CN104549108A - Alkylation reactor and alkylation reaction process - Google Patents
Alkylation reactor and alkylation reaction process Download PDFInfo
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- CN104549108A CN104549108A CN201310503471.XA CN201310503471A CN104549108A CN 104549108 A CN104549108 A CN 104549108A CN 201310503471 A CN201310503471 A CN 201310503471A CN 104549108 A CN104549108 A CN 104549108A
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- 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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- 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
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Abstract
The invention discloses an alkylation reactor and an alkylation reaction method. The reactor comprises a reactor tube body, closure heads, a revolving bed, a charging pipe, a charge distribution pipe, a discharging opening, a circulating cooling gas inlet, a circulating gas cooling tank and a circulating cooling gas outlet, wherein a closed reactor shell body is formed by the reactor tube body and the closure heads, and the revolving bed is vertically located at the internal middle part of the shell body; a static bed layer is arranged at the radial outer side of the revolving bed, and a suitable gap exists between the static bed layer and the revolving bed; a sealing member is arranged between the upper part of the revolving bed and the reactor shell body, the upper part of the revolving bed and the sealing member are of rotatable connection, the circulating cooling gas inlet and the circulating cooling gas outlet are respectively formed in the shell body at the upper and lower sides of the sealing member, and the circulating gas cooling tank is located between the circulating cooling gas inlet and the circulating cooling gas outlet. According to the alkylation reaction method disclosed by the invention, alkylation reaction is carried out by taking concentrated sulfuric acid as a catalyst and taking isobutane and alkene as raw materials. According to the alkylation reactor and the alkylation reaction method, the alkylation reaction can be carried out at low temperature, the acid consumption is low, and the equipment scale is small.
Description
Technical field
The present invention relates to a kind of alkylation reactor and alkylation reaction method, specifically a kind of alkylation reactor and alkylation reaction method adopting Trimethylmethane and C3 ~ C5 olefin catalytic alkylated reaction.
Background technology
Along with Economic development, the particularly fast development of transportation, the discharge of Vehicular exhaust is one of air-polluting main source, and improving quality of gasoline is the main approach reducing Vehicular exhaust pollution.The alkylate oil that the alkylated reaction of Trimethylmethane and C3 ~ C5 alkene obtains, having, research octane number (RON) high without sulphur, high-octane rating and the feature such as motor-method octane number difference is little, is the important blend component of high quality clean gasoline.
Alkylated reaction is the conventional art in refining of petroleum field, mainly contains sulfuric acid process alkylation techniques and hydrogen fluoride alkylation techniques, and under the effect of catalyzer (sulfuric acid or hydrofluoric acid), isobutane and olefins is obtained by reacting isoparaffin.Sulfuric acid process alkylation is compared with hydrogen fluoride alkylation, and technique differs from one another, and also all very close from aspects such as initial cost, production cost, product yield and quality producies, therefore this two kinds of method energy long-term co-existence, is all widely adopted.On the whole, from the quantity of alkyl plant and the output of alkyl oil, current hydrofluoric acid alkylation unit is dominant, but in recent years along with the increasingly stringent of environmental regulation requirement and the hypertoxic characteristic of hydrofluoric acid, new device many employings alkyl sodium sulfate metallization processes.
In sulfuric acid process alkylation techniques, reaction is carried out at relatively low temperature, and reaction unit needs to have refrigerating function.In hydrogen fluoride alkylation techniques, temperature of reaction is relatively high, and namely the general water-cooled that adopts can meet reaction requirement.Therefore, both reactor assembly differences are larger.Traditional sulfuric acid process alkylation reactor structure species is more, and what use was more at present has two kinds, and one is cascade sulfuric acid alkylation reaction unit, and one is Stratco formula reactor (i.e. the inner indirect refrigeration reactor arranging heat-obtaining tube bank).
The reactor of cascade sulfuric acid alkylation device is generally made up of several conversion zones, separate with over-pass between each conversion zone, each conversion zone is equipped with agitator, and reaction product and sulfuric acid finally enter settling section and is separated, and the sulfuric acid recycle pump separated is sent into conversion zone and reused.Adopt reactant Trimethylmethane self-evaporatint n. refrigeration, the advantage of this reactive system be alkane alkene in each conversion zone than high, power consumption is little, do not need another refrigerant feeding.But because alkane and alkene are not pre-mixed, thus reduce alkylate oil quality, add sour consumption.And influence each other between each conversion zone, a conversion zone operation is abnormal, and whole reactor is all affected.
A kind of concrete structure of indirect refrigeration reactor that inside arranges heat-obtaining tube bank is that to adopt be horizontal eccentric reactor, the shell of reactor is a horizontal pressurized vessel, a powerful agitator is equipped with in inside, internal recycle sleeve and heat-obtaining tube bank, hydrocarbon raw material enters reactor by upper and lower two feed-pipes, reactor is sprayed into towards impeller after converging before paddle wheel, 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, thus make sulfuric acid and hydro carbons obtain reasonable dispersion and mix.Acid hydrocarbon emulsion is turned back in reactor head again and is entered sleeve inner, again flows to agitating vane, forms the logistics of a high-speed circulating.Have recycle stock in this reactor, the reaction times of partial material is longer, and side reaction can increase, and acid consumption is comparatively large, unfavorable to the raising of product octane value.
Disclose the sulfuric acid alkylation reaction process of a kind of C3-C5 alkene and Trimethylmethane, cancel traditional mechanical stirring mode, injector is adopted to mix reaction mass and then react, but in sulfuric acid alkylation reaction process, the density difference of sulfuric acid and hydrocarbon material is comparatively large, and the effect of spraying hybrid mode needs to improve further.US
5,785,933disclosing a kind of sulfuric acid catalysis alkylation reactor system, multiple injection pipeline entrances that inside reactor is put by arranging baffle plate and tangential height, making reaction mass form mix and blend in reactor, and then cancel mechanical moving element.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, rotating bed is arranged on reactor internal upper part, reactor lower part is container for storing liquid, reactor center arranges whipping appts, and container for storing liquid and feed liquid recycle pump connect and compose rotating 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, be unwell to the sulfuric acid process alkylated reaction that heat release is larger, container for storing liquid and the employing reaction mass cyclical operation mode of reactor lower part can increase side reaction.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of alkylation reactor and alkylation process, improve the contact efficiency of catalyzer and hydrocarbon reaction raw material, reduce the acid consumption of sulfuric acid catalyst, reduce temperature of reaction, improve the quality of products.
Alkylation reactor of the present invention comprises following content: reactor shell, end socket, rotating bed, feed-pipe, charging distribution pipe, discharge port, circulating cooling gas entrance, and circulating cooling gas exports, circulation gas cooling tank; Reactor shell and end socket form closed reactor housing, rotating bed is vertically set on middle part in housing, rotating bed is connected with drive unit by turning axle, rotating bed center is empty barrel structure, charging distribution pipe is arranged in the empty barrel structure at rotating bed center, charging distribution pipe is communicated with feed-pipe, and discharge port is arranged on reactor shell bottom; Rotating bed radial outside arranges static bed, has suitable gap between static bed and rotating bed; Between rotating bed top and reactor shell, containment member is set, for being rotatably connected between rotating 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 circulation gas cooling tank is arranged between circulating cooling gas entrance and the outlet of circulating cooling gas; Described circulation gas cooling tank comprises housing and cooling gas phase coil pipe, and cooling gas phase coil pipe is arranged on middle part in housing.
In alkylation reactor of the present invention, arrange circulation gas refrigeration system between circulating cooling gas entrance and the outlet of circulating cooling gas, circulating cooling gas formed circulation before circulating cooling gas refrigeration system and reactor, for reaction process provides suitable temperature environment.
In alkylation reactor of the present invention, static bed at least arranges more than half cycle, preferably arranges one week.The concrete modes such as the fixed form of static bed can adopt bottom fixed form, top fixed form, and radial direction is fixing.When adopting top fixed form, preferably 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 rotating bed are coaxially set.The height of static bed is preferably same high with rotating bed.Clearance distance between static bed and rotating bed is 10mm ~ 700mm, preferred 50mm ~ 200mm.The thickness of static bed is 0.2 times ~ 1.5 times of rotating bed thickness, preferably 0.5 times ~ 0.8 times.
In alkylation reactor of the present invention, feed-pipe one end is communicated with charging distribution pipe, the outlet of the feed-pipe the other end and jet mixer; Jet mixer comprises head-on collision room and charging jet orifice, two charging jet orifices that the indoor setting position that clashes is relative, is formed and sprays mixing zone, utilize charging pump lift residual power, realize the pre-mixing of material between two charging jet orifices.
In alkylation reactor of the present invention, reactor shell is preferably cylindrical tube, and end socket comprises upper cover and lower cover, and cylindrical reactor preferred vertical is arranged; Rotating bed preferably adopts corrosion-resistant framework and bed to form, and bed preferably adopts corrosion resistant metal silk screen or filler to form; Rotating bed profile is cylinder barrel shaped, arranges suitable space between rotating bed and reactor shell, forms annulus; Rotating bed center is cylindrical empty cylinder, and charging distribution pipe is arranged in this cylindrical empty cylinder, has suitable space between charging distribution pipe and rotating bed, forms annulus; Charging distribution pipe is arranged suitable material distribution hole, the length of material distribution pipe is corresponding with the axial length of rotating bed; Turning axle is fixedly connected with rotating bed one end retaining plate, and turning axle preferred vertical is arranged; The drive unit that turning axle is arranged by the outer top of end socket and reactor or bottom is connected, and drive unit is preferably arranged on the outer bottom of reactor.
In alkylation reactor of the present invention, circulating cooling gas entrance and circulating cooling gas outlet setting position are one of following two kinds: (1) with the containment member arranged between rotating 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) with the containment member arranged between rotating bed top and reactor shell for boundary, circulating cooling gas entrance is arranged on the housing of containment member bottom, circulating cooling gas outlet be arranged on the housing on containment member top.When adopting aforesaid way (1), circulating cooling gas and reaction mass pass rotating bed in the same way, because rotating bed has suction function to gas, therefore, circulating cooling gas power delivery unit can not be set, 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 rotating bed, need to arrange circulating cooling gas power delivery unit.Therefore, preferred aforesaid way (1).
In alkylation reactor of the present invention, circulation gas cooling tank comprises housing and cooling gas phase coil pipe, cooling gas phase coil pipe is arranged on middle part in housing, described circulation gas cooling tank is provided with gas inlet, pneumatic outlet, refrigerant inlet and refrigerant exit, wherein, pneumatic outlet and gas inlet are arranged on circulation gas cooling tank housing, and gas inlet exports with circulating cooling gas and is connected, and pneumatic outlet is connected with circulating cooling gas entrance; Refrigerant inlet and refrigerant exit are separately positioned on circulation gas cooling tank top and bottom.
In alkylation reactor of the present invention, circulation gas refrigeration system is set, rotating bed is utilized to rotate the tiny structure formed, promote circulating cooling gas phase to realize from the flowing laterally of bed center, when reaction process needs heating or cooling, using circulating cooling gas as the carrier of Cooling and Heat Source, the circulating cooling gas of discharging from the outlet of circulating cooling gas enters cooling gas phase coil pipe through the gas inlet of circulation gas cooling tank, refrigerant enters thermal cycling gas cooling tank through refrigerant inlet, heat exchange is carried out with the circulating cooling gas in cooling gas phase coil pipe, circulating cooling gas in cooling gas phase coil pipe and refrigerant are after heat exchange, after circulating cooling temperature degree reaches temperature requirement, alkylation reactor is entered through pneumatic outlet and circulating cooling gas entrance, complete the adjustment to temperature of reaction, refrigerant after heat exchange is discharged through refrigerant exit.Refrigerant is liquefied ammonia, dry ice, hypothermic saline, ethanol etc.
Alkylation of the present invention, adopts abovementioned alkyl reactor of the present invention, with Trimethylmethane and C3 ~ C5 alkene for raw material, take sulfuric acid as catalyzer, carries out alkylated reaction and obtain alkylate oil.
In alkylated reaction of the present invention, be total hydrocarbon feed by Trimethylmethane and C3 ~ C5 olefin, the mol ratio of Trimethylmethane and C3 ~ C5 alkene is mol ratio is 1:1 ~ 300:1, is preferably 3:1 ~ 50:1.C3 ~ C5 alkene is monoolefine, is preferably butylene.
In alkylated reaction of the present invention, catalyst sulfuric acid is the vitriol oil, and the sour hydrocarbon volume ratio of the hydrocarbon mixture of the vitriol oil and Trimethylmethane and C3 ~ C5 alkene is 0.1:1 ~ 5:1, is preferably 0.5:1 ~ 1.5:1.The mass concentration of the vitriol oil is 90% ~ 97%, and be preferably 93% ~ 96%, the sulfuric acid of Reaction Separation recycles, and sulfuric acid concentration can supplement the fresh vitriol oil to maintain suitable concentration after reducing.Sulfuric acid concentration is relevant to its zero pour, and in reaction system, the concentration of the vitriol oil needs to mate with temperature of reaction, namely should higher than the zero pour of working concentration sulfuric acid in temperature of reaction.
In alkylated reaction of the present invention, temperature of reaction is-20 ~ 15 DEG C, is preferably-10 ~ 10 DEG C, most preferably is-5 ~ 5 DEG C.Reaction pressure, to maintain the pressure that hydrocarbon mixture is at the reaction temperatures liquid phase, is generally 0.2 ~ 1.5MPa, is preferably 0.3 ~ 0.8MPa.The rotating speed of rotating bed is generally 50 ~ 5000 revs/min (rpm), is preferably 150 ~ 2000rpm.Reaction mass residence time in reactor is generally 2 ~ 600 seconds, is preferably 10 ~ 100 seconds.
In alkylated reaction of the present invention, adopt circulating cooling pneumatic control temperature of reaction, circulating cooling gas adopt not with the arbitrary gas of material reaction in reactive system, be preferably nitrogen, hydrogen, rare gas element, carbon monoxide, carbonic acid gas, methane, ethane etc., most preferably be nitrogen or methane.
In alkylated reaction of the present invention, reacted material, through sedimentation and follow-up separating step, isolates sulfuric acid, the alkylate oil that reaction generates, and unreacted material etc.Unreacted material such as Trimethylmethane and rare hydrocarbon etc. can recycle.
Compared with prior art, the present invention adopts rotating bed sulfuric acid alkylation method and reacting appliance to have the following advantages:
1, lower temperature of reaction can be adopted.In sulfuric acid process alkylated reaction, temperature of reaction is low has many-sided advantage, is embodied in the octane value, minimizing side reaction, reduction acid consumption etc. that can improve product.Adopt in the sulfuric acid process alkylation techniques of conventional reactor, temperature of reaction is generally 4 ~ 10 DEG C of operations, reason is in existing reactor, and main employing mechanical stirring mode, when temperature of reaction is lower, reaction mass viscosity significantly reduces (mainly the viscosity of the vitriol oil when low temperature is very large), when adopting pre-existing reactors, because the viscosity of the vitriol oil significantly reduces, the vitriol oil and hydrocarbon raw material cannot form sufficient dispersion system, when causing temperature of reaction lower than 5 DEG C, reaction effect is poor.Adopt rotating bed alkylation reactor of the present invention, due to the hypergravity effect that rotating bed produces in rotation process, the large material of viscosity can be made still to obtain sufficient dispersion, the vitriol oil can be realized when lesser temps and the abundant dispersing contact of hydrocarbon raw material, obtain desirable reaction effect.Experiment shows, when the inventive method is below-15 DEG C, still has good reaction effect.
2, the scale of conversion unit reduces greatly.In sulfuric acid process alkylated reaction, Trimethylmethane solubleness is in concentrated sulfuric acid lower, belongs to two phase reaction in addition, and resistance to mass transfer is comparatively large, and speed of response mainly controls by mass transfer step.When adopting existing conversion unit, because two-phase dispersion effect is not enough, speed of response is comparatively slow, and complete identical reaction, required conversion unit is larger.Adopt rotating bed alkylation reactor of the present invention, can reinforcing mass transfer process greatly, speed of response is fast, and the required reaction times is short, and conversion unit scale can reduce greatly, and then reduces equipment cost and process cost.
3, reaction process temperature field reaches the homogeneous of micron order yardstick.Sulfuric acid process alkylated reaction belongs to reactive liquid solution, in traditional reactor, is pure liquid phase reaction, liquid phase is moving material, realize macroscopically temperature of reaction by the strong stirring of liquid phase reacting material even, and due to material viscosity comparatively large, effectively cannot get rid of the reaction focus of local.In the inventive method, adopt circulating cooling gas to be heat-eliminating medium, gas phase is external phase, and liquid phase is disperse phase, and reaction mass is dispersed in circulating cooling medium with atomic little liquid mist, completely different from traditional indirect heat exchange heat-obtaining mode.The inventive method, under the hypergravity effect of rotating 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 heat-eliminating medium, and heat interchanging area far operated and uses tube bank to be the reactor connecing heat exchange, and temperature of reaction is more even, do not produce focus, temperature of reaction realizes even on micron order yardstick, and traditional reactor can only realize homogeneous temperature macroscopically, cannot get rid of the focus of local.And focus is the root causing a series of harmful effect, as quality product declines, acid consumption increases.In addition, rotary drill reactor in prior art, does not have suitable temperature control mode, cannot be used for sulfuric acid process alkylation process.
4, rotating bed alkylation reactor of the present invention is more suitable for sulfuric acid process alkylated reaction.Such as: adopt jet mixer to carry out pre-mixing to the vitriol oil and hydrocarbon material, utilize charging pump lift to remain, realize the shock of two kinds of liquid phases, enhancing mixed effect; When utilizing rotating bed to operate, liquid phase material is to the suction function of gas phase, and realize the circulation of circulating cooling medium, equipment is simple.The flexible operation of the inventive method, can operating restraint wide, different operational conditions can be adapted to.
5, rotating bed alkylation reactor adopts the mode that rotating bed coordinates with static bed, speed when material is thrown away lathe by rotating bed is higher, there is higher motion capacity, static bed is set, realizes the shock again of two kinds of liquid phases, enhancing mixed effect, fully reaction further, make full use of the kinetic energy in material, when reaching same reaction effect, the power consumption of needs reduces.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, 3 is upper cover, 4 is bed assembly, 5 is cylindrical shell, 6 is lower cover, 7 is lower cover mechanical seal, 8 is shaft coupling, 9 is motor, 10 is material outlet, 11 is the outlet of circulating cooling gas, 12 is material distribution pipe, 13 is bed containment member, 14 is circulating cooling gas entrance, 15 is spray tube, 16 is vitriol oil entrance, 17 is static bed, 18 is circulation gas cooling tank, 19 is circulation gas cooling tank housing, 20 is cooling gas phase coil pipe, 21 pneumatic outlets, 22 gas inletes, 23 refrigerant inlet, 24 refrigerant exits.
Embodiment
As shown in Figure 1, alkylation reactor structure of the present invention is percussion flow-rotary drill reactor, for taking the vitriol oil as catalyzer, and the alkylation process being raw material with Trimethylmethane and rare hydrocarbon.Utilize the powerful centrifugal force of rotating bed, full-bodied reaction mass is fully disperseed, realize good reaction effect.The equipment of suitable material pre-mixing is set, utilizes charging pump lift to remain, realize the shock of two kinds of liquid phases, enhancing mixed effect.
In reactor operation process, rotating bed is utilized to rotate the hypergravity effect formed, liquid phase material is disperseed, utilize liquid phase material to the suction function of gas phase, promote gas phase to realize from the flowing laterally of bed center, realizing with gas phase is continuous print heat-eliminating medium, to the abundant effective cooling of the liquid phase of high dispersing, realizes the high uniformity in temperature field.Described circulating cooling gas regulates temperature through circulation gas cooling tank, when reaction process needs heating or cooling, using circulating cooling gas as the carrier of Cooling and Heat Source, the circulating cooling gas of discharging from the outlet of circulating cooling gas enters cooling gas phase coil pipe through the gas inlet of circulation gas cooling tank, refrigerant enters thermal cycling gas cooling tank through refrigerant inlet, heat exchange is carried out with the circulating cooling gas in cooling gas phase coil pipe, circulating cooling gas in cooling gas phase coil pipe and refrigerant are after heat exchange, after circulating cooling temperature degree reaches temperature requirement, alkylation reactor is entered through pneumatic outlet and circulating cooling gas entrance, complete the adjustment to temperature of reaction, refrigerant after heat exchange is discharged through refrigerant exit.Refrigerant is liquefied ammonia, dry ice, hypothermic saline, ethanol etc.
Mixed material enters material distribution pipe from head-on collision room, and by material dispersion on bed, material, on the bed assembly inwall of high-speed rotation, forms hard hit, realizes enhancing mixed 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, can realize enhancing mixed again, and the Appropriate application kinetic energy of material, realizes hybrid reaction again.Material collects reactor lower cover under gravity from static bed and cylinder inboard wall (partial material can arrive cylinder inboard wall by static bed), by material outlet outflow reactor, so far completes reactive liquid solution process.
Head-on collision is indoor arranges relative spray tube, spray tube is made up of several nozzles, and nozzle total sectional area is 1/3 ~ 4/5 of charging pipe connecting sectional area, and liquid hydrocarbon spray tube overlaps with vitriol oil spray tube horizontal axis, nozzle is corresponding, to ensure good head-on collision dispersion effect.
Below in conjunction with embodiment, reaction effect of the present invention is described, but does not therefore limit the scope of the invention.
Embodiment 1 ~ 3
Adopt the reactor of structure as shown in Figure 1, the bed of rotating 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 4000m
2/ m
3, wire diameter is 1mm, rotates bed volume and accounts for 45% of rotary drill reactor cubic capacity.Static bed adopts the wire packing identical with rotating bed, and the thickness of static bed is 50% of rotating bed layer thickness.Take mass concentration as the vitriol oil of 95% be catalyzer, with Trimethylmethane and butylene for raw material carries out alkylated reaction.
The mol ratio of isobutane and butene is 1:1 ~ 300:1, is preferably 3:1 ~ 50:1.Acid hydrocarbon volume ratio is 0.1:1 ~ 5:1, is preferably 0.5:1 ~ 1.5:1.Temperature of reaction is-20 ~ 15 DEG C, is preferably-10 ~ 10 DEG C, most preferably is-5 ~ 5 DEG C.Reaction pressure is 0.2 ~ 1.5MPa, is preferably 0.3 ~ 0.8MPa.The rotating speed of rotating bed is generally 50 ~ 5000 revs/min (rpm), is preferably 150 ~ 2000rpm.Reaction mass residence time in reactor is generally 2 ~ 600 seconds, is preferably 10 ~ 100 seconds.
In alkylated reaction of the present invention, circulating cooling gas adopts nitrogen, and circulation gas cooling tank uses refrigerant 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 see shown in 02 phase " the alkylating process unit of isobutane and butene is summarized " one texts and pictures 2 in 2002 such as Liu Zhigang " Sweet natural gas and oil ") of refrigeration tube bank is set, reaction conditions is see the optimized commercial operating conditions in table 1(this area), reaction result is see table 2.
Table 1 embodiment and comparative example alkylated reaction underlying 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 |
| Temperature of reaction, 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 |
| Rotating 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 value (motor method) | 93.2 | 92.0 | 91.5 | 90.5 |
| Identical amount of finish reactor scale, volume calculation relative value | 5 | 1.5 | 10 | 100 |
As can be seen from above-described embodiment and comparative example, alkylation reactor of the present invention has small scale, and acid consumption is low, quality product high.
Claims (23)
1. an alkylation reactor, is characterized in that: described reactor comprises reactor shell, end socket, rotating bed, feed-pipe, charging distribution pipe, discharge port, circulating cooling gas entrance, and circulating cooling gas exports, circulation gas cooling tank; Reactor shell and end socket form closed reactor housing, rotating bed is vertically set on middle part in housing, rotating bed is connected with drive unit by turning axle, rotating bed center is empty barrel structure, charging distribution pipe is arranged in the empty barrel structure at rotating bed center, charging distribution pipe is communicated with feed-pipe, and discharge port is arranged on reactor shell bottom; Rotating bed radial outside arranges static bed, has suitable gap between static bed and rotating bed; Between rotating bed top and reactor shell, containment member is set, for being rotatably connected between rotating 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 circulation gas cooling tank is arranged between circulating cooling gas entrance and the outlet of circulating cooling gas; Described circulation gas cooling tank comprises housing and cooling gas phase coil pipe, and cooling gas phase coil pipe is arranged on middle part in housing.
2. reactor according to claim 1, is characterized in that: in alkylation reactor, feed-pipe one end is communicated with charging distribution pipe, the outlet of the feed-pipe the other end and jet mixer.
3. reactor according to claim 2, it is characterized in that: jet mixer comprises head-on collision room and charging jet orifice, two charging jet orifices that the indoor setting position that clashes is relative, are formed between two charging jet orifices and spray mixing zone, realize the pre-mixing of material.
4. reactor according to claim 1, is characterized in that: in alkylation reactor, and reactor shell is cylindrical tube, and end socket comprises upper cover and lower cover, and cylindrical reactor is vertically arranged.
5. reactor according to claim 1, is characterized in that: in alkylation reactor, and rotating bed adopts corrosion-resistant framework and bed to form, and bed adopts corrosion resistant metal silk screen or filler to form; Rotating bed profile is cylinder barrel shaped, arranges suitable space between rotating bed and reactor shell, forms annulus; Rotating bed center is cylindrical empty cylinder, and charging distribution pipe is arranged in this cylindrical empty cylinder, has suitable space between charging distribution pipe and rotating bed, forms annulus; Charging distribution pipe is arranged suitable material distribution hole, the length of material distribution pipe is corresponding with the axial length of rotating bed; Turning axle is fixedly connected with rotating bed one end retaining plate, and rotational axis vertical is arranged; The drive unit that turning axle 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: circulating cooling gas entrance and circulating cooling gas outlet setting position are one of following two kinds: (1) with the containment member arranged between rotating 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) with the containment member arranged between rotating bed top and reactor shell for boundary, circulating cooling gas entrance is arranged on the housing of containment member bottom, circulating cooling gas outlet be arranged on the housing on containment member top.
7. reactor according to claim 1, is characterized in that: arrange circulating cooling gas power delivery unit.
8. reactor according to claim 1, is characterized in that: static bed at least arranges more than half cycle, preferably arranges one week, and static bed and rotating bed are coaxially set.
9. the reactor according to claim 1 or 8, is characterized in that: static bed is made up of corrosion-resistant screen cloth, corrosion-resistant silk screen or corrosion-resistant filling.
10. the reactor according to claim 1 or 8, is characterized in that: the height of static bed and rotating bed are with high.
11. reactors according to claim 1 or 8, is characterized in that: the clearance distance between static bed and rotating bed is 10mm ~ 700mm, preferred 50mm ~ 200mm.
12. reactors according to claim 1 or 8, is characterized in that: the thickness of static bed is 0.2 times ~ 1.5 times of rotating bed thickness, preferably 0.5 times ~ 0.8 times.
13. reactors according to claim 1, is characterized in that: described circulation gas cooling tank is provided with gas inlet, pneumatic outlet, refrigerant inlet and refrigerant exit.
14. reactors according to claim 13, is characterized in that: refrigerant inlet is arranged on circulation gas cooling tank top, and refrigerant exit is arranged on bottom circulation gas cooling tank.
15. reactors according to claim 13, is characterized in that: gas inlet and pneumatic outlet are separately positioned on circulation gas cooling tank housing, and wherein gas inlet exports with circulating cooling gas and is connected, and pneumatic outlet is connected with circulating cooling gas entrance.
16. 1 kinds of alkylations, with Trimethylmethane and C3 ~ C5 alkene for raw material, take sulfuric acid as catalyzer, carry out alkylated reaction and obtain alkylate oil, it is characterized in that: use the alkylation reactor described in the arbitrary claim of claim 1 to 15.
17. methods according to claim 16, is characterized in that: in alkylated reaction, are total hydrocarbon feed by Trimethylmethane and C3 ~ C5 olefin, and the mol ratio of Trimethylmethane and C3 ~ C5 alkene is mol ratio is 1:1 ~ 300:1, are preferably 3:1 ~ 50:1.
18. methods according to claim 16, is characterized in that: in alkylated reaction, and catalyst sulfuric acid is the vitriol oil, and the sour hydrocarbon volume ratio of the hydrocarbon mixture of the vitriol oil and Trimethylmethane and C3 ~ C5 alkene is 0.1:1 ~ 5:1, are preferably 0.5:1 ~ 1.5:1; The mass concentration of the vitriol oil is 90% ~ 97%, is preferably 93% ~ 96%.
19. methods according to claim 16 or 18, it is characterized in that: in alkylated reaction, temperature of reaction is-20 ~ 15 DEG C, is preferably-10 ~ 10 DEG C, most preferably is-5 ~ 5 DEG C; Reaction pressure, to maintain the pressure that hydrocarbon mixture is at the reaction temperatures liquid phase, is preferably 0.2 ~ 1.5MPa, most preferably is 0.3 ~ 0.8MPa.
20. methods according to claim 16, is characterized in that: the rotating speed of alkylation reactor rotating bed is 50 ~ 5000 revs/min, are preferably 150 ~ 2000 revs/min.
21. methods according to claim 16, is characterized in that: reaction mass residence time in reactor is 2 ~ 600 seconds, are preferably 10 ~ 100 seconds.
22. methods according to claim 16, is characterized in that: in alkylated reaction, adopt circulating cooling pneumatic control temperature of reaction, circulating cooling gas adopt not with the arbitrary gas of material reaction in reactive system.
23. methods according to claim 22, is characterized in that: circulating cooling gas is nitrogen, hydrogen, rare gas element, carbon monoxide, carbonic acid gas, methane or ethane.
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| CN105642217A (en) * | 2016-03-24 | 2016-06-08 | 华东理工大学 | Transportation-reinforced external circulation type alkylation reactor and alkylation reaction method |
| CN105664826A (en) * | 2016-03-24 | 2016-06-15 | 华东理工大学 | External circulation type alkylation reactor and external circulation type alkylation reacting method |
| CN109082299A (en) * | 2018-09-25 | 2018-12-25 | 孙志良 | A kind of coal tar hydrocracking decomposition technique |
| CN117025252A (en) * | 2023-10-09 | 2023-11-10 | 东营联合石化有限责任公司 | Hydrocracking and hydrodesulfurization combined device |
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| CN105642217A (en) * | 2016-03-24 | 2016-06-08 | 华东理工大学 | Transportation-reinforced external circulation type alkylation reactor and alkylation reaction method |
| CN105664826A (en) * | 2016-03-24 | 2016-06-15 | 华东理工大学 | External circulation type alkylation reactor and external circulation type alkylation reacting method |
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| CN117025252B (en) * | 2023-10-09 | 2023-12-12 | 东营联合石化有限责任公司 | Hydrocracking and hydrodesulfurization combined device |
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