CN104549108B - A kind of alkylation reactor and alkylation reaction technique - Google Patents
A kind of alkylation reactor and alkylation reaction technique Download PDFInfo
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- CN104549108B CN104549108B CN201310503471.XA CN201310503471A CN104549108B CN 104549108 B CN104549108 B CN 104549108B CN 201310503471 A CN201310503471 A CN 201310503471A CN 104549108 B CN104549108 B CN 104549108B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00121—Controlling the temperature by direct heating or cooling
- B01J2219/00123—Controlling the temperature by direct heating or cooling adding a temperature modifying medium to the reactants
- B01J2219/00126—Cryogenic coolants
Abstract
The invention discloses a kind of alkylation reactor and alkylation reaction method, reactor includes reactor shell, end socket, revolving bed, feed pipe, charging distributor pipe, discharging opening, circulating cooling gas entrance, circulating air cooling tank, and circulating cooling gas exports；Reactor shell and end socket constitute closed reactor housing, in the middle part of revolving bed is vertically positioned in housing；Revolving bed radial outside arranges static bed, has suitable gap between static bed and revolving bed；Between revolving bed top and reactor shell, containment member is set, revolving bed top and containment member are for being rotatably connected, circulating cooling gas entrance and the outlet of circulating cooling gas are separately positioned on the housing of containment member the upper side and lower side, and circulating air cooling tank is between circulating cooling gas entrance and circulating cooling gas export.Alkylation of the present invention, with concentrated sulphuric acid for catalyst, is alkylated reaction with iso-butane and alkene for raw material.Alkylated reaction of the present invention can carry out at low temperatures, and acid consumption is low, and equipment scale is little.
Description
Technical field
The present invention relates to a kind of alkylation reactor and alkylation reaction method, specifically a kind of alkylation reactor adopting iso-butane and C3～C5 olefin catalytic alkylated reaction and alkylation reaction method.
Background technology
Along with the fast development of economic development, particularly transportation, the discharge of Vehicular exhaust is one of air-polluting main source, and improving quality of gasoline is reduce the main approach that Vehicular exhaust pollutes.The alkylate oil that the alkylated reaction of iso-butane and C3～C5 alkene obtains, has without features such as sulfur, high-octane rating height, research octane number (RON) and motor octane number difference are little, is the important blend component of high-quality clean gasoline.
Alkylated reaction is the conventional art in petroleum refining field, mainly has sulfuric acid process alkylation techniques and hydrogen fluoride alkylation techniques, and under the effect of catalyst (sulphuric acid or Fluohydric acid .), isobutane and olefins is obtained by reacting isoparaffin.Sulfuric acid process alkylation is compared with hydrogen fluoride alkylation, differs from one another in technique, is also all sufficiently close to from aspects such as capital expenditure, production cost, product yield and product qualities, therefore both approaches energy long-term co-existence, is all widely adopted.On the whole, from the yield of the quantity of alkyl plant and alkyl oil, current hydrofluoric acid alkylation unit is dominant, but the increasingly stringent required recently as environmental regulation and the hypertoxic characteristic of Fluohydric acid., new device many employings alkyl sodium sulfate metallization processes.
In sulfuric acid process alkylation techniques, reaction carries out at relatively low temperature, and reaction unit needs have refrigerating function.In hydrogen fluoride alkylation techniques, reaction temperature is of a relatively high, is generally adopted water-cooled and namely can meet reaction requirement.Therefore, both reactor assembly differences are bigger.Traditional sulfuric acid process alkylation reactor structure species is more, and currently used more have two kinds, and one is cascade sulfuric acid alkylation reaction unit, and one is Stratco formula reactor (i.e. the internal indirect refrigeration reactor arranging heat-obtaining tube bank).
The reactor of cascade sulfuric acid alkylation device is generally made up of several conversion zones, the intersegmental overflow baffle of each reaction separates, each conversion zone is equipped with agitator, product and sulphuric acid and finally enters settling section and be easily separated, and the sulphuric acid circulating pump separated is sent into conversion zone and reused.Adopt reactant iso-butane spontaneous evaporation refrigeration, the advantage of this response system be alkane alkene in each conversion zone than high, power consumption is little, do not need another refrigerant feeding.But owing to alkane and alkene are not pre-mixed, thus reduce the quality of alkylate oil, add acid consumption.And influencing each other between each conversion zone, a conversion zone operation is abnormal, and whole reactor is affected by impact.
It is that to adopt be horizontal eccentric reactor that inside arranges a kind of concrete structure of indirect refrigeration reactor of heat-obtaining tube bank, the shell of reactor is a horizontal pressure vessel, internal equipped with a powerful agitator, internal recycle sleeve and heat-obtaining tube bank, hydrocarbon raw material is entered reactor by upper and lower two feed pipes, reactor is sprayed into towards impeller after converging before agitator arm, the impeller run up is in reactor undergauge place, make the logistics of inside reactor due to impeller suction, tuze bundle resistance force, linear differential etc. and cause the hole of some flow liquids, so that sulphuric acid obtains reasonable dispersion with hydro carbons and mixes.Acid hydrocarbon emulsion is turned back entrance sleeve inner in reactor head again, again flows to stirring vane, forms the logistics of a high-speed circulating.Having recycle stock in this reactor, the response time of partial material is longer, and side reaction can increase, and acid consumption is relatively big, and the raising of product octane number is unfavorable.
Disclose the sulfuric acid alkylation course of reaction of a kind of C3-C5 alkene and iso-butane, cancel traditional mechanical agitation mode, ejector is adopted reaction mass to be mixed and then reacts, but in sulfuric acid alkylation course of reaction, sulphuric acid is relatively big with the density contrast of hydrocarbon material, and the effect of injection hybrid mode need to improve further.US5,785,933 disclose a kind of sulfuric acid catalysis alkylation reactor system, and inside reactor, by the multiple injection pipeline entrances arranging baffle plate and tangential height is put, makes reaction mass form mix and blend and then cancellation mechanical moving element in reactor.This technology utilizes the principle design of static mixer sulfuric acid alkylation reactor, but mixed effect needs to improve further.
CN1907924A discloses a kind of ionic liquid-catalyzed reaction process and reaction unit, hydrocarbon raw material and ionic-liquid catalyst react in rotary drill reactor, revolving bed is arranged on reactor internal upper part, reactor lower part is fluid reservoir, reactor center arranges agitating device, and fluid reservoir and feed liquid circulating pump connect and compose revolving bed recirculation reactor.This reactor is not suitable for sulfuric acid process alkylation process, because the heat exchange mode adopted is recycle stock heat-obtaining mode, it is unsuitable for the sulfuric acid process alkylated reaction that heat release is bigger, the fluid reservoir of reactor lower part and employing reaction mass circulation mode of operation and can increase side reaction.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of alkylation reactor and alkylation process, improves the contacting efficiency of catalyst and hydrocarbon reaction raw material, reduces the acid consumption of sulfuric acid catalyst, reduces reaction temperature, improve product quality.
Alkylation reactor of the present invention includes following content: reactor shell, end socket, revolving bed, feed pipe, charging distributor pipe, discharging opening, circulating cooling gas entrance, and circulating cooling gas exports, circulating air cooling tank；Reactor shell and end socket constitute closed reactor housing, in the middle part of revolving bed is vertically set in housing, revolving bed is connected with driving device by rotating shaft, revolving bed center is empty barrel structure, charging distributor pipe is arranged in the empty barrel structure at revolving bed center, charging distributor pipe connects with feed pipe, and discharging opening is arranged on reactor shell bottom；Revolving bed radial outside arranges static bed, has suitable gap between static bed and revolving bed；Between revolving bed top and reactor shell, containment member is set, for being rotatably connected between revolving bed top and containment member, circulating cooling gas entrance and the outlet of circulating cooling gas are separately positioned in the reactor shell of containment member the upper side and lower side, and circulating air cooling tank is arranged between circulating cooling gas entrance and the outlet of circulating cooling gas；Described circulating air cooling tank includes housing and cooling gas phase coil pipe, in the middle part of cooling gas phase coil pipe is arranged in housing.
In alkylation reactor of the present invention, arranging circulating air refrigeration system between circulating cooling gas entrance and the outlet of circulating cooling gas, circulating cooling gas is previously formed circulation in circulating cooling gas refrigeration system and reactor, provides suitable temperature environment for course of reaction.
In alkylation reactor of the present invention, static bed is at least provided with more than half cycle, it is preferable that arrange one week.The fixed form of static bed can adopt bottom fixed form, top fixed form, radially fixed concrete mode such as grade.When adopting top fixed form, it is preferable that static bed is fixed on containment member bottom.Static bed is made up of corrosion-resistant screen cloth, corrosion-resistant silk screen or corrosion-resistant filling.Static bed and revolving bed are coaxially set.Highly preferred and the revolving bed of static bed is with high.Clearance distance between static bed and revolving bed is 10mm～700mm, it is preferable that 50mm～200mm.The thickness of static bed is 0.2 times～1.5 times of revolving bed thickness, it is preferable that 0.5 times～0.8 times.
In alkylation reactor of the present invention, feed pipe one end connects with charging distributor pipe, the outlet of the feed pipe other end and ejector mixing；Ejector mixing includes head-on collision room and charging jet, and head-on collision indoor arrange two charging jets that position is relative, forms injection mixed zone, utilize charging pump lift residual power, it is achieved the premixing of material between two charging jets.
In alkylation reactor of the present invention, the preferably cylindrical cylinder of reactor shell, end socket includes upper cover and low head, and cylindrical reactor preferred vertical is arranged；Revolving bed preferably employs corrosion-resistant framework and bed is constituted, and bed preferably employs corrosion resistant metal silk screen or filler is constituted；Revolving bed profile is cylinder barrel shaped, arranges suitable space between revolving bed and reactor shell, forms annulus；Revolving bed center is cylindrical empty cylinder, and charging distributor pipe is arranged in this cylindrical empty cylinder, has suitable space between charging distributor pipe and revolving bed, forms annulus；Arranging suitable material distribution hole on charging distributor pipe, the length of material distributor pipe is corresponding with the axial length of revolving bed；Rotating shaft is fixing with the fixing plate in revolving bed one end to be connected, and rotating shaft preferred vertical is arranged；The driving device that rotating shaft is arranged by the outer top of end socket and reactor or bottom is connected, and driving device is preferably provided at the outer bottom of reactor.
In alkylation reactor of the present invention, it is one of following two that circulating cooling gas entrance and the outlet of circulating cooling gas arrange position: (1) is with the containment member of setting between revolving bed top and reactor shell for boundary, circulating cooling gas entrance is arranged on the housing on containment member top, and the outlet of circulating cooling gas is arranged on the housing of containment member bottom；(2) so that between revolving bed top and reactor shell, the containment member of setting is for boundary, circulating cooling gas entrance is arranged on the housing of containment member bottom, and the outlet of circulating cooling gas is arranged on the housing on containment member top.When adopting aforesaid way (1), circulating cooling gas and reaction mass are in the same direction through revolving bed, owing to gas is had swabbing action by revolving bed, therefore, circulating cooling gas power delivery unit can be not provided with, or lower-powered circulating cooling gas power delivery unit is set；When adopting aforesaid way (2), circulating cooling gas and reaction mass pass back through revolving bed, it is necessary to arrange circulating cooling gas power delivery unit.It is therefore preferable that aforesaid way (1).
In alkylation reactor of the present invention, circulating air cooling tank includes housing and cooling gas phase coil pipe, in the middle part of cooling gas phase coil pipe is arranged in housing, described circulating air cooling tank is provided with gas access, gas outlet, refrigerant inlet and refrigerant exit, wherein, gas outlet and gas access are arranged on circulating air cooling tank housing, and gas access is connected with the outlet of circulating cooling gas, and gas outlet is connected with circulating cooling gas entrance；Refrigerant inlet and refrigerant exit are separately positioned on circulating air cooling tank top and bottom.
In alkylation reactor of the present invention, circulating air refrigeration system is set, revolving bed is utilized to rotate the tiny structure formed, circulating cooling gas phase is promoted to realize from bed center flowing laterally, when needing heating or cooling when course of reaction, using circulating cooling gas as the carrier of Cooling and Heat Source, the circulating cooling gas discharged from the outlet of circulating cooling gas enters cooling gas phase coil pipe through the gas access of circulating air cooling tank, coolant enters thermal cycle gas cooling tank through refrigerant inlet, heat exchange is carried out with the circulating cooling gas in cooling gas phase coil pipe, cool down the circulating cooling gas in gas phase coil pipe and coolant after heat exchange, after circulating cooling temperature reaches temperature requirement, alkylation reactor is entered through gas outlet and circulating cooling gas entrance, complete the adjustment to reaction temperature, coolant after heat exchange is discharged through refrigerant exit.Coolant is liquefied ammonia, dry ice, hypothermic saline, ethanol etc..
Alkylation of the present invention, adopts abovementioned alkyl reactor of the present invention, with iso-butane and C3～C5 alkene for raw material, with sulphuric acid for catalyst, is alkylated and is obtained by reacting alkylate oil.
In alkylated reaction of the present invention, being total hydrocarbon feed by iso-butane and C3～C5 olefin, the mol ratio of iso-butane and C3～C5 alkene is mol ratio is 1:1～300:1, it is preferred to 3:1～50:1.C3～C5 alkene is monoolefine, it is preferred to butylene.
In alkylated reaction of the present invention, catalyst sulfuric acid is concentrated sulphuric acid, and the sour hydrocarbon volume ratio of the hydrocarbon mixture of concentrated sulphuric acid and iso-butane and C3～C5 alkene is 0.1:1 ~ 5:1, it is preferred to 0.5:1 ~ 1.5:1.The mass concentration of concentrated sulphuric acid is 90%～97%, it is preferred to 93%～96%, and the sulphuric acid of Reaction Separation recycles, after sulfuric acid concentration reduces, it is possible to supplement fresh concentrated sulphuric acid to maintain suitable concentration.Sulfuric acid concentration is relevant to its freezing point, and in reaction system, the concentration of concentrated sulphuric acid needs to mate with reaction temperature, namely should be higher than that the freezing point of working concentration sulphuric acid in reaction temperature.
In alkylated reaction of the present invention, reaction temperature is-20～15 DEG C, it is preferred to-10～10 DEG C, it is most preferred that for-5～5 DEG C.Reaction pressure, to maintain the pressure that hydrocarbon mixture is liquid phase at the reaction temperatures, is generally 0.2 ~ 1.5MPa, it is preferred to 0.3 ~ 0.8MPa.The rotating speed of revolving bed is generally 50～5000 revs/min (rpm), it is preferred to 150～2000rpm.Reaction mass time of staying in reactor is generally 2～600 seconds, it is preferred to 10～100 seconds.
In alkylated reaction of the present invention, adopt circulating cooling gas control reaction temperature, circulating cooling gas adopt not with the arbitrary gas of material reaction in response system, it is preferred to nitrogen, hydrogen, noble gas, carbon monoxide, carbon dioxide, methane, ethane etc., it is most preferred that for nitrogen or methane.
In alkylated reaction of the present invention, reacted material, through sedimentation and follow-up separating step, isolates sulphuric acid, the alkylate oil that reaction generates, and unreacted material etc..Unreacted material such as iso-butane and rare hydrocarbon etc. can recycle.
Compared with prior art, the present invention adopts revolving bed sulfuric acid alkylation method and reactor to have the advantage that
1, less reaction temperature can be adopted.In sulfuric acid process alkylated reaction, reaction temperature is low has many-sided advantage, be embodied in can improve product octane number, reduce side reaction, reduce acid consumption etc..Adopt in the sulfuric acid process alkylation techniques of conventional reactor, reaction temperature is generally 4～10 DEG C of operations, reason is in existing reactor, and main employing mechanical agitation mode, when reaction temperature is relatively low, reaction mass viscosity is greatly lowered (mainly the concentrated sulphuric acid viscosity when low temperature is very big), when adopting pre-existing reactors, owing to the viscosity of concentrated sulphuric acid is greatly lowered, concentrated sulphuric acid and hydrocarbon raw material cannot form sufficient dispersion, when causing reaction temperature lower than 5 DEG C, reaction effect is poor.Adopt the revolving bed alkylation reactor of the present invention, due to the hypergravity effect that revolving bed produces in rotation process, the material that viscosity is big can be made still to obtain sufficient dispersion, it is possible to achieve concentrated sulphuric acid is fully dispersed with hydrocarbon raw material when lower temperature to be contacted, and obtains desirable reaction effect.Experiments show that, when the inventive method is below-15 DEG C, still there is good reaction effect.
2, the scale of consersion unit is greatly reduced.In sulfuric acid process alkylated reaction, iso-butane dissolubility in concentrated sulfuric acid is relatively low, belongs to two phase reaction in addition, and resistance to mass tranfer is relatively big, and response speed is limited mainly by mass transfer step and controls.When adopting existing consersion unit, owing to biphase dispersion effect is not enough, response speed is relatively slow, completes identical reaction, and required consersion unit is larger.Adopting the revolving bed alkylation reactor of the present invention, it is possible to significantly strengthen mass transport process, response speed is fast, and the required response time is short, and consersion unit scale can be substantially reduced, and then reduces equipment cost and operating cost.
3, course of reaction temperature field reaches the homogeneous of micron order yardstick.Sulfuric acid process alkylated reaction belongs to reactive liquid solution, in traditional reactor, for pure liquid phase reactor, liquid phase is moving material, macroscopically reaction temperature is realized uniform by the strong stirring of liquid phase reacting material, and owing to material viscosity is bigger, it is impossible to effectively get rid of the reaction focus of local.In the inventive method, adopting circulating cooling gas is cooling medium, and gas phase is continuous phase, and liquid phase is dispersion phase, and reaction mass is dispersed in circulating cooling medium with atomic little liquid mist, entirely different with traditional indirect heat exchange heat-obtaining mode.The inventive method, under the hypergravity effect of revolving bed, reaction mass can be made to realize the dispersion of micron order yardstick, liquid phase material is with small Granular composite in gas phase cooling medium, and it is the reactor connecing heat exchange that heat exchange area far operated use tube bank, and reaction temperature is more uniform, do not produce focus, reaction temperature realizes uniform on micron order yardstick, and traditional reactor can only realize homogeneous temperature macroscopically, it is impossible to get rid of the focus of local.And focus is the root causing a series of adverse effect, as product quality declines, acid consumption increase etc..It addition, rotary drill reactor in prior art, it does not have suitable temperature control mode, it is impossible to for sulfuric acid process alkylation process.
4, the revolving bed alkylation reactor of the present invention is more suitable for sulfuric acid process alkylated reaction.Such as: adopt ejector mixing that concentrated sulphuric acid and hydrocarbon material are carried out premixing, utilize charging pump lift to remain, it is achieved the shock of two kinds of liquid phases, strengthen mixed effect；The liquid phase material swabbing action to gas phase when utilizing revolving bed to operate, it is achieved the circulation of circulating cooling medium, equipment is simple.The flexible operation of the inventive method, operable wide ranges, it is possible to adapt to different operating conditions.
5, revolving bed alkylation reactor adopts the mode that revolving bed coordinates with static bed, speed when material is thrown away lathe by revolving bed is higher, there is higher motion capacity, static bed is set, it is achieved the shock again of two kinds of liquid phases, strengthens mixed effect, fully reaction further, make full use of the kinetic energy in material, when reaching same reaction effect, it is necessary to power consumption reduce.Be conducive to the collection of fog-like liquid material simultaneously.
Accompanying drawing explanation
Fig. 1 is alkylation reactor structural representation of the present invention.Wherein: 1 is liquid hydrocarbon entrance, 2 is head-on collision room, and 3 is upper cover, 4 is bed assembly, and 5 is cylinder, and 6 is low head, 7 is low head mechanical seal, and 8 is shaft coupling, and 9 is motor, 10 is material outlet, and 11 export for circulating cooling gas, and 12 is material distributor pipe, 13 is bed containment member, 14 is circulating cooling gas entrance, and 15 is playpipe, and 16 is concentrated sulphuric acid entrance, 17 is static bed, 18 is circulating air cooling tank, and 19 is circulating air cooling tank housing, and 20 is cooling gas phase coil pipe, 21 gas outlets, 22 gas accesses, 23 refrigerant inlet, 24 refrigerant exits.
Detailed description of the invention
As it is shown in figure 1, alkylation reactor structure of the present invention is percussion flow-rotary drill reactor, it is used for concentrated sulphuric acid for catalyst, the alkylation process being raw material with iso-butane and rare hydrocarbon.Utilize the powerful centrifugal force of revolving bed, by fully dispersed for full-bodied reaction mass, it is achieved good reaction effect.The equipment of suitable material premixing is set, utilizes charging pump lift to remain, it is achieved the shock of two kinds of liquid phases, strengthen mixed effect.
In reactor operation process, revolving bed is utilized to rotate the hypergravity effect formed, liquid phase material is made to disperse, utilize the liquid phase material swabbing action to gas phase, gas phase is promoted to realize from bed center flowing laterally, realize with gas phase for continuous print cooling medium, the liquid phase of high degree of dispersion is fully effectively cooled down, it is achieved the high uniformity in temperature field.Described circulating cooling gas regulates temperature through circulating air cooling tank, when needing heating or cooling when course of reaction, using circulating cooling gas as the carrier of Cooling and Heat Source, the circulating cooling gas discharged from the outlet of circulating cooling gas enters cooling gas phase coil pipe through the gas access of circulating air cooling tank, coolant enters thermal cycle gas cooling tank through refrigerant inlet, heat exchange is carried out with the circulating cooling gas in cooling gas phase coil pipe, cool down the circulating cooling gas in gas phase coil pipe and coolant after heat exchange, after circulating cooling temperature reaches temperature requirement, alkylation reactor is entered through gas outlet and circulating cooling gas entrance, complete the adjustment to reaction temperature, coolant after heat exchange is discharged through refrigerant exit.Coolant is liquefied ammonia, dry ice, hypothermic saline, ethanol etc..
Mixed material enters material distributor pipe from head-on collision room, and by material dispersion to bed, material, on the bed assembly inwall of high-speed rotation, forms hard hit, it is achieved strengthening mixing again；Material, when flowing through bed, is constantly cut by bed, and material realizes dispersion-coalescence process repeatedly at this, enhances mixed effect.Material is thrown off bed under the bed effect run up, and high-speed impact is on static bed, it may be achieved again strengthen mixing, the Appropriate application kinetic energy of material, it is achieved hybrid reaction again.Material collects reactor low head under gravity from static bed and cylinder inboard wall (partial material can be passed through static bed and arrive cylinder inboard wall), by material outlet outflow reactor, so far completes reactive liquid solution process.
Head-on collision indoor arrange relative playpipe, playpipe is made up of several nozzles, and nozzle total sectional area is the 1/3 ~ 4/5 of charging connecting tube sectional area, and liquid hydrocarbon playpipe overlaps with concentrated sulphuric acid playpipe horizontal axis, nozzle is corresponding, to ensure good head-on collision dispersion effect.
The reaction effect of the present invention is described below in conjunction with embodiment, but does not therefore limit the scope of the invention.
Embodiment 1～3
Adopting the reactor of structure as shown in Figure 1, the bed of revolving bed is made up of stainless steel cloth filler, and the bed voidage of stainless steel cloth filler is 0.95, and specific surface area is 4000m2/m3, wire diameter is 1mm, rotates bed volume and accounts for the 45% of rotary drill reactor total measurement (volume).Static bed adopts the wire packing identical with rotating bed, and the thickness of static bed is the 50% of revolving bed layer thickness.With mass concentration be 95% concentrated sulphuric acid for catalyst, be alkylated reaction with iso-butane and butylene for raw material.
The mol ratio of isobutane and butene is 1:1～300:1, it is preferred to 3:1～50:1.Acid hydrocarbon volume ratio is 0.1:1 ~ 5:1, it is preferred to 0.5:1 ~ 1.5:1.Reaction temperature is-20～15 DEG C, it is preferred to-10～10 DEG C, it is most preferred that for-5～5 DEG C.Reaction pressure is 0.2 ~ 1.5MPa, it is preferred to 0.3 ~ 0.8MPa.The rotating speed of revolving bed is generally 50～5000 revs/min (rpm), it is preferred to 150～2000rpm.Reaction mass time of staying in reactor is generally 2～600 seconds, it is preferred to 10～100 seconds.
In alkylated reaction of the present invention, circulating cooling gas adopts nitrogen, and circulating air cooling tank uses coolant to be ethanol.
Concrete operations condition is in Table 1, and reaction result is in Table 2.
Comparative example
Adopt conventional inside that the horizontal mechanical stirred reactor (structure is referring to shown in 02 phase in 2002 such as Liu Zhigang " natural gas and oil " " the alkylating process unit summary of isobutane and butene " texts and pictures 2) of refrigeration tube bank is set, reaction condition is referring to the optimized commercial operating conditions in table 1(this area), reaction result is referring to table 2.
Table 1 embodiment and comparative example alkylated reaction essential condition
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example | |
| Isobutane and butene mol ratio | 2:1 | 40:1 | 8:1 | 8:1 |
| Acid hydrocarbon volume ratio | 0.2:1 | 3:1 | 1:1 | 1:1 |
| Reaction temperature, DEG C | -6 | -2 | 6 | 6 |
| Reaction pressure, MPa | 0.5 | 0.9 | 0.7 | 0.7 |
| Reaction time, minute | 0.6 | 2 | 2 | 20 |
| Revolving bed rotating speed, rpm | 2500 | 1200 | 500 | / |
Table 2 embodiment and comparative example alkylated reaction result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example | |
| Butene conversion, mol% | ～100 | ～100 | ～100 | ～100 |
| Acid consumption, kg acid/t alkylate oil | 22 | 25 | 32 | 64 |
| Alkylate oil octane number (motor method) | 93.2 | 92.0 | 91.5 | 90.5 |
| Identical processing capacity reactor scale, volume calculations relative value | 5 | 1.5 | 10 | 100 |
From the above with comparative example it can be seen that alkylation reactor of the present invention has small scale, acid consumption is low, product quality high.
Claims (32)
1. an alkylation reactor, it is characterised in that: described reactor includes reactor shell, end socket, revolving bed, feed pipe, charging distributor pipe, discharging opening, circulating cooling gas entrance, and circulating cooling gas exports, circulating air cooling tank；Reactor shell and end socket constitute closed reactor housing, in the middle part of revolving bed is vertically set in housing, revolving bed is connected with driving device by rotating shaft, revolving bed center is empty barrel structure, charging distributor pipe is arranged in the empty barrel structure at revolving bed center, charging distributor pipe connects with feed pipe, and discharging opening is arranged on reactor shell bottom；Revolving bed radial outside arranges static bed, has suitable gap between static bed and revolving bed；Between revolving bed top and reactor shell, containment member is set, for being rotatably connected between revolving bed top and containment member, circulating cooling gas entrance and the outlet of circulating cooling gas are separately positioned in the reactor shell of containment member the upper side and lower side, and circulating air cooling tank is arranged between circulating cooling gas entrance and the outlet of circulating cooling gas；Described circulating air cooling tank includes housing and cooling gas phase coil pipe, in the middle part of cooling gas phase coil pipe is arranged in housing.
2. reactor according to claim 1, it is characterised in that: in alkylation reactor, feed pipe one end connects with charging distributor pipe, the outlet of the feed pipe other end and ejector mixing.
3. reactor according to claim 2, it is characterized in that: ejector mixing includes head-on collision room and charging jet, head-on collision indoor arrange two charging jets that position is relative, form injection mixed zone, it is achieved the premixing of material between two charging jets.
4. reactor according to claim 1, it is characterised in that: in alkylation reactor, reactor shell is cylindrical tube, and end socket includes upper cover and low head, and cylindrical reactor is vertically arranged.
5. reactor according to claim 1, it is characterised in that: in alkylation reactor, revolving bed adopts corrosion-resistant framework and bed to constitute, and bed adopts corrosion resistant metal silk screen or filler to constitute；Revolving bed profile is cylinder barrel shaped, arranges suitable space between revolving bed and reactor shell, forms annulus；Revolving bed center is cylindrical empty cylinder, and charging distributor pipe is arranged in this cylindrical empty cylinder, has suitable space between charging distributor pipe and revolving bed, forms annulus；Arranging suitable material distribution hole on charging distributor pipe, the length of charging distributor pipe is corresponding with the axial length of revolving bed；Rotating shaft is fixing with the fixing plate in revolving bed one end to be connected, and rotating shaft is vertically arranged；The driving device that rotating shaft is arranged by the outer top of end socket and reactor or bottom is connected.
6. reactor according to claim 1, it is characterized in that: it is one of following two that circulating cooling gas entrance and the outlet of circulating cooling gas arrange position: (1) is with the containment member of setting between revolving bed top and reactor shell for boundary, circulating cooling gas entrance is arranged on the housing on containment member top, and the outlet of circulating cooling gas is arranged on the housing of containment member bottom；(2) so that between revolving bed top and reactor shell, the containment member of setting is for boundary, circulating cooling gas entrance is arranged on the housing of containment member bottom, and the outlet of circulating cooling gas is arranged on the housing on containment member top.
7. reactor according to claim 1, it is characterised in that: circulating cooling gas power delivery unit is set.
8. reactor according to claim 1, it is characterised in that: static bed is at least provided with more than half cycle, and static bed and revolving bed are coaxially set.
9. reactor according to claim 8, it is characterised in that: static bed arranges one week.
10. the reactor according to claim 1 or 8, it is characterised in that: static bed is made up of corrosion-resistant screen cloth, corrosion-resistant silk screen or corrosion-resistant filling.
11. the reactor according to claim 1 or 8, it is characterised in that: the height of static bed and revolving bed are with high.
12. the reactor according to claim 1 or 8, it is characterised in that: the clearance distance between static bed and revolving bed is 10mm～700mm.
13. reactor according to claim 12, it is characterised in that: the clearance distance between static bed and revolving bed is 50mm～200mm.
14. the reactor according to claim 1 or 8, it is characterised in that: the thickness of static bed is 0.2 times～1.5 times of revolving bed thickness.
15. reactor according to claim 14, it is characterised in that: the thickness of static bed is 0.5 times～0.8 times of revolving bed thickness.
16. reactor according to claim 1, it is characterised in that: described circulating air cooling tank is provided with gas access, gas outlet, refrigerant inlet and refrigerant exit.
17. reactor according to claim 16, it is characterised in that: refrigerant inlet is arranged on circulating air cooling tank top, and refrigerant exit is arranged on bottom circulating air cooling tank.
18. reactor according to claim 16, it is characterised in that: gas access and gas outlet are separately positioned on circulating air cooling tank housing, and wherein gas access is connected with the outlet of circulating cooling gas, and gas outlet is connected with circulating cooling gas entrance.
19. an alkylation, with iso-butane and C3～C5 alkene for raw material, with sulphuric acid for catalyst, it is alkylated and is obtained by reacting alkylate oil, it is characterised in that: use the alkylation reactor described in claim 1 to 18 any claim.
20. method according to claim 19, it is characterised in that: in alkylated reaction, being total hydrocarbon feed by iso-butane and C3～C5 olefin, the mol ratio of iso-butane and C3～C5 alkene is 1:1～300:1.
21. method according to claim 20, it is characterised in that: the mol ratio of iso-butane and C3～C5 alkene is 3:1～50:1.
22. method according to claim 19, it is characterised in that: in alkylated reaction, catalyst sulfuric acid is concentrated sulphuric acid, and the sour hydrocarbon volume ratio of the hydrocarbon mixture of concentrated sulphuric acid and iso-butane and C3～C5 alkene is 0.1:1 ~ 5:1, and the mass concentration of concentrated sulphuric acid is 90%～97%.
23. method according to claim 22, it is characterised in that: the sour hydrocarbon volume ratio of the hydrocarbon mixture of concentrated sulphuric acid and iso-butane and C3～C5 alkene is 0.5:1 ~ 1.5:1；The mass concentration of concentrated sulphuric acid is 93%～96%.
24. method according to claim 19, it is characterised in that: in alkylated reaction, reaction temperature is-20～15 DEG C, and reaction pressure is to maintain the pressure that hydrocarbon mixture is liquid phase at the reaction temperatures.
25. method according to claim 19, it is characterised in that: in alkylated reaction, reaction temperature is-10～10 DEG C, and reaction pressure is 0.2 ~ 1.5MPa.
26. method according to claim 25, it is characterised in that: in alkylated reaction, reaction temperature is-5～5 DEG C, and reaction pressure is 0.3 ~ 0.8MPa.
27. method according to claim 19, it is characterised in that: the rotating speed of alkylation reactor revolving bed is 50～5000 revs/min.
28. method according to claim 27, it is characterised in that: the rotating speed of alkylation reactor revolving bed is 150～2000 revs/min.
29. method according to claim 19, it is characterised in that: reaction mass time of staying in reactor is 2～600 seconds.
30. method according to claim 29, it is characterised in that: reaction mass time of staying in reactor is 10～100 seconds.
31. method according to claim 19, it is characterised in that: in alkylated reaction, adopt circulating cooling gas control reaction temperature, circulating cooling gas employing not with the arbitrary gas of material reaction in response system.
32. method according to claim 31, it is characterised in that: circulating cooling gas is nitrogen, hydrogen, noble gas, carbon monoxide, carbon dioxide, methane or ethane.
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| CN2790575Y (en) * | 2005-03-24 | 2006-06-28 | 兰州炼油化工设计院 | Horizontal allkylation reactor |
| CN101104570A (en) * | 2006-06-23 | 2008-01-16 | 催化蒸馏技术公司 | Paraffin alkylation |
| CN103357369A (en) * | 2012-03-29 | 2013-10-23 | 中国石油化工股份有限公司 | Alkylation reaction device and method |
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| US5443799A (en) * | 1993-08-03 | 1995-08-22 | Orgral International Technologies Corporation | Process for the alkylation of olefins and apparatus for carrying out this process and others |
| CN2790575Y (en) * | 2005-03-24 | 2006-06-28 | 兰州炼油化工设计院 | Horizontal allkylation reactor |
| CN101104570A (en) * | 2006-06-23 | 2008-01-16 | 催化蒸馏技术公司 | Paraffin alkylation |
| CN103357369A (en) * | 2012-03-29 | 2013-10-23 | 中国石油化工股份有限公司 | Alkylation reaction device and method |
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