CN104549109B - A kind of temp. controllable alkylation reactor and alkylation reaction method - Google Patents

A kind of temp. controllable alkylation reactor and alkylation reaction method Download PDF

Info

Publication number
CN104549109B
CN104549109B CN201310503478.1A CN201310503478A CN104549109B CN 104549109 B CN104549109 B CN 104549109B CN 201310503478 A CN201310503478 A CN 201310503478A CN 104549109 B CN104549109 B CN 104549109B
Authority
CN
China
Prior art keywords
reactor
revolving bed
reaction
circulating cooling
heat
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310503478.1A
Other languages
Chinese (zh)
Other versions
CN104549109A (en
Inventor
方向晨
彭德强
李欣
王璐瑶
陈建兵
王岩
孟凡飞
陈新
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Original Assignee
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Fushun Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201310503478.1A priority Critical patent/CN104549109B/en
Publication of CN104549109A publication Critical patent/CN104549109A/en
Application granted granted Critical
Publication of CN104549109B publication Critical patent/CN104549109B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G50/00Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00121Controlling the temperature by direct heating or cooling
    • B01J2219/00123Controlling the temperature by direct heating or cooling adding a temperature modifying medium to the reactants
    • B01J2219/00126Cryogenic coolants

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a kind of alkylation reactor and alkylation reaction method, comprise reactor shell, end socket, revolving bed, feed pipe, charging distributor pipe, discharging opening, circulating cooling gas entrance, circulating cooling gas exports, heat-pipe elements; Reactor shell and end socket form closure casing, and revolving bed is arranged on middle part in housing, and is connected with drive unit by rotating shaft, and charging distributor pipe is arranged on revolving bed center, and charging distributor pipe is communicated with feed pipe, and discharging opening is arranged on lower housing portion; Between revolving bed and housing, containment member is set, revolving bed arranged outside heat-pipe elements, heat-pipe elements is successively through containment member and housing, and the outer heat-pipe elements chuck of housing seals, chuck is provided with refrigerant inlet and refrigerant exit, and circulating cooling gas entrance and exit is arranged on housing.Alkylation of the present invention take the concentrated sulfuric acid as catalyst, with iso-butane and alkene for raw material carries out alkylated reaction.Alkylated reaction of the present invention can carry out at low temperatures, and acid consumption is low, and equipment scale is little.

Description

A kind of temp. controllable alkylation reactor and alkylation reaction method
Technical field
The present invention relates to a kind of alkylation reactor and alkylation reaction technique, specifically a kind of alkylation reactor and alkylation reaction technique adopting iso-butane 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 iso-butane and C3 ~ C5 alkene obtains, having, research octane number (RON) high without sulphur, high-octane rating and the feature such as motor octane number difference is little, is the important blend component of high-quality clean gasoline.
Alkylated reaction is the conventional art in petroleum refining field, mainly contains sulfuric acid process alkylation techniques and hydrogen fluoride alkylation techniques, and under the effect of catalyst (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 capital expenditure, production cost, product yield and product qualities, 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, reaction temperature 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 overflow baffle between each conversion zone, each conversion zone is equipped with agitator, and product and sulfuric acid finally enter settling section and is separated, and the sulfuric acid circulating pump separated is sent into conversion zone and reused.Adopt reactant iso-butane spontaneous evaporation refrigeration, the advantage of this reaction 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 pressure vessel, a powerful agitator is equipped with in inside, Inner eycle 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 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, 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 stirring vane, forms the logistics of a high-speed circulating.Have recycle stock in this reactor, the reaction time of partial material is longer, and side reaction can increase, and acid consumption is comparatively large, unfavorable to the raising of product octane number.
Disclose the sulfuric acid alkylation course of reaction of a kind of C3-C5 alkene and iso-butane, cancel traditional mechanical agitation mode, injector is adopted to mix reaction mass and then react, but in sulfuric acid alkylation course of reaction, the density contrast of sulfuric acid and hydrocarbon material is comparatively large, and the effect of spraying hybrid mode needs to improve further.US5,785,933 disclose 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, make 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, 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, be unwell to the sulfuric acid process alkylated reaction that heat release is larger, fluid reservoir and the employing reaction mass cycling 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 contacting efficiency of catalyst and hydrocarbon reaction raw material, reduce the acid consumption of sulfuric acid catalyst, reduce reaction temperature, improve the quality of products.
Alkylation reactor of the present invention comprises following content: described reactor comprises reactor shell, end socket, revolving bed, feed pipe, charging distributor pipe, discharging opening, circulating cooling gas entrance, and circulating cooling gas exports, heat-pipe elements, coolant storage tank and cold medium compressor, reactor shell and end socket form closed reactor housing, revolving bed is vertically set on middle part in housing, revolving bed is connected with drive unit 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 is communicated with feed pipe, and discharging opening is arranged on reactor shell bottom, between revolving bed top and reactor shell, containment member is set, for being rotatably connected between revolving bed top and containment member, revolving bed radial outside arranges heat-pipe elements, suitable gap is had between heat-pipe elements and revolving bed, heat-pipe elements is successively through containment member and reactor upper body, heat-pipe elements chuck outside housing seals, chuck is provided with refrigerant inlet and refrigerant exit, coolant storage tank and cold medium compressor are arranged between refrigerant inlet and refrigerant exit, 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.
In alkylation reactor of the present invention, feed pipe one end is communicated with charging distributor pipe, the outlet of the feed pipe other end and ejector mixing; Ejector mixing comprises head-on collision room and charging jet, two charging jets that the indoor setting position that clashes is relative, is formed and sprays mixed zone, realize the premixed of material between two charging jets.
In alkylation reactor of the present invention, reactor shell is preferably cylindrical tube, and end socket comprises upper cover and low head, and cylindrical reactor preferred vertical is arranged; Revolving bed preferably adopts corrosion-resistant framework and bed to form, and bed preferably adopts corrosion resistant metal silk screen or filler to form; 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; Charging distributor pipe is arranged suitable material distribution hole, the length of material distributor pipe is corresponding with the axial length of revolving bed; Rotating shaft is fixedly connected with revolving bed one end fixed head, and rotating shaft preferred vertical is arranged; The drive unit that rotating shaft 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, in order to promote gas phase circulation in housing, realize gas phase flowing, reach the even of temperature field, alkylation reactor of the present invention is provided with circulating cooling gas entrance and the outlet of circulating cooling gas, circulating cooling gas entrance and circulating cooling gas outlet setting position are one of following two kinds: (1) with the containment member arranged 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) with the containment member arranged between revolving 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), gas phase and reaction mass through revolving bed, because revolving bed has swabbing action to gas, therefore, can not arrange gas power delivery unit, or arrange lower-powered gas power delivery unit in the same way; When adopting aforesaid way (2), gas phase and reaction mass pass back through revolving bed, need to arrange gas power delivery unit.Therefore, preferred aforesaid way (1).
In alkylation reactor of the present invention, described heat-pipe elements arranges at least 1 layer, and preferably arrange 3 ~ 5 layers, heat-pipe elements and revolving bed are coaxially set.Every layer arranges 10 ~ 30 heat-pipe elements, evenly arranges along reactor circumferencial direction.Clearance distance between heat-pipe elements and revolving bed is 5mm ~ 300mm, preferred 10mm ~ 100mm.Clearance distance between two-layer heat-pipe elements is 5mm ~ 300mm, preferred 10mm ~ 100mm.
In alkylation reactor of the present invention, by arranging heat-pipe elements, material reaction heat can being realized to take away in time, by arranging containment member, to prevent liquid by Vapor Entrainment, ensureing reactive liquid solution effect.In rotary drill reactor of the present invention, heat-pipe elements outside housing is in chuck, chuck is provided with refrigerant inlet and refrigerant exit, when course of reaction needs heating or cooling, using circulating cooling gas as the carrier of Cooling and Heat Source, refrigerant in coolant storage tank enters in chuck through refrigerant inlet, heat exchange is carried out with heat-pipe elements, heat-pipe elements and refrigerant are after heat exchange, heat-pipe elements temperature reduces, through with refrigerant heat exchange after heat-pipe elements and circulating cooling gas carry out heat exchange, realize gas phase temperature in rotary drill reactor and regulate.With the refrigerant after heat-pipe elements heat exchange through refrigerant exit, and enter coolant storage tank and reuse after cold medium compressor compression.The refrigerant adopted in coolant storage tank is liquefied ammonia, dry ice, hypothermic saline, ethanol etc.
In alkylation reactor of the present invention, when material is through heat-pipe elements, cross-flow is formed with gas phase, realize heat transfer process, heat-pipe elements both sides are provided with fin, utilize the high-speed motion kinetic energy of material when throwing away rotary bed layer assembly, the fin colliding heat-pipe elements realizes the secondary impact of two kinds of liquid phases, further the mixed effect of strengthening liquid phase.
Alkylation of the present invention, adopts abovementioned alkyl reactor of the present invention, with iso-butane and C3 ~ C5 alkene for raw material, take sulfuric acid as catalyst, carries out alkylated reaction and obtain alkylate oil.
In alkylated reaction of the present invention, be 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, 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 concentrated sulfuric acid, and the sour hydrocarbon volume ratio of the hydrocarbon mixture of the concentrated sulfuric acid and iso-butane and C3 ~ C5 alkene is 0.1:1 ~ 5:1, is preferably 0.5:1 ~ 1.5:1.The mass concentration of the concentrated sulfuric acid is 90% ~ 97%, and be preferably 93% ~ 96%, the sulfuric acid of Reaction Separation recycles, and sulfuric acid concentration can supplement the fresh concentrated sulfuric acid to maintain suitable concentration after reducing.Sulfuric acid concentration is relevant to its freezing point, and in reaction system, the concentration of the concentrated sulfuric acid needs to mate with reaction temperature, namely should higher than the freezing point of working concentration sulfuric acid in reaction temperature.
In alkylated reaction of the present invention, reaction temperature 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 revolving bed is generally 50 ~ 5000 revs/min (rpm), is preferably 150 ~ 2000rpm.Reaction mass time of staying in reactor is generally 2 ~ 600 seconds, is preferably 10 ~ 100 seconds.
In alkylated reaction of the present invention, adopt circulating cooling pneumatic control reaction temperature, circulating cooling gas adopt not with the arbitrary gas of material reaction in reaction system, be preferably nitrogen, hydrogen, inert gas, carbon monoxide, carbon dioxide, 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 iso-butane and rare hydrocarbon etc. can recycle.
Compared with prior art, the present invention adopts revolving bed sulfuric acid alkylation method and reacting appliance to have the following advantages:
1. can adopt lower reaction temperature.In sulfuric acid process alkylated reaction, reaction temperature is low has many-sided advantage, is embodied in the octane number, minimizing side reaction, reduction acid consumption etc. that can improve product.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 lower, reaction mass viscosity significantly reduces (mainly the viscosity of the concentrated sulfuric acid when low temperature is very large), when adopting pre-existing reactors, because the viscosity of the concentrated sulfuric acid significantly reduces, the concentrated sulfuric acid and hydrocarbon raw material cannot form sufficient dispersion, when causing reaction temperature lower than 5 DEG C, reaction effect is poor.Adopt revolving bed alkylation reactor of the present invention, due to the hypergravity effect that revolving bed produces in rotation process, the large material of viscosity can be made still to obtain sufficient dispersion, the concentrated sulfuric acid can be realized when lower temperature 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 consersion unit reduces greatly.In sulfuric acid process alkylated reaction, iso-butane solubility is in concentrated sulfuric acid lower, belongs to two phase reaction in addition, and resistance to mass tranfer is comparatively large, and reaction speed mainly controls by mass transfer step.When adopting existing consersion unit, because two-phase dispersion effect is not enough, reaction speed is comparatively slow, and complete identical reaction, required consersion unit is larger.Adopt revolving bed alkylation reactor of the present invention, greatly can strengthen mass transport process, reaction speed is fast, and the required reaction time is short, and consersion unit scale can reduce greatly, 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, is pure liquid phase reactor, liquid phase is moving material, realize macroscopically reaction temperature 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 cooling medium, gas phase is continuous phase, and liquid phase is decentralized photo, 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 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 heat exchange area far operated and uses tube bank to be the reactor connecing heat exchange, and reaction temperature is more even, do not produce focus, reaction temperature 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 adverse effect, as product quality 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. revolving bed alkylation reactor of the present invention is more suitable for sulfuric acid process alkylated reaction.Such as: adopt ejector mixing to carry out premixed to the concentrated sulfuric acid and hydrocarbon material, utilize charging pump lift to remain, realize the shock of two kinds of liquid phases, strengthening mixed effect; When utilizing revolving bed to operate, liquid phase material is to the swabbing action of gas phase, and realize the circulation of circulating cooling medium, equipment is simple.The flexible operation of the inventive method, can opereating specification wide, different operating conditions can be adapted to.
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, realizes the shock again of two kinds of liquid phases, strengthening 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, and 3 is upper cover, 4 is bed assembly, and 5 is cylindrical shell, and 6 is low head, 7 is low head mechanical seal, and 8 is shaft coupling, and 9 is motor, 10 is material outlet, 11 is the outlet of circulating cooling gas, and 12 is material distributor pipe, and 13 is bed containment member, 14 is circulating cooling gas entrance, 15 is playpipe, and 16 is concentrated sulfuric acid entrance, and 17 is chuck, 18 is heat-pipe elements, 19 is cold medium compressor, and 20 is coolant storage tank, and 21 is refrigerant inlet, 22 is rotating shaft, and 23 is refrigerant exit.
Detailed description of the invention
As shown in Figure 1, alkylation reactor structure of the present invention is percussion flow-rotary drill reactor, for taking the concentrated sulfuric acid as catalyst, and the alkylation process being raw material with iso-butane and rare hydrocarbon.Utilize the powerful centrifugal force of revolving bed, full-bodied reaction mass is fully disperseed, realize good reaction effect.The equipment of suitable material premixed is set, utilizes charging pump lift to remain, realize the shock of two kinds of liquid phases, strengthening mixed effect.
In reactor operation process, revolving bed is utilized to rotate the hypergravity effect formed, liquid phase material is disperseed, utilize liquid phase material to the swabbing action of gas phase, promote gas phase to realize from the flowing laterally of bed center, realizing with gas phase is continuous print cooling medium, to the abundant effective cooling of the liquid phase of high degree of dispersion, realizes the high uniformity in temperature field.Described circulating cooling gas regulates temperature through circulating cooling gas refrigeration system, when course of reaction 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 heat exchange of heat pipe bottom through the gas access of heat exchange of heat pipe, refrigerant in coolant storage tank enters heat exchange of heat pipe top through refrigerant inlet, heat exchange is carried out with heat-pipe elements, heat-pipe elements and refrigerant are after heat exchange, heat-pipe elements temperature reduces, through with refrigerant heat exchange after heat-pipe elements and the circulating cooling gas of heat exchange of heat pipe bottom carry out heat exchange, after reaching temperature requirement, alkylation reactor is entered through circulating cooling gas entrance, complete the adjustment to reaction temperature, with the refrigerant after heat-pipe elements heat exchange through refrigerant exit, and coolant storage tank is entered after cold medium compressor compression.The refrigerant adopted in coolant storage tank is liquefied ammonia, dry ice, hypothermic saline, ethanol etc.
Mixed material enters material distributor 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 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, can realize again strengthening mixing, and the Appropriate application kinetic energy of material, realizes hybrid reaction again.Material collects reactor low head 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 playpipe, playpipe is made up of several nozzles, and nozzle total sectional area is 1/3 ~ 4/5 of charging tube connector sectional area, and liquid hydrocarbon playpipe overlaps with concentrated sulfuric acid playpipe 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 revolving bed is made up of stainless steel cloth filler, and the bed voidage of stainless steel cloth filler is 0.95, and specific area is 4000m 2/ m 3, wire diameter is 1mm, rotates bed volume and accounts for 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 50% of revolving bed layer thickness.Take mass concentration as the concentrated sulfuric acid of 95% be catalyst, with iso-butane 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.Reaction temperature 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 revolving bed is generally 50 ~ 5000 revs/min (rpm), is preferably 150 ~ 2000rpm.Reaction mass time of staying 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 the refrigeration system of circulating cooling gas uses ethanol refrigeration system.
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 " natural gas and oil ") of refrigeration tube bank is set, reaction condition 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 essential condition
Table 2 embodiment and comparative example alkylated reaction result
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, product quality high.

Claims (29)

1. an alkylation reactor, is characterized in that: described reactor comprises reactor shell, end socket, revolving bed, feed pipe, charging distributor pipe, discharging opening, circulating cooling gas entrance, and circulating cooling gas exports, heat-pipe elements, coolant storage tank and cold medium compressor, reactor shell and end socket form closed reactor housing, revolving bed is vertically set on middle part in housing, revolving bed is connected with drive unit 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 is communicated with feed pipe, and discharging opening is arranged on reactor shell bottom, between revolving bed top and reactor shell, containment member is set, for being rotatably connected between revolving bed top and containment member, revolving bed radial outside arranges heat-pipe elements, suitable gap is had between heat-pipe elements and revolving bed, heat-pipe elements is successively through containment member and reactor upper body, heat-pipe elements chuck outside housing seals, chuck is provided with refrigerant inlet and refrigerant exit, coolant storage tank and cold medium compressor are arranged between refrigerant inlet and refrigerant exit, 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.
2. reactor according to claim 1, is characterized in that: in alkylation reactor, feed pipe one end is communicated 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 comprises head-on collision room and charging jet, two charging jets that the indoor setting position that clashes is relative, are formed between two charging jets and spray mixed zone, realize the premixed 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 low head, and cylindrical reactor is vertically arranged.
5. reactor according to claim 1, is characterized in that: in alkylation reactor, and revolving bed adopts corrosion-resistant framework and bed to form, and bed adopts corrosion resistant metal silk screen or filler to form; 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; Charging distributor pipe is arranged suitable material distribution hole, the length of charging distributor pipe is corresponding with the axial length of revolving bed; Rotating shaft is fixedly connected with revolving bed one end fixed head, and rotational axis vertical is arranged; The drive unit 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: circulating cooling gas entrance and circulating cooling gas outlet setting position are one of following two kinds: (1) with the containment member arranged 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) with the containment member arranged between revolving 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 6, is characterized in that: arrange circulating cooling gas power delivery unit.
8. reactor according to claim 1, is characterized in that: described heat-pipe elements arranges at least 1 layer, and heat-pipe elements and revolving bed are coaxially set.
9. reactor according to claim 8, is characterized in that: described heat-pipe elements arranges 3 ~ 5 layers.
10. reactor according to claim 8, is characterized in that: every layer arranges 10 ~ 30 heat-pipe elements, evenly arranges along reactor circumferencial direction.
11. reactors according to claim 1 or 8, is characterized in that: the clearance distance between heat-pipe elements and revolving bed is 5mm ~ 300mm.
12. reactors according to claim 11, is characterized in that: the clearance distance between heat-pipe elements and revolving bed is 10mm ~ 100mm.
13. reactors according to claim 8, is characterized in that: the clearance distance between two-layer heat-pipe elements is 5mm ~ 300mm.
14. reactors according to claim 13, is characterized in that: the clearance distance between two-layer heat-pipe elements is 10mm ~ 100mm.
15. 1 kinds of alkylations, with iso-butane and C3 ~ C5 alkene for raw material, take sulfuric acid as catalyst, 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 14.
16. methods according to claim 15, is characterized in that: in alkylated reaction, are total hydrocarbon feed by iso-butane and C3 ~ C5 olefin, and the mol ratio of iso-butane and C3 ~ C5 alkene is 1:1 ~ 300:1.
17. methods according to claim 16, is characterized in that: the mol ratio of iso-butane and C3 ~ C5 alkene is 3:1 ~ 50:1.
18. methods according to claim 15, is characterized in that: in alkylated reaction, and catalyst sulfuric acid is the concentrated sulfuric acid, and the sour hydrocarbon volume ratio of the hydrocarbon mixture of the concentrated sulfuric acid and iso-butane and C3 ~ C5 alkene is 0.1:1 ~ 5:1, and the mass concentration of the concentrated sulfuric acid is 90% ~ 97%.
19. methods according to claim 18, is characterized in that: in alkylated reaction, and catalyst sulfuric acid is the concentrated sulfuric acid, and the sour hydrocarbon volume ratio of the hydrocarbon mixture of the concentrated sulfuric acid and iso-butane and C3 ~ C5 alkene is 0.5:1 ~ 1.5:1; The mass concentration of the concentrated sulfuric acid is 93% ~ 96%.
20. methods according to claim 15, is characterized in that: in alkylated reaction, and reaction temperature is-20 ~ 15 DEG C, and reaction pressure is to maintain the pressure that hydrocarbon mixture is at the reaction temperatures liquid phase.
21. methods according to claim 15, is characterized in that: in alkylated reaction, and reaction temperature is-10 ~ 10 DEG C, and reaction pressure is 0.2 ~ 1.5MPa.
22. methods according to claim 21, is characterized in that: in alkylated reaction, and reaction temperature is-5 ~ 5 DEG C; Reaction pressure is 0.3 ~ 0.8MPa.
23. methods according to claim 15, is characterized in that: the rotating speed of alkylation reactor revolving bed is 50 ~ 5000 revs/min.
24. methods according to claim 23, is characterized in that: the rotating speed of alkylation reactor revolving bed is 150 ~ 2000 revs/min.
25. methods according to claim 15, is characterized in that: reaction mass time of staying in reactor is 2 ~ 600 seconds.
26. methods according to claim 25, is characterized in that: reaction mass time of staying in reactor is 10 ~ 100 seconds.
27. methods according to claim 15, is characterized in that: in alkylated reaction, adopt circulating cooling pneumatic control reaction temperature, circulating cooling gas adopt not with the arbitrary gas of material reaction in reaction system.
28. methods according to claim 27, is characterized in that: circulating cooling gas is hydrogen, inert gas, carbon monoxide, carbon dioxide, methane or ethane.
29. methods according to claim 27, is characterized in that: circulating cooling gas is nitrogen.
CN201310503478.1A 2013-10-24 2013-10-24 A kind of temp. controllable alkylation reactor and alkylation reaction method Active CN104549109B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310503478.1A CN104549109B (en) 2013-10-24 2013-10-24 A kind of temp. controllable alkylation reactor and alkylation reaction method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310503478.1A CN104549109B (en) 2013-10-24 2013-10-24 A kind of temp. controllable alkylation reactor and alkylation reaction method

Publications (2)

Publication Number Publication Date
CN104549109A CN104549109A (en) 2015-04-29
CN104549109B true CN104549109B (en) 2016-04-13

Family

ID=53066819

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310503478.1A Active CN104549109B (en) 2013-10-24 2013-10-24 A kind of temp. controllable alkylation reactor and alkylation reaction method

Country Status (1)

Country Link
CN (1) CN104549109B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110339796B (en) * 2019-06-28 2021-04-02 中北大学 Reaction device and method for preparing alkylated gasoline by sulfuric acid alkylation method
CN111167399A (en) * 2020-01-16 2020-05-19 中北大学 Heat pipe type hypergravity reactor and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3501536A (en) * 1969-02-26 1970-03-17 Universal Oil Prod Co Alkylation with spiralling flow path of reactants and alkylate
CN1425493A (en) * 2002-12-26 2003-06-25 华北工学院 Impact flow-rotary filler bed device and using method
CN1907924A (en) * 2005-08-02 2007-02-07 北京化工大学 Alkylation reaction technique catalyzed by ion liquid and reactor apparatus

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8119084B2 (en) * 2008-05-16 2012-02-21 Exxonmobil Research & Engineering Company Reactor for isoparaffin olefin alkylation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3501536A (en) * 1969-02-26 1970-03-17 Universal Oil Prod Co Alkylation with spiralling flow path of reactants and alkylate
CN1425493A (en) * 2002-12-26 2003-06-25 华北工学院 Impact flow-rotary filler bed device and using method
CN1907924A (en) * 2005-08-02 2007-02-07 北京化工大学 Alkylation reaction technique catalyzed by ion liquid and reactor apparatus

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
混合过程强化及其设备的研究进展;李友凤等;《化工进展》;20101231;第29卷(第10期);第593-599页 *

Also Published As

Publication number Publication date
CN104549109A (en) 2015-04-29

Similar Documents

Publication Publication Date Title
CN103801242B (en) Reactor and the alkylation reaction method utilizing this reactor
CN104549114B (en) A kind of method of alkylation reactor and alkylated reaction
CN104549086A (en) Alkylation reactor and alkylation process method
CN104549110B (en) Alkylation reactor and alkylation reaction technique method
CN205042452U (en) Percussion flow heterogeneous reaction ware
CN104549108B (en) A kind of alkylation reactor and alkylation reaction technique
CN104549087A (en) Sectional feeding type alkylation reactor and alkylation reaction method
CN104560143B (en) A kind of two section feeding alkylation reaction technique methods
CN104549109B (en) A kind of temp. controllable alkylation reactor and alkylation reaction method
CN104560142B (en) A kind of sectional feeding alkylation reaction technique method
CN104667856B (en) Alkylation reactor and alkylation reaction method
CN104560144B (en) A kind of sectional feeding alkylation reaction method
CN104549116B (en) Segmented charging alkylation reactor and alkylation reaction technique
CN104549111B (en) A kind of alkylation reactor and alkylation reaction method
CN204380586U (en) A kind of high-efficiency stirring formula synthesis tank
CN115430379A (en) Alkylation reactor
CN104549115B (en) A kind of alkylation reactor strengthening mass transfer and alkylation process
CN106929669A (en) A kind of Rare Earth Mine precipitation coprecipitated settler of the type of stirring
CN106966930B (en) A kind of method of supergravity reactor Green synthesis petroleum sulfonate for tertiary oil recovery
CN111992166B (en) Novel horizontal alkylation reactor of sulfuric acid process
CN116059940A (en) Self-rotating bed super/microgravity-micro interface reaction device and use method thereof
CN116474689A (en) Alkylation multistage reactor and alkylation reaction method
CN110396038A (en) A kind of reaction process for heterogeneous reaction system and the application system

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant