid collecting respectively and injects working order, according to the operation operating mode, the ionic liquid flow of independent regulation injecting reactor keeps feed liquid and ionic liquid circular flow ratio between 300: 1～1000: 1.
2, reaction process according to claim 1 is characterized in that: ionic-liquid catalyst and the mixture that reacts the back feed liquid, and before supercooler, introduce the filling tube that aluminium wire is housed earlier and carry out original position benefit reactive aluminum from the pipeline branch road.
3, reaction process according to claim 1 is characterized in that: during mixing/reaction, if the benzene alkene mol ratio of charging is lower, adopt the mode along reaction tubes side line distribution charging.
4, a kind of device that is used for described ion liquid catalyzing benzene of claim 1 and long chain olefin alkylation reaction, this device is linked in sequence by valve and pipeline and forms with lower member: feed liquid recycle pump, pipeline flowmeter, ionic liquid injector, static mixing/reactor, high-performance heat exchanger, liquid-liquid continuous sedimentation phase separator, the ionic liquid collector is characterized in that:
(1) reactor is formed by premixed device and static mixing/reactors in series, static mixing/reactor is a unitized construction, inner member can optionally draw off or reequip, and static mixing/reactor one side is provided with arm and fresh feed or the export pipeline connection of side line into and out of feed liquid;
(2) liquid-liquid continuous sedimentation phase separator is the decanter type phase separator, separator has upper and lower circulation feed liquid liquid outlet, lay respectively on the above and following sidewall of feed liquid ingress pipe outlet, and connect mutually by outer communicating pipe between upper and lower material liquid outlet, be positioned on the above wall of feed liquid ingress pipe outlet and also have overflow port;
(3) on the ionic liquid recirculating line after phase separator, be connected to two ionic liquid collectors in parallel, each ionic liquid collector is equipped with the ionic liquid import and export, and is respectively arranged with the pipeline and the valve of logical nitrogen and emptying on two collector tops.
5, device according to claim 4 is characterized in that: be serially connected with the packed bed of filling aluminium wire behind mixing/reactor.
6, device according to claim 4 is characterized in that: liquid-liquid continuous sedimentation phase separator adopts the spinning liquid settling vessel.
7, device according to claim 4 is characterized in that: pre-mixing/reactor is a Venturi tube.
8, device according to claim 4 is characterized in that: liquid distributor is equipped with in liquid liquid continuous sedimentation phase separator its top feed pipe lower end, the liquid distributor placement parallel baffle that has a down dip.
9, device according to claim 4 is characterized in that: have under a plurality of circulation feed liquids on liquid-liquid continuous sedimentation phase separator and export.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410096840 CN1313422C (en) | 2004-12-08 | 2004-12-08 | Technology of ion liquid catalyzing benzene and long chain olefin alkylation reaction and its device |
Applications Claiming Priority (1)
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|---|---|---|---|
| CN 200410096840 CN1313422C (en) | 2004-12-08 | 2004-12-08 | Technology of ion liquid catalyzing benzene and long chain olefin alkylation reaction and its device |
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| CN1313422C CN1313422C (en) | 2007-05-02 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101234945B (en) * | 2007-02-01 | 2011-04-20 | 北京化工大学 | Method for on-line producing alkymer from regenerative ionic liquid catalyst |
| CN102660322A (en) * | 2012-05-15 | 2012-09-12 | 锦州康泰润滑油添加剂有限公司 | Process for preparing heavy alkylbenzene |
| US9328037B2 (en) | 2014-07-09 | 2016-05-03 | Uop Llc | Benzene alkylation using acidic ionic liquids |
| CN106478331A (en) * | 2016-08-31 | 2017-03-08 | 苏州乔发环保科技股份有限公司 | A kind of benzene and long-chain olefin alkylation reaction processing system |
| CN108290085A (en) * | 2015-11-24 | 2018-07-17 | 环球油品公司 | Vertical separator for ionic-liquid catalyst effluent |
| US10618858B2 (en) | 2015-07-24 | 2020-04-14 | Uop, Llc | Ionic liquid reactor with hydrocyclones |
| CN112844180A (en) * | 2020-12-29 | 2021-05-28 | 煤炭科学技术研究院有限公司 | External forced dispersing device for improving dispersing and mixing capacity of stirring kettle |
-
2004
- 2004-12-08 CN CN 200410096840 patent/CN1313422C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101234945B (en) * | 2007-02-01 | 2011-04-20 | 北京化工大学 | Method for on-line producing alkymer from regenerative ionic liquid catalyst |
| CN102660322A (en) * | 2012-05-15 | 2012-09-12 | 锦州康泰润滑油添加剂有限公司 | Process for preparing heavy alkylbenzene |
| CN102660322B (en) * | 2012-05-15 | 2015-03-18 | 锦州康泰润滑油添加剂股份有限公司 | Process for preparing heavy alkylbenzene |
| US9328037B2 (en) | 2014-07-09 | 2016-05-03 | Uop Llc | Benzene alkylation using acidic ionic liquids |
| US10618858B2 (en) | 2015-07-24 | 2020-04-14 | Uop, Llc | Ionic liquid reactor with hydrocyclones |
| CN108290085A (en) * | 2015-11-24 | 2018-07-17 | 环球油品公司 | Vertical separator for ionic-liquid catalyst effluent |
| US10654033B2 (en) | 2015-11-24 | 2020-05-19 | Uop Llc | Vertical separation vessel for ionic liquid catalyzed effluent |
| CN108290085B (en) * | 2015-11-24 | 2021-06-25 | 环球油品公司 | Vertical separator for ionic liquid catalyst effluent |
| CN106478331A (en) * | 2016-08-31 | 2017-03-08 | 苏州乔发环保科技股份有限公司 | A kind of benzene and long-chain olefin alkylation reaction processing system |
| CN112844180A (en) * | 2020-12-29 | 2021-05-28 | 煤炭科学技术研究院有限公司 | External forced dispersing device for improving dispersing and mixing capacity of stirring kettle |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1313422C (en) | 2007-05-02 |
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